JPH0743519B2 - 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 applied to, for example, a direct positive type silver halide color photographic light-sensitive material for reproducing an original image having image information such as characters and paintings with high quality.

[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 cases, the reproducibility of fine lines is not sufficient for some applications, and the reproducibility of image information remains a problem. In addition, the color reproducibility may be insufficient, such as when reproducing from a printed matter with halftone dots. to solve this problem,
It is conceivable 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 coating is added to the antihalation layer to prevent halation, but an antihalation layer is formed by a mordant layer of a 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]

In view of the above problems, the present invention has an object to obtain a direct positive type silver halide color photographic light-sensitive material excellent in sharpness, whiteness and color reproducibility, and has high contrast in a highlight portion, The purpose is to obtain the above-mentioned light-sensitive material having good sharpness.

[Structure and Action of Invention]

The present invention has, on a support, a photographic constituent layer containing a silver halide emulsion layer having different color sensitivities containing a cyan coupler and a magenta coupler respectively, and three silver halide emulsion layers having different color sensitivities. Is a direct-positive type silver halide emulsion layer which directly forms a positive image by light fogging, and an antihalation layer is formed on the side closer to the support than the silver halide emulsion layer. In order to achieve the above object, a direct positive type silver halide photographic material is provided by incorporating a compound represented by the general formula [I] described below in at least one of the photographic constituent layers.

In the present invention, the compound represented by the general formula [I] is contained in at least one layer of the photographic constituent layers such as a silver halide emulsion layer. This compound can function as a so-called anti-stain agent. In the present invention, the compound represented by the general formula [I] is preferably contained in the antihalation layer or a layer adjacent thereto.

The general formula [I] is as shown below.

In the formula [I], R ₁ and R ₂ each represent a hydrogen atom or an alkyl group, and the number of carbon atoms in each of the alkyl groups R ₁ and R ₂ is 5 or less, and n is 1 to 3 It is preferable to select a numerical value.

As the compound represented by the general formula [I], specifically, the compounds shown in the following (A) to (H) are preferable. However, what can be used in the present invention is not particularly limited to these compounds.

(Compound example) The amount of this compound added to at least one of the photographic constituent layers is preferably 0.001 to 0.50 g / m ² , and more preferably 0.005 to 0.20 g / m ² . Each of the above compounds may be used alone, or two or more compounds may be arbitrarily selected and mixed, and a quinone derivative having 5 or more carbon atoms is represented by the above general formula [I]. It can also be used by adding to the compound. However, in any of these cases, the amount used is 0.001 as a whole even if it is a mixture.
It is preferably in the range of 0.50 g / m ² .

The photographic constituent layer is a multi-layer composed of a color-sensitive layer and a non-color-sensitive layer containing at least an antihalation layer, and the color-sensitive layer is a silver halide emulsion layer containing a cyan coupler and a magenta coupler. A silver halide emulsion layer containing a yellow coupler and a silver halide emulsion layer containing a yellow coupler, and the non-color-sensitive layer is an antihalation layer, an intermediate layer formed as necessary, an emulsion protective layer, etc. It is composed of layers. The above compound is added to at least one of these photographic constituent layers, but the processing conditions such as the addition timing and the addition method are not particularly limited to specific conditions. In this way, by containing the above compound in at least one of the photographic constituent layers, it is possible to obtain a light-sensitive material excellent in whiteness and color reproducibility by reducing the stain of the image obtained by development. .
This is because by containing the above compound, the minimum density of the developed photograph can be suppressed to be low, the sharpness in the characteristic curve can be improved, and the contrast of the shadow portion can be kept high.

The amount of the above compound used is 0.001 to 0.50 g / m ² as described above.
The range is good, and if the content is less than this range, the above effect gradually decreases, and conversely if it increases, it has the effect of preventing foot clipping, but the contrast in the shadow part tends to be low, and the overall value is Therefore, the content within the above range is preferable.

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. Representative supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, polyethylene laminated paper, etc., which are optionally subbed.

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.

