JPH04306641A - Direct positive type silver halide photosensitive material for photograph - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material which possesses high sensitivity and provides a distinct image having the min. concentration by forming a halation preventing layer between an emulsion layer and a supporting layer. CONSTITUTION:A direct positive type silver halide photosensitive material for photograph having at least one layer of emulsion layer containing the inside latent image type silver halide particles which are not previously fogged is formed on a supporting body. This inside latent image type silver halide particle has a dislocation line, and the particle has a core/shell structure. The core is formed from the normal crystal particles which are substantially made of silver bromide. After the core is sensitized by sulfur, selenium, or noble metals, the core/shell structure is formed by the covering with the silver halide shell.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a direct positive silver halide photographic material.

0002

[Prior Art] It is well known to directly obtain a positive image by using an internal latent image type silver halide emulsion that has not been fogged in advance and performing a surface image after image exposure and then performing a fogging treatment, or while performing a fogging treatment. It is being

The above-mentioned internal latent image type silver halide photographic emulsion is a type of halogen that has photosensitive nuclei mainly inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. A silver oxide photographic emulsion.

Various techniques are known in the art. For example, US Patent No. 2,592,250
No. 2466957, No. 2497875, No. 25
No. 88982, No. 3317322, No. 3761266
No. 3761276, No. 3796577 and British Patent No. 1151363, No. 1150553, No. 1
The main ones are those described in each specification of No. 011062.

By using these known methods, it is possible to produce direct positive type photographic materials with relatively high sensitivity.

For details of the above-mentioned direct positive image forming mechanism, see, for example, T. H. The Theory of the Photographic Process by James
theory of the Photographic
Process), 4th edition, Chapter 7, pp. 182-193
Page and US Pat. No. 3,761,276.

In other words, due to the surface desensitization effect caused by the so-called internal latent image produced inside the silver halide by the initial imagewise exposure, the fogging treatment selectively affects only the surface of the silver halide grains in the unexposed areas. It is believed that a photographic image (direct positive image) is formed in the unexposed area by generating fog nuclei and then performing a normal so-called surface development process.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called a "photofogging method" (for example, the method described in British Patent No. 1,151,363) is used. ) and a nucleating agent called the “chemical fogging method.”
A method using t) is known.

[0009] The term "nucleating agent" as used herein refers to a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance.

[0010] Regarding this latter method, for example, ``Research Disclosure'' (Research Disclosure)
Closure) Magazine, Volume 151, No. 1516
2 (published November 1976), pages 76-78.

A hydrazine compound is well known as a nucleating agent used in the above-mentioned "chemical fogging method".

[0012] Heterocyclic quaternary ammonium salts are also known as other nucleating agents, such as those disclosed in US Patent No. 36
No. 15615, No. 3719494, No. 3734738
, No. 3759901, No. 3854956, No. 409
No. 4683, No. 4306016 and British Patent No. 12
It is described in the specifications of No. 83835 and Japanese Patent Application Laid-open Nos. 52-3426 and 52-69613.

Various techniques have been developed to improve the photographic properties of direct positive imaging materials using such chemical fogging methods. For example, U.S. Patent No. 4,471,044
A quaternary salt-based nucleating agent having a thioacidic silver halide adsorption promoting group as described in the specification of JP-A No. 63-3453
By using the quaternary salt-based nucleating agents described in No. 5 and JP-A-1-309049, certain effects, such as high maximum image density and low minimum image density, have been obtained.

In order for a direct positive photographic light-sensitive material to be put to practical use, the maximum density (Dmax) must be high and the minimum density (Dm
in) must be low and sharp. Particularly when it is used in reflective photosensitive materials such as color reversal paper, color hard copies for storing images from full-color copiers and CRTs, whiteness (here, whiteness refers to It is desired to improve the color reproducibility (referring to the color reproducibility of Regarding whiteness, since the exposure area of these photosensitive materials is limited, not only the minimum image density but also the gradation of the toe area is important. The harder the gradation of the foot, the higher the whiteness. As a method to solve these problems, for example, as disclosed in JP-A-1-145647, metals such as manganese, copper, zinc, cadmium, etc. are added to internal latent image type silver halide grains that have not been fogged in advance. Although it has been found that by incorporating it, it is possible to obtain a high maximum density and a low minimum density while increasing the contrast of highlight areas, but a sufficiently satisfactory degree of whiteness has not yet been obtained.

Furthermore, in the above-mentioned applications, the reproducibility of fine lines is not sufficient, leaving problems in the reproducibility of image information. Further, when duplicating a printed matter using halftone dots, there remains a problem particularly in the reproducibility of halftone dots. In order to solve this problem, it is conceivable to provide an antihalation layer in a direct positive photosensitive material. However, although providing an antihalation layer is effective in solving the above-mentioned problems, it inevitably lowers sensitivity and increases minimum image density, and direct positive silver halide photography with higher sensitivity and lower minimum image density The advent of photosensitive materials is eagerly awaited.

Several reports have been made regarding dislocation of silver halide grains. Regarding silver halide tabular crystals, ■C. R. Berry, J. Appl. Phys. ，
27, 636 (1956) ■C. R. Berry,
D. C. Skillman, J. Appl. Phys.
．． , 35, 2165 (1964) ■J. F. Hamilton, Phot. Sci. E
ng. , 11, 57 (1967) ■T. Shioz
awa, J. Soc. Photo. Sci. Jpn. ，
34, 16 (1971) ■T. Shiosawa
, J. Soc. Photo. Sci. Jpn. , 35
, 213 (1972), etc., and it is possible to observe dislocations in a crystal by X-ray diffraction or low-temperature transmission electron microscopy, and it is possible to observe various dislocations in a crystal by applying strain to the crystal. It has been stated that dislocations occur.

On the other hand, as for the influence of dislocation on photographic performance, G. C. Famell, R. B. Flint a
nd J. B. Chanter, J. Photo. Sc
i. , 13, 25 (1965),
It has been shown that in large-sized, high aspect ratio tabular silver bromide grains, there is a close relationship between the location where latent image nuclei are formed and the defects within the grain.

[0018] JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains into which dislocations are intentionally introduced. It has been shown that tabular grains with dislocations have better photographic properties such as sensitivity and reciprocity than tabular grains without dislocations, and when used in photosensitive materials, they have superior sharpness and graininess. .

Direct positive silver halide photographic light-sensitive materials in which dislocation lines are expected to be introduced include internal latent image conversion silver halide emulsions, which are disclosed in US Pat. No. 2,592,250, Kosho 58-54
This method is disclosed in Japanese Patent Application Laid-open No. 379 and Japanese Patent Application Laid-Open No. 127549/1983. However, in these cases, the halogen composition of the core part is silver chlorobromide, and the halogen composition of the core part is not substantially silver bromide. There is no sense of feeling. As disclosed in JP-A No. 63-5342, it is preferable that the halogen composition of the core part has a high silver bromide content. Silver core particles were coveted.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to provide a direct positive photographic material which is highly sensitive and has a low minimum image density and a high maximum image density. In particular, the object of the present invention is to provide a direct positive photographic light-sensitive material which has sufficient sensitivity, low minimum image density, and high maximum image density, by providing an antihalation layer to improve the reproducibility of fine lines and halftone dots.

[0021]

[Means for Solving the Problems] The above object of the present invention is to provide a direct positive silver halide photograph having at least one emulsion layer containing internal latent image type silver halide grains not previously fogged on a support. In a light-sensitive material, after the internal latent image type silver halide grains form a silver halide core with normal crystal grains consisting essentially of silver bromide, and then are sensitized with sulfur, selenium, and/or noble metals. This is achieved by a direct positive silver halide photographic material having a core/shell structure in which the core is covered with a silver halide shell, and in which dislocation lines are present in the silver halide grains. This can also be achieved by forming an antihalation layer between the emulsion layer and the support in the above-mentioned direct positive silver halide photographic light-sensitive material.

