JPS6381337A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the max. density, without increasing the min. density of the direct positive image by incorporating a metal colloid (except colloidal silver) to an emulsion layer or another hydrophilic colloidal layer. CONSTITUTION:The titled material is provided at least one layer of an inner latent image type silver halide emulsion layer which is not previously fogged, by applying said emulsion. In the titled material, the metal colloid (except colloidal silver) is incorporated in the emulsion layer or the another hydrophilic colloidal layer. The metal colloid dispersion comprises the metal colloid dispersion obtd. by reducing the corresponding metal ion in a polymer solution, or the colloid dispersion of a water insoluble metal sulfide, a metal selenide or a metal telluride which is obtd. by mixing the metal ion solution and the solution of the water soluble sulfide, the selenide or the telluride. Thus, the high max. image density, without increasing the min. image density, is obtd.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to direct positive photographic materials.

BACKGROUND OF THE INVENTION Photographic methods that provide direct positive images without the need for reversal processing steps or negative film are well known.

Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types, considering their practical usefulness. can.

One type uses a silver halide emulsion that has been fogged in advance and uses solarization or the Burschel effect to destroy fog nuclei (latent images) in exposed areas, thereby obtaining a positive image directly after development. It is something.

The other type uses an unfogged internal latent image type silver halide emulsion and directly obtains a positive image by carrying out surface development after or while carrying out fogging treatment after image exposure.

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

This latter type of method generally has higher sensitivity than the former type of method and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type of method.

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2.592.250, U.S. Pat.
No. 2,588,982, No. 3,317.322, No. 3. 761. No. 266, No. 3,761,2
No. 76, No. 3,796.577 and British Patent No. 1
．． 151. No. 363, No. 1,150,553 (
No. 1,011.062) The main ones are those described in each specification, etc.

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

For details on the direct positive image formation mechanism, see
The Theory of the Photographic Process J by T. H. James.
of the Photographic Proc
ess) 4th edition, Chapter 7, pages 182 to 193, and US Patent No. 3,761°276.

In other words, a so-called internal latent image (positive hole) formed inside the silver halide by the initial imagewise exposure.
), fog nuclei are selectively generated only on the surface of silver halide grains in unexposed areas, and then a photographic image ( It is believed that a direct positive image) is formed.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the angry light layer, which is generally called "light fogging method" (for example, British Patent No. 1,151,3
63) and a nucleating agent (nu
creating agent) is known. This latter method is discussed, for example, in ``Research Disclosure''.
Closure) Magazine Volume 151 No. 15162 (19
Published in November 1976), pages 76-78.

To form a direct positive image, after fogging with an internal latent image type halogenated obscurant material, or while performing fogging, surface color development is performed, and then bleaching and fixing (or bleach-fixing) are performed. can be achieved. After the bleaching and fixing treatments, washing and/or stabilizing treatments are usually performed.

(Problems to be Solved by the Invention) In direct positive image formation using such a light fogging method or chemical fogging method, the development speed is slower (processing time Since it takes a long time, conventional methods have been taken to shorten the processing time by increasing the pH and/or temperature of the developing solution.However, in general, when the pH is high, the minimum image density of the direct positive image that can be obtained is In addition, under high pH conditions, the developing agent is likely to deteriorate due to air oxidation, resulting in a significant decrease in its imaging activity.

In addition to increasing the pH, other methods for increasing the development speed for direct positive image formation include methods using hydroquinone derivatives (US Pat. No. 3,227,552) and methods using mercapto compounds having carboxylic acid groups or sulfonic acid groups ( JP-A No. 60-170843), etc. are known, but the effects of using these compounds are small, and no technology has been found that can effectively increase the maximum density of positive images without directly increasing the minimum density. Not served. In particular, a technique is desired that can provide sufficient maximum image density even when processed with a low pH developer.

On the other hand, direct positive photosensitive materials have the disadvantage that the graininess of the resulting images tends to be rougher than in the case of normal negative photosensitive materials. In particular, this drawback occurs when the developer deteriorates due to running processing, which causes oxidation of the developing agent in the developer, decreases in pH, increases in bromine ions, etc., or when the photosensitive material is stored under harsh conditions for a long time. become noticeable. Especially low p
There is a desire for a technique that can provide sufficient graininess even when processed with a H developer.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a direct-positive photographic material capable of obtaining a direct-positive image having a high maximum image density without increasing the minimum image density.

A further object of the present invention is to provide a window light material for direct positive photography that allows direct positive images with good graininess to be obtained.

Another object of the present invention is to provide a direct positive photographic light-sensitive material that has good graininess and high maximum image density even when subjected to running processing or stored under harsh conditions, and that produces less reversal negative images. be.

A further object of the present invention is to provide a light-sensitive material for direct positive photography that can form a direct positive image having a sufficiently high maximum density and good graininess even when processed with a highly stable low pH developer.

(Means for Solving the Problems) The present inventors have proposed a direct positive photographic light-sensitive material comprising at least one coated internal latent image type silver halide emulsion layer that is not previously fogged. or other metal colloids in the F layer (excluding colloidal silver)
It has been found that the above objectives can be effectively achieved by a direct positive photographic light-sensitive material containing the following.

Regarding colloidal silver, for example, it is known that yellow colloidal silver is included in a yellow filter of a photosensitive material to cut blue light, but in the present invention, it has conventionally been used as so-called physical development nuclei in an image-receiving layer for diffusion transfer. and was not used for photosensitive materials other than silver salt diffusion transfer.
The above-mentioned improvements in maximum image density and graininess have been achieved by a new attempt to incorporate a metal colloid other than colloidal silver into any layer of a light-sensitive material. Moreover, the use of the metal colloid according to the present invention has the advantage that the increase in capri (minimum image density) seen when using colloidal silver is not observed.

In the present invention, a metal colloid is contained as a dispersion in at least one arbitrary layer of a light-sensitive material.

Emulsion layer and other layers (e.g. intermediate layer, yellow filter layer, protective layer, undercoat layer, antihalation layer, etc.)
But that's fine. Preferably it is a layer adjacent to the emulsion layer.

The metal colloid dispersion of the present invention is a metal colloid dispersion made by reducing the corresponding metal ion in a polymer solution, or a metal colloid dispersion made by mixing a metal ion solution with a soluble sulfide, selenide, or telluride solution. means a colloidal dispersion of a water-insoluble metal sulfide, metal selenide or metal telluride.

The polymer used here may be either a water-soluble polymer or a water-insoluble polymer, but a water-soluble polymer is preferred.

