JPS6385740A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a highlight part having the lower tendency to the formation of a magenta color and to widen exposing latitude by incorporating at least one kind of specific magenta dye image forming coupler into at least one layer of silver halide emulsion layers so that leg parts have high contrast. CONSTITUTION:This material has at least one layers of the silver halide emulsion layer for direct positive formation contg. internal latent image type silver halide particles, the surfaces of which are not preliminarily fogged, on a base. At least one kind of the magenta color image forming coupler expressed by formula I is incorporated into at least one of the silver halide emulsion layers. In formula I, R11 denotes an aryl amino group, acyl amino group or ureide group, Z1 is a group which can be eliminated by coupling with the oxidant of a color developing agent (but not hydrogen atom), X1-X3 respectively denote a hydrogen atom, alkyl group, alkoxy group, alkoxy carbonyl group, acyl amino group or halogen atom.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a direct positive silver halide photographic light-sensitive material, and more specifically, after image exposure, fogging treatment (for example, full-surface exposure or addition of a fogging agent) is performed. The present invention relates to a photographic light-sensitive material having an internal latent image type silver halide emulsion layer from which a positive image can be directly obtained by surface development processing in the presence of the present invention.

[Conventional technology]

There are two main types of conventionally known methods for obtaining direct positive images. One type uses a silver halide emulsion that has fogging nuclei in advance, and creates a positive image after development by destroying the fogging nuclei or latent image in the exposed area using solarization or the Burschel effect. It's something you get. Another type uses an internal latent image type silver halide emulsion that has not been covered in advance, and performs fogging treatment (development nucleation treatment) after image exposure, and then surface development, or Buri treatment (
A positive image is obtained by performing surface development while performing a development nucleus generation process.

The above-mentioned fogging treatment (development nucleation treatment) may be performed by exposing the entire surface to light, chemically using a fogging agent, or using a strong developer, and further including heat treatment, etc. It may also be done by

Of the above two methods for forming a positive image, the latter type of method generally has higher sensitivity than the former type of method and is suitable for applications requiring high intensity. .

In this technical field, various techniques are known so far. For example, regarding this type of silver halide emulsion, US Pat.
-34213 publication, 58-1412 publication and 58-1412 publication
8-1415 and other publications clearly specify conversion type, core/shell type, or laminated type, and thioether, imidazole, etc. are used as particle growth agents in U.S. Patent No. 3.57.
It is described in No. 4.626 or Japanese Patent Application Laid-Open No. 100717/1983.

On the other hand, in a method for forming a color image using a silver halide color photographic light-sensitive material, a color image is formed by reacting an oxidized P-phenylenediamine color developing agent with a dye image-forming coupler. In this method, a subtractive color reproduction method is usually applied, and cyan, magenta, and yellow dye images are formed for red, green, and blue. Direct positive silver halide color photographic materials can also form color images using the same method, but when using direct positive emulsions, the minimum density is low because the development process is carried out while fogging is applied. In general, when a magenta image-forming coupler is used, the gradation of the legs becomes soft and the gradation balance with other layers is lost, and the highlighted area becomes pinkish. There is a tendency to

For example, Japanese Patent Publication No. 45-12709 discloses a technique for adding a heterocyclic thion compound, as described in US Patent No. 2.497.
No. 917 contains N such as 5-methylbenztriazole.
- Techniques using heterocyclic compounds are disclosed. Furthermore, Japanese Patent Publication No. 58-9939 discloses a technique using, for example, a specific pyrazolone magenta coupler and a mercapto compound, but both methods effectively harden the legs of a magenta image and reduce the highlight area. It is difficult to prevent the color from becoming pinkish.

Furthermore, in silver halide photographic materials, silver is usually removed from the material by bleaching and fixing or bleach-fixing after development, but according to the findings of the present inventors, In this processing step, if a fixer or bleach-fixer containing a halogenated S-solvent is accidentally mixed into the color developing solution, the magenta image will become softer and the minimum density will increase, as described above. was found to occur significantly. Therefore, it has been found that it is necessary to take measures to deal with the above-mentioned adverse effects on images that occur when a fixer or the like accidentally mixes into a color developing solution. In particular, the above-mentioned softening and increase in minimum density are noticeable when silver halide grains for forming magenta images contain silver chloride. It is also a big problem to make the most of it.

[Purpose of the invention]

Therefore, in the present invention, the maximum density is sufficiently large, the minimum density is sufficiently small, the leg gradation is high contrast, the highlight part tends to be magenta, and the exposure latitude is wide. The object of the present invention is to provide a direct positive silver halide photographic material containing a Vf& type silver halide emulsion.