[0022] The internal latent image type silver halide grains which are not prefogged for use in the present invention will be explained. The silver halide grains have a core/shell structure, and dislocation lines are present in the grains.

Dislocations of tabular grains are described, for example, in the above-mentioned J. F.
Hamilton, Phot. Sci. Eng. ，
11, 57 (1967) and T. Shiosaw
a, J. Soc. Photo. Sci. Jpn. , 3
5, 213 (1972) using a low-temperature transmission electron microscope.

However, tabular grains with a thickness of 0.3 μm or more or normal crystal grains with a diameter of 0.3 μm or more cannot be observed by the method using a transmission electron microscope as described above because electron beams cannot pass through them. It's impossible.

Observation of dislocations in normal crystal grains as in the present invention can be carried out by the following method.

That is, the silver halide grains taken out from the emulsion are etched by dipping them in a dilute silver halide solvent for an appropriate period of time, being careful not to apply pressure that would cause dislocations to the grains. The thickness should be 0.3 μm or less. As the silver halide solvent, a KBr aqueous solution, a sodium thiosulfate aqueous solution, a potassium cyanide aqueous solution, etc. are used.

The thin plate-like crystal thus obtained from the silver halide normal crystal is observed by a transmission method while the sample is cooled to prevent damage (printout, etc.) caused by electron beams. Dislocations can be confirmed in each particle from photographs of particles obtained by such a method.

The method of introducing dislocation lines into the silver halide normal crystal of the present invention will be described. The silver halide normal crystal grains of the present invention are prepared by: 1) Preparation of the base silver halide normal crystal grains (halogen composition is substantially silver bromide); 2) Addition of silver chloride or salt to the base silver halide normal crystal grains. It is prepared by three processes: formation of epitaxy of silver bromide; and 1) physical ripening of the epitaxy of the grains and/or conversion with halogen.

Since dislocations are generated at locations where silver chloride or silver chlorobromide epitaxy is attached, the locations where dislocations exist are determined by controlling the locations where epitaxy is generated.

By the way, in silver halide consisting essentially of silver bromide, microepitaxy is preferentially attached to the (111) surface. Therefore, (11
1) Dislocations can be selectively introduced onto the surface. In Japanese Patent Publication No. 58-24772, the (111
) A method for producing a hybrid silver halide crystal in which a second silver halide is preferentially added to the surface is described. However, this does not seem to be the intention of introducing dislocation lines, as it ultimately creates a cubic crystal by preferentially adding the second silver halide to the (111) surface of the dodecahedral crystal. I can't do it.

Regarding silver chloride or silver chlorobromide epitaxy, C. R. Berry and D. C.
Skillman, J. Appl. Phys 35
:2165 (1964) and J. E. Maska
Japanese Patent Laid-Open No. 59-133540 by SKY discloses grains in which silver chloride is epitaxially grown on the surface of silver bromide grains. However, for any of these particles,
After microepitaxy growth, there is no intention to introduce dislocations by physical ripening and/or conversion by halogen.

[0032] Furthermore, in silver chloride or silver chlorobromide epitaxy, the adhesion site can also be controlled by using a site directing agent. As the site indicator, methine dyes and other dyes are used. Examples of the dyes used include dianine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

By using these dyes as site-indicating agents, it is possible to selectively attach silver chloride or silver chlorobromide epitaxy to the tops and/or edges of normal crystal grains, thus allowing subsequent Dislocation lines can be selectively introduced into the tops and/or edges of normal crystal grains by physical ripening and/or conversion with halogen.

Site-directing agents for silver chloride epitaxy are described in J. E. Maskasky, J. Imag.
Sci. 32 160-177 (1988), but there is no intention to selectively introduce dislocations by physical ripening and/or conversion by halogen as described above. In addition, in normal crystal grains of silver iodobromide with a surface iodine content of 10 mol% or more, silver chloride and silver chlorobromide epitaxy occur on the top of the grain and/or even without a site indicator.
Or attach to the ridge.

The unfogged internal latent image type silver halide emulsion used in the present invention has silver halide grains whose surfaces are not fogged in advance and further contains silver halide which forms latent images mainly inside the grains. More specifically, a silver halide emulsion is coated on a transparent support in a fixed amount (0.5 to 3 g/m2), and then applied for a fixed time of 0.01 to 10 seconds. Apply exposure to the following developer solution A.
(Internal type developer) When developed at 20°C for 6 minutes, the maximum density measured by a normal photographic density measurement method was obtained by applying the same amount of silver halide emulsion and exposing it in the same manner as above, using the following developer. It is preferred that the density is at least 5 times greater, more preferably at least 10 times greater than the maximum density obtained when developed in B (surface type developer) at 18° C. for 5 minutes.

Internal developer A Metol
2g sodium sulfite (anhydrous)
90g hydroquinone
8g soda carbonate (monohydrate)
52.5gKBr

5gKI
Add 0.5g water
1 liter

Surface developer B Metol
2.5gL-ascorbic acid
10g NaB
O2 ・4H2 O
35g KBr
Add 1g water
1 liter

Specific examples of latent type emulsions include conversion type silver halide emulsions described in US Pat. No. 2,592,250; US Pat. Nos. 3,761,276, 3,850,637, and 392;
Specifications of No. 3513, No. 4035185, No. 4395478, and No. 4504570, JP-A-52-1566
No. 14, No. 55-127549, No. 53-50222
No. 56-22681, No. 59-208540,
No. 60-107641, No. 61-3137, No. 62
-215272 publications, and Research Disclosure magazine No. 23510 (issued November 1983)
The patent disclosed on page 236 also includes U.S. Pat.
Examples include core/shell type silver halide emulsions described in Japanese Patent Application No. 766, Japanese Patent Application No. 1-2467, and Japanese Patent Application Laid-Open Nos. 191145-1988 and 52146-1999 regarding emulsions doped with metal ions.

Next, the introduction of dislocation lines into the silver halide normal crystal grains used in the present invention will be explained. The introduction of dislocation lines is performed as follows.

In the plane of the base grain consisting essentially of silver bromide,
Alternatively, deposit silver chloride or silver chlorobromide epitaxy on the vertices and/or edges. Substantially silver bromide as used herein refers to silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide having a silver bromide content of 97% or more.

The base grains may be normal crystal grains, and cubic, octahedral, tetradecahedral grains, or other polyhedral grains may be used. Cubic, octahedral, and tetradecahedral particles,
T.H. James “The Theory of the Photographic Process” 4th edition Macmillan Publishing
of the Photographic Proc
ess”4th ed.Macmillan) No. 3
It can be easily prepared by referring to the description in Chapter (pp. 88-104). Regarding other polyhedral particles, see J. E. Ma
skasky. J. Img. Sci 30 247-2
It can be prepared by referring to the method reported in detail in 54 (1986) and the like.

In the preparation of silver chloride or silver chlorobromide epitaxy of the present invention, epitaxy preparation can be carried out directly after the formation of grains to serve as base grains. Alternatively, epitaxy can be prepared after washing the base particles with water for desalination. The halogen composition of the epitaxy of the present invention is different from the halogen composition near the surface of the base grain, and is silver chloride or silver chlorobromide, preferably silver chlorobromide with a silver chloride content of 30 mol% or more. , particularly preferably silver chloride. Iodine may be contained in epitaxy as long as it does not substantially affect photographic properties (particularly developability).

When depositing epitaxy, it is preferable to deposit the epitaxy so that the base particles and epitaxy do not mix with each other. A specific method for the deposition is preferably carried out by adding a water-soluble silver salt and a water-soluble halide salt corresponding to the silver halide epitaxy composition. At this time, the addition rate of the water-soluble silver salt is preferably as fast as possible without causing re-nucleation.