Examples of the resin used for the hydrophobic resin coating layer coated on the surface include polyolefins such as polyethylene, polypropylene and polybutene, olefins such as ethylene, propylene and butene, and monomers such as vinyl acetate, vinylidene chloride and maleic anhydride. And copolymers (for example, ethylene-vinyl acetate copolymer, propylene-vinylidene chloride copolymer, propylene-maleic anhydride copolymer, etc.), or polystyrene, polyvinyl chloride, polyacrylate, saturated polyester, polycarbonate, etc. A homopolymer or co-polymer of
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 a polyethylene resin is used, the molecular weight thereof is not particularly limited as long as extrusion coating is possible, but polyethylene having a molecular weight of 20,000 to 200,000 is usually 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 transparent density can be obtained by forming voids to be whitened by admixing and then extruding or stretching, or by adhering the voids.

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.

As the inorganic compound used when carrying out the present invention,
Colloidal silver and colloidal manganese are suitable. 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 reduced by keeping silver nitrate in gelatin in 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.

Further, each color-sensitive layer of the present invention comprises, on the above-mentioned support, a red-sensitive direct positive silver halide emulsion layer containing a cyan coupler, a green-sensitive direct positive silver halide emulsion layer containing a magenta coupler, According to the yellow filter layer,
And a blue-sensitive direct positive silver halide emulsion layer containing a yellow coupler.

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, as a yellow dye-forming coupler, a benzoylacetanilide type, a pivaloylacetanilide type, or a so-called split in which a carbon atom at the coupling position can be released at the time of coupling 2-equivalent yellow couplers substituted with off groups 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 a cyan dye forming coupler, a phenol type,
A 2-equivalent cyan coupler having a naphthol type, a pyrazoquinazolone type, or 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 to prevent discoloration of the dye image due to an actinic ray having a short wavelength, and examples thereof include thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds.
120, 320, 326, 327, and 328 (all manufactured by Ciba-Geigy) are preferably used alone or in combination.

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, 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. Or a silver halide emulsion having silver halide grains containing a polyvalent metal ion described in U.S. Pat.Nos. 3,271,157, 3,447,927 and 3,531,291, or U.S. Patents
No. 3,761,276, a silver halide emulsion containing a silver halide grain containing a doping agent, the surface of which is weakly chemically sensitized, or JP-A Nos. 50-8524, 50-38525 and 5
So-called core-shell type silver halide emulsions by the laminating method described in 3-2408, and others, JP-A-52-156614.
The silver halide emulsions described in JP-A-55-127549 and JP-A-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, JP-A-50-8524
No. 50, 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. Examples thereof include a method of adding a halide to silver nitrate and laminating it, or a method of forming silver iodobromide grains in a state in which excess halogen is small, and further laminating silver chloride and silver bromide in order.

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 the crystal habit, cubic crystal, octahedron, tetradecahedral, twin crystal or tabular crystal habit can be preferably used.

The emulsion may be prepared by any of the acidic method, neutral method, alkaline method, ammoniacal method and the like. Further, any of a forward mixing method, a reverse mixing method and a simultaneous mixing method can be used, and a pAg control 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 layer type silver halide emulsion is used, the emulsion has a stabilizer which is usually used for suppressing the surface sensitivity as low as possible and 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.

In addition, 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, mouldants, 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, the hydrophilic colloid layer may contain other hydrophilic binder in addition to gelatin.

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 suitable for the purpose. A plasticizer, a lubricant, 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 form a positive image directly by light fog. 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 layer type silver halide color photographic light-sensitive material, and can 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 the color developing solution 1, and more preferably about 1 g to about 30 g for the color developing solution 1.
Use at a concentration of 15g.

As the p-phenylenediamine-based developer, the first aromatic amino-based color developing agent is particularly useful, which is an N, N-dialkyl-p-phenylenediamine-based compound, in which an alkyl group and a phenyl group are substituted. Or may not be substituted. Among them, examples of particularly useful compounds include N, N-diethyl-p-phenylenediamine hydrochloride.

The alkaline color developing solution which can be used in the present invention is, in addition to the above-mentioned first aromatic amino color developing agent, various components which are usually added to the color developing solution, such as sodium hydroxide, sodium carbonate and potassium carbonate. Alkali agents such as, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners may optionally be contained. The pH value of this color developing solution is preferably usually 7
Above, 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, thioethers, high-concentration bromides, and iodides. 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. Further, borate, oxalate, acetate, carbonate, phosphate and other pH buffering agents, 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 carried out 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 replenisher may contain these salts to replenish the treatment 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 of 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 a fixing ability, a usual washing treatment may be carried out, but 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 performed, the water washing step is substantially unnecessary, and thus the piping equipment for the water washing treatment is unnecessary,
There is an advantage that the device itself can be easily installed in any place.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited to these examples. Prior to the description of specific examples, the general formula [I] used in the following examples
The preparation of the compounds (A) to (H) as the compound (hereinafter referred to as the compound of the present invention) will be described, and then the preparation of a light-sensitive material in which a photographic constituent tank is formed on a support will be described.