Examples of water-soluble polymers include gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sodium alginate, and starch. Sugar derivatives such as derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyacrylamide, polyvinylpyrrolidone, polyvinylimidazole, polyvinylpyrazole, and the like.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin, rBull Soc, Sc1. Photo, Japan
Enzyme-treated gelatin as described in An J Na, p. 16, 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

Gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The product obtained by reacting is used.

Metals used in the present invention include heavy metals such as mercury, iron, lead,
Zinc, nickel, cadmium, tin, chromium, copper, cobalt, gold, platinum, palladium, or sulfides, selenides, and tellurides of these metals and aluminum, silver, antimony, bismuth, cerium, and magnesium.

Preferably nickel, iron, cobalt, copper, palladium,
Gold, platinum, and sulfides of these metals.

and silver sulfide, more preferably nickel, palladium, gold, platinum, and sulfides of nickel, palladium, gold, and silver.

The amount of these metal colloids added is 10-IO to 1 per lrd.
O-3 mol, preferably 10-9 to 10-'-T-/I
/, more preferably lo-8 to 10-4 mol.

These metals are used in the form of nitrates, sulfates, carbonates, silicates, borates, acetates, phosphates, halides, cyanides, thiocyanides, etc.

On the other hand, as reducing agents, phenols such as hydroquinone, methylhydroquinone, t-butylhydroquinone, chlorohydroquinone, pyrogallol, pyrocatechin, paraphenylenediamine, 1,4-dihydronaphthalene, 1-phenyl-3-pyrazolidone, 1- 5 such as (p-aminophenol)-3-amino-2-pyrazolidone
Examples include ring-membered compounds. Many examples of these reducing agents are given in The Theory of the Photographic Process, 3rd edition, by C.E., K., Mies, and T.H. James, pages 278-306. . Further, reducing sugars such as dextrin and glucose may be used, and sodium borohydride, potassium borohydride, t-butylamine borane, dithionite salts, hydrazine compounds and the like are preferred. Alternatively, it may be prepared by reduction with hydrogen gas. Further, as the sulfurizing agent for sulfiding, sodium sulfide, potassium sulfide, etc. are preferable.

The amount of these reducing agents and sulfurizing agents is approximately 0.0% per mole of precious metal.
5 mol - about 10 mol used, preferably 0.8-5
It is a mole.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, 0.5 to 3 g of silver halide emulsion is deposited on a transparent support.
/+y? It was then exposed to light for a fixed time of 0.01 to 10 seconds and developed for 5 minutes at 18°C in the following developer A (internal developer). A silver halide emulsion coated in the same amount as above and exposed in the same manner was treated with the following developer B (
Preferred are those having a density that is at least 5 times greater, more preferably at least 10 times greater than the maximum density obtained when developed for 6 minutes at 20° C. in a surface-type developer.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Soda carbonate (-hydrate)
52.5gKBr
5 gKI
Q. Add 5g of water and 2.5g of 11 surface type image solution Metol! -Ascorbic acid 10 gNa BO2・4 Hz
o 35 gKBr
Add 1g water
1 Specific examples of β inner layer type emulsions include U.S. Pat.
No. 2-156614, No. 57-79940, No. 58-
Conversion-type silver halide emulsions described in the specification of No. 70221 and shelled emulsions thereof, U.S. Pat. Nos. 3,761.276 and 3,850,63
No. 7, No. 3923.513, No. 4,035,185
No. 4.395.478, No. 4,431,730, No. 4,504,570, JP-A No. 53-60222, No. 56-22681, No. 59-208540, No. 60-107641 No. 61-3137, patent application No. 61-3137.
No. 1-3642, Research Disclosure Magazine No.
, 23510 (issued November 1983) P236,
Same No. 18155 (published in May 1979) P2
Mention may be made of the core/shell type silver halide emulsions in which metal is doped inside, as disclosed in the patents disclosed in US Pat.

The shapes of the silver halide grains used in the present invention include regular crystal shapes such as cubes, octahedrons, dodecahedrons, and tetradecahedrons, irregular crystal shapes such as spherical shapes, and length/ Tabular particles having a thickness ratio of 5 or more may be used. Further, an emulsion having a composite form of these various crystal forms or a mixture thereof may be used.

The composition of silver halide includes silver dichloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide or contains less than 3% mole of silver iodide.
(iodine) silver bromide, (iodine) silver chloride or (iodine) silver bromide.

The average grain size of the silver halide grains is 2μ or less and 0.
It is preferably 1 μ or more, but particularly preferably 1 μ or less 0
．． It is 15μ or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the number or weight of particles should be within ±40% of the average particle size, preferably within ±20% of the total particle size. % or more, so-called "monodisperse" silver halide emulsions having a narrow grain size distribution are preferably used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two emulsion layers having substantially the same color sensitivity have two different grain sizes.
More than one type of monodisperse silver halide emulsion or a plurality of grains of the same size but different in sensitivity 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 silver halide emulsion used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium aggravation, reduction sensitization, noble metal sensitization, etc. alone or in combination. A detailed example can be found in the patent described in, for example, Research Disclosure Magazine No. 17643-1 [[(published December 1978) P23.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes 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. A detailed example can be found in the patent described in Research Disclosure Magazine No. 17643-IV (published December 1978), 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. For detailed examples, see Research Disclosure Magazine No. 17643-
Vl (published December 1978) pages 24-25 and
E. J. Birr “5 tabilization of
Photographic 5ilver Hali
de Emulsions” (PocalPress)
, published in 1974.

A variety of color couplers can be used to form direct positive color images. Useful color couplers are
A compound that generates or releases a dye, preferably a substantially non-diffusible dye, by a coupling reaction with an oxidized form of an aromatic primary amine color developer, and which itself is substantially non-diffusible. It is a compound. Typical types of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazolone azole 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 can be found in Research Disclosure, Issue 17643 (December 1978), p.
25■-ri section, same issue No. 18717 (issued in November 1979) and patent application No. 32462 (Sho 61-32462) (issued in November 1979)
Page) and the patents cited therein.

Among them, representative examples of yellow couplers that can be used in the present invention include oxygen atom elimination type and nitrogen atom elimination type yellow m:equivalent couplers. Especially α−
Pivaloylacetanilide couplers are preferred because they provide excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Further, as the 5-pyrazolone magenta coupler that can be preferably used in the present invention, a 5-pyrazolone coupler in which the 3-position is substituted with an arylamino group or an acylamino group (especially a sulfur atom-eliminated two-equivalent coupler) is used.

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, but coloring dyes The imidazo[1°2-b]pyrazoles described in U.S. Pat. No. 4,500.630 are more preferred in terms of low yellow side absorption and light fastness; The described pyrazolo(1,5-b)(1,2,4)h riazoles are particularly preferred.

