JPH0830868B2 - Color photosensitive material that can be processed quickly - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color light-sensitive material. At times, it relates to a direct positive silver halide color light-sensitive material capable of rapid processing.

[Conventional technology]

It has been conventionally desired that color light-sensitive materials can be processed quickly. Therefore, an emulsion containing silver chloride is used as a silver halide emulsion that enables rapid processing.

On the other hand, in a color light-sensitive material, a colloidal silver layer containing a colloidal silver dispersion is generally included in a photographic constituent layer as a yellow filter layer or the like. When such a colloidal silver layer (yellow filter layer, etc.) is in direct contact with the emulsion layer, a phenomenon called contact fog is likely to occur. This contact fog is particularly likely to occur when a silver chloride-containing emulsion is used as described above for rapid processing. As a measure for preventing this, a non-photosensitive auxiliary layer may be provided between the colloidal silver layer and the emulsion layer. By interposing this auxiliary layer, contact can be cut off, and thus contact fog can be suppressed. However, by simply providing this auxiliary layer,
Although contact fog can be suppressed, the photographic characteristics of the legs, in particular, tend to be softened in terms of photographic performance. This tendency is particularly remarkable when an emulsion containing silver chloride is used.

On the other hand, as a measure against pollution, it is required that the photographic processing liquid does not contain substances that are not desirable for pollution prevention as much as possible. In particular, benzyl alcohol has been conventionally contained in the color developing solution in order to function as a color developing agent.
Since BOD and COD are increased, it is not desirable in terms of pollution prevention, and therefore it is desirable to reduce the concentration of benzyl alcohol in the color developer as much as possible. If the concentration of benzyl alcohol falls below about 1 ml / l, it is thought that pollution problems can be avoided.

However, if the concentration of benzyl alcohol in the color developing solution is reduced, the functions such as color forming, which were the actions of benzyl alcohol, are compensated.Therefore, the color developing solution has some measures, for example, a small amount of an inhibitor or color developing. It is necessary to take measures such as increasing the amount of the main drug. Even when such measures are taken, the photographic characteristics of the photographic performance are generally softened, especially the photographic characteristics of the legs. The above-mentioned contact fog also easily occurs. These problems tend to occur particularly in direct positive silver halide color light-sensitive materials.

[Object of the Invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to enable rapid processing, and even when an auxiliary layer adjacent to a colloidal silver layer is provided to prevent contact fog, benzyl alcohol is also used. Another object of the present invention is to provide a direct positive silver halide color light-sensitive material capable of avoiding the softening of the legs in the photographic characteristics even when a color developing solution having a small content of is used.

[Structure and Action of Invention]

The present invention has a silver halide emulsion layer containing a coupler, and the coupler reacts with an oxidized product of a color developing agent to form a dye, thereby forming a dye. And an internal latent image type silver halide emulsion layer having a silver chloride content of 10 mol% or more, a colloidal silver layer containing a colloidal silver dispersion, and adjacent to the colloidal silver layer,
Further, at least one non-photosensitive auxiliary layer is provided between the colloidal silver layer and the internal latent image type silver halide emulsion layer having a silver chloride content of 10 mol% or more. The total silver / gelatin ratio with the photosensitive auxiliary layer is 0.3 or less, and the benzyl alcohol content is 1 ml.
A direct positive silver halide color light-sensitive material characterized by being color-developed with a color-developing solution having a volume ratio of / l or less, thereby achieving the above object.

In the present invention, since the total silver / gelatin ratio of the colloidal silver layer and the non-photosensitive auxiliary layer is 0.3 or less, the auxiliary layer is provided and the benzyl alcohol content of the developing solution is It was possible to avoid the softening of the legs due to the reduced amount.

The colloidal silver layer can be constructed, for example, as a yellow filter layer. Further, it can be formed as an antihalation layer by forming it on the side closer to the support than the emulsion layer. When it is constituted as a yellow filter layer, a non-photosensitive auxiliary layer may be provided on both sides so as to sandwich the yellow filter layer, or it may be provided on one side so as to be interposed between the yellow filter layer and an emulsion layer for which contact fog is particularly desired to be prevented. It can also be configured to. In the case of being constituted as an antihalation layer, this auxiliary layer can be usually formed on the upper side (the side farther from the support) so as to be interposed between the auxiliary layer and the emulsion layer.