In order to deposit silver halide epitaxy, it is generally desirable to adjust the silver potential at a high silver potential during deposition. However, it varies depending on the halogen composition of the epitaxy, temperature, additives coexisting during preparation, etc. Silver potential (with saturated calomel electrode as reference electrode) is between +30 mV and +300 mV, preferably +5
0 mV to +250 mV. Further, the temperature during epitaxy preparation is preferably lower. The temperature of the reaction vessel is 70℃
-30°C, preferably 60°C - 35°C, more preferably 50°C - 35°C. The amount of silver salt (mainly silver nitrate) and halide to be added is 0.1 to 30 mol% of the base particle,
Preferably 0.5-20 mol%, more preferably 1-20 mol%
It is 10 mol%.

Next, in-plane epitaxy or top and/or edge epitaxy of the base grain is subjected to physical ripening and/or conversion using halogen. When physical ripening is performed, the epitaxy collapses and becomes a larger hill. It is believed that dislocation lines are introduced at this time.

Physical ripening temperature: 40°C to 90°C, preferably 50°C to 90°C, more preferably 60°C to 80°C
It is ℃. After physical ripening, the particles may be washed with water to desalt them, which may be followed by halogen conversion.

[0047] Halogen conversion is the substitution of a halogen forming a silver halide crystal with a different halogen. Conversion is triggered by the addition of halogen and starts from the more soluble part of the silver halide. Therefore, the halogen used for halogen conversion can be any halogen as long as it has a composition that results in silver halide having a lower solubility than the epitaxially grown silver halide.

The amount of halogen added is at least 50 mol %, more preferably 100 mol % or more, based on the amount of epitaxially grown silver.

The halogen used is essentially a bromide, which is added as an aqueous solution. Further, as a method of adding these halogens, they may be added substantially as fine particles of silver bromide. The size of the fine particles is 0.1 μm or less, preferably 0.06 μm. Although it is possible to prepare a fine grain emulsion with these fine grains in advance, it is preferable to supply these fine silver halide grains from a mixer according to the method disclosed in US Pat. No. 4,879,208.

By the above method, the formation of silver halide normal crystal grains consisting essentially of silver bromide is completed. Although the dislocation lines may be introduced at any stage of grain growth, it is preferable to introduce them into the core portion of the core/shell structure.

The core particles used in the present invention are chemically sensitized by sulfur or selenium sensitization, noble metal sensitization, etc. alone or in combination. As the chemical sensitization method for core particles, the methods described in Japanese Patent Application Laid-open Nos. 2-199450 and 2-199449 can be used. Japanese Patent Publication No. 1-197
Chemical sensitization can also be carried out in the presence of a mercapto compound as described in Japanese Patent No. 742. Also, JP-A-1-25494
6, No. 2-69738 and No. 2-273735, thiosulfinic acid, sulfinic acid,
Sulphites may also be added. For detailed specific examples, see Research Disclosure Magazine No. 17643-II
I (issued December 1978), page 23, etc., in the patent.

Next, the silver halide shell portion of the present invention will be explained. The halogen composition of the shell part is silver chloride,
Examples include silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloroiodobromide, and preferably silver iodide content is 3 mol%.
The following silver chloride (iod) bromide, silver chloride (iod) bromide, and silver chloride (iod) bromide.

The silver halide grains of the present invention are preferably coated with a shell portion and then chemically sensitized by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination.

The core-to-shell silver halide molar ratio of the internal latent image type core-shell silver halide emulsion is 20/1 or less,
Particularly preferred is 1/100 or more.

In the present invention, Mn, Cu, Zn, Cd, P are added to internal latent image type silver halide grains which are not fogged in advance.
At least one selected from the group consisting of B, Bi, Re, and metals belonging to Group VIII of the periodic table may be incorporated.

Mn, Cu, Zn, Cd contained in the internal latent image type silver halide grains of the present invention which are not fogged in advance
, Pb, Bi, Re or metals belonging to Group VIII of the periodic table, per mole of silver halide, the amount is 10-9
-10-2 mol is preferable, and 10-7 - 10-3 mol is more preferable. Among the above metals, lead, iridium,
Particular preference is given to using ruthenium, bismuth and rhodium.

When these metals are mixed with a silver ion solution and an aqueous halogen solution to form silver halide grains, the metal ions can be made to coexist in the form of an aqueous solution or an organic solvent solution and incorporated into the grains. Alternatively, after the grains are formed, metal ions may be added in the form of an aqueous or organic solvent solution and then further coated with silver halide. A method of incorporating these metals is described in U.S. Patent No. 37.
It is described in the specifications of No. 61276 and No. 4395478, and in Japanese Patent Application Laid-open No. 59-216136.

The average grain size of the silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the length is taken as the grain size, respectively) and is expressed as an average based on the projected surface. 0.1μm below 5μm
or more is preferable, but particularly preferable is 1.2 μm or less.
．． It is 2 μm or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or weight may be within ±40% of the average particle size.
A so-called "monodisperse" silver halide emulsion having a narrow grain size distribution in which 90% or more, particularly 95% or more of all grains are preferably within ±30%, most preferably within ±20%, is used in the present invention. It is preferable to do so. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes or two or more types of monodisperse silver halide emulsions with different grain sizes or two or more types of monodisperse silver halide emulsions with substantially the same color sensitivity, or two or more types of monodisperse silver halide emulsions with the same size and sensitivity A plurality of different particles can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

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 cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. Detailed examples, such as Research Disclosure Magazine No. 17643-IV (19
(published in December 1978) on pages 23-24.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Can be done. For detailed specific examples, see Research Disclosure Magazine No.
17643-VI (issued December 1978) and E.
J. “Stabilization of
Photographic Silver Haild
e Emulsion” (Focal Press)
It is described in publications such as 1974.

In the present invention, various color couplers can be used in combination. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in combination in the present invention are given in "Research Disclosure" magazine No.
17643 (published December 1978) 25 pages, VII-
Section D, same No. 18717 (issued November 1979)
and the compounds described in JP-A-62-215272 and the patents cited therein.

Among them, 5-
The pyrazolone-based magenta coupler is a 5-pyrazolone-based coupler (particularly a sulfur atom separation type two-equivalent coupler) in which the 3-position is substituted with an arylamino group or an acylamino group. More preferred are pyrazoloazole couplers, and among them, pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Pat. No. 3,725,067 are preferred; U.S. Patent No. 45006 in terms of low side absorption and light fastness.
Even more preferred are the imidazo[1,2-b]pyrazoles described in US Pat. No. 30, pyrazolo[1,5-b][1,2,4] described in US Pat.
Triazoles are particularly preferred.

Cyan couplers that can be preferably used in the present invention include US Pat. Nos. 2,474,293 and 4,052.
Naphthol-based and phenol-based couplers described in the specifications of No. 212, etc.; phenolic cyan couplers having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002; and others. , 2,5-diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness.

Examples of the yellow coupler include US Pat. No. 3,933,501, US Pat. No. 4,022,620, US Pat.
Those described in the specifications of No. 0 and No. 1476760 are preferred.

Colored couplers for correcting unnecessary absorption in the short wavelength region of the generated dyes, couplers in which coloring dyes have appropriate diffusivity, colorless couplers, and releasing development inhibitors along with coupling reactions. DIR couplers and polymerized couplers can also be used. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. A DIR coupler that releases a development inhibitor is described in the aforementioned Research Disclosure no. 17643, patents described in sections VII to F, JP-A-57-151944, JP-A-57-15423
No. 4, Publications No. 60-184248, U.S. Patent No. 42
What is described in the specification of No. 18962 and JP-A-63
The one described in Japanese Patent No.-146035 is preferred. Couplers that release a nucleating agent or a development accelerator in an image form during development include those described in British Patent No. 2097140 and British Patent No. 2131188, and Japanese Patent Application Laid-open No. 15763/1983.
No. 8, No. 59-170840, International Application Publications (
Those described in WO) 88/01402 are preferred.

