JPH05100354A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a direct positive photographic sensitive material giving contrasty gradation and fit to form a color proof. CONSTITUTION:When at least one photosensitive emulsion layer contg. unprefogged internal latent image type silver halide particles is formed on a base to obtain a direct positive photographic sensitive material, a nitrosyl or thionitrosyl coordinated complex of ruthenium is incorporated into the silver halide particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive photographic light-sensitive material utilizing an internal latent image type silver halide emulsion which makes it possible to obtain a direct positive image. More specifically, the present invention relates to a direct positive photographic light-sensitive material suitable for producing a color proof used for plate inspection and adjustment in color plate making and printing processes.

[0002]

BACKGROUND OF THE INVENTION Photographic processes for obtaining direct positive images without the need for reversal processing steps or negative films are well known. As a method for producing a positive image using a conventionally known direct positive silver halide photographic light-sensitive material,
There is a method of using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method in which a photographic light-sensitive material is subjected to surface development after image exposure, after fog treatment or while performing fog treatment to directly obtain a positive image. The internal latent image type silver halide photographic emulsion which is not previously fogged is a type of halogenated type in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. A silver photographic emulsion. Various techniques have been known so far in this field. For example, U.S. Pat. Nos. 2,592,250, 2,466,957, 2,497,875 and 2,588,89.
No. 82, No. 3317322, No. 3761266, No. 3761276, No. 3796577, and British Patent Nos. 1151333, 11505053, 1011.
Those described in each specification of No. 062 are the main ones. The formation mechanism of the direct positive image is explained as follows. That is, when imagewise exposure is performed, a so-called internal latent image is formed on the silver halide, and then a fog treatment is performed to cause a surface desensitizing action due to the internal latent image (that is, the halogen in the exposed portion is affected). Development nuclei (fog nuclei are not generated on the surface of silver halide), development nuclei are selectively generated only on the surface of unexposed areas of silver halide, and then normal surface development processing is performed to unexpose the unexposed areas. A photographic image (positive image) is formed on. The fog treatment method includes a so-called "light fog method" for exposing the entire photosensitive layer, and a "chemical fog method" for using a nucleating agent. A direct positive silver halide photographic light-sensitive material using an internal latent image type silver halide emulsion which has not been previously fogged as described above has recently been used for copying purposes and the like because the simplicity of its processing step has been accepted. ing.

The working process of the color printed matter includes the steps of color-separating a color original and converting it into a halftone dot image to produce a transmission type halftone dot image. A printing plate is made from the obtained transmission type halftone dot image, but prior to this, the final printed matter (main printing)
There is a step of inspecting the state, characteristics, etc., and performing necessary calibration (color calibration). As a color proofing method, conventionally, a method of preparing a printing plate and making a test print has been used. However, in recent years, various color proofs have been produced for the purpose of speeding up the calibration process and reducing costs.
As a method for producing a color proof, a photopolymer, a diazo method, a surprint method using a photoadhesive polymer, an overlay method and the like are known (for example, US Pat. No. 3,582,327, JP-A-56-50121).
7 and 59-97140). However, all of these methods require superposition and transfer of images, and also require superposition and transfer of a plurality of figures, and the process is complicated and requires a lot of time and cost. .. Japanese Unexamined Patent Publication No. 56-104335 discloses a method for producing a color proof using a color photographic light-sensitive material, and this method has a great merit in that the process is simple and the cost is low. It has features such as excellent tone reproducibility. The method for producing a color proof using the above color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a coloring method having a continuous tone, to which magenta (M) color, cyan (C) color, yellow ( Y)
This is a method of obtaining a color proof by sequentially exposing each color plate of black and black (B) to a color paper so as to print a color negative, and then performing a designated color development processing. This method has the features that the process is simple and easy to automate as compared with the various methods described above. There are several possible silver halide color photographic light-sensitive materials that can be used in such color proofs. Among them, the transmission type black and white halftone image used in the production process of the color printed matter described above is often a positive type especially in Japan and Europe, and therefore, as a silver halide color photographic light-sensitive material for color proofing. A lot of posi-positive type photosensitive materials are used. Among them, the direct positive type color photographic light-sensitive material, which has been rapidly advanced in practical use technology in recent years, has been attracting attention as being most suitable for use in color proof because of its ease of processing. As described above, an image (image quality) to be obtained is an image in which the ratio of the maximum image density and the minimum image density is large (that is, an image having a good contrast) with the diversification of uses of the direct positive color photographic light-sensitive material. Is desired. Especially in color proofing applications, gradation (mainly)
Is desired to be even harder. Examples of the light-sensitive material capable of obtaining the above-described hardened image include Mn, Cu, Zn and C described in JP-A-1-145647.
A direct positive light-sensitive material using the internal latent image type silver halide emulsion, which comprises silver halide grains containing d, Pb and at least one metal selected from the group consisting of metals belonging to Group VIII of the periodic table. Proposed.

[0004]

However, even if a direct positive light-sensitive material using the internal latent image type silver halide emulsion containing the above metal is used, the gradation of the image obtained is sufficiently satisfactory. There was room for further improvement, especially as a material for making color proofs. Therefore, an object of the present invention is to provide a direct positive photographic light-sensitive material suitable for producing a color proof, which is capable of obtaining a higher gradation.

[0005]

The present inventor has conducted earnest studies for a direct positive photographic light-sensitive material suitable for producing a color proof as described above. As a result, the above periodic rate table VI
Among the metals belonging to Group II, particularly for Ru, it was found that the object of the present invention can be achieved by using a nitrosyl or thionitrosyl coordination complex, and the present invention has been completed. The present invention provides a direct positive photographic light-sensitive material comprising at least one photosensitive emulsion layer containing an internal latent image type silver halide grain which has not been fogged on a support, wherein the silver halide grain is It is a direct positive photographic light-sensitive material characterized by containing a Ru nitrosyl or thionitrosyl coordination complex. In order to improve photographic characteristics such as increase in sensitivity, a specific halogen containing a nitrosyl or thionitrosyl coordination ligand and a transition metal selected from elements of Groups 5 to 10 of the periodic table in the grain. A silver halide photographic emulsion has been disclosed (see JP-A-2-20852).