Furthermore, even if a constant RI solution or a bleach-fix solution is mixed into the color developer and the developer becomes fatigued, the color tone does not soften significantly or the minimum density increases, and the fogging process is affected. It is an object of the present invention to provide the above-mentioned direct positive silver halide photographic light-sensitive material which has excellent processing stability without any problems.

[Structure and operation of the invention]

The present invention provides a direct positive silver halide photograph having a small number of direct positive forming silver halide emulsion layers containing internal latent image type silver halide grains whose grain surfaces are not fogged in advance on a support. In the light-sensitive material, the following general formula [I
The object of the present invention is to provide a direct positive silver halide photographic material containing at least one magenta image-forming coupler represented by the above formula, thereby achieving the above object.

The above general formula (1) is expressed as follows.

Crystal form In the above general formula (1), R11 is an aryl amino group (e.g., phenylamino group, α- or β-naphthylamino group,
4-methylphenylamino group, 2.4゜6-dolichlorophenylamino group, 4-(α(3-tart-butyl-
4-hydroxyphenoxy)tetradecanamide) -
2,6-cyclophenylamino group) or acylamino group (e.g. acetylamino group, benzamide group, 3-
(2,4-di-tert-amylphenoxy)butyramide group, 3-(3-pentadecylphenoxy)butyramide group, etc.) or ureido group (for example, N-methylureido group, N-phenylreido group, N,N-dimethyl ureido group, N-methyl-N-dodecylureido group, N-hesadecylureido group, N,N-dioctadecylureido group, etc.), zl represents 104+*・-5-Rat, and the R1g is an alkyl group (e.g. methyl group, probylyl group, t-butyl group, hexadecyl group, 2- (2,
4,6-)lichlorophenyl)ethyl group, 3-(3-pentadecylphenoxy)propyl group, 3-(2,4,
-di-tert-amyluphenoxy)propyl group, 2
-[α-(3-tert-butyl-4-hydroxyphenoxy)tetradecanamidoethyl group, etc.], aryl group (e.g. phenyl group, α- or β-naphthyl group, 4-methylphenyl group, 2.4°6-doly chlorophenyl group,
4-[α-(3-tert-butyl-4-hydroxyphenoxy)tetradecanamide)-2,6-dichlorophenyl group, etc.) or a heterocyclic group (e.g., a 5-membered heteroatom containing a nitrogen atom, an oxygen atom, a sulfur atom) or 6
A membered heterocyclic ring, a bonded heterocyclic group (pyridyl group, quinolyl group, furyl group, benzothiazolyl group, oxasilyl group, imidazoyl group, naphthoxacyl group, etc.), and the R
1 and RI4 may be the same or different and each represents a hydrogen atom, an alkyl group (e.g. methyl group, propyl group, t-
butyl group, etc.), and R+3R+a are bonded to each other,
May form a 5- or 6-membered ring with the nitrogen atom,
This 5- or 6-membered ring may further be bonded to a benzene ring or a heterocycle, xl, X! and X may be the same or different, and each represents a hydrogen atom, an alkyl group (
For example, methyl group, probylyl group, t-butyl group, hexadecyl group, 2-(2,4,6-dolichlorophenyl)ethyl! , 3-(3-pentadecylphenoxy)propyl group, 3-(2,4,4-di-tert-amylphenoxy)propyl &, 2-(α-(3-tert-butyl-
1 group of 4-hydroxyphenoxy)tetradecanamidoethyl, etc.] myeno group, alkoxy group (e.g., methoxy group, ethoxy group, propoxy group, tso-propoxy group, etc.)
Butoxy group, tert-butoxy group, hexyloxy group, octyloxy group, dodecyloxy group, hexadecyloxy group, etc.) alkoxycarbonyl group, (e.g. methoxycarbonyl group, ethoxycarbonyl group, tert-butoxy group,
-butoxycarbonyl group, dodecyloxycarbonyl group, 2-ethoxyethyloxycarbonyl group, 1-dodecyloxycarbonyl ethoxycarbonyl group, 1-(2
,4-tert7mi)Lt7e/xycarbonyl group,)ethoxycarbonyl group, etc.)amylamino group (e.g. acetamido group, pivaloylamide group,
Silaroylamide group, α-(2,4-di-tert-amylphenoxy)butanamide group, γ-(2,4-di-tert-amylphenoxy)butanamide group, α-(
n-dodecyloxyphenoxy)butanamide group, α-
(n-butanesulfonamidophenoxy)tetradecanamide group, α-(p-dimethylaminosulfonamidophenoxy)tetradecanamide group, etc.), benzamide group, n-dodecyloxybenzamide group 1,3-chloro-4 -dodecyloxybenzamide group), n-(2,
The 4-di-tertamylphenoxy)carbonylbenzamide group represents a p-hexadecyloxycarbonylbenzamide group or a halogen atom (for example, chlorine, bromine, fluorine, etc.). However, X2
At least one of and and 1 is not a hydrogen atom.