The standard usage amount of color couplers is in the range of 0.001 to 1 mole per mole of photosensitive silver halide, preferably 0.01 for yellow couplers.
0.03 mol to 0.5 mol for magenta couplers, and 0.002 mol for cyan couplers.
The amount is between 1.0 mol and 1.0 mol.

As the binder or protective colloid that can be used in the emulsion layer or 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.

[0068] In the light-sensitive material of the present invention, a color fog preventive agent or a color mixture preventive agent can be used. Representative examples of these are described on pages 185 to 193 of Japanese Patent Application Laid-Open No. 62-215272.

Compounds that release photographically useful groups include:
Examples include compounds described in JP-A-63-153540, JP-A-63-259555, JP-A-2-61636, JP-A-2-244401, and JP-A-2-308240.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. Representative examples of compounds are 121 to 125 of JP-A-62-215272.
Examples include those listed on page.

The photosensitive material of the present invention contains dyes that prevent irradiation and halation (for example, JP-A-2-85
The dyes described in the publications No. 850 and No. 2-89047 may also be used. Further, as a dye dispersion method, a solid microcrystal dispersion method may be used. ), ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air antifogging agents, coating aids, hardeners, antistatic agents, slipperiness improvers, etc. can be added. Representative examples of these additives are listed in Research Disclosure magazine no. 17643 VII to XIII (1
December 1878) pages 25-27, and December 1871
6 (published November 1979), pages 647-651.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. . Usually, 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. Different combinations can be taken, such as mixing and using.

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation agent, a back layer, and a white reflective layer. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are as described in Research Disclosure Magazine No. 17643V to VII (December 1978)
Issued on page 28 and European Patent No. 010
It is coated on the supports described in No. 2253 and JP-A-61-97655. Also, Research Disclosure Magazine No. The coating method described in Section 17643XV, pages 28-29 can be used.

The fogging treatment of the present invention is carried out by the following "photofogging method" and/or "chemical fogging method". The entire surface exposure in the "light fogging method", that is, the fogging exposure, is
This is carried out after imagewise exposure, after or during color development. That is, a photosensitive material that has been imagewise exposed is immersed in a color developer, or in a prebath of a color developer, or taken out from these solutions and exposed before drying. is most preferable.

For light development in fogging exposure, a light source with high color rendering properties (as close to white as possible) as described in, for example, Japanese Patent Laid-Open Nos. 56-137350 and 58-70223 is preferable. Light illuminance is 0.01-2000
lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux. The more sensitive a light-sensitive material uses an emulsion, the more preferable it is to be exposed to light at a lower illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the exposure using various filters, the distance between the photosensitive material and the light source, or the angle between the photosensitive material and the light source. In addition, the above-mentioned fogging light illuminance can be changed continuously from low illuminance to high illuminance.
Alternatively, it can be increased stepwise.

It is preferable that the light-sensitive material is immersed in a color developing solution or its pre-bath solution, and that the solution is sufficiently penetrated into the emulsion layer of the light-sensitive material before it is irradiated with light. The time from penetration into the liquid to photofogging 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, and more preferably 1 second to 40 seconds.

In the present invention, the nucleating agent used in the so-called "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it can be contained in a photosensitive material. Here, the "nucleating agent" is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance. In the present invention, fogging using a nucleating agent is particularly preferred.

[0078] When a nucleating agent is contained in a light-sensitive material,
Although it is preferably added to the latent silver halide emulsion layer, it may be added to other layers, such as interlayers, subbing layers, It may be added to the back layer.

When the nucleating agent is added to the processing solution, it may be contained in the developer solution or a low pH pre-bath as described in JP-A-58-178350. Furthermore, two or more types of nucleating agents may be used in combination.

Nucleating agents that can be used in the present invention include, for example, "Research Disclosure" magazine, No.
．． 22534 (January 1983) pp. 50-54, same magazine,
No. 15162 (November 1976) pp. 76-77,
The same magazine, No. 23510 (November 1983) 346~
Examples include quaternary heterocyclic compounds and hydrazine compounds described on page 352.

Examples of quaternary heterocyclic nucleating agents include US Pat. Nos. 3,615,615, 3,719,494 and 373
Specifications of No. 4738, No. 3759901, No. 3854956, No. 4094683, No. 4306016,
British Patent No. 1283835, Japanese Patent Publication No. 49-381
No. 64, No. 52-19452, No. 52-47326, JP-A-52-69613, No. 52-3426
No. 55-138742, No. 60-11837, and the aforementioned "Research Disclosure" magazine No. No. 22534, same magazine No. 23213 (19
(Published August 1983, pages 267-270). Furthermore, as highly active quaternary salt compounds, JP-A-63-121042, JP-A 63-301942, JP-A 1-191132, JP-A 2-101450, JP-A 2-
Those described in each publication No. 79038 and No. 2-101451 can be used.

Particularly preferred are quaternary heterocyclic nucleating agents represented by the following formula.

[Chemical formula 1]

(In the formula, Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle, and Z may be substituted with a substituent. R1 is an aliphatic group, R2
is a hydrogen atom, an aliphatic group or an aromatic group. R1
and R2 may be substituted with a substituent. Also, R
2 may further be combined with a heterocycle completed by Z to form a ring. However, among the groups represented by R1, R2 and Z,
at least one contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R1 and R2
and form a 6-membered ring to form a dihydropyridinium skeleton. Furthermore, at least one of the substituents R1, R2 and Z may have a group that promotes adsorption to silver halide. Y is a counter ion for charge balance, and n is 0 or 1. )

Examples of the heterocycle completed by Z include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolium nuclei. More preferred are quinolinium and benzothiazolium, and most preferred is quinolinium. Substituents for Z include alkyl groups, alkenyl groups, aralkyl groups, aryl groups,
Alkynyl group, hydroxy group, alkoxy group, aryloxy group, halogen atom, amino group, alkylthio group,
Arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate ester group, hydrazine group , hydrazone group,
Alternatively, examples include imino groups. The substituent of Z may be provided via a suitable linking group.

The aliphatic groups R1 and R2 are preferably unsubstituted alkyl groups having 1 to 18 carbon atoms and substituted alkyl groups having 1 to 18 carbon atoms in the alkyl moiety. R
The aromatic group represented by 2 preferably has 6 to 20 carbon atoms.
For example, phenyl group, naphthyl group, etc.

Examples of adsorption-promoting groups to silver halide that R1, R2 and Z substituents may have include thioamide groups, mercapto groups, and 5- or 6-membered nitrogen-containing heterocyclic groups.

The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.). As mercapto groups, in particular heterocyclic mercapto groups (e.g. 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto-1,
3,4-oxadiazole, etc.) are preferred. The 5- to 6-membered nitrogen-containing heterocycle is one consisting of a combination of nitrogen, oxygen, sulfur, and carbon, and preferably produces iminosilver, such as benzotriazole and aminothitriazole.

These adsorption-promoting groups to silver halide may be via a linking group. Examples of the linking group include alkylene group, alkenylene group, arylene group, -O-, -S-
, -NH-, -N=, -CO-, -SO2 -, -CO
-O-, -CO-NH-, -SO2 -NH-, -NH
-CO-NH-, -NH-SO2 -NH-, -CH2
Examples include CH2-CO-NH- and a group represented by the following formula.