The preferred embodiments of the present invention will be described below. (1) The Ru nitrosyl or thionitrosyl coordination complex is a hexacoordination complex. (2) The Ru nitrosyl coordination complex (anion) is
[Ru (NO) Cl ₅ ] ^-2 , [Ru (NO) Br
₅ ] ^-2 , [Ru (NO) Cl ₄ (CN)] ^-2 , [Ru
(NO) Cl ₄ (SCN)] ^-2 , [Ru (NO) Cl ₃
(CN) ₂ ] ^-2 , [Ru (NO) Br ₂ (CN)
₃ ] ^-2 , [Ru (NO) Cl (CN) ₄ ] ^-2 , and [R
It is at least one compound selected from u (NO) Br (SCN) ₄ ] ^-2 . (3) Thionitrosyl coordination complex of Ru (anion)
Is [Ru (NS) Cl ₅ ] ^-2 , [Ru (NS) Cl ₄
(CN)] ^-2 , [Ru (NS) Br ₄ (SCN)] ^-2 ,
[Ru (NS) Br ₃ (CN) ₂ ] ^-2 , [Ru (NS)
Br ₂ (SCN) ₃ ] ^-2 , and [Ru (NS) Cl (S
CN) ₄ ] ^-2 . (4) The above silver halide grains are formed by growing grains in the presence of the above complex so that the pAg of the emulsion is in the range of 6.0 to 7.0. (5) The internal latent image type silver halide grain has a core / shell structure. (6) The internal latent image type silver halide grain has a core / shell structure, and both the core portion and the shell portion are chemically sensitized. (7) In the above item (6), the chemical sensitization is performed with a sulfur sensitizer and a gold sensitizer. (8) The light-sensitive emulsion layer comprises a blue-sensitive emulsion layer containing an internal latent image type silver halide emulsion not previously fogged and a yellow coupler, an internal latent image type silver halide emulsion not previously fogged and a magenta coupler. It contains a green-sensitive emulsion layer containing a red-sensitive emulsion layer containing an internal latent image type silver halide emulsion and a cyan coupler which have not been previously fogged.

[0007]

By using the direct positive color photographic light-sensitive material of the present invention, it is possible to obtain an image having a high gradation of gradation. Therefore, the light-sensitive material of the present invention can be advantageously used as a material for producing a color proof.

[Detailed Description of the Invention] The direct positive photographic light-sensitive material of the present invention will be described in detail below. As described above, the direct positive photographic light-sensitive material of the present invention comprises a light-sensitive emulsion layer containing a pre-fogged internal latent image type silver halide grain containing a Ru nitrosyl or thionitrosyl coordination complex. At least one layer is provided on the support. The light-sensitive emulsion layer may contain any one of a yellow coupler, a magenta coupler and a cyan coupler. As a result, a positive color image can be obtained. The light-sensitive emulsion layer may have a single-layer structure containing the above-mentioned components, but it is usually provided with a three-color emulsion layer of a red-sensitive emulsion layer (red-sensitive layer), a green-sensitive layer and a blue-sensitive layer. preferable. And a cyan coupler for the red-sensitive layer, a magenta coupler for the green-sensitive layer,
The blue-sensitive layer generally contains a yellow coupler. With this configuration, a color image of three colors (full color image) can be obtained.

The light-sensitive material of the present invention will be described below by taking as an example a light-sensitive material having the above-described three-color emulsion layer. The non-pre-fogged internal latent image type silver halide grains contained in the light-sensitive emulsion layer of the photographic light-sensitive material of the present invention contain Ru nitrosyl (NO) or thionitrosyl (NS) coordination complex. ing. The internal latent image type silver halide grains which have not been fogged in advance will be described later. In the present invention, the nitrosyl or thionitrosyl coordination complex of Ru is preferably a hexacoordinated complex. An example of a hexacoordinated complex (only an anion) is shown below, but the counterion (cation) constituting the hexacoordinated complex is
It is not particularly important because it dissociates in an aqueous medium such as used for silver halide grain formation. However, ammonium or alkali metal (particularly potassium) is known as a suitable counter ion for silver halide precipitation operation, and the following examples are particularly suitable for these counter ions. is there.

Examples of Ru nitrosyl coordination complexes include:
[Ru (NO) Cl ₅ ] ^-2 , [Ru (NO) Br
₅ ] ^-2 , [Ru (NO) I ₅ ] ^-2 , [Ru (NO)
F ₅ ] ^-2 , [Ru (NO) Cl ₃ (H ₂ O) ₂ ] ⁰ ,
[Ru (NO) Cl ₃ Br (H ₂ O)] ^-1 , [Ru (N
O) Cl ₄ (OCN)] ^-2 , [Ru (NO) Cl ₄ (C
N)] ^-2 , [Ru (NO) I ₄ (TeCN)] ^-2 , [R
u (NO) Cl ₄ (SCN)] ^-2 , [Ru (NO) Br
₄ (SeCN)] ^-2 , [Ru (NO) I ₄ (SeC)
N)] ^-2 , [Ru (NO) Cl ₃ (CN) ₂ ] ^-2 , [R
u (NO) Br ₂ (CN) ₃ ] ^-2 , [Ru (NO) I ₂
(CN) ₃ ] ^-2 , [Ru (NO) Cl ₄ (N) ₃ ] ^-2 ,
[Ru (NO) Cl (CN) ₄ ] ^-2 , [Ru (NO) B
r (SCN) ₄ ] ^-2 , [Ru (NO) I (CN)
₄ ] ^-2 , and [Ru (NO) (CN) ₅ ] ^-2 .

Among these, [Ru (NO) Cl
₅ ] ^-2 , [Ru (NO) Br ₅ ] ^-2 , [Ru (NO) C
l ₄ (CN)] ^-2 , [Ru (NO) Cl ₄ (SCN)]
^-2 , [Ru (NO) Cl ₃ (CN) ₂ ] ^-2 , [Ru (N
O) Br ₂ (CN) ₃ ] ^-2 , [Ru (NO) Cl (C
N) ₄ ] ^-2 , and [Ru (NO) Br (SCN) ₄ ] ^-2
Is preferred.