Cyan couplers that can be preferably used in the present invention include:
U.S. Patent No. 2,474,293, 4°052.21
Naphthol-based and phenol-based couplers described in U.S. Pat. ,5
-Diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness.

Specific examples of particularly preferred yellow, magenta and cyan couplers include Japanese Patent Application No. 61-169523 (Showa 6
No. 35 (filed by Fuji Photo Film Co., Ltd. on July 18, 2013)
These are the compounds listed on pages 1 to 51, and the following compounds can also be mentioned as preferred examples.

O:! : :CZ Wisdom's 0:@@Eyellow coupler Ll(Jl;sMy(IJ --・λ O Engineering＾ 0 Colored coupler to correct unnecessary absorption of short wavelengths of the generated dye, coloring dye is moderate DIR couplers that release a development inhibitor or a development accelerator upon coupling reaction, colorless couplers, couplers that release a development inhibitor, and polymerized couplers can also be used.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide;
Preferably from 0.01 to 0.5 for yellow couplers.
moles, for magenta couplers 0.003 moles to 0
．． 5 mol, and for cyan couplers 0.002 to 0
．． It is 5 moles.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color-fogging inhibitors or color-mixing inhibitors. It may also contain derivatives and the like. Typical examples of color capri-preventing agents and color-mixing preventive agents are patent applications filed in 1983.
-32462, pages 600 to 630.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-hydroxychromans, 5-hydroxycoumarans, spirochroman I'I, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines Typical examples include ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent the deterioration of magenta dye images, especially the deterioration caused by light, the substitution of spiroindanes as described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

Representative examples of these anti-fading agents are disclosed in Japanese Patent Application No. 32462/1986.
No. 401-440.

The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the respective color couplers. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer. Further, an ultraviolet absorber can also be added to a hydrophilic colloid layer such as a protective layer. Representative examples of compounds are given in Japanese Patent Application No. 61-32462.
It is described on pages 391-400.

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.

The light-sensitive materials of the present invention include dyes that prevent eradication and halation, ultraviolet absorbers, plasticizers, fluorescent whitening agents, matting agents, air fog preventive agents, coating aids, hardeners, antistatic agents, and anti-slip agents. A sex improver, etc. can be added. Representative examples of these additives are [Research Disclosure]
Magazine No. 17643■ to
Published in January), 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. Furthermore, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, or two or more emulsion layers having the same sensitivity.
A non-light-sensitive layer may be present between the two or more emulsion layers, with a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer. Although this is usually included, different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, Haley silane inhibitor,
It is preferable to appropriately provide auxiliary layers such as 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 manufactured by Research Disclosure Magazine No. 17643X.
Items listed in section ■ (issued December 1978) p. 28 and European patents 0. 182. No. 253 and JP-A-61-
97655. Also, Research Disclosure Magazine No. 17643 Section XV p2
The coating methods described in 8 to 29 can be used.

The present invention can be applied to various color photosensitive materials.

For example, typical examples include color reversal film for slides or television, and color reversal paper. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention has also been published in "Research Disclosure" magazine no.

17123 (published in July 1978), etc., and which utilizes a mixture of three color couplers.

Furthermore, the present invention can also be applied to black and white photographic materials.

Black and white (B/W") photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-260.
B/W direct positive photographic light-sensitive materials described in 039 (for example, X-ray sensitive materials, duplex sensitive materials, micro sensitive materials,
phototypesetting materials, printing materials), etc.

After imagewise exposure, the light-sensitive material of the present invention is subjected to fogging treatment with light or a nucleating agent, and then developed with a surface developer containing an aromatic primary amine color developer, and subjected to bleaching and fixing treatment. By doing so, a positive color image can be directly formed.

As mentioned above, the fogging treatment in the present invention is carried out by applying a second exposure to the entire surface of the photosensitive layer, which is called the so-called "light fogging method," and by developing it in the presence of a nucleating agent, which is called the "chemical fogging method." Either method may be used. Development may be carried out in the presence of a nucleating agent and fogging light, or a photosensitive material containing a nucleating agent may be exposed to fogging.

The entire surface exposure, that is, fogging exposure in the "light fogging method" of the present invention is performed after imagewise exposure, before development processing, and/or during development processing. The imagewise exposed photosensitive material is placed in a developer solution.
Alternatively, the film may be exposed to light by immersing it in a pre-bath of a developer, or by taking it out from this solution and exposing it to light before it dries, but it is most preferable to expose it in a developer.

As a light source for fogging exposure, a light source within the wavelength range to which the photosensitive material is sensitive may be used, and generally any of fluorescent lamps, tungsten lamps, xenon lamps, sunlight, etc. can be used.

These specific methods are described, for example, in British Patent No. 1,151.
No. 363, Special Publication No. 45-12710, No. 45-127
No. 09, No. 58-6936, JP-A-48-9727, No. 56-137350, No. 57-129438 calyx,
No. 58-62652, No. 5B-60739, No. 58
-70223 (corresponding U.S. Pat. No. 4,440,851), No. 5
B-120248 (corresponding European Patent No. 89101A2), etc. For photosensitive materials that are sensitive to all wavelengths, such as color photosensitive materials, Japanese Patent Application Laid-Open No. 56-13735
A light source with high color rendering properties (as close to white as possible) such as those described in No. 0 and No. 58-70223 is preferable. The illuminance of the light is 0.01 to 2000 lux, preferably O005
-30 lux, more preferably 0.05-5 lux is suitable. For light-sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferred. To adjust the illuminance,
The luminous intensity of the light source may be changed, the light may be attenuated by various filters, the distance between the photosensitive material and the light source, and the angle between the photosensitive material and the light source may be changed. Using weak light at the beginning of exposure,
Exposure times can then be shortened by using stronger light.

It is preferable to immerse the light-sensitive material in a developer solution or a pre-bath solution, and to irradiate the light-sensitive material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material. 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, more preferably 1 second to 4 minutes
It is 0 seconds.