Among the magenta image-forming couplers represented by the general formula [I], a particularly preferred one can be represented by the general formula (1-1).

General formula (1-1) In the formula, RI-1 and RIg are Ro explained in general formula (I)
and R, t. Or Ar is a phenyl group which may have a substituent. Examples of substituents for Ar include general formula (1)
This is the same as the example of the group explained for X, SX, and X.

Examples of the magenta color image forming coupler represented by the general formula [I] of the present invention in which the active site substitution component is bonded via an oxygen atom include, for example, US Pat.
No. 19.391, No. 3,311.476, Japanese Unexamined Patent Publication No. 1973
No. 2-58533, No. 51-112343, No. 52-
No. 55529, No. 52-90932, No. 52-200
No. 23, No. 51-110328, No. 50-48922
No. 57-96334, No. 57-96335, No. 57-96336, No. 57-96337, No. 57-
No. 96338, No. 57-96339, No. 57-963
Examples thereof include compounds described in publications such as No. 40, No. 57-96341, No. 57-96342, and No. 57-96343.

In addition, as an example of an active site substitution component bonded via a sulfur atom, for example, US Pat. No. 3.227.55
No. 4, JP 53-34044, JP 51-169
No. 24, No. 54-80744, No. 55-62454, No. 56-126833, No. 55-135835,
No. 57-4044, No. 57-17950, No. 57-
No. 35858, No. 58-50537, No. 58-585
Compounds described in various publications such as No. 44 can be mentioned.

Furthermore, as an example of an active point substitution component bonded via a nitrogen atom, for example, Japanese Patent Publication No. 50-3754
No. 0, No. 51-10100, JP-A No. 50-13041
No. 50-159336, No. 51-3232, No. 51-3233, No. 51-20826, No. 51-3
No. 0228, No. 51-36938, No. 52-5892
No. 2, No. 53-123129, No. 55-118034
No. 56-38043, No. 56-384044,
Compounds described in various publications such as No. 56-40825 can be mentioned.

Specific examples of the magenta image-forming coupler represented by the general formula (I) of the present invention are listed below, but the invention is not limited thereto.

The magenta color image forming coupler of the present invention has the general formula (
Enolized compounds of 1) are also included.

The following margins (exemplary compounds) (M-1) (M-2) 2 (M-6) (M-7) (M-8) (M-9) (M-10) (M-11) (M-12) (M-13) (M-14) Shiy (M-15) Shini (M-16) (M-17) (M-18) (M-19) l (M-21) (M-22) Shi2 (M-24) CE ShiL (M-31) (M-33) Shiy (M-36) I'd (M-38) (M-39) Shini (M- 41) (M-42) ShiE ShiE (M-48> (M-49) (M-50) (M-53) Shig %;g Shit (M-60) Shig (M-63) (M-64) (M-65) (M-68) Next, the silver halide emulsion layer containing internal latent image type silver halide in the present invention will be described.

In the present invention, various conventionally known internal latent image type silver halide emulsions can be used as the emulsion for forming the emulsion layer. For example, U.S. Pat.
Converted silver halide emulsions described in Japanese Patent Publication No. 2.250, laminated structure silver halide emulsions described in Japanese Patent Publication No. 5B-1412, etc., Japanese Patent Publication No. 52-34213 and Japanese Patent Publication No. 60-55821. Core/shell type silver halide with chemically sensitized grain interior described in publications, etc., 1986
Examples include core/shell type emulsions described in JP-A-55820.

The halogen composition of the internal latent image type silver halide used in the present invention is arbitrary, for example, any one of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver chloroiodide. These can be used alone or in appropriate combinations. It is preferable that the silver chloride content is 5 mol% or more, more preferably 30 mol% or more.
This is the case when silver chloride is contained in an amount of mol % or more.

The shape of the silver halide grains may be any shape, for example, cubic, octahedral, dodecahedral, or a mixture thereof, and grains may be spherical, tabular, or irregularly shaped. There may be. The average particle size and particle size distribution of the silver halide grains can be varied widely depending on the required photographic performance, but a narrower particle size distribution is more preferable, that is, the silver halide grains of the present invention The silver halide weight included in the grain size range of ±20% based on the average grain size is 60% of the total silver halide weight.
It is preferably at least 70%, more preferably at least 70%.