Examples of Ru thionitrosyl coordination complexes include [Ru (NS) Cl ₅ ] ^-2 and [Ru (NS) I.
₅ ] ^-2 , [Ru (NS) Br ₄ (N ₃ )] ^-2 , [Ru
(NS) Cl ₄ (CN)] ^-2 , [Ru (NS) I ₄ (C
N)] ^-2 , [Ru (NS) Br ₄ (SCN)] ^-2 , [R
u (NS) Cl ₄ (SeCN)] ^-2 , [Ru (NS) I
₄ (SeCN)] ^-2 , [Ru (NS) Br ₃ (CN)
₂ ] ^-2 , Ru (NS) Cl ₂ (SeCN) ₂ ] ^-2 , [R
u (NS) Cl ₂ (N ₃ ) ₃ ] ^-2 , [Ru (NS) I ₃
(CN) ₃ ] ^-2 , [Ru (NS) Cl ₂ (SeCN)
₃ ] ^-2 , [Ru (NS) Cl ₂ (N ₃ ) ₃ ] ^-2 , [Ru
_{(NS) Br 2 (SCN)} 3] -2, [Ru (NS) I
(CN) ₄ ] ^-2 , [Ru (NS) Cl (SCN)
₄ ] ^-2 , [Ru (NS) (CN) ₅ ] ^-2 , [Ru (N
S) (SCN) ₅ ] ^-2 and [Ru (NS) (N ₃ ).
₅ ] ^-2 .

Among these, [Ru (NS) Cl
₅ ] ^-2 , [Ru (NS) Cl ₄ (CN)] ^-2 , [Ru
(NS) Br ₄ (SCN)] ^-2 , [Ru (NS) Br ₃
(CN) ₂ ] ^-2 , [Ru (NS) Br ₂ (SCN) ₃ ]
^-2 , and [Ru (NS) Cl (SCN) ₄ ] ^-2 are preferable.

One of these Ru complexes may be incorporated in the silver halide grains, or two or more thereof may be incorporated. The Ru complex is in the form of a solution prepared by dissolving the complex in an aqueous solution or an organic solvent when silver halide grains are formed by mixing and stirring a silver ion solution and an aqueous halogen solution (in the course of grain growth). It can be incorporated in the silver halide grains by adding it to the mixed reaction solution (or coexisting in an aqueous halogen solution). Alternatively, after the silver halide grains are formed, they can be incorporated in the emulsion in the form of an aqueous solution of the above complex or a solution of the complex dissolved in an organic solvent. In this case, it may be further covered with silver halide.

In the present invention, as described above, the silver halide grains preferably have a core / shell structure. In this case, the complex is added at the time of core formation or at the time of shell formation. But it's okay. That is, the complex may be added at any time during the growth process of silver halide grains. As a result, the complex will be present in the core portion of the particle, the shell portion, or both. The pAg of the emulsion during silver halide grain formation (growth process) is 5.0 to
It is preferably in the range of 8.0, and more preferably,
The range is 6.0 to 7.0. When the growth of silver halide grains is carried out with pAg within this range, the introduction of the Ru complex into the silver grains can be efficiently achieved.

The amount of complex contained in the silver halide grains (the amount of Ru added) is 10 per mol of silver halide.
The range of ^-9 to 10 ^-2 mol is preferable, and 1 is more preferable.
It is in the range of 0 ^-8 to 10 ^-3 mol, especially 10 ^-8 to 10 ^-4
It is in the molar range.

When chemically sensitizing the silver halide grains, the operation of introducing the complex into the grains as described above is carried out to incorporate the Ru complex into the silver halide grains, and then chemically react. Sensitization processing is performed.

The unfogged pre-fogged internal latent image type silver halide emulsion of the present invention is an emulsion in which the surface of silver halide grains is not fogged and which contains silver halide mainly forming a latent image inside the grains. However, more specifically, a certain amount of silver halide emulsion (0.5
To 3 g / m ²⁾ was applied, the following developer giving exposure at fixed time of 0.01 to 10 seconds to in (internal developer), 20 ° C., conventional photographic density when developed 5 minutes The maximum density measured by the measuring method is the maximum obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed at 18 ° C. for 6 minutes in the following developer (surface type developer). Those having a concentration of at least 5 times greater than the concentration are preferred, and those having a concentration of at least 10 times greater are preferred. Internal type developer Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.8 g KBr 5.0 g KI 0.5 g Water-added 1000 ml Surface type developer Metol 2. 5 g L-ascorbic acid 10.0 g NaBO ₂ .4H ₂ O 35.0 g KBr 1.0 g Water added 1000 ml

Specific examples of the internal latent image type silver halide emulsion include conversion type silver halide emulsions described in US Pat. No. 2,592,250; or US Pat. Nos. 3,761,276, 3,850,637 and 3,923,513. , 4035185 and 43954.
78, 4504570, JP-A-52-1
No. 156614, No. 55-127549, No. 53-6
0222, 56-22681, 59-2085
No. 40, No. 60-107641, No. 61-1337.
No. 62-215272, German Patent No. 2332802c2, Research Disclosure No. 23510 (issued in November 1983), page 236; specification of U.S. Pat. No. 4,789,627, further having a silver chloride shell; JP-A-63-10160 relating to silver chlorobromide core-shell emulsions;
JP-A-63-47766 and Japanese Patent Application No. 1-24
No. 67; Japanese Patent Application Laid-Open No. 63-191145 and Japanese Patent Application Laid-Open No. 1-5214 relating to emulsions doped with metal ions.
Examples thereof include core / shell type silver halide emulsions described in JP-A No. The internal latent image type silver halide grains which have not been fogged in the present invention are preferably core / shell type. The internal latent image type core / shell silver halide emulsion has a silver halide core / shell molar ratio of 20/1 or less and 1/10.
0 or more is particularly preferable.

As described above, the internal latent image type silver halide grains which have not been fogged already contain the nitrosyl or thionitrosyl coordination complex of Ru. The metal described in JP-A 1-145647 (Mn, Cu, Zn, Cd, Pb, Bi or at least one metal selected from the group consisting of metals belonging to Group VIII of the periodic table) may be incorporated. .. The amount of the metal incorporated (content in silver halide grains) is preferably 10 ^-9 to 10 ^-2 mol, and more preferably 10 ^-7 to 10 ^-3 mol, per mol of silver halide. The method of incorporating these metals is described in US Pat.
No. 761276, No. 4395478, and JP-A-59-216136.

The silver halide grains used in the present invention have a cubic shape, an octahedron shape, a dodecahedron shape and a tetradecahedron shape (JP-A-2-22).
3948), an irregular crystal form such as a sphere, and JP-A-1-131547.
Emulsions in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more, which occupy 50% or more of the total projected area of the grains, may be used. .. Further, it may be an emulsion having a complex form of these various crystal systems, or an emulsion comprising a mixture thereof. The composition of silver halide includes silver chloride, silver bromide, and mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide or may contain silver iodide. 3 mol%
The following are silver (iodo) silver bromide, (iodo) silver chloride or (iodo) silver bromide. The average grain size of the silver halide grains (the grain diameter in the case of spherical grains or grains close to spheres, the vertical length in the case of cubic grains, and the average length based on the projected surface) is 1.5 μm. Hereinafter, 0.1 μm or more is preferable, but 1.2 μm or less is particularly preferable,
It is 0.2 μm or more. The particle size distribution may be narrow or wide, but in order to improve graininess, sharpness, etc., the number or weight of particles is within ± 40% of the average particle size, preferably within ± 30%, and most preferably. ± 20%
It is preferred to use in the present invention so-called "monodisperse" silver halide emulsions having a narrow grain size distribution such that 90% or more, especially 95% or more, of all the grains are contained therein.