As the nucleating agent that can be used in the present invention, all compounds conventionally developed for the purpose of nucleating smooth silver halide can be used. Two or more types of nucleating agents may be used in combination. To explain in more detail, the nucleating agent includes, for example, “
Research Disclosure+-J (Research
h Disclosure) Magazine 22゜534 (19
Published in January 1983, 50-54 true) Same issue 15.162 (1
Published in November 1976, pages 76-77) and the same magazine 11m23
, 510 (Published November 1983, pp. 346-352)
These include quaternary heterocyclic compounds (compounds represented by the general formula (N-■)), hydrazine compounds (compounds represented by the general formula (N-n)), and other compounds. It is broadly divided into

General formula (N-1) (wherein, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, Z may be substituted with a substituent, R1 is an aliphatic group and R2 is a hydrogen atom, an aliphatic group, or an aromatic group.R' and R2 may be substituted with a substituent.However, at least one of the groups represented by R1, R2, and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R1 and R2 form a 6-membered ring to form a dihydropyridinium skeleton.Furthermore, at least one of the substituents of R1, R2 and Z One may have XI →L')-m. Here, Xl is a group promoting adsorption to silver halide, and LI is a divalent linking group. Y is a counterion for charge balance, n is O or 1, and m is 0 or 1. ) To explain in more detail, the heterocycle completed by Z is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, Mention may be made of indolenium, pyrrolinium, acridinium, phenanthridinium, indolenium, oxacillium, naphthoxacilium, naphthopyridinium and benzoxacillium nuclei. Substituents for Z include alkyl groups, alkenyl groups, aralkyl groups, aryl groups, alkynyl groups, hydroxy groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylthio groups, arylthio groups, acyloxy groups, acylamino groups, Sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate group, hydrazine group, hydrazone group, or imino group, etc. can give. As the substituent for Z, for example, at least one substituent is selected from the above substituents, but in the case of two or more substituents, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents.

Furthermore, as a substituent for Z, a heterocyclic quaternary ammonium group completed with 2 via a suitable linking group may be included. In this case, it takes a so-called dimer structure.

The heterocycle completed by Z preferably includes quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, naphthopyridinium and isoquinolinium nuclei.

More preferred are quinolinium, benzothiazolium, and naphtopyridinium, and most preferred is quinolinium.

The aliphatic groups of R1 and R1 are an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl portion. Examples of the substituent include those described as the substituent for Z.

The aromatic group represented by Rt has 6 to 20 carbon atoms, and includes, for example, a phenyl group and a naphthyl group. Examples of the substituent include those described as the substituent for Z. Rt is preferably an aliphatic group, most preferably a methyl group and a substituted methyl group.

At least one of the groups represented by R1, R1, and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R1 and R1 form a 6-membered ring, and a dihydropyridinium core is formed. However, these may be substituted with the groups described above as substituents for the group represented by Z. The hydrazine group preferably has an acyl group or sulfonyl group as a substituent, and the hydrazone group preferably has an aliphatic group or an aromatic group as a substituent. As the acyl group, for example, a formyl group, an aliphatic group, or an aromatic ketone is preferable.

It is preferable that at least one of the substituents on the group or ring represented by RISRt and Z is an alkynyl group or an acyl group, or that R1 and R2 are linked to form a dihydropyridinium core; It is most preferable that it contains at least one group.

Preferred examples of the adsorption promoting group to silver halide represented by XI include a thioamide group, a mercapto group, and a 5- to 6-membered nitrogen-containing heterocyclic group.

These may be substituted with the substituents mentioned above for Z. The thioamide group is preferably an acyclic thioamide group (e.g., thiourethane group, thiourido group, etc.)
It is.

The mercapto group of
, 4-thiadiazole, etc.) are preferred.

The 5- to 6-membered nitrogen-containing heterocycle represented by XI consists of a combination of nitrogen, enzyme, sulfur, and carbon,
Preferred examples include those that produce imino silver, such as benzotriazole.

The divalent linking group represented by Ll includes C1N, S,
It is an atom or atomic group containing one type of O.

Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -〇-1-S-1-NH
-1-N-1-CO-1-SOt (these groups may have a substituent), alone or in combination.

Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion,
Examples include trifluoromethanesulfonate ion and thiocyanate ion.

Examples of these compounds and their synthesis methods can be found, for example, in Research Disclosure.
Closure) magazine N1122, 534 (published January 1983, pages 50-54), and Kaimagai 23,213 (
Patent cited in Japanese Patent Publication No. 49-38.164 (Published August 1983, pp. 267-270), No. 52-19゜45
No. 2, No. 52-47.326, JP-A-52-69.6
No. 13, No. 52-3.426, No. 55-138.74
No. 2, No. 60-11,837, U.S. Patent No. 4,306
, No. 016, and No. 4,471.044.

Specific examples of the compound represented by general formula (N-1) are listed below, but the invention is not limited thereto.

(N-I-1), 6-nitoxy-2-methyl-1
-Propargylquinolinium bromide (N-I-2), 2,4-dimethyl-1-propargylquinolinium bromide (N-1-3), 2-methyl-1-(3-(2-(
4-methylphenyl)hydrazonocobutyl)quinolinium iosito(N-1-4), 3,4-dimethyl-dihydropyrido(
2,1-b) Benzothiazolylam promide (N-1-5), 6-nitoxythiocarponylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-6), 2 -Methyl-6-(3-phenylthioureido)-1-propargylquinolinium Bromide (N-1-7), 6-(5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium Trifluoromethanesulfonate (N-1-8), 6-(3-(2-mercaptoethyl)ureido]-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-9), 6- (3-ca-<5-mercapto-thiadiazol-2-ylthio)propyl]ureido)-2-methyl-1-propargylquinolinium triple oromethanesulfonate (N-I-10), 6-(5-mercapto Tetrazol-1-yl)-2-methyl-1-propargylquinolinium iosito General formula (N-II) R''-N-N-G-R22 R2'1R24 (wherein, R21 is an aliphatic group, aromatic R22 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group; G represents a carbonyl group, a sulfonyl group, a sulfoxy group, or a phosphoryl group; R21 and RZ4 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group. represents.However, G, R
A hydrazone structure (/N−N=08) may be formed by including 2:l, RZ4, and hydrazine nitrogen. Further, the groups described above may be substituted with a substituent if possible. ) 2 To explain in more detail, R21 may be substituted with a substituent, and examples of the substituent include the following.

These groups may be further substituted. For example, an alkyl group, an aralkyl group, a T□rekoxy group, an alkyl or aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a srefamoyl group, a carbamoyl group,
Aryl group? These include a lukylthio group, an arylthio group, a sulfonyl group, an X-rufinyl group, a hydroxy group, a halogen atom, an ano group, a sulfo group, and a carboxyl group.

Among these, ureido groups are particularly preferred.

These groups may be linked to each other to form a ring when possible.

R21 is preferably an aromatic group, an aromatic ring or an aryl-substituted methyl group, and more preferably an aryl group (for example, a phenyl group, a naphthyl group, etc.).