A silver / gelatin ratio of 0.3 or less means 0.3 or less by weight. Preferably
It is 0.25 or less, more preferably 0.2 or less. In this case, the amount of silver is the amount (weight) of silver contained in the colloidal silver layer.
The gelatin amount is the total weight of the gelatin amount in the colloidal silver layer and the gelatin amount in the non-photosensitive auxiliary layer adjacent thereto.

The non-photosensitive auxiliary layer is a layer consisting essentially of a hydrophilic binder,
For example, it may be formed as a gelatin layer. This auxiliary layer binds non-photosensitive additives such as UV absorbers, developers, stabilizers, baths of silver salts, development inhibitors (such as water-soluble halides) and diffusible developer oxidation products. Compounds, non-photosensitive silver halides, and other compounds.

The colloidal silver layer is configured to contain various kinds of colloidal silver. The preparation of various types of colloidal silver that can be used is described in various documents. For example, Carey Lea's literature on the preparation of yellow colloidal silver by the dextrin reduction method (Wiley & Sons, New York, 1933, Welser
Colloidal Ele-ments) or German Patent No. 10961
No. 93 (brown and black colloidal silver) or U.S. Pat. No. 2,868,601 (blue colloidal silver). There is also a related description in German Laid-Open Publication No. 1917745.

Yellow colloidal silver is contained in, for example, a layer disposed between the uppermost blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer thereunder, and the colloidal silver layer is used as a yellow filter layer. Can be materialized. Dark colloidal silver, for example, brown or black colloidal silver, is contained in a layer between the support and the photosensitive silver halide emulsion layer closest to the support, and this colloidal silver layer functions as an antihalation layer. It is possible to improve the sharpness of the image.

The direct positive color light-sensitive material of the present invention has at least one internal latent image type silver halide emulsion layer having a silver chloride content of 10 mol% or more based on pre-silver halide. When the present invention is embodied as a single-layer (monochromatic) color light-sensitive material, this layer contains silver chloride in the above content. When embodied as a multi-layer (multi-color) color light-sensitive material, at least one layer is a silver chloride-containing emulsion layer having the above content, and preferably all layers are silver chloride-containing emulsion layers as described above. is there. This allows for rapid processing.

As the internal latent image type silver halide emulsion used in the direct positive color photographic material of the present invention, those described in Research Disclosure No. 15162 can be used. The internal latent image type silver halide grain used in the present invention is a silver halide grain containing silver chloride, and the content of silver chloride is 10 mol% or more based on the total silver halide of the grain, More preferably, it is 10 to 80 mol%. In this case, the silver iodide content of the silver halide grains is 10
It is preferably not more than mol%.

As the internal latent image type silver halide grain, for example, a core / shell type emulsion in which a core is chemically sensitized or a dopant is occluded in the grain is used as described in JP-B-52-34213. be able to. In this case, the shell preferably contains silver chloride.

Examples of internal latent image type silver halide grains include U.S. Pat.
The conversion type emulsion described in No. 592,250 can be used.
Further, the laminated silver halide emulsion described in JP-B-58-1412 can be used. In the case of laminated internal latent image type silver halide grains, the silver halide composition of the surface layer (shell) is preferably 5 to 100 mol% silver chloride and 1 mol% or less silver iodide. The silver halide composition of the inner layer (core) is
Although not particularly limited, silver chloride is 30 mol% or less and silver iodide is 5 mol% or less. Suitably it is silver chlorobromide.

Further, an emulsion in which silver chloride is precipitated on monodisperse type grains mainly composed of silver bromide, which is produced by the double jet method while controlling pAg and pH, can be used.