Further, as the silver halide emulsion of the present invention, one obtained by mixing silver halide grains having different average grain sizes can be used. The difference in average particle size means that the average particle size of the smaller particles is 80% or less, preferably 70% or less of the average particle size of the larger particles. The halogenated tlu composition or particle shape of large particles and small particles may be the same or different, and the mixing ratio of large particles and small particles may vary depending on the required photographic performance. (It can be selected freely. In this case, two or more types of silver halide grains can be mixed.

Further, in order to widen the exposure latitude of the internal latent image type silver halide used in the present invention, emulsions having different sensitivities can be stacked or mixed as emulsion layers. In this case, the ratio of the amount of coated silver in each emulsion layer can be arbitrarily determined depending on the required photographic properties.

In the present invention, as internal latent image type silver halide grains,
Internal latent image type silver halide grains that are not prefogged are used.

In the present invention, the meaning that the internal latent image type silver halide grain surface is not fogged in advance means that the emulsion used is coated on a transparent film support at 355 g A g/cI+''
It means that the density obtained when a test piece coated so as to have the following density does not exceed 0.6, preferably 0.4, is developed with the following surface developer A at 20° C. for 10 minutes without exposure.

Surface developer A Metol 2.5g! -Ascorbic acid 10 g NaB Ox ・
4) 1z0 35 gKBr
Add 1g water
11 Furthermore, the silver halide emulsion used in the present invention provides sufficient density when the test piece prepared as described above is exposed and then developed with internal developer B having the following formulation.

Internal developer B Metol 2g Sodium sulfite (
Anhydrous) 90g Hydroquinone 8g Soda carbonate (-water salt) 52.5g KBr
5 gKI
Add 0.5g water
11 More specifically, when a portion of the above specimen is exposed to a light intensity scale for a defined period of time up to about 1 second and developed in internal developer B at 20°C for 10 min. , exhibiting a maximum density that is at least 5 times, preferably at least 10 times, that obtained when another part of the specimen exposed under the same conditions is developed with surface developer A for 10 minutes at 20°C. be.

The silver halide emulsion in the present invention can be optically sensitized using commonly used sensitizing dyes. It is also useful for the silver halide emulsion of the present invention to use a combination of sensitizing dyes used for supersensitization of internal latent image type silver halide emulsions, negative silver halide emulsions, and the like.

Regarding the sensitizing dye, Research Disclosure (R
esearch port 1 closure) No, 151
No. 62 and No. 17643.

In the photographic light-sensitive material of the present invention, there is a method of directly obtaining a positive image by carrying out surface development after image exposure (photographing). That is, the main step of directly creating a positive image is to remove fogging nuclei by chemical or optical action after image exposure of the photographic light-sensitive material having an internal latent image type silver halide emulsion layer that has not been fogged in advance. It consists of performing surface development after and/or while performing a process to generate a fog, that is, a fog process. Here, the fogging treatment can be carried out using a compound that provides full exposure or generates fogging nuclei, that is, a fogging agent.

In the present invention, the entire surface exposure is carried out by immersing or moistening the image-exposed photosensitive material in a developer or other aqueous solution, and then exposing the entire surface uniformly to light.

The light source used here may be any light within the sensitive wavelength range of the above-mentioned photographic light-sensitive materials, and high-intensity light such as flash light can be applied for a short time, or weak light can be applied for a long time. Furthermore, the total exposure time can be varied over a wide range depending on the photographic material, development processing conditions, type of light source used, etc. so as to ultimately obtain the best positive image. In addition, it is most preferable to give an exposure amount of light within a certain range in combination with the photosensitive material.Usually, giving an excessive amount of exposure will cause an increase in the minimum density and desensitization, resulting in poor image quality. However, when the photosensitive material of the present invention is used, the degree of image quality deterioration is reduced and stable images can be obtained.

Next, the fogging agent used in the present invention will be described.

A wide variety of compounds can be used as the fogging agent used in the present invention, and it is sufficient that the fogging agent is present during the development process. It is preferable to add halogen to the silver emulsion layer, or it may be included in the developer or the processing solution prior to development.The amount used can be varied over a wide range depending on the purpose. When added to the silver emulsion layer, the amount is 1 to 1.500 mg per mole of halide 11, preferably 10 to 1.0OOn+g.When added to a processing solution such as a developer, the preferred amount is 0.01~5g
/l, particularly preferably 0.05 to Ig/l.