Among the groups represented by Rzz, preferable ones include a water atom, an alkyl group (e.g. methyl group), or an aralkyl group (e.g. methyl group).
For example, O-hydroxybenzyl group (bi), etc., and a hydrogen atom is particularly preferred.

As the substituent for R12, in addition to the substituents listed for R'', for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, etc. can be applied.

These substituents may be further substituted with these substituents. Further, if possible, these groups may be linked to each other to form a ring.

RlI or R'', especially R21, may contain a diffusion-resistant group such as a coupler, a so-called ballast group (particularly preferred when linked with a ureido group), a group that promotes adsorption to the surface of silver halide grains. X”-+L”←m”
It may have.

X here! represents the same meaning as Xl in general formula (N-I), preferably a thioamide group (excluding thiosemicarbazide and its substituted products), a mercapto group, or 5 to 6
It is a nitrogen-containing heterocyclic group.

L2 represents a divalent linking group, and represents 1. of general formula (N-1).
It has the same meaning as 1. m' is 0 or 1.

More preferred Xt is an acyclic thioamide group (e.g., thioureido group, thiourethane group, etc.), a cyclic thioamide group (i.e., a mercapto-substituted nitrogen-containing heterocycle, such as a 2-mercaptothiadiazole group, a 3-mercapto-1
, 2,4-1-riazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or nitrogen-containing heterocyclic group (e.g. benzotriazole group,
(benzimidazole group, indazole group, etc.).

The most preferable value for X2 is 0, which varies depending on the photosensitive material used. For example, in a color photosensitive material, when using a coloring material (so-called coupler) that forms a dye by a campling reaction with an oxidized product of a p-phenylenediamine developer, Xz As such, a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming iminosilver is preferable. In addition, when using a coloring material (so-called DRR compound) that generates a diffusible dye by cross-oxidizing an oxidized developer in a color sensitive material, X2 is an acyclic thioamide group or a mercapto-substituted nitrogen-containing heterocyclic ring. is preferred.

Furthermore, in a black-and-white sensitive material, X2 is preferably a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming iminosilver.

Hydrogen atoms are most preferred as RZ2 and R24.

G in general formula (N-n) is most preferably a carbonyl group.

Further, as the general formula (N-n), those having an adsorption group to silver halide or those having a ureido group are more preferable.

Examples of these compounds and their synthesis methods are described in US Patent No. 4. 030. No. 925, No. 4,0
No. 80,207, No. 4,031.127, No. 3,
No. 718.470, No. 4.269.929, No. 4
．． 276.364, 4.278.748, 4,385゜108, 4,459,347, 4゜478.928, 4.560,638,
British Patent No. 2.011.391B, Japanese Unexamined Patent Publication No. 1974-74
．． No. 729, No. 55-163, 533, No. 55-74
, No. 536, and No. 60-179°734.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86.829, U.S. Pat. No. 4,560.638, U.S. Pat. No. 4,478, and U.S. Pat.

Specific examples of the compound represented by general formula (N-11) are shown below. However, the present invention is not limited to the following compounds.

(N-n-1), 1-formyl-2-(4-(3-(2
-methoxyphenyl)ureido]-phenyl)hydrazine (N-If -2), 1-formyl-2-(4-(
3-(3-(3-(2,4-di-tert-pentylphenoxy)propyl]ureido)phenylsulfonylaminotuphenyl)hydrazine (N-n-3), 1-formyl-2-(4-(3)
-(5-merkabutotetrazol-1-yl)benzamido]phenyl)hydrazine (N-n-4), 1-formyl-2-(4-(3
-(3-(5-mercaptotetrazol-1-yl)phenyl]ureido)phenyl]hydrazine (N-n-5), 1-formyl-2-(4-(3
-(N-(5-mercapto-4-methyl-1,2,4-1-riazol-3-yl)carbamoyl]propanamido)phenyl]hydrazine (N-n-6), 1-formyl-2-( 4-(3
-(N-(4-(3-mercapto-1,2,4-)lyazol-4-yl)phenylcarbamoyl)-17'lobanamido]phenyl)hydrazine (N-I[-7), 1-formyl-2 -(4-(3
-(N-(5-mercapto-1,3゜4-thiadiazol-2-yl) carbamoyl]propanamide) phenyl]hydrazine (N-11-8), 2-(4-(,benzotriazole-5-carboxamide) ) phenyl]-1-formylhydrazine (N-11-9), 2- (4-(3-(N-(hensitriazole-5-carboxamide)carbamoyl]propanamido)phenyl]-1-formylhydrazine (N- 11-10), 1-formyl-2-(4-(
1-(N-phenylcarbamoyl)thiosemicarbazide]phenyl)hydrazine (N-11-11), 1-formyl-2-(4-(
3-(3-phenylthioureido)benzamido]phenyl)hydrazine (N-n-12), 1-formyl-2-(4-(3
-Hexylureido)phenyl]hydrazine The nucleating agent used in the present invention can be contained in the sensitive material or in the processing solution for the sensitive material, preferably in the sensitive material.

When incorporated into a light-sensitive material, it is preferably added to a smooth silver halide emulsion, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers, e.g. , an intermediate layer, an undercoat layer or a back layer. When adding a nucleating agent to the processing solution, it should be added to the developer solution or a low p
It may be contained in the HO pre-bath.

When a nucleating agent is included in the sensitive material, the amount used is preferably 10-2 to 10-2 mol, more preferably 10-7 to 10-3 mol, per 811 mol of halogen.

In addition, when adding a nucleating agent to the processing solution, the amount used is:
The amount is preferably 10-5 to 101 mol, more preferably 10-' to 10-2 mol per 11.

The following compounds can be added for the purpose of increasing the maximum image density, decreasing the minimum image density, improving the storage stability of the photosensitive material, or speeding up development.

Hydroquinones (e.g. U.S. Pat. No. 3,227.5
No. 52, 4,279. ．． Compounds described in No. 987): Chromans (for example, U.S. Patent No. 4,268.621, Japanese Patent Application Laid-open No. 103031/1983, Research Disclosure No. 18264 (published June 1979) 333-3
Compounds described on page 34) Quinones (e.g. compounds described in Research Disclosure Magazine 111I121206 (December 1981, pages 433-434)) Amines (e.g. U.S. Pat. No. 4,150,993 and JP-A-58-174
Compounds described in No. 757): Oxidizing agents (for example, JP-A No. 6
No. 0-260039, Research Disclosure 11
h16936 (published in May 1978, compounds described on pages 10-11): Catechols (e.g., JP-A-55-2
Compounds described in No. 1013 and No. 55-65944):
Compounds that release nucleating agents during development (for example, JP-A-60
-107029): thioureas (for example, the compounds described in JP-A No. 60-95533), nispirobisindanes (for example, the compounds described in JP-A-55-65944).