[0089]

[Chemical 2]

[0090]

[Chemical formula 3]

[0091]

[C4]

R2 is preferably an aliphatic group,
Most preferably, it forms a ring by bonding with a methyl group, a substituted methyl group, or a heterocycle further completed by Z.

[0093] When at least one of the substituents on the group or ring represented by R1, R2 and Z is an alkynyl group or an acyl group, or when R1 and R2 are linked to form a dihydropyridinium core. is preferred, and further preferably contains at least one alkynyl group, most preferably a propargyl group.

Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchloride ion, trifluoromethanesulfonate ion, thiocyanine ion, and tetrafluoromethanesulfonate ion. Examples include boron fluoride ion and phosphorus hexafluoride ion.

Specific examples of the compound represented by the above-mentioned general formula are listed below, but the invention is not limited thereto.

(C-1) 5-ethoxy-2-methyl-1
-Propargylquinolinium bromide

[0097](
C-2) 2,4-dimethyl-1-propargylquinolinium bromide

(C-3) 3,4-dimethyl-dihydropyrido[2,1-b]benzothiazolium bromide

0
(C-4) 6-ethoxythiocarbonylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate

(C-5) 6-(5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate

0101
](C-6)6-(5-mercaptotetrazole-1-
yl)-2-methyl-1-propargylquinolinium.
iodide

(C-7) 6-Ethoxythiocarbonylamino-2-(2-methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate

(C-8) 10-propargyl-1,2,
3,4-tetrahydroacridinium trifluoromethanesulfonate

(C-9) 7-Ethoxythiocarbonylamino-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate

(C-10) 7-[3-(5-mercaptotetrazol-1-yl)benzamide]-10-propargyl-1,2,3,4-tetrahydroacridinium benchlorate

(C-11) 7-(5-mercaptotetrazol-1-yl)-9-methyl-10-propargyl-1,2,3,4-tetrahydroacridinium bromide

(C-12) 7-ethoxythiocarbonylamino-10-propargyl-1,2-dihydroacridinium trifluoromethanesulfonate

0108
](C-13)10-propargyl-7-[3-(1,
2,3,4-thiatriazol-5-ylamino)benzamide]-1,2,3,4-tetrahydroacridinium verchlorate

(C-14) 7-(3-Cyclohexylmethoxythiocarbonylaminobenzamide)-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate

[0110](
C-15) 7-(3-methoxythiocarbonylaminobenzamide)-10-propargyl-1,2,3,4-
Tetrahydroacridinium trifluoromethanesulfonate

(C-16) 7-[3-(3-ethoxythiocarbonylaminophenyl)ureido]-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate

(C-17) 7-(3-Ethoxythiocarbonylaminobenzenesulfonamide)-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate

(C-18)7-[3-{3-[3-(5
-mercaptotetrazol-1-yl)phenyl]ureido}benzamide]-10-propargyl-1,2,
3,4-tetrahydroacridinium trifluoromethanesulfonate

(C-19) 7-[3-(5-mercapto-1,3,4-thiadiazol-1-ylamino)benzamide]-10-propargyl-1,2,3,4-tetrahydroacridinium. trifluoromethanesulfonate

(C-20) 7-[3-(3-butylthioureido)benzamide]-10-propargyl-1,
2,3,4-tetrahydroacridium trifluoromethanesulfonate

(C-21) 6-(3-eoxythiocarbonylaminobenzamide)-1-propargyl-2,
3-trimethylenequinolinium trifluoromethanesulfonate

[0117] As the hydrazine compound, for example, the above-mentioned Research Disclosure No. 15162 (1
Published in November 1976, pp. 76-77) and the same magazine No. 23
510 (published in November 1983, pages 346-352). More specifically, those described in the following patent specifications can be mentioned. First, examples of hydrazine-based nucleating agents having silver halide adsorption groups include US Pat. No. 4,030,925 and US Pat.
No. 80207, No. 4031127, No. 37184
No. 70, No. 4269929, No. 4276364, No. 4278748, No. 4385108, No. 4459347, British Patent No. 2011391
B specification, JP-A-54-74729, JP-A-55-16
No. 3533, No. 55-74536, No. 60-1797
Examples include those described in No. 34 and No. 63-231441.

Other hydrazine-based nucleating agents include, for example, JP-A-57-86829 and US Pat. No. 4,560.
Examples include compounds described in the specifications of No. 638, No. 4478928, No. 2563785, and No. 2588982. Highly active hydrazine compounds include JP-A Nos. 63-231441, 63-234244, and 6
No. 3-234245, No. 63-234246, No. 63
-204256, JP-A No. 2-18558, JP-A No. 2-1
Examples include compounds described in each publication of No. 31557. Representative hydrazine-based nucleating agents are shown below.

(B-1) 1-formyl-2{4-[3-
(2-methoxyphenyl)ureido]-phenyl}hydrazine

(B-2) 1-formyl-2-{4-[3
-(5-mercaptotetrazol-1-yl)benzamido]phenyl}hydrazine

(B-3) 1-formyl-2-[4-{3
-[3-(5-mercaptotetrazol-1-yl)phenyl]ureido}phenyl]hydrazine

[0122]
As the nucleating agent, quaternary heterocyclic compounds are preferable because they greatly exhibit the effects of the present invention. A quaternary heterocyclic compound and a hydrazine compound may be used in combination. When adding a nucleating agent to the processing solution, add it to the developer or JP-A-178350.
It may also be included in a low pH pre-bath as described in the above publication. When a nucleating agent is added to the treatment liquid, the amount used is preferably 10-8 to 10-3 mol, more preferably 10-7 to 101 mol per liter.

In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but
It is preferably contained in the silver halide emulsion layer. The amount added depends on the characteristics of the silver halide emulsion actually used.
Depending on the chemical structure of the nucleating agent and the development conditions, it can vary over a wide range, but from about 1 x 10-8 mole to about 1 x 10-2 mole per mole of silver in the silver halide emulsion.
A range of moles is useful in practice, with the preferred range being from about 1.times.10@-7 mole to about 1.times.10@-3 mole per mole of silver.

[0124] When using a nucleating agent, it is preferable to use a nucleating accelerator to promote the action of the nucleating agent. A nucleation accelerator is a substance that has virtually no function as a nucleation agent, but
A substance that acts to enhance the action of a nucleating agent to increase the maximum density of a direct positive image and/or to reduce the development time required to obtain a constant direct positive image density. Such nucleation accelerators include tetrazaindenes, triazaindenes and pentazaindenes, which have at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, and Compounds described on pages 5 to 16 of Publication No. 63-106656 can be mentioned. Also, JP-A-63-2266
No. 52, No. 63-106656 and No. 63-874
Compounds described in each publication No. 0 can be mentioned. Specific examples of nucleation accelerators are given below.

[0125]S-1

[C5]

[0126]S-2

[C6]

[0127]S-3

[C7]

[0128]S-4

[Chemical formula 8]

[0129]S-5

[Chemical formula 9]

[0130] S-6

[Chemical formula 10]

[0131]S-7

[Chemical formula 11]

[0132]S-8

[Chemical formula 12]

[0133]S-9

[Chemical formula 13]

The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but it can also be contained in internal latent image type silver halide emulsions and other hydrophilic colloid layers (
It is preferable to include it in an intermediate layer, a protective layer, etc.). Particularly preferred is a layer in or adjacent to a silver halide emulsion. The amount of the nucleation accelerator added is preferably 10-6 to 10-2 mol, more preferably 1 mol per mol of silver halide.
It is 0-5 to 10-2 mol. Further, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, the amount is preferably 10-8 to 10-3 mol, more preferably 10-7 to 10-4 mol per liter. be.

[0135] Two or more types of nucleation accelerators can also be used in combination. Known photographic additives that can be used in the present invention include the aforementioned Research Disclosure No. 17643(
December 1978) and the same No. 18716 (197
(November 1999), and the relevant parts are shown below.