As the fogging agent used in the present invention, for example, US Pat.
, 563,785 and 2.588.982, or U.S. Pat. No. 3,22
7.552; U.S. Patent No. 3,615,615, U.S. Patent No. 3.7
18°479, same No. 3. ．． No. 719,494, same No. 3
．． Heterocyclic quaternary nitrogen salt compounds described in US Pat. No. 734.738 and US Pat. No. 3,759.901;
．． Examples thereof include compounds having an adsorption group on the silver halide surface, such as acylhydrazinophenylthioureas described in No. 030,925. These fogging agents can also be used in combination. For example, Research Disclosure + - (Research Disclosure)
) No. 15162 describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention. As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, and they can also 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, l-benzoyl-2-phenylhydrazine, 1
- Hydrazine compounds such as methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine and 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-benzoxacilium bromide, 2-methyl-3
-(3-(phenylhydrazino)propyl]benzothiazolium bromide, 2-methyl-3-(3-(p-)
lylhydrazino)propyl]benzothiazolium bromide, 2-methyl-3-(3-(p-sulfophenylhydrazino)propyl)benzothiazolium bromide, 2-methyl-3-(3-(p-sulfophenylhydrazino)propyl) phenylhydrazino)pentyl]penzothiazolium iodide, l,
2-dihydro-3-methyl-4-phenylpyrido (2,
1-b) Benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyride (2,1-b)
-5-phenylbenzothiazolium bromide, 4.4
'-ethylenebis(1°2-dihydro-3-methylpyrido(2,1-b)benzothiazolium bromide, 1.
2-dihydro-3-methyl-4-phenylpyrido (2,
1-b) N-substituted quaternary cycloammonium salt such as benzoselenazolium bromide: 5-(1-ethylnaf)
(1,2-b)thiazolin-2-ylideneethylidene)-1-(2-phenylcarbazoyl)methyl-3-(
4-sulfamoylphenyl)-2-thiohydantoin, 5-(3-ethyl-2-penzothiazolinidene)-3
-(4-(2-formylhydrazino)phenyl]rhodanine, 1-(4-(2-formylhydrazino)phenyl) 3-phenylthiourea, 1.3-bis(4-(
Examples include 2-formylhydrazino)phenylcothiourea.

In the photographic light-sensitive material having a silver halide emulsion layer in the practice of the present invention, after image exposure, a positive image is directly formed by exposing the entire surface to light or by surface development treatment in the presence of a fogging agent. This surface development processing method means processing with a developer substantially free of silver halide solvent.

The layer formed by the internal latent image type silver halide emulsion used in the present invention only needs to have at least one layer, and of course may have multiple layers as necessary to form the photographic light-sensitive material of the present invention. can do.

Developers that can be used in the surface developer used for developing the photographic light-sensitive material according to the present invention include common silver halide developers, such as polyhydroxybenzenes such as hydroquinone, aminophenols, and 3-pyrazolidones. , ascorbic acid and its derivatives, reductones, phenylenediamines, etc., or mixtures 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-0
-) luidine, 4-amino-3-methyl-N-ethyl-
N-(β-methanesulfonamidoethyl)aniline,
Examples include 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline. It is also possible to include these developers in advance in the emulsion and allow them to act on the silver halide during immersion in the high pH aqueous solution.

The developer used in the photographic material of the present invention may further contain specific antifoggants and development inhibitors,
Alternatively, it is also possible to optionally incorporate these developer additives into the constituent layers of the photographic light-sensitive material.

If the direct positive silver halide photographic material according to the present invention contains a magenta image-forming coupler represented by the general formula CI), a fixer or a bleach-fixer may be accidentally mixed into a color developing solution. Even with this, significant softening and increase in minimum density in the legs are reduced. Therefore, even if the fixer or bleach-fixer gets mixed into the color developing solution due to an operational error or a paper jam, or if it gets mixed in during automatic development processing using a bell feed, With the above photosensitive materials, stable processing can be continued. Therefore, even if the above-mentioned contamination occurs, by using the photosensitive material of the present invention, unnecessary work such as renewing the color developing solution each time the contamination occurs is reduced, resulting in economical and
You can save time. In addition, when a processing solution containing the above-mentioned silver halide solvent is accidentally mixed into a color developing solution, significant deterioration in image quality due to softening of the legs and increase in minimum density occurs when the developer temperature is 35. It tends to occur at high temperatures above ℃. Therefore, the photosensitive material of the present invention is also useful as a photosensitive material for rapid processing, which is developed at a high temperature of 35° C. or higher.

Next, additives added to the silver halide emulsion used in carrying out the present invention will be explained.

