JPH03293346A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress the lowering of the max. image density of a sensitive material during storage and to lower the min. image density by chemically sensitizing the core particles of internal latent image type silver halide particles in the presence of a prescribed amt. of a Pd compd. CONSTITUTION:The core particles of internal latent image type silver halide particles having core/shell structure used for a direct positive photographic sensitive material are chemically sensitized in the presence of a Pd compd. (e.g., (NH4)2PdCl6) added by >=10<-4> mol per 1 mol silver halide preferably in combination with a compd. represented by formula I (where M1 is H or a group protecting a mercapto group and Z is a group of atoms required to form a 5- or 6-membered hetero ring). A compd. represented by formula II may be used as the compd. represented by the formula I. Thiocyanic acid may further be added.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a direct positive photographic light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains which have not been previously fogged.

In particular, it relates to direct positive photographic materials with high stability over time.

(Prior Art) Several chemical sensitization methods using palladium compounds have been known so far.

U.S. Pat. No. 2,448,060 discloses that sensitivity can be increased by adding a palladium compound and ascorbic acid to the emulsion after sulfur sensitization and before coating. U.S. Pat. No. 2,598,079 discloses that adding a palladium compound to the emulsion after gold/sulfur sensitization and before coating increases sensitivity, particularly at low light. l, d6. Brande
re (el des blancpres), P, Paele
ns (P Farens), Photography
ic 5science and engineering
G (Photographic Science and Engineering), I, 63 (1981) reports on the mechanism of action of palladium salts on gold-sensitized silver halide suspensions. J, L Mitchell
(JW Mitchell), Photogr
aphic 5science Engineering
(Photographic Science and Engineering), LL, 1 (1979) reports on the effects of palladium salts on silver halide deposited films.

In addition, regarding reduction sensitization method and palladium compound sensitization,
There are patent applications No. 63-283929 and No. 63-305825.

However, these relate to negative photographic materials.

(Problems to be Solved by the Invention) In direct positive light-sensitive materials, unexposed areas during image exposure are covered during fogging processing to provide maximum image density.In order to obtain a sufficiently high density during fogging processing, It is sufficient to have strong surface chemical sensitizing nuclei on the surface, but in that case, the exposed areas are also covered, resulting in a high minimum image density, which is undesirable. The chemical sensitizing nuclei deteriorate and the maximum image density decreases.

For this reason, there has been a desire for a direct positive photosensitive material that does not increase the minimum image density and does not reduce the maximum image density during storage of the photosensitive material.

(Means for solving the problem) Palladium compound silver halide 1 mol particles have been known to have a chemical sensitizing effect, but unexpectedly they have a stabilizing effect directly in positive photographic light-sensitive materials. This discovery led to the present invention.

That is, the present invention is as follows.

(1) having at least one photographic emulsion layer containing internal latent image type silver halide grains that are not prefogged;
In the direct positive photographic light-sensitive material, the internal latent image type silver halide grains have a core/shell structure, and the core grains are chemically sensitized in the presence of 10 −4 mol or more of a palladium compound per 1 mol of silver halide. A direct positive photographic material characterized by being

(2) The direct positive photographic light-sensitive material according to (1) above, wherein the core grains of the internal latent image type silver halide grains are chemically sensitized in the presence of general formula (1). .

General formula (1) In the formula, Ml represents a hydrogen atom, a cation or a protecting group for a mercapto group that is cleaved with an alkali, and Z represents an atomic group required to form a 5- to 6-membered heterocycle, The two heterocycles may have a substituent or be fused.

Here, palladium compound refers to palladium divalent salt or
It means salt of high value. Preferably the palladium compound is Rz
It is expressed as Pdχ, or R, Pdχ4.

Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group, and X represents a halogen atom and represents a chlorine, bromine or iodine atom, specifically KtPdCl
a, (NHa)zPdcj! 6. NazPd
Cf4 or (NH4) rich PdCl a is preferred,
PdC1t, PdCj! z・28zO, Pd (NHz)
acj! □, (NHs) tPdc 1. z, Pd
1i, Pd(OH)z, Pd(SO4),
Pd(NOs)z, NazPd(Not)a or (N
Although water-soluble palladium compounds are preferably used, most preferably these palladium compounds are used in combination with thiocyanate ions in an amount of 5 times the mole or more of the palladium compound for chemical sensitization. be done.

Next, the compound represented by the general formula (1) will be explained in more detail.