[Formulation of Compound of the Present Invention]

Each of the compounds (A) to (H) of the present invention is weighed in a predetermined amount and dissolved in acetic acid ester and dioctyl phthalate, and this solution is mixed with a predetermined amount of a gelatin solution containing sodium dodecylbenzenesulfonate. Is ultrasonically dispersed to prepare a dispersion solution containing the compounds (A) to (H). At this time, when two or more compounds (A) to (H) are mixed, the total amount of each is adjusted to a predetermined amount.

Antihalation layer (first layer) Gray colloidal silver produced by reduction under an alkaline weak reducing agent (however, the weak reducing agent was removed by neutralized silver noodle washing method), a surfactant [S-1], and Hardener [S-3]
Prepare a 2.6% gelatin solution containing
2 g / m ^2, it is coated so that the amount with gelatin is 0.9 g / m ^2.

First intermediate layer (second layer) A gelatin solution containing a surfactant [S-2] and a hardener [H-1] is prepared and coated so that the gelatin coating amount will be 0.9 g / m ² .

Red photosensitive emulsion layer (third layer) 2.0% inactive gelatin solution was kept at 50 ° C., and the following solutions A and B were added at the same time with stirring and the mixture was injected over 3 minutes. After 10 minutes, the following solution C was injected and added 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] and 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, Tinuvin 328 was applied at a coating amount of 0.15 g / m ² .

Green light-sensitive emulsion layer (fifth layer) Silver halide grains were prepared in the same manner as the red light-sensitive emulsion.
A liquid containing sensitizing dye [D-2], 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate, and magenta coupler [MC-1], 4-hydroxy-6-methyl-1,3,3a, 7-Tetrazaindene, 1-phenyl-5-mercaptotetrazole, gelatin, and coating aid [S-2] are added in appropriate amounts. 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 coating amount of Tinuvin 328 was 0.2 g / m ² .

Yellow filter layer (7th layer) Yellow colloidal silver made by oxidizing under alkaline weak reducing agent (however, weak reducing agent is removed by neutralized acid noodle washing method) and 2,5 dispersed in dioctyl phthalate −
A dioctyl hydroquinone solution, a coating aid [S-2], and a film hardener [H-1] (added immediately before coating) were added and coating was carried out so that the coating silver amount was 0.15 g / m ² .

4th intermediate layer (8th layer) With the same formulation as the 2nd intermediate layer, the amount of Tinuvin 328 applied was 0.15 g / m ²
Was applied so that

Blue-sensitive emulsion layer (9th 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. After 15 minutes, inject the following solution C over 2 minutes, and after 1 minute, hypo 3mg / Ag
A considerable amount was added and the mixture was aged for 40 minutes. In addition, when sampling and compositional analysis, AgCl4 mol%, AgBr96 mol%, AgI2
It was silver chlorobromoiodide composed of mol%.

After removing the excess salt by the precipitation water washing method, the following liquids D and E were added to form a surface layer of 97 mol% AgCl and 3 mol% AgBr, and then the excess salt was removed again by the precipitation water washing method to add gelatin for dispersion. It was

Yellow coupler [YC-1] dispersed with sensitizing dye [D-3] and dioctyl phthalate in this silver halide emulsion.
, 2-mercaptobenzothiazole, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, gelatin, coating aid [S-3] and hardener [H-2] ( A solution containing (added immediately before coating) was used so that the coated silver amount was 0.5 g / 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-1] was added immediately before coating.

Protective layer (11th layer) Amorphous silica with 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
Was applied so that

Example-1 In this example, a formulation dispersion of the compound of the present invention obtained by the above formulation was mixed with a coating liquid for forming an antihalation layer, and the addition amount of each compound (A) to (H) was 0.01. g /
It was applied at m ² or 0.05 g / m ² . Further, a photographic constituent layer such as a first intermediate layer and a red light-sensitive emulsion layer was coated to obtain a light-sensitive material to which the present invention was applied. Samples obtained by adding the compounds (A) to (H) thus obtained were designated as sample Nos. 2 to 17, respectively. Sample No. 1 is a comparative sample to which the above compound was not added. After that, each of the above samples was subjected to wedge exposure using a KS-7 type sensitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.) and developed according to the following steps.