Depending on the purpose, various photographic additives such as wetting agents, film property improvers, and coating aids may be added to the silver halide emulsion used in the practice of the present invention. Examples of wetting agents include dihydroxyalkanes, and examples of film property improving agents include copolymers of alkyl acrylates or alkyl methacrylates and acrylic acid or methacrylic acid, styrene-maleic acid copolymers, and styrene maleic anhydride. Water-dispersible particulate polymeric substances obtained by emulsion polymerization such as acid half-alkyl ester copolymers are suitable, and examples of coating aids include saponin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants,
Brighteners, development speed regulators, matting agents, etc. may also be used.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc. as necessary to obtain the direct positive silver halide photographic light-sensitive material of the present invention. Can be done.

It is useful to apply the photographic light-sensitive material according to the present invention to full-color applications, and in this case, it is preferable to include cyan and yellow dye image-forming couplers in the halogenated emulsion in addition to the magenta color image-forming coupler. As the coupler, commonly used couplers can be used.

In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent fading of dye images due to short-wavelength actinic rays.
It is advantageous to use 0, 326, 327, and 328 (all manufactured by Ciba Geigy) alone or in combination.

Examples of the support used in the photographic material of the present invention include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, polyethylene laminate paper, etc., which have been subjected to undercoating as necessary. It will be done.

In addition to gelatin, suitable gelatin derivatives can be used as protective colloids or binders in the silver halide emulsion layers used in the practice of the present invention depending on the purpose. Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

In addition, in the present invention, other hydrophilic binders can be included depending on the purpose, and colloidal albumin, agar, gum arabic, dextran, alginic acid, and acetyl can be hydrolyzed to 10 to 20% containing acetyl. Cellulose derivatives such as cellulose acetate, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl aminoacetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrated Contains decomposed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with heptamers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc., and can be used as an emulsion layer or intermediate layer, or as a protective layer. The hydrophilic binder can be added to constituent layers of photographic materials such as layers, filter layers, backing layers, etc. depending on the purpose, and the hydrophilic binder can also contain suitable plasticizers, lubricants, etc. depending on the purpose. can.

Further, the constituent layers of the photographic light-sensitive material according to the present invention can be hardened with any suitable hardening agent. These hardening agents include chromium salts, zirconiums, aldehydes such as formaldehyde and mucono-10-genic acid, halotriazine-based, boric acid compounds, ethyleneimine-based, vinylsulfone-based, and acryloyl-based hardening agents. agents, etc.

Further, the photographic light-sensitive material according to the present invention has a small amount of (
In addition to each having one layer of a photosensitive emulsion layer containing internal latent image type silver halide grains according to the present invention, a filter layer, an intermediate layer,
It is possible to provide a large number of various photographic constituent layers such as protective layers, subbing layers, backing layers, antihalation layers, etc.

The photographic light-sensitive material according to the present invention is suitable for color use, false color use,
It can be effectively applied to various uses such as printing, infrared, micro, silver dye bleaching, etc. It can also be applied to colloid transfer, silver salt diffusion transfer, and Rogers' U.S. Patent No. 3.087.
．． 817, 3.185.567 and 2.9
No. 83.606, U.S. Patent No. 3.25 to Weyertz et al.
No. 3.915, U.S. Pat. No. 3.227 to Whitemore et al.
．． No. 550, U.S. Patent No. 3.227.551 to Barr et al.
No. 3,227,552 to Whitemore et al. and U.S. Pat. It can be applied to color image transfer methods and color diffusion transfer methods.

〔Example〕

Next, the present invention will be specifically explained below with reference to Examples, but it goes without saying that the embodiments of the present invention are not limited to the following Examples.

Example 1 An octahedral silver bromide internal latent image type core/shell emulsion with an average grain size of 066 μm was prepared by a method similar to that described in Japanese Patent Publication No. 52-34213, and this emulsion was used to produce the following. A sample Nal of a silver halide photographic light-sensitive material was prepared.

That is, a magenta image-forming coupler (using exemplified compound (M-1)) dissolved in dioctyl phthalate in the above emulsion.
A spreading agent and a hardening agent were added, and the mixture was coated on a cellulose triacetate support and dried.
I got it. The coating amount of the internal latent image type emulsion on the support for Sample Light 1 was 1.0 g/nl in terms of silver. The magenta color image forming coupler has a coating amount of 1.8 g.
/rd, and it was contained in the above emulsion in such an amount.

More samples! Similarly to 1h1, only the magenta color image forming coupler was replaced with the compound shown in Table 1, and sample 11h2 was used.
-8 were created.

The photosensitive material sample lights 1 to 8 prepared above were exposed through an optical wedge and then processed in the following steps.