In the formula, M represents a hydrogen atom, a cation, or a protecting group for a mercapto group that is cleaved with an alkali, and Z represents an atomic group required to form a 5- to 6-membered heterocycle. M may have a substituent or be fused. To explain in more detail, M is a hydrogen atom,
Cations (e.g. sodium ions, potassium ions,
(e.g. ammonium ion) or a protective layer of mercapto group that is cleaved with alkali (e.g. -COR', -coon')
-CEtCHzCOR", etc., where R" represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, etc.).

Z represents an atomic group necessary to form a 5- or 6-membered heterocycle; the second heterocycle contains a sulfur atom, a selenium atom, a nitrogen atom, an oxygen atom, etc. as a heteroatom. , may be fused, and may have a substituent on the heterocycle or the fused ring.

Examples of Z include tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetraazaindene, triazaindene, pentaazaindane, benztriazole, benzimidazole, benzoxazole, benz These include thiazole, benzselenazole, and naphthimidazole. Substituents for these rings include alkyl groups (e.g. methyl, ethyl, n-hexyl, hydroxyethyl, carboxyethyl, etc.), alkenyl groups (e.g. allyl), aralkyl groups (e.g. benzyl group, phenethyl group), aryl group (e.g. phenyl group, naphthyl group, P-acetamidophenyl group, p-carboxyphenyl group, m-hydroxyphenyl group, p-sulfamoylphenyl group, p-acetylphenyl group, O-methoxyphenyl group, 2.4-diethylaminophenyl group, 2.4-dichlorophenyl group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (e.g. phenylthio group,
Naphthylthio group, etc.), aralkylthyl group (e.g., benzylthio group, etc.), mercapto group, etc. On the condensed ring, in addition to the above substituents, nitro group, amino group, A halogen atom, carboxyl group, sulfo group, etc. may be substituted.

Preferred specific examples of the compounds represented by formula (1) are shown below, but the invention is not limited thereto.

(Summer -1) (1-3) (1-5) S Riku Ni.

(1-2) (1-4) (1-6) (r-7) (1-9) (1-11) (1 13) (1-8) (1-10) (■ 12) (1 -14) (I -16) (1-18) (1-20) tl (1-15) (1-17) ■! (1-19) (I-21) (I 24) H (1-26) R (I-25) (1-27) (1-28) The compound represented by the general formula (1) of the present invention has a core It is preferably added before particle formation, during core particle formation, before chemical sensitization of core particles, or during sensitization.

For boat fishing, the amount used is in the range of 10-' to 10" mole, preferably 10-" to 10-2 mole, per mole of the internal latent image type halogenated il of the present invention.

The compounds represented by the general formula (1) of the present invention may be used alone or in combination of two or more.

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. But, more specifically,
A certain amount (0.5 to 3
g/nf) and exposed to light for a fixed time of 0.01 to 10 seconds, as shown below in developer A (internal developer).
The maximum density measured by a normal photographic density measurement method when developed at 18°C for 5 minutes was determined by using the following developer B for a silver halide emulsion coated in the same amount and exposed in the same manner as above.
Preferred are those that have 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 developer.

Kichi Plate 11 8 Metol 2g Sodium Sulfite (Anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKI
Add 5g of water
11 Kisara-ri 1 Okadan Metol 2.58L-Ascorbic acid 10gNaBOt ・4
Ht 0 35gKBr
Add 1g water
Specific examples of 11 internal type emulsions include:
The conversion silver halide emulsion described in U.S. Pat. No. 2,592,250, U.S. Pat.
761,276 calyx, 3,850,637, 3,9
No. 23,513, No. 4,035,185, No. 4,39
No. 5,478, No. 4,504,570, Japanese Unexamined Patent Publication No. 1973-
No. 156614, No. 55-127549, No. 53-6
No. 0222, No. 56-22681, No. 59-2085
No. 40, No. 60-107641, No. 61-3137, No. 62-215272, Research Disclosure Magazine No. 23510 (published in November 1983) P2S
Mention may be made of core/shell type silver halide emulsions described in the patent disclosed in No. 5.

The internal latent image type silver halide grains of the present invention may be a convergence bond type emulsion or a core/shell type emulsion, but the photographic sensitivity,
It is preferable to have a core/shell laminated structure in terms of easy control of gradation, etc. The core and shell preferably contain silver bromide and 10 mol% or less, preferably 3 mol% or less of silver iodide. It consists of silver iodobromide, silver chlorobromide, silver chloride or silver chloroiodobromide, and the core may be a so-called converted type or a normal grain, and the halogen composition of the core and shell are the same. As a silver halide emulsion having a core/shell type structure, which may have a different structure, e.g.
Emulsions described in US Pat. No. 5-127549, US Pat. No. 4,395,478, and German Patent No. 2.332.802 C2 can be used as appropriate.