0136] ──────────────────────────
──────────── Additive type
RD17643
RD18716──────────────────
──────────────────────1 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity increasing agent
Same as above 3
Spectral sensitizers, supersensitizers pages 23-24
Page 648 right column to page 649 right column 4 Brightener
24 pages 5
Antifogging agents, stabilizers pages 24-25
Page 649 right column 6 Light absorber,
Pages 25-26 Page 649 right column - Page 650 left column Filter dye,

UV absorber

7 Stain inhibitor
Page 25 right column Page 650 left to right column 8 Dye image stabilizer
Page 25 9 Hardener
26 pages
Page 651 left column 10 binder
26 pages
Same as above 11 Plasticizer, lubricant
27 pages
Page 650, right column 12 Coating aids, surfactants
Pages 26-27 Same as above 13 Static inhibitor 2
Page 7 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 plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal, which is commonly used in photographic light-sensitive materials. is applied to. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments.

[0138] Various known methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the silver halide photographic emulsion layer and other hydrophilic colloid layers. . In addition, as necessary, U.S. Patent No. 2681294, U.S. Patent No. 2761791
Multiple layers may be applied simultaneously by the methods described in US Pat. No. 3,526,528, US Pat.

[0139]

[Examples] The present invention will be specifically explained below with reference to Examples. However, the present invention is not limited only to these examples.

Example 1 "Preparation of Emulsion 1-A" An aqueous solution of potassium bromide and silver nitrate (24 g) was simultaneously added to an aqueous gelatin solution at 65°C for 15 minutes with vigorous stirring, until the average particle size was 0. Silver bromide octahedral grains of .23 μm were obtained. At this time, 0.3 g of 3,4-
Dimethyl-1,3-thiazoline-2-thione was added. A chemical sensitization treatment was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating at 75° C. for 80 minutes. Using the particles obtained in this way as cores, an aqueous solution of potassium bromide and silver nitrate (96 g) was added simultaneously in the same precipitation environment as in the first precipitation to further grow the particles, resulting in eight particles with an average particle size of 0.4 μm. A hedral monodisperse core/shell silver bromide emulsion was obtained. The coefficient of variation in particle size was approximately 10%. After this, the emulsion was cooled to 35°C, washed by a conventional flocculation method, 80g of gelatin was added, and the emulsion was heated to 40°C.
Adjusted to H6.4. 1.5 per mole of silver in this emulsion.
mg of sodium thiosulfate and 1.5 mg of chloroauric acid (4
water salt) was added thereto, and chemical sensitization was carried out by heating at 60 DEG C. for 60 minutes to obtain emulsion 1-A, which was an internal latent image type silver halide emulsion.

"Preparation of Emulsion 1-B" An aqueous solution of potassium bromide and silver nitrate (21 g) was simultaneously added to an aqueous gelatin solution at 65° C. for 15 minutes with vigorous stirring to form an emulsion with an average particle size of 0.22 μm. Silver bromide octahedral particles were obtained. At this time, 0.3 g of 3,4-
Dimethyl-1,3-thiazoline-2-thione was added. After this, sodium chloride and silver nitrate (3 g) were added while maintaining a potential of +190 mV (vs. saturated calomel electrode) at 50°C.
An aqueous solution of was added over a period of 5 minutes using a controlled double jet method. After that, the temperature was raised to 75°C and physical ripening was performed for 12 minutes, and then an aqueous solution of potassium bromide (18 g) was added.
Conversion completed in minutes.

[0142] To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver were sequentially added and heated at 75° C. for 80 minutes to perform chemical sensitization treatment to prepare core particles. . When the halogen composition of the core grains was measured by X-ray diffraction, it was found that the core grains had a silver chloride content of less than 1% and were essentially silver bromide grains.

[0143] Using the thus obtained particles as cores, an aqueous solution of potassium bromide and silver nitrate (96 g) was added at the same time to further grow the particles, and finally an octahedral monodisperse core/shell with an average particle size of 0.4 μm was obtained. A silver bromide emulsion was obtained. The coefficient of variation in particle size was approximately 10%.

[0144] Thereafter, the emulsion was cooled to 35°C, washed by a conventional flocculation method, and 80 g of gelatin was added to adjust the pH to 6.4 at 40°C. This emulsion was added with 1.5 mg of sodium thiosulfate per mole of silver and
．． 5 mg of chloroauric acid (tetrahydrate) was added and chemical sensitization was carried out by heating at 60 DEG C. for 60 minutes to obtain emulsion 1-B, which is an internal latent image type silver halide emulsion.

"Confirmation of dislocation lines introduced into silver halide grains" Dislocation lines were directly observed on the silver halide grains of Emulsion 1-A and Emulsion 1-B using a transmission electron microscope. The electron microscope was JEOL4000EX manufactured by JEOL Ltd., and the observation was performed at an acceleration voltage of 400 kV and a temperature of -180°C. Figure 1 shows an example of a transmission electron micrograph of the grains of emulsion 1-A.
The grains of Emulsion 1-B are shown in FIG. It can be seen that no dislocation lines are found in the grains of Emulsion 1-A, whereas dislocation lines are present in the grains of Emulsion 1-B.

"Preparation of Photosensitive Material" (Preparation of Sample 101) Sample 101 was obtained by coating the following first layer and second layer on the surface of a paper support (thickness 220 μm) which was laminated on both sides with polyethylene.

[0147] The coating amount (g/m2) of each component is shown below. Regarding silver halide, the coating amount is shown in terms of silver.

First layer (emulsion layer) Emulsion (emulsion 1-A)
0.20 gelatin

2.00 cyan coupler (ExC-1, 2 equivalents)
0.60 coupler solvent (Solv-1)
0.29

0149 Second layer (protective layer) Gelatin
2.00 gelatin hardener (
H-1) 0.0
4

[0150] In the first layer, ExZK-1 and ExZK-2 were used as nucleating agents at a ratio of 10-3 to silver halide, respectively.
Cpd-22 was used as a nucleation accelerator in an amount of 10-2% by weight.

(Preparation of sample 102) Emulsion 1 of sample 101
Sample 102 was obtained by replacing Emulsion 1-A with Emulsion 1-B. Wedge exposure (1/10 seconds, 100CMS) to the above sample
After that, the following treatment was performed.

0152] ────────────────────────
────────────Processing process Time Temperature Mother liquor tank capacity
Replenishment amount──────────────────
──────────────────Color development
135 seconds 38℃ 11 liters
300ml/m2 bleach fixing 4
0 seconds 33℃ 3 liters
300ml/m2 Water washing (1) 40
seconds 33℃ 3 liters
--- Water washing (2)
40 seconds 33℃ 3 liters
320ml/m2 drying
30 seconds 80℃──────────
──────────────────────────
─

[0153] The washing water replenishment method is to replenish the washing bath (2) and transfer the overflow liquid from the washing bath (2) to the washing bath (1).
A so-called countercurrent replenishment method was adopted, which leads to At this time, the amount of bleach-fix solution brought in from the bleach-fix bath to the washing bath (1) by the photosensitive material was 35 ml/m2, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times. . The composition of each treatment liquid was as follows.