The silver halide emulsion used in the present invention can be chemically sensitized by an ordinary method at any stage of production. Furthermore, the silver halide grains used in the present invention can occlude polyvalent metal ions inside the grains. Specific preferred examples of the polyvalent metal ion include iridium ion, lead ion, antimony ion, bismuth ion, gold ion, platinum ion, osmium ion and rhodium ion.

In the practice of the present invention, as the internal latent image type silver halide grain, it is preferable that the grain surface is not chemically sensitized, or is sensitized to a slight extent.

The internal latent image type silver halide grains are those in which the grain surface is not pre-fogged, but the meaning that the grain surface is not pre-fogged means that the emulsion used is on a transparent film support. The test piece coated so as to have a concentration of 35 mgAg / dm ² was exposed to the following surface developer A without exposing to 10 ° C at 20 ° C.
The density obtained when developed for 0.6 minutes is 0.6, preferably 0.4.
It means not to exceed.

Surface developer A Metol 2.5 g 1-Ascorbic acid 10 g NaBO ₂ .4H ₂ O 35 g KBr 1 g Water was added 1 l The internal latent image type silver halide emulsion preferably used in the present invention was prepared as described above. The test piece thus prepared gives a sufficient density when exposed and then developed with an internal developer B having the following formulation.

Internal developer B Metol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Add water 1 l More specifically, one of the test pieces Part was exposed to a light intensity scale for a defined period of time up to about 1 second and developed with internal developer B for 4 minutes at 20 ° C., another part of the test piece exposed under the same conditions was surfaced. 20 with developer A
It exhibits a maximum density of at least 5 times, preferably at least 10 times that obtained when developed at 4 ° C. for 4 minutes.

The silver halide emulsion that can be used in the practice of the present invention can be optically sensitized with a commonly used sensitizing dye. Combinations of sensitizing dyes generally used for supersensitization such as internal latent image type silver halide emulsions and negative type silver halide emulsions are also useful for the present invention. Research Disclosure (Research D
isclosure) No.15162 can be referred to.

The direct positive color light-sensitive material of the present invention can easily obtain a direct positive image by surface development after being photographed by an ordinary method. That is, the main step of directly producing a positive image is a treatment for generating a surface development nucleus by a chemical action or a photochemical action after exposing a light-sensitive material having an internal latent image type silver halide emulsion layer which has not been fogged. (After referred to as fog treatment) and /
Alternatively, the surface development is performed while performing the fog treatment. The fog treatment here is a compound that gives an overall exposure or generates a fog nucleus (hereinafter referred to as a fog agent).
Can be done using.

When the whole surface is exposed, it can be performed by immersing or moistening the imagewise exposed light-sensitive material in a developing solution or other aqueous solution, and then uniformly exposing the whole surface. The light source used here may be any light within the light-sensitive wavelength range of the light-sensitive material, and can be exposed to high-illuminance light such as flash light for a short time or weak light for a long time. Good. Also, the total exposure time depends on the photosensitive material, development processing conditions, type of light source used, etc.
It can be varied over a wide range to obtain the final positive image.

When the present invention is directly applied to a positive color light-sensitive material using a fogging agent, a wide variety of compounds can be used as the fogging agent. This fog agent may be present at the time of development processing, and for example, in the constituent layers other than the support of the light-sensitive material (among them, particularly in the silver halide emulsion layer),
Alternatively, it may be contained in a developing solution or a processing solution prior to the developing process. The amount used can be varied over a wide range according to the purpose, and the preferable addition amount is 1 to 1500 mg, and more preferably 10 to 1000 mg per mol of silver halide when added to the silver halide emulsion layer. Is. When it is added to a processing solution such as a developing solution, the addition amount is preferably 0.01 to 5 g / l, particularly preferably 0.05 to 1 g / l.

Examples of the fogging agent that can be used include hydrazines described in U.S. Pat.Nos. 2,563,785 and 2,588,982, or hydrazones or hydrazone compounds described in U.S. Pat.No. 3,227,552; U.S. Pat.
No. 3,718,470, No. 3,719,494, No. 3,734,738 and No. 3,759,901, and heterocyclic quaternary nitrogen salt compounds; and silver halides such as acylhydrazinophenylthioureas described in US Pat. No. 4,030,925. Examples thereof include compounds having an adsorption group on the surface. Further, these fog agents may be used in combination. For example, research
Disclosure (Research Disclosure) No.15162
Describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent.