In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes or emulsions having the same size in the emulsion layers having substantially the same color sensitivity are used. It is possible to mix a plurality of different particles in the same layer or to coat multiple layers in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be mixed or laminated and used.

As described above, the silver halide emulsion used in the present invention is chemically sensitized inside or on its grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination. It is preferable that it is chemically sensitized by sulfur and gold sensitization. In addition, as a chemical sensitization method for core particles, Japanese Patent Application Laid-Open No. HEI-2
The methods described in JP-A-199450 and JP-A-2-199449 can be used. In the presence of a mercapto compound as described in JP-A-1-197742, and as described in JP-A-1-254946, JP-A-2-69738, and JP-A-2-273735, thiosulfinic acid and sulfinic acid. Sulfite may be added. For specific examples, see Research Disclosure No.
17643-III (issued in December 1978), page 23, etc.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. For specific examples, see Research
Disclosure magazine No. 17643-IV (197
Issued in December, 1996) See patents on pages 23-24. The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the production process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. For a detailed example,
For example, Research Disclosure No. 1764
3-VI (issued in December 1978) and E.I. J. B
irr by "Stabiliaution of Photographic Silver Hai
lde Emulsion "(Focal Press), published in 1974.

Various color couplers can be used in the present invention. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in "Research Disclosure" N.
o. 17643 (published December 1978) page 25, VI
Item I-D, ibid. 18717 (issued in November 1979) and the compounds described in JP-A No. 62-215272 and the patents cited therein. Among them, the 5-pyrazolone-based magenta coupler preferably used in the present invention is a 5-pyrazolone-based coupler in which the 3-position is substituted with an arylamino group or an acylamino group (among others, a sulfur atom-eliminating type two-equivalent coupler). is there. Pyrazoloazole-based couplers are more preferable, and among them, pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3725067 are preferable, but a coloring dye yellow. The imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 are more preferable in view of low side absorption and light fastness, and pyrazolo [1,5- b] [1,2,4] triazole is particularly preferred. Cyan couplers that can be preferably used in the present invention include U.S. Pat. Nos. 2,474,293 and 405.
No. 2212 and the like are naphthol-based and phenol-based couplers, and the phenol-based cyan couplers described in US Pat. No. 3,777,2002 have a methyl group or higher alkyl group at the meta position of the phenol group. A 2,5-diacylamino-substituted phenol coupler is also preferable in terms of color fastness. Yellow couplers include, for example, US Pat. Nos. 3,933,501 and 4
No. 022620, No. 4326024, No. 44017
Those described in each specification of No. 52, Japanese Examined Patent Publication No. 58-10739, British Patent Nos. 1425020 and 1476760, and the like are preferable.

Colored couplers for correcting unnecessary absorption in the short wavelength region of the dyes produced, couplers in which the coloring dyes have an appropriate diffusivity, non-color-forming couplers, and development inhibitors released in association with the coupling reaction. DIR couplers and polymerized couplers can also be used. A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. DIR couplers that release development inhibitors are Research Disclosure N
o. 17643, Patents described in VII to F, JP-A-57-151944, 57-154234, and 60.
-184248, JP-A-63-146035 and those described in U.S. Pat. No. 4,248,962.
Those described in the publication are preferred. Examples of couplers that release a nucleating agent or a development accelerator in an image during development include British Patent Nos. 2097140 and 2131188.
Each specification, JP-A-59-157638, 59-1
No. 70840, International Application Publication (WO) 88/01
The one described in Japanese Patent No. 402 is preferable. The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.03 for the magenta coupler. Mole to 0.5 mole,
For cyan couplers, it is 0.02-1.0 mol.

As the binder or protective colloid that can be used in the emulsion layer or the intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. The light-sensitive material of the present invention includes
An antifoggant or a color mixing inhibitor can also be used. Typical examples of these are JP-A-62-215272 and 185.
The compounds described on page 193 can be mentioned. As a compound that releases a photographically useful group, Japanese Patent Laid-Open No.
No. 3-153540, No. 63-259555,
Japanese Patent Laid-Open Nos. 2-61636, 2-244041, and 2
The compounds described in each publication of -308240 are mentioned. In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. Typical examples of the compounds include those described in JP-A No. 62-215272, pages 121 to 125. Dyes that prevent irradiation or halation may be used in the light-sensitive material of the present invention (for example, the compounds described in JP-A Nos. 2-85850 and 2-89047) may be used. Solid fine crystal dispersion method may be used.), UV absorber, plasticizer, fluorescent whitening agent, matting agent, air antifoggant, coating aid, film hardening agent, antistatic agent, slipperiness improver, etc. Can be added. Typical examples of these additives are Research
Disclosure magazine No. 17643VII-XII
Item I (published December 1978), pages 25-27, and 18716 (published November 1979), pages 647-651.

The light-sensitive material of the present invention preferably has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on the support. The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. .. It is usual that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but in some cases, the green-sensitive layer contains a yellow coupler and a magenta coupler. It is also possible to use different combinations such as mixed use. In the light-sensitive material of the present invention, in addition to the silver halide emulsion layer, a non-light-sensitive layer, such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a back layer, and a white reflective layer may be appropriately provided. preferable.

The fog treatment of the photographic light-sensitive material of the present invention is carried out by the following "optical fog method" and / or "chemical fog method". The entire exposure in the "light fog method", that is, the fog exposure is performed after imagewise exposure, before color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being dried. Is most preferred. As the light source for the fogging exposure, for example, JP-A-56-137350 and JP-A-58-70223 are used.
A light source having a high color rendering property (as close to white as possible) as described in each publication is preferable. The illuminance of light is 0.01 to 20
00 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. Light-sensitive materials using higher sensitivity emulsions are preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the photosensitivity by various filters, the distance between the photosensitive material and the light source, or the angle between the photosensitive material and the light source. Further, the illuminance of the above-mentioned fogging light can be increased from low illuminance to high illuminance continuously or stepwise. It is preferable to immerse the light-sensitive material in a color developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the permeation of the liquid to the light fog exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 seconds to 2 minutes, preferably 0.1.
Seconds to 1 minute, more preferably 1 second to 40 seconds.