Processing steps (35° C.) Color development processing 4 minutes Bleach-fixing processing 2 minutes Stabilization processing 2 minutes However, in the above processing steps, white light of 1 lux was irradiated over the entire surface for a period of 10 to 20 seconds after the start of color development.

As each of the above-mentioned processing liquids, those having the compositions shown below were used.

(a) Color developer composition: Consists of an aqueous solution of chemicals of the following types and concentrations (g/l).

(b) Bleach-fix solution composition: Consists of an aqueous solution of chemicals with the following types and concentrations (g/jt).

(c) Stable liquid composition Sensitometry was performed on each sample treated with the above treatment liquid to determine gamma (γ), which is an index of leg gradation, and the minimum density (Dnin) of each sample.

Here, T indicates the slope of the characteristic curve in the concentration range shown in Table 1 below.

Table-1 r: Density point of Dmin+0.1 and Dmin+Q
Comparative compounds using the absolute value of the slope connecting the concentration points of , and 5 are as follows.

Below, margin C-゛ Comparative compound (A) I It Comparative compound (B) rρ As is clear from the results in Table 1, when sample magnets 1 to 6 according to the present invention are used, comparative sample number Compared to Sample Light 7.8, which has a higher T as an index of leg gradation and provides a clear and good image, sample light 7.8, which is a comparison sample, shows no leg gradation and has a lower T. It can be seen that the image is unclear.

Example 2 The constituent layers of the photographic light-sensitive material in this example were formed by preparing and coating emulsions for each constituent layer as described below.

By a method similar to the method described in Japanese Patent Publication No. 60-55820, two particles with an average particle size of 0.9μ and an average particle size of 0.6μ were prepared.
Different types of internal latent image type silver halide emulsions were prepared. All of the obtained emulsions had a halogen composition of AgBr/A.
It was an emulsion of gC1-60740.

These emulsions having different average grain sizes were mixed at a molar ratio of 1/1 to prepare a blue-sensitive emulsion. In addition, a mixed edge-sensitive emulsion with a molar ratio of 1/1 enhanced with a green-sensitive sensitizing dye and a molar ratio of 1/1 enhanced with a red-sensitive sensitizing dye are used.
A mixed red-sensitive emulsion of No. 1 was obtained.

Sample light 9 was prepared by sequentially coating the following emulsion layers on a paper support laminated with polyethylene on both sides.

(1) Red-sensitive emulsion layer The red-sensitive emulsion layer contains the above red-sensitive emulsion at a rate of 0.4 g/rd.
and oil protection dispersed cyan coupler (C-
This layer contains 0.8 g/cd of 1), and the amount of gelatin is 1.5 g/rd.

(2) Middle layer: The middle layer is oil-protected 2,5-tert.
- This is a layer containing octylhydroquinone, and the amount of gelatin is 8B/rrr.

(3) Green-sensitive emulsion layer The green-sensitive emulsion layer contains the above green-sensitive emulsion at a density of 0.4 g/nf.
and 0.8 g/rd of the magenta image-forming coupler shown in Oil Protected Exemplary Compound (T1)
and the gelatin amount is 1.5 g/rd.
It is.

(4) Yellow filter layer The yellow filter layer contains 0.12 yellow colloidal silver.
This is a layer containing 2,5-tert-octylhydroquinone dispersed in oil protection with g/rrl, and the amount of gelatin is 1.5 g/rrl.

(5) Blue-sensitive emulsion layer The blue-sensitive emulsion layer contains the above blue-sensitive emulsion at 0.5 B/rrr and oil-protected yellow coupler (Y-1) at 0.5 B/rrr.
．． 7B/rrr, and the amount of gelatin is 1.5
B/rrr.

(6) Protective layer This layer has a gelatin amount of 1.5 B/rrr.

The compounds used in each of the above layers are as follows.

Cj! CI! Furthermore, Samples Na1O to 16 were prepared in the same manner as Sample No. 9 except that only the magenta image-forming coupler in the green-sensitive emulsion layer was changed as shown in Table 2.

Samples created in this way! After exposing lh9 to lh16 through an optical wedge, they were treated in the next step using the treatment liquid shown in Example-1.

Processing process: 38°C Color development processing: 2 minutes 30 seconds Bleach-fixing processing: 1 minute 30 seconds Stabilization processing: 1 minute 30 seconds However, white light of 2 lux is applied to the entire surface for 10 seconds from 10 seconds to 20 seconds after the start of color development. This treatment was designated as treatment-1.