As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, or they can be used in combination.

Specific examples of useful fogging agents include hydrazine hydrochloride, phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2- (4-methylphenyl) hydrazine, 1-acetyl-2-phenylhydrazine. , 1-acetyl-2- (4-acetamidophenyl) hydrazine, 1-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine, 1-methylsulfonyl-2- (3-phenylsulfonamidophenyl) hydrazine , Hydrazine compounds such as formaldehyde phenylhydrazine; 3- (2-
Formylethyl) -2-methylbenzothiazolium bromide, 3- (2-formylethyl) -2-propylbenzothiazolium bromide, 3- (2-acetylethyl) -2-benzylbenzoselenazolium bromide,
3- (2-Acetylethyl-2-benzyl-5-phenyl-benzoxazolium bromide, 2-methyl-3
-[3- (Phenylhydrazono) propyl] benzothiazolium bromide, 2-methyl-3- [3- (p-tolylhydrazono) propyl] benzothiazolium bromide, 2-methyl-3- [3- (p -Sulfophenylhydrazono) propyl] benzothiazolium bromide, 2-methyl-3- [3- (p-sulfophenylhydrazono) pentyl] benzothiazolium iodode, 1,
2-dihydro-3-methyl-4-phenylpyrido [2,1-
b] Benzothiazolium bromide, 1,2-dihydro-3
-Methyl-4-phenylpyrido [2,1-b] -5-phenylbenzoxazolium bromide, 4,4'-ethylenebis (1,2-dihydro-3-methylpyrido [2,1-b] benzothiazo Lithium bromide), 1,2-dihydro-3-methyl-4-phenylpyrido [2,1-b] benzoselenazolium bromide and other N-substituted quaternary cycloammonium salts; 5- [1-ethylnaphtho (1, 2-b) Thiazoline-2-
Ylidene ethylidene] -1- (2-phenylcarbazoyl) methyl-3- (4-sulfamoylphenyl) -2
-Thiohydantoin, 5- (3-ethyl-2-benzothiazolinylidene) -3- [4- (2-formylhydrazino) phenyl] rhodamine, 1- [4- (2-formylhydrazino) Phenyl] 3-phenylthiourea, 1,
3-bis [4- (2-formylhydrazino) phenyl] thiourea and the like can be mentioned.

The direct positive color light-sensitive material generally forms a direct positive image by subjecting it to imagewise exposure followed by overall exposure or development in the presence of a fogging agent. The development processing method in this case may be any development processing method, but the 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.

Examples of the developer that can be used in the developer include conventional silver halide developers such as polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, and phenylenediamine. And the like or a mixture thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-
Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, N, N-
Diethyl-p-phenylenediamine, diethylamino-
o-toluidine, 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (β-
Hydroxyethyl) aniline and the like. These developing agents may be contained in the emulsion in advance so that they act on the silver halide during the immersion in the high pH aqueous solution.

The developer used in the present invention has a benzyl alcohol content of 1 ml / l or less. The developer may contain specific antifoggants and development inhibitors, or these developer additives may optionally be incorporated into the constituent layers of the photographic material. Usually useful antifoggants include benzotriazoles such as 5-methylbenzotriazole, benzimidazoles, benzothiazoles, benzoxazoles, 1-phenyl-
Heterocyclic thiones such as 5-mercaptotetrazole, aromatic and aliphatic mercapto compounds and the like are included. Further, the developer may contain a development accelerator such as a polyalkylene oxide derivative or a quaternary ammonium salt compound.

It is optional to add various photographic additives to the silver halide emulsion used in the present invention.