The silver halide grains of the present invention preferably contain the following metal ions: manganese, copper, zinc, cadmium, lead, bismuth, indium, thallium, zirconium, lanthanum, chromium, rhenium, mercury, or metal ions listed in the periodic table. The amount of group metal is from 1o-9 per mole of silver halide
10-'' mol is preferred, and 10-'' to 10-' mol is more preferred.

Among the metals mentioned above, particular preference is given to using lead, iridium, rhodium, rhenium, iron and bismuth.

Furthermore, lead, iridium and rhodium are particularly preferred.

There is no particular restriction as to where the metal is incorporated in the internal latent image type emulsion that is not prefogged for use in the present invention.

These metals can be incorporated into the particles by allowing the metal ions to coexist in the form of an aqueous solution or an organic solvent solution when silver halide particles are formed by mixing a silver ion solution and an aqueous halogen solution. Alternatively, the metal ions may be added in the form of an aqueous or organic solvent solution after the grains are formed and then further coated with silver halide.

U.S. Patent No. 3761 describes the method for incorporating these metals.
No. 276, U.S. Patent No. 4,395,478 and JP-A-59
It is also described in No.-216136.

The average grain size of 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 ridge length is taken as the grain size, and the projected area is calculated as the average): 1. It is preferably 5μ or less and 0.1μ or more, and particularly preferably 1.2μ or less and 0.2μ or more.0 Particle size distribution may be narrow or wide, but it is important to improve graininess and sharpness. Therefore, particles in which 90% or more, especially 95% or more of all particles fall within ±40% (more preferably within ±30%, most preferably within ±20%) of the average particle size in terms of particle number or weight. It is preferable to use a so-called "monodisperse" silver halide emulsion with a narrow size distribution in the present invention, and in order to satisfy the target gradation of the light-sensitive material, emulsions having substantially the same color sensitivity are preferably used. In a layer, two or more types of monodisperse silver halide emulsions with different grain sizes or multiple grains of the same size but with different sensitivities can be mixed in the same layer or coated in separate layers in a layered manner, and two or more types of polydisperse halides can be added. It is also possible to use a combination of a silver oxide emulsion or a monodisperse emulsion and a polydisperse emulsion in a mixed or layered manner.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. As a chemical sensitization method for core particles, Japanese Patent Application No. 1-1748
The method described in No. 8, No. 1-17487 can be used. In the presence of a mercapto compound as described in JP-A-1-197742, thiosulfinic acid, sulfinic acid, Detailed specific examples in which sulfites may be added can be found, for example, in Research Disclosure Magazine N[L17643-1[[(197
It is in the patent described on page 23 (published in December 2008).

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, for example, Research Disclosure magazine Nα17643-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 NcL17643-
VI (published December 1978) and E, J, Bi
Written by rr'5tabiliaution of Photo
graphic 5ilver Hailde Emu
lsion” (Focal Press), published in 1974.

Various color couplers can be used in combination in the present invention. 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 [
Research Disclosure” magazine Nα17643 (
(Published December 1978) Page 25, Section ■-〇, NCL1
8717 (published in November 1979) and JP-A-62
-215272 and the patents cited therein.

Among these, the 5-pyrazolone-based magenta couplers preferably used in the present invention include 5-pyrazolone-based couplers in which the 3-position is substituted with an arylamino group or an acylamino group (especially, a sulfur atom-eliminating two-equivalent coupler). be.

More preferred are pyrazoloazole couplers, and among them are pyrazolo(5,1-c] [1,2,4) triazoles described in U.S. Pat. No. 3,725,067. imidazoEl described in U.S. Pat. No. 4,500,630 for its low yellow side absorption and light fastness.

2-b] Pyrazoles are even more preferred, pyrazolo[1,5-b) as described in U.S. Pat. No. 4,540.654.
[l,2,4)) Riazole is 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 US Pat. ,5
-Diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness.