Next, a process similar to Process-1 was performed as Process-2. However, in Process-2, 0.1% bleach-fix solution was added to the color developer.
Processing was carried out using a color developing solution mixed with %.

Sensitometry was performed on each sample after the above treatment,
T and the minimum density (Dmin) as the leg gradation for the magenta color image were determined for each process of process-1 and process-2. The results obtained are shown in Table-2.

Table 2 As is clear from the results in Table 2 above, sample magnets 9 to 15, which are photosensitive materials of the present invention, were obtained when a bleach-fix solution was mixed in a color developer (processing 2). In addition, T decreased only slightly, and the leg part became significantly softer and the minimum density (On+in
) No significant increase was observed.

On the other hand, in comparative sample 11h16, magenta staining occurs in the white background area, the minimum density (Onin) increases, and the image is significantly deteriorated.

Example-3 Among the samples obtained in Example-2, sample fish 9. The same process as Process-1 was repeated using Block 12 and Block 16. Furthermore, apart from treatment-1, treatment-3 and treatment-4 described below were applied to the sample 1Ih9. I went to Na12 and floor 16.

Process-3 was the same process as Process-1 except that the illuminance for full-surface exposure was 4 lux, and Process-4 was the same as Process-1 except that the illuminance for full-face exposure was 8 lux. .

Sensitometry was performed on each of the above samples after treatment,
Sensitivity (S) and minimum density (Dmin) of magenta color image
The results shown in Table 3 were obtained.

Table 3 As is clear from the results in Table 3 above, Samples No. 9 and No. 12, which are photosensitive materials of the present invention, are stable with little decrease in sensitivity (S) against changes in illuminance during full-surface exposure. It can be seen that the product has high quality.

On the other hand, it is clear that the sensitivity (S) of comparative sample No. 16 was significantly affected by the change in illuminance during full-surface exposure and decreased rapidly.

Therefore, it can be seen that the photosensitive material of the present invention is stable with respect to sensitivity (S).

Example 4 In this example, the koji samples 9°12 and 16 obtained in Example 2 were exposed through an optical wedge and then treated in the following processing step, and this treatment was designated as Treatment 5.

Processing process (38°C) Color development process 2 minutes bleach-fixing process 1 minute 30 seconds Stabilization process 1 minute 30 seconds A processing solution was used, but only the color developing solution was changed to the following composition.

1 which is a fogging agent in the color developer in the above processing-5
-Additional amount of formyl-2-phenylhydrazine: 0.2g
Process-6 was performed in the same manner as Process-5 except that /l was changed to 0.3 g/l.

After each of the above treatments, sample No. 9.12 and 1 after each treatment
6 was subjected to sensitometry to determine the sensitivity (S) and minimum density (Dmin) for magenta images, and the results are shown in Table 4 below.

Table 4 As is clear from the results of Table 4 above, Samples No. 9 and No. 12 according to the present invention showed that the sensitivity (S
) does not change much and is stable.

On the other hand, it can be seen that the sensitivity (S) of Comparative Sample 1k16 changes greatly with respect to changes in the amount of fogging agent added.

Therefore, it can be seen that the light-sensitive material of the present invention is capable of producing images that are stable against variations in the composition of the color developing solution, especially variations in the amount of fogging agent added.

〔Effect of the invention〕

As described above, according to the present invention, the maximum density of an image is sufficiently large;
It is possible to obtain a direct positive silver halide photographic light-sensitive material with a sufficiently small minimum density, high contrast in the legs, less tendency toward magenta in the highlight areas, and a wide exposure latitude.

Furthermore, even if a fixer or a bleach-fixer gets mixed into the color developer and the developer becomes fatigued, the tone will not become significantly softer or the minimum density will increase. The above-mentioned silver halide photographic material having stable sensitivity can be obtained.

Claims (1)

[Claims] 1. Direct positive halogenation having at least one silver halide emulsion layer for direct positive formation containing internal latent image type silver halide grains whose grain surfaces are not fogged in advance on a support. In the silver photographic material, at least one of the silver halide emulsion layers has the following general formula [I].
at least one magenta color imaging coupler represented by
A direct positive silver halide photographic material containing seeds. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_1 is an arylamino group, an acylamino group,
or represents a ureido group, Z_1 represents a group (however, not a hydrogen atom) that can be separated by coupling with an oxidized product of a color developing agent, and X_1, X_2, and X_3 may be the same or different, and each represents a hydrogen atom. , represents an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acylamino group, or a halogen atom. 2. The direct positive silver halide photographic light-sensitive material according to claim 1, wherein the direct positive image formed on the silver halide emulsion layer is obtained by a photofogging treatment.