In the present invention, the nucleating agent used when the so-called "chemical fog method" is applied can be contained in the photosensitive material or in the processing liquid for the photosensitive material. A method in which it is contained in a light-sensitive material and used is preferable. Here, the nucleating agent is a substance which acts when the surface latent image of an internal latent image type silver halide emulsion which has not been fogged in advance is subjected to a direct image formation. In the present invention, the fog treatment is preferably performed using a nucleating agent. When it is contained in the light-sensitive material, it is preferably added to the internal latent image type silver halide emulsion layer, but as long as it is diffused during coating or during processing and the nucleating agent is adsorbed to silver halide, It may be added to a layer such as an intermediate layer, an undercoat layer or a back layer. Examples of the nucleating agent that can be used in the present invention include, for example, Research Disclosure Magazine,
No. 22534 (January 1983), pp. 50-54, ibid., No. 15162 (November 1976) 76-77
Page, No. 23510 (November 1983) 346
Quaternary heterocyclic compounds and hydrazine compounds described on page 352. Two or more kinds of these nucleating agents may be used in combination. In the present invention, the nucleating agents described in the following publications can be preferably used. That is, 510 of JP-A-3-155543
To 514, a quaternary heterocyclic compound represented by the general formula (N-I), and 60 to 60 of JP-A-3-95546.
The hydrazine compound represented by the general formula (N-II) on page 65; typical nucleating agents represented by the general formulas (N-I) and (N-II) are as follows. (N-I-1) 7- (3-Cyclohexylmethoxythiocarbonylaminobenzamide) -10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-I-2) 6- ( 3-Ethoxythiocarbonylaminobenzamido) -1-propargyl-2,3-trimethylenequinolinium trifluoromethanesulfonate (N-I-3) 6-ethoxythiocarbonylamino-2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-4) 7- [3- (5-mercaptotetrazol-1-yl) benzamide] -10-propargyl-
1,2,3,4-tetrahydroacridinium perchlorate (N-II-1) 1-formyl-2- {4- [3- {3-
[3- (5-Mercaptotetrazol-1-yl) phenyl] ureido} benzsulfonamide] phenyl} hydrazine (N-II-2) 1-formyl-2- {4- [3- (5-
Mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine

In the present invention, it is preferable to use the quaternary heterocyclic compound and the hydrazine compound in combination. When the nucleating agent is added to the processing solution, it is contained in a developing solution or a low pH pre-bath as described in JP-A-58-178350. When the nucleating agent is added to the treatment liquid, the amount used is 10 ^-8 to 10 ^-1 per liter.
The amount is preferably mol, and more preferably 10 ⁻⁷ to 10 ⁻³ mol. In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is preferably contained in the silver halide emulsion layer. The amount added varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the developing conditions, and therefore can be varied over a wide range, but it is about 1 × per mol of silver in the silver halide emulsion. A range of 10 ⁻⁸ to about 1 × 10 ⁻² mol is practically useful, with a preferred range of about 1 × 10 ⁻⁵ to about 1 × 10 ⁻³ mol per mol of silver.

When a nucleating agent is used, it is preferable to use a nucleating accelerator for promoting the action of the nucleating agent. A nucleation accelerator does not substantially function as a nucleating agent,
A substance that promotes the action of a nucleating agent to increase the maximum density of a direct positive image and / or accelerates the development time necessary to obtain a certain maximum density of a direct positive image. Such a nucleation accelerator has at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, thiadiazoles, oxadiazoles, benzotriazoles, tetrazaindenes, Examples thereof include triazaindenes and pentazaindenes, and the compounds described in JP-A-63-106656, pages 5 to 16. In addition, JP-A-63-
No. 226652, No. 63-106656, No. 63-8
The compounds described in No. 740 can be mentioned.

Two or more of these nucleation accelerators can be used in combination. The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but in the light-sensitive material, it can be used in internal latent image type silver halide emulsions and other hydrophilic colloid layers (intermediate layer, protective layer, etc.). Preferably contained in Particularly preferred is in a silver halide emulsion or its adjacent layer. The amount of the nucleation accelerator added is preferably 10 ⁻⁶ to 10 ⁻² mol, and more preferably 10 ⁻⁵ to 10 ⁻² mol, per mol of silver halide. When the nucleation accelerator is added to the processing solution, that is, the developing solution or its pre-bath, it is preferably 10 ^-8 to 10 ^-3 mol, and more preferably 10 ^-7 to 10 ^-4 mol per liter. is there.

Known photographic additives that can be used in the present invention are those described in Research Disclosure No. 17643
(December 1978) and the same No. 18716 (19
(November 1979), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 ───────────────────────────── 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4 whitening agent, page 24 5 Fog inhibitor, pages 24 to 25, page 649, right column to stabilizing agent, page 650, right column 6 Light absorber, page 25, right column, page 649, right column ~ Filter dye, page 650, left column UV absorber 7 Stain inhibitor, page 25, right column 8 Dye image stabilizer, page 25, 9 Hardener, page 26, page 651, left column 10 Binder page 26 Same as above ─────────────────────────────

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a flexible support such as a plastic film, paper or cloth usually used for photographic light-sensitive materials or a rigid support such as glass, earthenware or metal. It is coated on a support.
What is useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryter layer or an α-olefin polymer. Examples include paper coated or laminated with (for example, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. For coating silver halide photographic emulsion layers and other hydrophilic colloid layers,
For example, various known methods such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used. Also, if necessary, US Pat.
No. 1294, No. 2761791, No. 352652
No. 8, No. 3508947, etc. may be used to simultaneously apply multiple layers.

Next, an image forming method using the above direct positive photographic light-sensitive material will be briefly described. That is, a positive image can be obtained by subjecting the above-mentioned light-sensitive material to imagewise exposure and then developing it. As the development processing, black-and-white phenomenon processing or color development processing is performed depending on the type of photosensitive material. The color developing solution used for color developing processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine derivative is preferable. Typical examples are shown below, but the invention is not limited thereto. (1) 4-amino-N-ethyl-N-β-hydroxyethylaniline, (2) 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,
(3) 3-methyl-4-amino-N-ethyl-N-β-
Examples thereof include hydroxyethylaniline, and their sulfates, hydrochlorides or p-toluenesulfonates. The amount of the above-mentioned aromatic primary amine developing agent used is preferably 50% by mole or more of the entire developing solution. The photographic light-sensitive material after the above color development processing is usually bleached,
A desilvering process consisting of a fixing process is applied, and after the desilvering process,
Generally, washing and / or stabilization treatment is performed. Regarding the above-mentioned series of processing steps, JP-A-3-12
The method described on pages 380 to 381 of Japanese Patent No. 0537 can be preferably used. As the black and white development method, the method described on pages 379 to 380 of the above publication can be preferably used.