Nucleation accelerators that can be used in the present invention include tetrazaindenes, triazaindenes and pentazaindenes, which have at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. and Japanese Patent Application Publication No. 1983-136948 (pages 2-6 and pages 16-43), Japanese Patent Application No. 136949-1980,
(pages 12-43) and No. 61-15348 (pages 10-29)
Examples include the compounds described on page 1).

Specific examples of the nucleation accelerator are listed below, but the invention is not limited thereto.

(A-1) 3-mercapto-1,2,4-triazolo(4,5-a) and lysine (A~2) 3-mercapto-1,2,4-)riazolo(
4,5-a) pyrimidine (A-3) 5-mercapto-1,2,4-1-riazolo(1,5-a) pyrimidine (A-4) ? -(2-dimethylaminoethyl)-5
-Mercapto-1,2,4-) Riazolo [1°5-a]
Pyrimidine (A-5) 3-mercapto-7-methyl-1,2,
4-triazolo(4,5-a) pyrimidine (A-6)
3. 6-dimercabuto 1.2.4-)riazolo(4,5-b)pyridazine (A-7) 2-mercapto-5-methylthio-1,
3゜4-thiadiazole (A-8) 3-mercapto-4-methyl-1,2,
4-triazole (A-9) 2- (3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (A-10) 2- (2-morpholinoethylthio)-
5-mercapto-1,3,4-thiadiazole hydrochloride (A-11) 2-mercapto-5-methylthiomethylthio-1,3,4-thiadiazole sodium salt.

(A-12) 4- (2-morpholinoethyl)-3-
Mercapto-1,2,4-)lyazole (A-13) 2- (2-(2-dimethylaminoethylthio)ethylthio)-5-mercapto-1゜3.4-
Thiadiazole Hydrochloride The nucleation promoter in this case is preferably added to the silver halide emulsion or to a layer adjacent thereto.

The amount of the nucleation accelerator added is 10 - per 111 moles of halogenide.
6 to 10-1 mol is preferable, more preferably 10-'
~10-t mol.

In addition, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, 10-8 to 10-'
It is preferably mol, more preferably 101 to 10-4 mol.

Moreover, two or more kinds of nucleation accelerators can also be used together.

The color developer used in the development of the light-sensitive material of the present invention does not substantially contain a silver halide solvent, and is preferably an alkaline solution containing an aromatic primary amine color developing agent as a main component. Although aminophenol compounds are also useful as color developing agents, p-phelenediamine compounds are preferred. A typical example is 3-methyl-
4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline, 3-methyl-4-amino-N
-ethyl-N-(β-hydroxyethyl)aniline, 3
Examples include -methyl-4-amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfates and hydrochlorides. As the background color developing agent, F
, A. Mason, Photographic Processing Chemistry, Focal Press (196
6th year) (L.

F, A, Mason"Photographic
Processing Chen+1try”, F
p. 226-229 of U.S. Pat. Those described in No. 592°364, JP-A-48-64933, etc. may be used. Moreover, two or more types of color-producing agents can be used in combination, if necessary.

The amount of color developing agent used is from 0.1 g to 20 g, more preferably from 0.5 g to 15 g, per 11 of the developer solution.

Furthermore, as a preservative, JP-A-52-49828, JP-A No. 52-49828,
No. 6-47038, No. 56-32140, No. 59-1
Aromatic polyhydroxy compounds described in US Pat. No. 60142 and US Pat. No. 3,746,544; US Pat. No. 3,615,503
Hydroxyacetones described in JP-A-52-143020 and British Patent No. 1306.176;
α-aminocarbonyl compounds described in JP-A No. 89425; various metals described in JP-A-57-44148 and JP-A-57-53749; various saccharides described in JP-A-52-102727; Hydroxamic acids; α-α'-dicarbonyl compounds described in No. 59-160141; salicylic acids described in No. 59-180588; alkanolamines described in No. 54-3532; poly(alkylene) described in No. 56-94349; Imin)
Examples include gluconic acid derivatives described in No. 56-75647. These preservatives can be used as needed.
More than one species may be used together. Especially 4,5-dihydroxy-
m-benzenedisulfonic acid poly(ethyleneimine),
It is preferable to add triethanolamine and the like. Furthermore, it is preferable to add substituted phenol such as p-nitrophenol. Furthermore, it is also preferable to use an alkylhydroxylamine compound disclosed in JP-A-54-3532. In particular, it is preferable to use an alkylhydroxylamine compound in combination with the above-mentioned preservative.

The amount of these preservatives used is from 0.1 g to 20 g, more preferably from 0.5 g to 10 g, per developer solution 11.

The pH of the color developer of the present invention can range from 9 to 14, preferably from 9.5 to 12.0, particularly preferably from 9.8 to 11.5. Various buffers can be used to maintain the above pH. Examples of buffering agents include carbonates such as potassium carbonate, phosphates such as potassium phosphate, etc.
The compounds described on pages 22 to 22 can be used.

Furthermore, various chelating agents can be used in the color developer to prevent precipitation of calcium or magnesium or to improve the stability of the color developer.

As a chelating agent, for example, Japanese Patent Publication No. 4B-030496
and aminopolycarboxylic acids described in JP-A No. 44-30232, JP-A No. 56-97347, JP-A No. 56-39
359 and the organic phosphonic acids described in West German Patent No. 2゜227.6'39, JP-A-52-102726 and JP-A-52-102726;
-42730, 54-121127, 55-1
Phosphonocarboxylic acids described in No. 26241 and No. 55-65956 equivalently, and others JP-A-58-195845
No. 58-203440 and Special Publication No. 53-4090
Examples include the compounds described in No. 0 and the like. Two or more of these chelating agents may be used in combination, if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per ρ.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 381324
Thioether compounds described in No. 7, etc.; JP-A-52-4
p-phenylenediamine compounds described in No. 9829 and No. 50-15554, JP-A-50-137726
No., Special Publication No. 44-30074, Japanese Patent Publication No. 1568-1983
Quaternary ammonium salt necks described in U.S. Patent No. 26 and U.S. Pat. No. 52-43429, etc.;
p-amine phenols described in US Pat. No. 119,462; US Pat. No. 2,494,903, US Pat. No. 3,128,182, US Pat.
Special Publication No. 41-11431, U.S. Patent No. 2,482,54
No. 6, No. 2゜596.926 and No. 3,582,34
Amine compounds described in No. 6, etc.; Japanese Patent Publication No. 37-1608
No. 8, No. 42-25201, U.S. Patent No. 3,128.1
No. 83, Special Publication No. 41-11431, No. 42-2388
No. 3 and U.S. Patent 3. 532. Polyalkylene oxide described in No. 501, etc., l-phenyl-3
- Pyrazolidones, hydrazines, meso ion type compounds, thousand ion type compounds, imidazoles, etc. can be added as necessary. Particularly preferred are thioether compounds and 1-phenyl-3-pyrazolidones.