0154] ──────────────────────────
──────────── Color developer
Mother liquid replenishment liquid ──
──────────────────────────
────────── D-Sorvit
0.15g
0.20g naphthalenesulfonic acid
0.15g
0.20g Sodium formalin condensate
Ethylenediaminetetrakis 1.5g
1.5g methylenephosphonic acid diethylene glycol
12.0ml 16.0ml Benzyl alcohol 13
．． 5ml 18.0ml Potassium bromide
0.70g --- Benzotriazole 0
．． 003g 0.004g Sodium sulfite 2
．． 4g 3.2g N,N-
Bis(carboki) 4.0g
5.3g dimethyl)
Hydrazine D-glucose
2.0g 2.4
g triethanolamine
6.0g 8.0g
N-ethyl-N-(β-methane 6.
4g 8.5g Sulfonamidoethyl)-3-

Methyl-4-aminoaniline sulfate

potassium carbonate
30.0g
25.0g Fluorescent brightener (diaminostilbene type) 1.0g 1.2g
add water
1000ml 1000ml──────
──────────────────────────
────── pH (25℃)
10.25
11.00

0155] ──────────────────────────
──────────── Bleach-fix solution

Mother liquor Replenisher ──
──────────────────────────
───────── Ethylenediaminetetraacetic acid, disodium, 2.0g Same as mother liquor Disodium, dihydrate

Ethylenediaminetetraacetic acid/Fe(III)/70.0g
Ammonium dihydrate salt

Ammonium thiosulfate (700
g/l) 180ml Sodium p-toluenesulfinate 45.0g
sodium bisulfite
35.0g 5-mercapto-1,3,4-triazole 0.5g Ammonium nitrate

Add 10.0g water
1000ml
────────────────────────
──────────── pH (25℃)

6.10

"Washing water" Both the mother liquor and the replenisher were washed with tap water using H-type strongly acidic cation exchange resin (Amberlite IR-120 manufactured by Rohm and Haas).
B) and OH type anion exchange resin (Amberlite I)
Water was passed through a mixed bed column packed with R-400) to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, followed by 20 m of sodium isocyanurate dichloride.
g/l and 1.5 g/l of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

The cyan coloring density of the obtained direct positive image was measured, and the results are shown in Table 1. Table 1

[Table 1]

Relative sensitivity is determined by the optical density being the minimum image density (DM
IN) is expressed as a relative value of the reciprocal of the exposure amount required to achieve +0.6. Sample 102 of the present invention has a maximum image density (D
The minimum image density (DMI) is the same while the
N) is low and sensitivity is high, and favorable results can be obtained.

Example 2 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material was prepared in which the following first to eleventh layers were coated on the front side and the twelfth to thirteenth layers were coated on the back side. The polyethylene on the first layer coating side contains titanium oxide (4 g/m2) as a white pigment and a trace amount (0.003 g/m2) of ultramarine as a blue-tinged dye (the chromaticity of the surface of the support is L* , a*, b* system is 88.
0, -0.20, -0.75).

Emulsion 1-A and Emulsion 1- prepared in Example 1
B is a red sensitizing dye (ExS-1, 2, 3, equal amounts of each, total 3
．． After spectral sensitization with 8 x 10-4 mol), the following third
Samples 201A and 202A were used in place of Emulsion 1 contained in the layer. In addition, samples 201A and 2
201B and 202B were obtained by applying multilayer coating in 02A except for the first layer (antihalation layer).

(Photosensitive layer composition) The components and coating amount (g/
m2). However, the amount of sensitizing dye added is expressed in moles per mole of silver. Regarding silver halide, the coating amount is shown in terms of silver. The emulsions used in the fifth and ninth layers were prepared by changing the grain size by changing the grain formation temperature according to the manufacturing method of Emulsion 1-A. However, as the emulsion for the 12th layer, a Lippmann emulsion without surface chemical sensitization was used.

[0162] First layer (antihalation layer)
black colloidal silver
0.1
0 gelatin

0.70

0163 Second layer (middle layer) Gelatin

0.70

3rd layer (red sensitive layer) Emulsion 1

0.25 Gelatin

1.00 Cyan coupler (ExC-1, 2, 3 1:1:0.2) 0
．． 30 Anti-fading agent (Cpd-1, 2, 3, 4,
30 each equivalent amount) 0.18 Stain inhibitor (Cpd-5)
0.003 Coupler dispersion medium (Cpd-6)
0.03 Coupler solvent (S
olv-1, 2, 3 each equal amount)
0.12

0165 4th layer (middle layer) Gelatin

1.00 Color mixing prevention agent (Cpd-7)

0.08 Color mixing inhibitor solvent (Solv-
4, 5 each equal amount) 0.16
Polymer latex (Cpd-8)
0.10

016
6] Fifth layer (green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4, 2.6 x 10-4) (average grain size 0.40μ, grain size distribution 10%, octahedron)

0.25 Gelatin

0.80 Magenta coupler (ExM-1, 2, 3 each equal amount)
0.11 Yellow coupler (Ex
Y-1)
0.03 Antifading agent (Cpd-9, 26
, 30 each) 0.15
Stain inhibitor (Cpd-10, 11, 12, 13 in 10:7:7:1 ratio)
0.0
25 Coupler dispersion medium (Cpd-6)
0.05
Coupler solvent (Equivalent amounts of Solv-4 and 6)
0.15

0167 Layer 6 (middle layer) Same as layer 4

7th layer (yellow filter layer)
Yellow colloidal silver (particle size 100Å)
0.12 Gelatin

0.70
Color mixing inhibitor (Cpd-7)
0.03
Color mixing inhibitor solvent (Solv-4, 5 equivalents)
0.10 Polymer latex (Cpd-8)
0.07

[0169] 8th layer (middle layer) Same as 4th layer

9th layer (blue sensitive layer) Blue sensitizing dye (ExS-5, 6 equivalent amount total 3.5 x 10-
4) spectrally sensitized silver bromide (average grain size 0.60
μ, particle size distribution 11%, octahedral)


0.40 Gelatin

0.80 Yellow coupler (
Equivalent amounts of ExY-1, 2, and 3) 0.
35 Anti-fading agent (Cpd-14)
0.1
0 Anti-fading agent (Cpd-30)
0.05
Stain inhibitor (Cpd-5, 15 in 1:5 ratio) 0.007 Coupler dispersion medium (Cpd-6)
0.05 Coupler solvent (S
olv-2)
0.10

0171 Layer 10 (ultraviolet absorbing layer) Gelatin

1.00 Ultraviolet absorber (Cp
d-2, 4, 16 each equivalent) 0
．． 50 Color mixing prevention agent (Equivalent amounts of Cpd-7 and 17)
0.03
Dispersion medium (Cpd-6)
0.02
Ultraviolet 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

017
2] Eleventh layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1μ)

0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 500
00)

0.01 Equivalent amount of polymethyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ)
0.0
5 Gelatin

1.80 Gelatin hardening agent (H-1,
H-2 each equivalent amount) 0.
18

[0173] 12th layer (back layer) Gelatin

2.50 Ultraviolet absorber (Cpd-2,
4, 16 each equivalent) 0.50
Dye (equal amounts of Cpd-18, 19, 20, 21, 27) 0.06

13th layer (back layer protective layer) Polymethyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5
μ) Equal amount
0.05 gelatin

2.00 Gelatin hardening agent (equal amounts of H-1 and H-2)
0.14

[0175] Each photosensitive layer includes:
As nucleating agents, ExZK-1 and ExZK-2 were used in an amount of 10-3 and 10-2% by weight, respectively, based on the silver halide, and as nucleation accelerators, Cpd-22, 28, and 29 were used in an amount of 10-2% by weight, respectively. Further, in each layer, Alkanol XC (Du Pont) and sodium alkylbenzenesulfonate were used as emulsification dispersion aids, and succinate ester and Magefac F-120 (manufactured by Dainippon Ink Co., Ltd.) were used as coating aids. (Equivalent 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 number 101. The compounds used in the examples are shown below.