I. Processing process (processing temperature and processing time) [1] Immersion (color developing solution) 38 ° C for 8 seconds [2] Fog exposure 1 lux for 10 seconds [3] Color development 38 ° C for 2 seconds [4] Bleach fixing 35 ° C for 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 Fluorescent brightener (4,4'-diaminostilbenz sulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Water was added. Adjust the total amount to 1 and adjust to pH 10.20.

(Bleaching fixer) 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-isothiazoline-3-
On 1.0 g Ethylene glycol 10 g 1-Hydroxyethylidene-1,1'-diphosphonic acid 2.5
g Bismuth chloride 0.2g Magnesium chloride 0.1g Ammonium hydroxide (28% aqueous solution) 2.0g Sodium nitrilotriacetate 1.0g Add water to make the total 1 and adjust to pH 7.0 with ammonium hydroxide or sulfuric acid. And blue light (B), green light (G), red light (R) in each of these samples
Table 1 shows the gamma-1 (γ ₁ ) and minimum concentration (Dmin) at. Where γ ₁ is the concentration 0.15 to 0.5 on the characteristic curve.
Is a tangent of an angle formed by using the density origin of as a horizontal axis, represents contrast, and Dmin represents the minimum density. As is clear from these experimental results, the present invention samples Nos. 2 to 17 have a larger γ ₁ value than the comparative sample No. _1, and it is clear that the contrast is high and the foot is cut off. It was It is also clear that Sample Nos. 2 to 17 have smaller Dmin than Sample No. 1 and have good whiteness with less stain. This shows that sample Nos. 2 to 17 have better color reproducibility than sample No. 1.

Example-2 In this example, the compound dispersion of the present invention was added to the first intermediate layer adjacent to the antihalation layer in the same manner as in Example-1, and the addition amount in this intermediate layer was 0.03 g / m ^2. And the other photographic constituent layers were coated to obtain the light-sensitive material of the present invention.
And each sample was made into sample No. 18-26. For these samples, γ ₁ and Dmin for each sample as in the first embodiment.
The results are shown in Table 2 below. As is clear from these results, the light-sensitive material of the present invention has excellent contrast and minimum density as compared with those in which the compound of the present invention is not added, as in the first embodiment.

Example-3 In this example, 0.10 g / m ^{2 of} the above compound prepared in Example-1 was added to a layer other than the photographic constituent layers in Example-1 and Example-2 to prepare a sample in the invention. No.30
~ 34 was prepared. Sample No. 29 in this table is a comparative sample to which the above compound was not added. As is clear from these results, as in the above-mentioned examples with respect to γ ₁ and Dmin,
The samples in the present invention are all superior in contrast to the comparative samples.

[Effects of the Invention] According to the present invention, the compound of the present invention is added to at least one of the photographic constituent layers of the direct positive type silver halide color photographic light-sensitive material to obtain excellent whiteness and excellent color reproducibility. A good photographic image can be obtained, and an image with high contrast in the shadow portion can be obtained.

Continuation of front page (56) References JP-A-50-156438 (JP, A) JP-A-50-110337 (JP, A) JP-A-63-108336 (JP, A) JP-B-50-21249 (JP , B2)

Claims (1)

[Claims] 1. A support having a photographic constituent layer comprising a silver halide emulsion layer having different color sensitivity containing a cyan coupler, a magenta coupler and a yellow coupler, respectively, and three halogens having different color sensitivity. The silver halide emulsion layers are all composed of a direct positive type silver halide emulsion layer that directly forms a positive image by light fog, and an antihalation layer is formed on the side closer to the support than the silver halide emulsion layer. A direct positive type silver halide color photographic light-sensitive material, characterized in that, in the silver halide light-sensitive material, at least one of the photographic constituent layers contains a compound represented by the following general formula [I]. General formula [I] In the formula, R ₁ and R ₂ represent a hydrogen atom or an alkyl group, the alkyl groups of R ₁ and R ₂ each have 5 or less carbon atoms, and n represents 1, 2, or 3 .