In the present invention, an arbitrary anti-capri agent may be added to the color developer if necessary. As anti-capri agents, alkali metal halides such as potassium bromide, sodium chloride, potassium iodide and organic anti-capri agents may be used. Examples of organic anti-capri agents include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole and hydroxyazaindolizine; mercapto-substituted heterocyclic compounds such as 2-mercaptobenzimidazole and 2-mercaptobenzothiazole; and mercapto-substituted heterocyclic compounds such as adenine and thiosalicylic acid. Aromatic compounds can be used. These anti-capri agents are
They may be eluted from the color photosensitive material during processing and accumulated in the color developer, but from the viewpoint of reducing the amount of discharge, it is preferable that the amount of these substances accumulated is small.

The color developer of the present invention preferably contains a fluorescent brightener.
, 2'-disulfostilbene type compounds are preferred. The amount added is 0 to 5 g/Il, preferably 0.1 g to 2 g/2.

Furthermore, various surfactants such as alkylphosphonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process in a single bath bleach-fixing process, or may be carried out separately. Furthermore, in order to speed up the processing, a method may be employed in which bleaching is followed by bleach-fixing, or a method in which fixing is followed by bleach-fixing. In the bleaching solution or bleach-fixing solution of the present invention, an aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent. Specification pages 22-30
A variety of compounds described on page can be used. After the desilvering step (bleach-fixing or fixing), it is preferable to use water that has been softened as the washing water or stabilizing solution used for washing and/or stabilization. Examples of the water softening treatment include a method using an ion exchange resin or a reverse osmosis device as described in Japanese Patent Application No. 131632/1982. These specific methods are described in Japanese Patent Application 1986-
Preferably, the method described in No. 131632 is carried out.

Further, as additives used in the water washing and stabilization steps, various compounds described in Japanese Patent Application No. 32462/1983, pages 30 to 36 can be used.

The smaller the amount of replenisher in each treatment step, the better. The amount of replenisher is preferably 0.1 to 50 times, more preferably 3 times, the amount of prebath brought in per unit area of the photosensitive material.
~30 times.

On the other hand, various known developing agents can be used to develop the black and white light-sensitive material in the present invention. i.e. polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol, etc.; aminophenols such as p-aminophenol, N-methyl-p
-Aminophenol, 2,4-diaminophenol, etc.; 3-pyrazolidones, such as l-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3-
Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1
-phenyl-3-pyrazolidone and the like; ascorbic acids and the like can be used alone or in combination. Further, the developer described in Japanese Patent Application No. 56-154116 can also be used. Such a developer may be included in the alkaline processing composition (processing element) or in an appropriate layer of the photosensitive element.

The developer may contain preservatives such as sodium sulfite, potassium sulfite, ascorbic acid, and reductones (eg, piperidinohexose reductone).

A positive image can be directly obtained from the photosensitive material of the present invention by developing it using a surface developer.

A surface developer is one in which the development process is substantially induced by latent images or fog nuclei on the surface of silver halide grains. Although it is preferred not to include silver halide solubilizers in the developer solution, unless the internal latent image contributes substantially to the completion of development by the surface development centers of the silver halide grains, silver halide solubilizers (e.g. sulfite salt) may be included.

The developer contains sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
May include trisodium phosphate, sodium metaborate, and the like. The content of these agents (agentS) is selected so that the pH of the developer is 9 to 13, preferably pH 1O-11.2.

The developer also contains, for example, benzimidazoles, such as 5-
Nitrobenzimidazole; benzotriazoles, such as benzotriazole, 5-methyl-benzotriazole, etc., are advantageously included, compounds commonly used as antifoggants.

For detailed examples of developers, preservatives, buffers, and development methods for black and white photosensitive materials, and how to use them, see
Research Disclosure” magazine It17643 (1
Published in December 1978) Sections xIX to XXI, etc.

(Example) In carrying out an example, a sulfide metal colloid, a metal colloid, and an emulsion A were produced as follows.

Arsenic sulfide colloid i,' To 100 cc of a 2% aqueous phthalated gelatin solution, 3Qcc of 0.01 mol of nickel chloride was added with stirring, and then 6 cc of a 0.1 mol NO□S solution was added to form a nickel sulfide colloidal sol. was prepared.

Similarly, colloidal sols of palladium sulfide, silver sulfide, and gold sulfide were prepared using palladium chloride, silver nitrate, and sodium chloroaurate, respectively.

Metal Strain Adjustment 1 10 cc of 2N sodium hydroxide aqueous solution was added to 100 cc of 2% phthalated gelatin aqueous solution, and 30 cc of 0.01 mol palladium chloride was added with stirring. Add 4 cc of sodium borohydride 0°1N aqueous solution to this.
added. Thereafter, the mixture was cooled to 18° C. to gelatin and washed with running water for 5 hours.

Similarly, using sodium chloroaurate and chloroplatinic acid,
Colloids of gold and platinum were prepared.

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate was added to an aqueous gelatin solution containing 0.3 g of 3,4-dimethyl-1°3-thiazoline-2-thione per mole of Ag at about 75°C with vigorous stirring. They were added simultaneously over a period of 20 minutes to obtain an octahedral monodisperse silver bromide emulsion with an average grain size of 0.4 μm. Chemical sensitization was carried out by adding 6 mg of sodium periosulfate and potassium chloroaurate (tetrahydrate) per mole of silver to this emulsion and heating at 75° C. for 80 minutes.

Using the thus obtained silver bromide grains as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and finally octahedral monodisperse core/shell bromide grains with an average grain size of 0.7 μm were obtained. An emulsion was obtained. After washing and desalting, use this emulsion! I! Sodium periosulfate and chloroauric acid (tetrahydrate) were added in an amount of 1.5 μm per mole, respectively, and heated at 57°C for 40 minutes to perform a chemical sensitization treatment to obtain an internal latent image type silver halide emulsion A. Obtained.