In the present invention, the additive used according to the purpose,
Examples of the wetting agent include dihydroxyalkane and the like, and further examples of the film physical property improving agent include, for example, a copolymer of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid, and a styrene-maleic acid copolymer. , Styrene maleic anhydride half alkyl ester copolymers and the like are suitable water-dispersible particulate polymer substances obtained by emulsion polymerization, and the coating aids include, for example, saponin, polyethylene glycol lauryl ether, etc. Be done. Other photographic additives include gelatin plasticizers, surfactants, UV absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, moldants, brighteners, development speeds. The use of regulators, matting agents, etc. is optional.

In the silver halide photographic emulsion are included conventional dye forming couplers, typically cyan, magenta and yellow dye image forming couplers. As the coupler, those usually used can be used.

Further, it is useful to use an ultraviolet absorber, for example, thiazolidone, benzotriazole, acrylonitrile, or a benzophenone compound in order to prevent browning due to actinic rays having a short wavelength in a dye image, and particularly, tinuvin PS, 32
0, statues 326, 327, 328 (all manufactured by Ciba Geigy)
It is advantageous to use singly or in combination.

Any support may be used as the support of the color light-sensitive material of the present invention. As a typical support, a polyethylene terephthalate film which has been subjected to undercoating, if necessary,
Polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, polyethylene laminated paper and the like are included.

In the silver halide emulsion according to the present invention, a gelatin derivative suitable for the purpose can be used as a protective colloid or a binder in addition to gelatin. Examples of suitable gelatin derivatives include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, esterified gelatin and the like.

Further, in the present invention, other hydrophilic binder may be contained depending on the purpose, and as this suitable binder, in addition to gelatin, colloidal albumin, agar, gum arabic, dextran, alginic acid, and acetyl-containing material are contained. 19 ~
Cellulose derivatives such as cellulose acetate hydrolyzed to 20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethanecarboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl aminoacetate copolymer, polyvinyl Emulsion layer containing alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymer obtained by polymerization of protein or saturated acylated protein and monomer having vinyl group, polyvinylpyridine, polyvinylamine, polyaminoethylmethacrylate, polyethyleneamine, etc. Or an intermediate layer, a protective layer,
It can be added to a photographic material constituting layer such as a filter layer or a backing layer according to the purpose, and the hydrophilic binder can contain an appropriate plasticizer, lubricant or the like according to the purpose.

The constituent layers of the light-sensitive material of the present invention can be hardened with any appropriate hardener. Examples of these hardeners include chromium salts, zirconiums, aldehydes such as formaldehyde and mucohalic acid, halotriazines, polyepoxy compounds, ethyleneimine, vinylsulfone, and acryloyl hardeners. .

〔Example〕

Examples of the present invention will be described below. Of course, the present invention is not limited to the examples below.

Example 1 In this example, the internal latent image type silver halide emulsion defined above was prepared as described in detail below to obtain a direct positive silver halide color light-sensitive material.

In this embodiment, a direct inversion emulsion is used, which is prepared as described below.

First, a monodisperse type silver bromide core emulsion was prepared as follows.
While controlling the temperature of the solution containing gelatin at 40 ° C, an aqueous ammonia solution containing the same number of moles of silver nitrate as shown in Table 1 below and an aqueous solution containing the same number of moles of potassium bromide (KBr) were prepared. , Was added over the time shown in Table 1. During this addition, pH and pA were adjusted so that cubic particles were obtained.
The g was controlled to be constant. Then, after washing with water to remove the water-soluble salt, gelatin and water were added to finish the amount shown in Table 1 to obtain a core emulsion.

Next, with respect to the above-mentioned silver bromide core emulsion, an aqueous solution containing the same number of moles of silver nitrate as shown in Table 1 and an aqueous solution containing the same number of moles of sodium chloride (NaCl) were added over the time shown in Table 1. A shell layer was formed on the silver bromide core by adding at the same time, and then washed with water. As a result, seven kinds of emulsions containing AgCl mol% shown in Table 1 based on the total silver halide were obtained. Emulsions No. 1 to No. 7 shown in Table 1 had uniform grain sizes and were monodisperse emulsions.

Using the emulsion thus obtained, a light-sensitive material was prepared as described below and used as a sample.