[0037]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples. [Example 1] Preparation of silver halide emulsion (Preparation of emulsion EM-1) (Comparative example) An aqueous solution of potassium bromide and silver nitrate was added to 0.3 g of 3,4-dimethyl-1,3 per mol of silver. Halogenation containing slightly rounded octahedral silver bromide grains having an average grain size of 0.23 μm, which were simultaneously added to an aqueous gelatin solution containing thiazoline-2-thione with vigorous stirring at 65 ° C. for 15 minutes. A silver solution was obtained.
To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added per mol of silver, and the mixture was stirred at 75 ° C. for 8 hours.
The chemical sensitization treatment was performed by heating for 0 minutes. Using the grains thus obtained as a core, an aqueous solution of potassium bromide and silver nitrate (96 g) was simultaneously added in the same manner as in the first time to further grow silver halide grains. However, the addition amount of the potassium bromide aqueous solution was controlled so that the pAg of the emulsion during the growth of silver halide grains was 6.3. Thus, a slightly rounded cubic monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μm was finally obtained. The coefficient of variation of particle size was about 10%. After that, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, and then 80 g of gelatin was added to the emulsion.
In, the pH was adjusted to 6.4. To this emulsion, 1.5 mg sodium thiosulfate and 1.5 mg per mole silver
Chloroauric acid (4 hydrate) was added, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion (EM-1).

(Preparation of Emulsion EM-2) (Example of the Present Invention) Emulsion EM-1 Above
In the shell formation process (second precipitation environment), the aqueous solution of potassium bromide and silver nitrate was added at the same time as K ₂ Ru was added.
The amount of Ru (ruthenium) added to the (NO) Cl ₅ aqueous solution was 3.0 × 1 per mol of silver containing particles after shelling.
Emulsion EM-2 was obtained in the same manner as Emulsion EM-1 above, except that the addition amount was 0 ^-8 mol / Ag mol. (Preparation of emulsions EM-3 and EM-4) (Example of the present invention) In the preparation of the emulsion EM-2, the addition amount of Ru (ruthenium) was 1.
The above emulsion EM except that it was added so as to be 0 × 10 ⁻⁷ mol / mol Ag and 3.0 × 10 ⁻⁷ mol / Ag mol.
Emulsions EM-3 and EM-4 were obtained in the same manner as in Example 2.

A light-sensitive material (sample) was prepared according to the following formulation using each silver halide emulsion prepared as described above. (Preparation of Photosensitive Material) (Preparation of Sample 101) Sample 101 was prepared by coating the following first layer and second layer on the front side of a paper support (thickness: 220 microns) laminated on both sides with polyethylene. The coating amounts (g / m ² ) of the components of each layer are shown below. For silver halide, the coating amount in terms of silver is shown. First layer (emulsion layer) Emulsion (EM-1) 0.20 Gelatin 2.00 The following cyan coupler (ExC-1, 2 equivalent amounts) 0.60 Coupler solvent (di (2-ethylhexyl) sebacate) 29 Second Layer (Protective Layer) Gelatin 2.00 Gelatin Hardener 0.04 (1,2-Bis (vinylsulfonylacetamido) ethane) The first layer has the following ExZK-1 and ExZK as nucleating agents.
-2 Each 10 ^-3% by weight with respect to the silver halide was used Cpd-22 below ^10-2% by weight nucleation accelerator.

[0040]

[Chemical 1]

Nucleating agent (ExZK-1) 7- (3-Ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3,3
4-Tetrahydroacridinium trifluoromethanesulfonate Nucleating agent (ExZK-2) 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxy Carbonylethoxycarbonyl) phenylcarbamoyl] -4-hydroxy-1
-Naphthylthio} -tetrazol-1-yl] phenyl} ureido] benzenesulfonamide} phenyl]-
1-Formylhydrazine (Preparation of Samples 102 to 104) In the preparation of Sample 101, emulsions EM-2 to EM- were used instead of emulsion EM-1.
Samples 102 to 104 were prepared in the same manner as the sample 101 except that the sample No. 4 was changed. However, the addition amount of the nucleating agent (ExZK-1 and ExZK-2) contained in the first layer was changed to an appropriate amount for each emulsion.

[Evaluation as a direct positive color photographic light-sensitive material] Each sample obtained was subjected to wedge exposure (1/10).
Second, 300 CMS), the following color development processing was performed. The characteristic curve is calculated from the obtained image, and the gradation (γ)
Was measured and evaluated. The gradation (γ) is represented by log ΔH (ΔH is the exposure amount), which is the difference in exposure amount between the point of Dmin (minimum density) +0.5 and the point of Dmin + 1.5. That is, the larger the value of log ΔH, the softer the gradation (main gradation, the same applies below), and the smaller the value of log ΔH, the harder the gradation. (Color development processing) The exposed sample was continuously processed by an automatic developing machine by the method described below until the cumulative replenishment amount of the solution became 3 times the tank capacity. ──────────────────────────────────── Treatment process time Temperature Tank capacity Replenishment amount ─────── ────────────────────────────── color development 135 sec 38 ° C. 30 liters 240 ml / m ² bleach-fixing 40 seconds 33 ° C. 10 liters 300 ml / m ² Washing with water (1) 40 seconds 33 ° C 7 liters --- Washing with water (2) 40 seconds 33 ° C 7 liters 320 ml / m ² Drying 30 seconds 80 ° C ─────────────── ────────────────────── The replenishing method of the washing water is such that the washing bath (2) is replenished, and the overflow liquid of the washing bath (2) is washed ( The so-called countercurrent replenishment method, which leads to 1), was adopted. At this time, the carry-in amount of the bleach-fixing solution from the bleach-fixing bath with the light-sensitive material to the washing bath (1) was 3
It was 5 ml / m ² , and the ratio of the replenishing amount of washing water to the carry-in amount of the bleach-fixing solution was 9.1 times. The composition of each treatment liquid was as follows.