Example 1 A full multilayer color photographic paper having the layer structure shown in Table 1 was prepared using core/shell type internal latent image emulsion A on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

Preparation of first layer coating solution Add 10 ml of ethyl acetate and 4 ml of solvent (C) to 10 g of nitrogen coupler (a) and 2.3 g of color image stabilizer (b), dissolve, and add 5 ml of 10% sodium dodecylbenzenesulfonate to this solution. The mixture was emulsified and dispersed in 99 ml of a 10% gelatin aqueous solution. Separately, 90 g of a red-sensitive emulsion was prepared by adding the following red-sensitive dye to the above-mentioned silver halide emulsion (containing 70 g/Kg of Ag) per mol of silver halide in an amount of 2.0.times.10@-' mol. The emulsified dispersion, emulsion, and development accelerator were mixed and dissolved, the concentration was adjusted with gelatin so that the composition shown in Table 1 was obtained, and the nucleating agent (N
-n-4) at 2°5 x 10-' mol per mol of Ag, and the nucleation accelerator (A-5) at 3.5 x 10 mol per mol of Ag.
-'mol was added to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. 1-oxy-3 as gelatin hardening agent in each layer
, 5-dichloro-5-) riazine sodium salt was used. However, the metal colloid of the present invention was added to the second layer as shown in Table 3.

The following spectral enhancers were used in each emulsion layer.

Table 1 l e 1(CHz)g
The following dyes were used as SOi (CHI) and SO3Na irradiation prevention dyes.

Anti-irradiation dye for green sensitive milk layer 11
The structural formulas of the compounds used in this example, such as the Kokonn coupler, are as follows.

(a) Cyan coupler Yes A 1:3:3 mixture of Construction ＼－〜／ (i) Ultraviolet absorber A 1:5:3 mixture of (molarized (j) Color mixing prevention agent (k) Solvent (iS OC9HuOh-P=0 / Do-ichi-ichi-ichi\,・ J゛ Engineering &-hehe .

\\--1// The color photographic paper thus prepared was subjected to wedge exposure (1/10 seconds, IOCMS) and then subjected to processing step A in Table 2 below to measure the cyan color image density. .

The results obtained are shown in Table 3.

2nd surface treatment step A Time Temperature color development 1 minute 50 seconds 35℃ bleach fixing
1 minute 10 seconds 35℃ stable ■
40 seconds Stable at 35℃ ■ 40 seconds
Stable at 35℃ ■ 40 seconds 35℃
The stabilizing bath replenishment method was a so-called countercurrent replenishment method in which the stabilizing bath (1) was replenished, the overflow liquid from the stable bath (2) was led to the stable bath (2), and the overflow liquid from the stable bath (2) was led to the stable bath (2).

[Color developer]

Mother liquor Diethylenetriaminepentaacetic acid 2.0 g Benzyl alcohol 12.8 g Diethylene glycol 3.4 g Sodium sulfite
2.0 g sodium bromide
0.26g hydroxylamine sulfate
2.60g sodium chloride
3.20g 3-methyl-4-amino-N-4, 25g
Ethyl-N-(β-methanesulfonamidoethyl)-aniline potassium carbonate 30.0 g Fluorescent brightener (stilbene type) 1.0 g Water was added to 1000 ml pH 10.20 9H was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 110 g Sodium bisulfite 10 g Diethylenetriamine 56 g Iron(II) acid
Ammonium monohydrate ethylenediaminetetraacetic acid 2 5g sodium.
Add 0.5 g of dihydrate 2-mercapto-1,3,4-triazole water to 1000 ml pH 6
, 5 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother liquor 1-hydroxyethylidene 1.5mj! -1
, 1'-diphosphonic acid (60%) Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Aqueous ammonia, 5ml Nitrilotriacetic acid/3Na 1;0g 5-Chloro-2-methyl-4 monoisothiazolin-3-one 50 mg2 −
Octyl-4-isothiazolin-3-one 50 ■Fluorescent brightener (4,4'-diaminostilbene type) Add 1.0g water l O00mlp) (7,
5. Adjust pH with potassium hydroxide or hydrochloric acid.

Similar results were obtained with colloids of silver sulfide, gold sulfide, and nickel sulfide.

Similarly, even when the pH of the color developing solution was set to 12.0, the maximum cyan density obtained when the metal colloid of the present invention was added to the second layer was significantly higher than that obtained without the addition. . However, when metallic silver colloid was used, no increase in cyan maximum image density was observed at pH 12.0, and it was equivalent to that without additives. Also low pH and high pH
Also, when metallic silver colloid was added to the second layer, the minimum image density was increased compared to that without additive, but the metal (metal sulfide) colloid of the present invention did not increase the minimum image density. .

Example 2 A full ffi layer color photographic paper was prepared in the same manner as in Example 1, except that the compounds and/or their added amounts were changed as shown in Table 4 below.

Table 4 (a-2) 1:1 mixture of cyan coupler (mole ratio) (f-2) magenta coupler (g-2) color image stabilizer (h-2) 2:1 mixture of solvent (weight ratio) (n-2) Yellow coupler nucleating agent (N-1-5) at 1.0% per mole of Ag. 5XIO
5.6×10 −′ mole and nucleation accelerator (A-13) were used per mole of Ag.

A positive color image was directly obtained by processing in the same manner as in Example 1, except that the amount of sodium bromide in the color developing solution was changed to 0.60 g/l, and the cyan grains were observed.

Adding palladium sulfide to the second layer clearly improved the graininess of the cyan image. Similar results were obtained using colloids of metallic palladium, metallic gold, metallic platinum, silver sulfide, gold sulfide, and nickel sulfide.

Example 3 Instead of adding the metal colloid of the present invention to the second layer,
A color photographic paper was produced in the same manner as in Example 2, except that it was added to the layer. Metal colloids used were metal palladium, metal gold, metal platinum, palladium sulfide, gold sulfide, nickel sulfide, and silver sulfide. The processing step A of Example 1 was performed, and the cyan color image density was measured. The same results as in Example 1 were obtained.

Example 4 The metal colloid used in Example 3 was added to the third layer instead of the first layer, resulting in a magenta colored image. Example 3 was repeated, except that the agricultural yield was measured, and similar results were obtained.

(Effects of the Invention) By using the internal latent image type direct positive image light-sensitive material of the present invention which is not pre-fogged, a high maximum image density can be obtained without increasing the minimum image density, and furthermore, very excellent graininess can be obtained. It is possible to obtain direct positive images with

These high maximum image densities and excellent graininess can be fully achieved even when processed with highly stable low p)l developers.

Representative patent attorney (8107) Kiyotaka Sasaki (3 idiots)

Claims (1)

[Claims] In a direct positive photographic light-sensitive material comprising at least one coated internal latent image type silver halide emulsion layer that is not pre-fogged, metal colloids (however colloidal silver Direct positive photographic light-sensitive material characterized by containing (excluding)