That is, the following dye [I] was added to each of the above emulsions to prepare silver halide 1
Spectral sensitization was performed by adding 100 mg each per mole.

Next, the magenta coupler 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-octadecylsuccinimidoanilino) -5-pyrazolone was dissolved in dibutyl phthalate and ethyl acetate to prepare a gelatin aqueous solution. To prepare an emulsion.

This emulsion dispersion was spectrally sensitized as described above for emulsion Nos. 1 to 7
And hardener, and the coated silver amount is 20mg / 1.
Samples No. ¹ to N were applied as a light-sensitive material by coating and drying the cellulose triacetate support so as to be 00 cm ^2.
o.7.

These samples No.1-1 to No.1-7 were wedge-exposed through a yellow filter and developed with a developer having the following formulation at 38 ° C. for 2 minutes.

However, 10 seconds after the start of development, the entire surface was uniformly exposed with a fluorescent lamp of 30 lux through an ND filter having a density of 1.0 for 10 seconds. Then, it was bleach-fixed, washed with water and dried.

For the obtained magenta positive image, maximum density Dmax.,
The results of measuring the minimum density Dmin. And gamma are shown in Table 2. However, gamma is represented by the absolute value of the gamma value that connects the density point of Dmin. + (Dmax.-Dmin.) × 0.2 and the density point of Dmin. + (Dmax.-Dmin.) × 0.8.

As can be seen from Table-2, from the viewpoint of rapid processing, a higher AgCl mol% ratio is preferred. And AgCl mol% is 5 mol%
It has been found that the above results give preferable results.

Example-2 In this example, a direct reversal color light-sensitive material was prepared as follows.

Red photosensitive emulsion layer (first layer) A 20% 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 liquid C was added by injection over 3 minutes. After aging for 40 minutes, remove excess salt by precipitation water washing method, and then add solution D and solution E,
A 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.

Then, the following sensitizing dye [II] was added to this silver halide emulsion,
2,5-Dioctylhydroquinone protected and dispersed with dibutyl phthalate and the following cyan coupler (C-
A liquid containing 1), 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene, 1-phenyl-5-mercaptotetrazole, gelatin, and a suitable amount of the following coating aid (S-1) are added. The coated silver amount was 0.4 g / m ² .

First intermediate layer (second 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 (third layer) Silver halide grains were prepared in the same manner as the red light-sensitive emulsion. A solution containing sensitizing dye [III], 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate and the following magenta coupler (M-1), 4-hydroxy-6-methyl-1,3,3a, 7 -Tetrazaindene, 1
-Phenyl-5-mercaptotetrazole Furthermore, gelatin and a coating aid (S-2) are added in appropriate amounts.

The coated silver amount was 0.4 g / m ² .

2nd intermediate layer (4th layer) The same formulation as the 1st intermediate layer, the amount of Tinuvin 328 applied was 0.2 g / m ²
And

Yellow filter layer (fifth layer) Yellow colloidal silver and 2,5-dioctylhydroquinone dispersed in yellow colloidal silver and dioctyl phthalate, which is formed by oxidizing under a weak alkaline reducing agent (weak reducing agent is removed by a noodle washing method after neutralization) Liquid, coating aid (S-2) and film hardener (H-1) (added just before coating) to add the amount of coated silver
It was set to 0.1 g / m ² . The gel coating amount was changed depending on the sample No. as shown in Table-3.

Third Intermediate Layer (Sixth Layer) A gelatin solution containing a coating aid (S-1) was prepared, and the gelatin coating amount was changed as shown in Table-3.

Blue light-sensitive emulsion layer (seventh layer) The following emulsions were used here. That is, the following liquids A and B were added at the same time while stirring a 1.5% inactive gelatin liquid at 60 ° C., and the mixture was injected over 15 minutes. After 15 minutes, the solution was injected over 2 minutes, and 1 minute later, hypo was added in an amount of 3 mg / mol Ag, and the mixture was aged for 40 minutes. Sampling and compositional analysis revealed that the silver chlorobromoiodide consisted of 4 mol% AgCl, 96 mol% AgBr, and 2 mol% AgI. About this, excess salt was removed by a precipitation water washing method, and then D liquid and E liquid were added to add AgCl 97 mol% and AgBr.
After laminating a surface layer of 3 mol%, excess salt was removed by a precipitation water washing method, and gelatin for dispersion was added.