──────────────────────────────────── Color developer Developer replenisher ───── ───────────────────────────────────── D-Sorbit 0.15 g 0.20 g Sodium naphthalenesulfonate 0.15 g 20 g Formalin condensate N, N, N-trimethylene 4.4 g 4.4 g Phosphonic acid diethylenetriamine pentaacetic acid 0.44 g 0.44 g 1-Hydroxyethylidene-1,1-0.27 g 0.27 g Diphosphonic acid diethylene glycol 12.0 ml 16 0.0 ml Benzyl alcohol 13.5 ml 18.0 ml Potassium bromide 0.80 g --- Benzotriazole 0.003 g 0.004 g Sodium sulfite 2.4 g 3.2 g N, N-bis 2-sulfoethyl) 8.0 g 10.6 g-N-hydroxyamine disodium salt D-glucose 2.0 g 2.4 g triethanolamine 6.0 g 8.0 g N-ethyl-N-hydroxy 6.4 g 8.5 g Ethyl-4-aminoaniline sulfate potassium carbonate 30.0 g 25.0 g Optical brightener (diaminostilbene type) 1.0 g 1.2 g Water was added 1000 ml 1000 ml ────────────── ─────────────────────── pH (25 ℃) (pH adjusted with KOH) 10.30 10.75 ────────── ──────────────────────────

──────────────────────────────────── bleach-fixing solution mother liquor replenisher ───── ──────────────────────────────── ethylenediaminetetraacetic acid ・ 4.0g same as mother liquor disodium ・ dihydrate ethylenediaminetetraacetic acid -Fe (III) -70.0 g ammonium dihydrate ammonium thiosulfate (700 g / l) 150 ml sodium p-toluenesulfinate 35.0 g ammonium bisulfite 35.0 g 5-mercapto-1,3,4-triazole 0. 5g Ammonium nitrate 10.0g Water added 1000ml ──────────────────────────────────── pH (25 ℃ ) (PH adjustment with acetic acid) 6.10 ──────── ────────────────────────────

[Washing water] Tap water for both mother liquor and replenisher
Type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400) are passed through a mixed bed column to give calcium and magnesium ions. The concentration was treated to 3 mg / l or less, and subsequently 20 mg / l sodium isocyanurate dichloride and 1.5 g / l sodium sulfate were added. The pH of this solution is 6.5 to 7.
It was in the range of 5. The results are shown in Table 1 below.

Table 1 ──────────────────────────────────── Ru addition amount Gradation (γ) Sample No. (Mol / silver mol) (log ΔH) ──────────────────────────────────── 101 (Comparison Example) -0.53 102 (Example of the present invention) 3x10 ^-8 0.28 103 (Example of the present invention) 1x10 ^-7 0.24 104 (Example of the present invention) 3x10 ^-7 0.20 ── ───────────────────────────────────

As is clear from the results shown in Table 1,
The photographic light-sensitive materials according to the present invention (Samples 102 to 104) containing the Ru nitrosyl coordination complex are higher than the photographic light-sensitive material for comparison (Sample 101) not containing the Ru nitrosyl coordination complex. It gives an image in which the tone is remarkably hardened.

[Example 2] (Preparation of emulsion EM-5) In the preparation of emulsion EM-1 of Example 1, an aqueous solution of potassium bromide and silver nitrate at the time of shell formation (second precipitation environment) is added. At the same time, the K ₂ Ru (NO) Cl ₅ aqueous solution was added to the R
The addition amount of u was 1 × 10 ⁻⁷ mol / Ag mol per mol of silver halide, and the addition of an aqueous potassium bromide solution so that the pAg of the emulsion during grain growth was 8.0. Emulsion E except that the amount was controlled
Emulsion EM-5 was prepared in the same manner as M-1. (Preparation of emulsions EM-6 and EM-7) The above emulsion EM-
In the preparation of 5, the pAg of the emulsion during grain growth was 7.1.
And emulsions EM-6 and E corresponding to the emulsions EM-5, respectively, except that the addition amount of the potassium bromide aqueous solution was controlled so as to be 6.3 and 6.3.
M-7 was prepared. (Preparation of Samples 201 to 203) Sample 10 of Example 1
In the preparation of 1, the emulsion EM- was used instead of the emulsion EM-1.
Samples 201 to 203 were prepared in the same manner as the sample 101, except that the samples Nos. 5 to EM-7 were used instead. However, the nucleating agent contained in the first layer (ExZK-1 and ExZ
The addition amount of K-2) was changed to an appropriate amount for each emulsion. [Evaluation as direct positive color photographic light-sensitive material] Each sample obtained as described above was exposed and color-developed under the same conditions as in Example 1 to form an image. And it evaluated by the same method. The results are shown in Table 2 below.

Table 2 ──────────────────────────────────── Ru addition amount Floor during shell formation Tone (γ) Sample No. (Mol / silver mol) pAg of emulsion (log ΔH) ───────────────────────────────────── 201 (Example of the present invention) 1 × 10 ⁻⁷ 8.0 0.28 202 (Example of the present invention) 1 × 10 ⁻⁷ 7.1 0.27 203 (Example of the present invention) 1 × 10 ⁻⁷ 6.3 6.3. 24 ────────────────────────────────────

As is clear from the results shown in Table 2,
The photographic light-sensitive materials (Samples 201 to 203) according to the present invention, which incorporate the nitrosyl coordination complex of Ru, give images in which the gradation is hardened.

Example 3 (Preparation of Photosensitive Material) (Preparation of Sample 301) On the front side of a paper support (thickness: 100 μm) laminated on both sides with polyethylene, the following first
Layers 11 to 11 and layers 12 to 13 on the back side were multilayer-coated to prepare a direct type color photographic light-sensitive material (comparative sample). For the polyethylene coated on the first layer, titanium oxide (4 g / m ² ) was used as a white pigment, and a slight amount (0.0
03 g / m ² ) of ultramarine blue as a bluing dye (the chromaticity of the surface of the support is 88.0 in the L *, a *, b * system, −
0.20, -0.75). (Photosensitive layer composition) The components and the coating amount (g / m ² unit) are shown below. However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was prepared according to the method for producing the emulsion EM-1 prepared in Example 1 above, by changing the grain size by changing the temperature during grain formation. However, as the emulsion of the 11th layer, a Lippmann emulsion which was not surface-sensitized was used. First layer (antihalation layer) Black colloidal silver 0.10 Gelatin 0.70 Second layer (intermediate layer) Gelatin 0.70 Third layer (red sensitive layer) Red sensitizing dye (ExS-1, 2, 3, Silver bromide (emulsion EM-1, average grain size: 0.4 μm, grain size distribution: [variation coefficient] 10%, cube) spectrally sensitized with each equivalence meter 3.8 × 10 ⁻⁴ ). 25 Gelatin 1.00 Cyan coupler (ExC-1, 2, 3 in a ratio of 0.30 1: 1: 0.2) Anti-fading agent (Cpd-1, 2, 3, 4, 30 in equal amounts) 0.18 Anti-staining agent (Cpd-5) 0.003 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, and 3 are equal amounts) 0.12