[0176]ExS-1

[Chemical formula 14]

0177 ExS-2

[Chemical formula 15]

0178 ExS-3

[Chemical formula 16]

0179 ExS-4

[Chemical formula 17]

[0180] ExS-5

[Chemical formula 18]

[0181] ExS-6

[Chemical formula 19]

Cpd-1

[C20]

Cpd-2

[C21]

Cpd-3

[C22]

Cpd-4

[C23]

Cpd-5

[C24]

Cpd-6

[C25]

Cpd-7

[C26]

Cpd-8

[C27]

Cpd-9

[C28]

Cpd-10

[C29]

Cpd-11

[C30]

Cpd-12

[Chemical formula 31]

Cpd-13

[C32]

Cpd-14

[Chemical formula 33]

Cpd-15

[C34]

Cpd-16

[C35]

Cpd-17

[C36]

Cpd-18

[C37]

[0200]Cpd-19

[C38]

[0201] Cpd-20

[C39]

[0202]Cpd-21

[C40]

[0203]Cpd-22

[C41]

[0204]Cpd-23

[C42]

[0205] Cpd-24

[C43]

[0206]Cpd-25

[C44]

[0207] Cpd-26

[C45]

Cpd-27

[C46]

[0209]Cpd-28

[C47]

[0210]Cpd-29

[C48]

[0211] Cpd-30

[C49]

[0212] ExC-1

[C50]

[0213] ExC-2

[C51]

[0214] ExC-3

[C52]

[0215] ExM-1

[C53]

[0216] ExM-2

[C54]

[0217] ExM-3

[C55]

[0218] ExY-1

[C56]

0219 ExY-2

[C57]

[0220]ExY-3

[C58]

[0221]Solv-1 Di(2-ethylhexyl) sebacate

[0222]Solv-2 trinonyl phosphate

[0223]Solv-3 Di(3-methylhexyl) phthalate

[0224]Solv-4 tricresyl phosphate

[0225]Solv-5 dibutyl phthalate

[0226]Solv-6 trioctyl phosphate

[0227]Solv-7 Di(2-ethylhexyl) phthalate

H-1 1,2-bis(vinylsulfonylacetamido)ethane

H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine/Na salt

ExZK-1 7-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-10propargyl-1,2,3,4-
Tetrahydroacridinium trifluoromethanesulfonate

ExZK-2 2-[4-{3-[3-{3-[5-{3-[2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl]-4-hydroxy- 1
-naphthylthio}tetrazol-1-yl]phenyl}
ureido]benzenesulfonamide}phenyl]-1-
Formylhydrazine

[0232] Samples 201A, 201B, 202A, 20
After applying wedge exposure (1/10 second, 300 CMS) to 2B, the following processing was performed. Continuous processing was carried out using an automatic developing machine according to the method described below until the cumulative amount of liquid replenishment reached three times the tank capacity.

0233] ──────────────────────────
──────────── Treatment process Time Temperature Tank capacity
Replenishment amount ──────────
──────────────────────────
─ Color development 135 seconds 38℃
30 liters 240ml/m2 Bleach fixing 60 seconds 35℃
15 liters 300ml/m2 Water washing (1
) 40 seconds 35℃ 10 liters --- Water washing (2
) 40 seconds 35℃ 3 liters 320ml/m2 drying
30 seconds 75℃────────
──────────────────────────
───

[0234] The method of replenishing the washing water is the washing bath (2).
The overflow liquid from the washing bath (2) is refilled to the washing bath (2).
A so-called countercurrent replenishment method was adopted, which leads to 1). At this time, the amount of bleach-fix solution brought into the washing bath (1) from the bleach-fixing of the photosensitive material was 35 ml/m2, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times. The composition of each treatment liquid was as follows.

0235] ────────────────────────
──────────── Color developer
Mother liquor
Refill fluid────────────
────────────────────────
D-Sorvit
0.15g 0.20g
Sodium naphthalene sulfonate 0
．． 15g 0.20g Formalin condensate Ethylenediaminetetrakismethylene 1.
5g 1.5g Phosphonic acid diethylene glycol
12.0ml 16.0ml Benzyl alcohol
13.5ml 18.0ml Potassium bromide
0.80g --- Benzotriazole 0
．． 003g 0.004g Sodium sulfite 2
．． 4g 3.2g N,N-bis(carboxymethyl) 6.0g
8.0g hydrazine D-glucose
2.0g 2.4
g Triethanolamine
6.0g 8.0g
N-ethyl-N-hydroxyethyl 4.
2g 5.6g -4-Aminoaniline sulfate Potassium carbonate
30.0g 25.0g
Fluorescent brightener (diaminostilbene type) 1.
0g 1.2g Add water
1000m
l 1000ml────────────
────────────────────────
pH (25℃)
10.50 11.00

0
236] ──────────────────────────
──────────── Bleach-fix solution

Mother liquid Replenisher──────
──────────────────────────
────── Ethylenediaminetetraacetic acid, disodium, dihydrate 4.0g Same as mother liquor Ethylenediaminetetraacetic acid, Fe(III), 70.0g
Ammonium dihydrate ammonium thiosulfate (700g/l)
180ml Sodium p-toluenesulfonate
20.0g Sodium bisulfite
20.0g 5-mercapto-1,3,4-triazole 0.5g Ammonium sulfate
Add 10.0g water
1000m
l────────────────────────
──────────── pH (25℃)

6.20

[Water water] Both the mother liquor and the replenisher were washed with tap water using H-type strongly acidic cation exchange resin (Amberlite IR-120 manufactured by Rohm and Haas).
B) and OH type anion exchange resin (Amberlite I)
Water was passed through a mixed bed column packed with R-400) to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, followed by 20 m of sodium isocyanurate dichloride.
g/l and 1.5 g/l of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

The cyan color density of the obtained direct positive image was measured, and the results are shown in Table 2. The sharpness is evaluated using the MTF (Modulation Transfer) of the color image.
Function) was determined and expressed as a value of 10 lines/mm. Relative sensitivity is the optical density (minimum image density (DMIN))
It is expressed as a relative value of the reciprocal of the exposure amount required to achieve +0.6.

[0239] Table 2

[Table 2]

[0240] As is clear from Table 2, sample 2 of the present invention
02A and 202B are samples 201A and 201 for comparison.
It can be seen that compared to B, the maximum image density (DMAX) and sharpness are the same, but the minimum image density (DMIN) is lower and the sensitivity is higher. Furthermore, it can be seen that the improvement effect is particularly remarkable when an antihalation layer is present.

[Brief explanation of drawings]

FIG. 1 is an electron micrograph showing the structure of silver halide grains without dislocation lines.

FIG. 2 is an electron micrograph showing the structure of silver halide grains of the present invention in which dislocation lines are present.

Claims (3)

[Claims] 1. A direct positive silver halide photographic light-sensitive material having at least one emulsion layer containing internal latent image type silver halide grains not previously fogged on a support, wherein the internal latent image type halogenated The silver particles formed a silver halide core with normal crystal grains consisting essentially of silver bromide, and then were sensitized with sulfur, selenium, and/or noble metal, and then covered with a silver halide shell. A direct positive silver halide photographic light-sensitive material having a core/shell structure and having dislocation lines in the silver halide grains. 2. The direct positive silver halide photographic material according to claim 1, further comprising an antihalation layer formed between the emulsion layer and the support. 3. A silver halide emulsion containing normal silver halide crystals having dislocation lines inside the grains is prepared by the following five processes, and then the obtained silver halide emulsion is coated on a support. A method for producing a silver halide photographic light-sensitive material characterized by: ■ Preparation of silver halide normal crystal grains substantially consisting of silver bromide as a base; ■ Adding silver chloride or Formation of epitaxy of silver chlorobromide; ■ Physical ripening of epitaxy of the grains and/or conversion with halogens; ■ Sulfur, selenium sensitization and/or noble metal sensitization of the grains; and ■ Coating with a silver halide shell. .