Next, a liquid containing a sensitizing dye [IV] and the following yellow coupler (Y-1) dispersed with dioctyl phthalate, 2-mercaptobenzothiazole, 4-hydroxy-6-methyl-1,3,3a, 7-tetra A solution containing Zaindene, gelatin, a coating aid (S-3) and a film hardener (H-3) (added just before coating) was used to coat silver at a coating amount of 0.5 g / m ² .

4th intermediate layer (8th layer) Similar to the 1st intermediate layer, Tinuvin 328 coating amount 0.3 g / m ²
It applied so that it might become. However, just before coating, a hardener (H-
3) was added.

Protective layer (9th layer) Colloidal silica, coating aid (S-3), hardener (H
-2) and (H-3) (added immediately before coating) were used to apply a gelatin coating amount of 1.0 g / m ² .

Nine layers from the red photosensitive emulsion to the protective layer were coated and dried on the surface-treated polyethylene laminated paper by the simultaneous coating method.

These samples No. 2-1 to No. 2-10 were wedge-exposed through magenta and cyan filters, and developed with a developer having the following formulation at 38 ° C. for 2 minutes.

1.4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 8g 2. Sodium sulfite (anhydrous) 2g 3. Sodium carbonate (monohydrate) 15g 4. Potassium bromide 1g 5 Benzyl alcohol 0.9 ml 6. Add water 1 (adjusted to pH 10.2 with potassium hydroxide) However, 10 seconds after the start of development, the entire surface is uniformed with a 30-lux fluorescent lamp for 10 seconds through an ND filter with a density of 1.0. Exposed. Then, it was bleach-fixed, washed with water and dried.

The results of measuring the obtained positive image with blue light are shown in Table-4.
Shown in

Here, the gamma value represents the slope when the density point of the minimum density Dmin. + 0.15 and the density point of the minimum density Dmax. + 0.5 are connected.

From this result, it is understood that the minimum density (fogging) is reduced and the degree of softening can be reduced by providing the intermediate layer between the yellow filter layer and the emulsion layer. Moreover, it was found that by reducing the silver / gelatin ratio, fog and softening can be further suppressed, and it is judged that good results can be obtained if the ratio is at least 0.3 or less.

[Effects of the Invention] As described above, the color light-sensitive material of the present invention is capable of rapid processing and has a benzyl alcohol content in the case where an auxiliary layer adjacent to the colloidal silver layer is provided to prevent contact fog. Even when a color developing solution having a small value is used, it is possible to avoid the softening of the legs in the photographic characteristics.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasuo Tohsaka 28 Horinouchi, Odawara-shi, Kanagawa Konishi Rokusha Shin Kogyo Co., Ltd. (56) References JP-A-58-147742 (JP, A) JP-A-60- 164742 (JP, A) JP 52-60621 (JP, A) JP 60-260945 (JP, A)

Claims (1)

[Claims] 1. A direct positive silver halide color light-sensitive material having a silver halide emulsion layer containing a coupler, wherein the coupler reacts with an oxidant of a color developing agent to form a dye. On the other hand, an internal latent image type silver halide emulsion layer having a silver chloride content of 10 mol% or more, a colloidal silver layer containing a colloidal silver dispersion, a layer adjacent to the colloidal silver layer, and the colloidal silver layer and At least one non-photosensitive auxiliary layer is provided between each of the internal latent image type silver halide emulsion layers having a silver chloride content of 10 mol% or more, and the colloidal silver layer and the non-photosensitive auxiliary layer as a whole. Silver / gelatin ratio as
0.3 or less and benzyl alcohol content of 1 ml / l
A direct positive silver halide color light-sensitive material, which is color-developed with the following color color developing solutions.