Fourth Layer (Intermediate Layer) Gelatin 1.00 Color Mixing Inhibitor (Cpd-7) 0.08 Color Mixing Inhibitor Solvent (Solv-4, 5 in Equivalent Amounts) 0.16 Polymer Latex (Cpd-8) 0.10 Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ ) (emulsion EM-1, average particle size: 0. 40 μm, particle size distribution: [variation coefficient] 10%, cubic) 0.25 gelatin 0.80 magenta coupler (ExM-1, 2 and 3 equivalent amounts) 0.11 yellow coupler (ExY-1) 0.03 Anti-fading agent (Equivalent amounts of Cpd-9, 26, 30) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in the ratio of 10: 7: 7: 1) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 0.15 Sixth layer (intermediate layer) Same as the fourth layer Seventh layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixing inhibitor (Cpd-7) ) 0.03 Color mixture inhibitor solvent (Equivalent amounts of Solv-4 and 5) 0.10 Polymer latex (Cpd-8) 0.07

Eighth Layer (Intermediate Layer) Same as Fourth Layer Ninth Layer (Blue Sensitive Layer) Spectral sensitized with blue sensitizing dye (Equivalent amount of ExS-5 and ExS-5, 3.5 × 10 ⁻⁴ in total). Sensitized silver bromide (emulsion EM-1, average grain size: 0.60 μm, grain size distribution: [variation coefficient] 11%, cubic) 0.40 gelatin 0.80 yellow coupler (ExY-1, 2, 0.35 Antifade agent (Cpd-14) 0.10 Antifade agent (Cpd-30) 0.05 Stain inhibitor (Cpd-5, 15 in a ratio of 1: 5) 007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 10th layer (UV absorbing layer) Gelatin 1.00 UV absorber (Equivalent amounts of Cpd-2, 4 and 16) 0.50 Color mixing inhibitor (Equivalent amounts of Cpd-7 and 17) 0.03 Dispersion medium (C pd-6) 0.02 UV absorber solvent (Equivalent amounts of Solv-2 and 7) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 10: 10: 13: 15: 20 ratio) 0.05 11th layer (protective layer) Fine particle silver chlorobromide (97 mol% silver chloride, average size 0.1 μm) 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight: 50,000) 0 .01 polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) in equal amounts 0.05 gelatin 1.80 gelatin hardening agent (H-1 and H-2 respectively) Equivalent) 0.18 12th layer (back layer) Gelatin 2.50 UV absorber (Equivalent amounts of Cpd-2, 4, 16) 0.50 Dye (Cpd-18, 19, 20, 21, 27) Each equivalent) 0.06 13th layer (back protective layer) Equal amounts of polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) 0.05 gelatin 2.00 Gelatin hardening agent (H- 1, H-2 equal amount) 0.14

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ^-3 % by weight and 10 ^-2 % by weight, respectively, relative to silver halide, Cpd-22 as a nucleation accelerator,
28 and 29 were used at 10 ^-2 wt% each. Further, alkanol XC (Du Pont
And sodium alkylbenzene sulphonate as coating aids and succinate and Magefac F
-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. Equal amounts of Cpd-23, 24, and 25 were used as stabilizers in the silver halide and colloidal silver-containing layers. This sample was designated as sample (301). The compounds used in the above sample preparation are shown below.

[0055]

[Chemical 2]

[0056]

[Chemical 3]

[0057]

[Chemical 4]

[0058]

[Chemical 5]

[0059]

[Chemical 6]

[0060]

[Chemical 7]

[0061]

[Chemical 8]

[0062]

[Chemical 9]

[0063]

[Chemical 10]

[0064]

[Chemical 11]

[0065]

[Chemical 12]

[0066]

[Chemical 13]

[0067]

[Chemical 14]

Solv-1 di (2-ethylhexyl) sebacate Solv-2 trinonyl phosphate Solv-3 di (3-methylhexyl) phthalate Solv-4 tricresyl phosphate Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate Solv- 7 Di (2-ethylhexyl) phthalate H-1 1,2-bis (vinylsulfonylacetamide) ethane H-2 4,6-dichloro-2-hydroxy-
1,3,5-Triazine / Na salt ExZK-17- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl) Carbamoyl] -4-hydroxy-1
-Naphthylthio} tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide} phenyl] -1-
Formyl hydrazine

(Preparation of Sample 302) Same as Sample 301 except that the emulsion EM-1 contained in each emulsion layer was changed to the emulsion EM-3 prepared in Example 1 in the preparation of the sample 301. Then, a sample 302 was prepared (comparative sample). The particle size of each layer was adjusted by changing the particle formation temperature.

[Evaluation as Direct Positive Color Photosensitive Material] The photosensitive materials 301 and 3 prepared as described above.
No. 02 was processed under the same processing conditions as in Example 1 to directly form a positive color image. Then, each color density of yellow, magenta and cyan was measured, and the gradation (γ) was evaluated in the same manner as in Example 1. The results obtained are shown in Table 3.

Table 3 ──────────────────────────────────── Ru addition amount Gradation (γ) (Log ΔH) Sample N0. (Mol / silver mol) Yellow magenta cyan ──────────────────────────────────── 301 (Comparative example) -0.67 0.53 0.49 ───────────────────────────────────── 302 (the present invention Example) 1 × 10 ^-7 0.32 0.29 0.26 ─────────────────────────────────── ──

As is clear from the results shown in Table 3,
By using the direct positive color photographic light-sensitive material (Sample 302) according to the present invention, in which a specific Ru complex is incorporated, a high contrast image can be obtained.

[Fig. 13]

Claims (2)

[Claims] 1. A direct positive photographic light-sensitive material comprising, on a support, at least one light-sensitive emulsion layer containing an internal latent image type silver halide grain which has not been fogged in advance. , A direct positive photographic light-sensitive material containing a nitrosyl or thionitrosyl coordination complex of Ru. 2. The direct silver halide grain according to claim 1, wherein the silver halide grain is formed by growing the grain in the presence of the complex so that the pAg of the emulsion is in the range of 5.0 to 8.0. Positive photographic light-sensitive material.