Colored couplers to correct unnecessary absorption in the short wavelength range of the dyes produced, couplers in which the coloring dye has appropriate diffusivity, non-coloring couplers, DIR couplers that release a development inhibitor upon coupling reaction, and Polymerized couplers can also be used.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the patents described in the aforementioned Research Disclosure magazine Nα17643, sections ① to F, and JP-A-57-151944 and JP-A-57-15423.
4, No. 60-184248, U.S. Patent No. 4,248.96
2 and JP-A-63-146035
Preferably, those listed in No.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140, British Patent No. 2,131,188, and JP-A-59-1576.
38, 59-170840 International Publication (WO) 8B
The one described in No. 101402 is preferred.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide;
Preferably from 0.01 to 0.01 for yellow couplers.
5 mol, for magenta couplers 0.03 mol to 0
．． 5 mol, and for cyan couplers 0.002 to 1
．． It is 0 mole.

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.

A color antifogging agent or a color mixing inhibitor can be used in the light-sensitive material of the present invention.

Representative examples of these are JP-A-62-215272 No. 185~
It is described on page 193.

Compounds that release photographically useful groups include JP-A-63-
No. 153540, No. 63-259555, Patent Application No. 1983
-212080, Japanese Patent Application No. 1-64715, 1-1
Examples include the compounds described in No. 30986.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
Examples include those described in No. 2-215272, pages 121 to 125.

The photosensitive material of the present invention contains dyes that prevent irradiation and tulsion (for example, Japanese Patent Application No. 63237985,
No. 63-240393 may also be used. In addition, a solid microcrystal dispersion method may be used as a method for dispersing dyes), ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air fog prevention agents, coating aids, hardeners, antistatic agents. It is possible to add a slip property improver, etc. Representative examples of these additives are published in Research Disclosure No. I 764.
3 ■ - ■ pages (published in December 1978), pages 25 - 27, and 18716 (published in November 1979), 647 -
It is described on page 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. It is also possible to use different combinations, such as mixing them.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation agent,
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 described in Research Disclosure Magazine k17643V section
Published in December 1978) on page 28, European Patent No. 0.102,253, and JP-A-61-9765.
It is coated on the support described in No. 5. Further, the coating method described in Research Disclosure Magazine N (117643, Section XV, pages 28-29) can be used.

The fogging treatment of the present invention is carried out by the following ``optical fogging method'' and/or ``chemical fogging method''. The entire surface exposure in the "light fogging method", that is, fogging exposure, is performed after imagewise exposure, after color development processing, or during color development processing. That is, the imagewise exposed photosensitive material is immersed in a color developer or a pre-bath of a color developer, or is taken out from these solutions and exposed before drying. is most preferred.

As a light source for fogging exposure, for example, JP-A-56-1
A light source with high color rendering properties (as close to white as possible) such as those described in No. 37350 and No. 58-70223 is preferable. The illuminance of the light is o, oi ~ 2000 mils 2000 lux 0.05 ~ 3 o lux, more preferably 0.05 ~ 5
Lux is suitable. For light-sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferable. 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. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

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 irradiation 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 01.1 seconds to 1 minute, more preferably 1 second to
It is 40 seconds.

In the present invention, the nucleating agent used when carrying out 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 incorporated into the 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.

When incorporated into a light-sensitive material, it is preferably added to the internal temperature silver halide emulsion layer, 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. For example, it may be added to an intermediate layer, undercoat layer or back layer.

When the nucleating agent is added to the processing solution, it may be contained in the developer solution or a low pH prebath 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, N (L2253
4 (January 1983) pp. 50-54, same magazine, Nα151
62 (November 1976) pp. 76-77, same magazine, N(
Examples include quaternary heterocyclic compounds and hydrazine compounds described in L23510 (November 1983), pages 346-352.

As quaternary heterocyclic nucleating agents, for example, U.S. Patent No. 3.61
No. 5,615, No. 3,719,494, No. 3-. 73
No. 4,738, No. 3,759.901, No. 3,854
, No. 956, No. 4.094.683, No. 4,306.
No. 016, British Patent No. 1゜283.835, Special Publication No. 1973
-38,164, 52-19,452, 52-
No. 47,326, JP-A-52-69,613, No. 52
-3゜426, 55-138,742, 60-
11.837, and the aforementioned “Research Disclosure” magazine Nα22534; the same magazine Nα23,213 (1
(Published August 1983, pp. 267-270).

Furthermore, as a highly active quaternary salt compound, JP-A-631210
No. 42, No. 63-301942, JP-A-1-1911
No. 32, Patent Application No. 63-255360, No. 63-230
Those described in No. 589 and No. 63-255361 can be used.

In particular, a quaternary heterocyclic nucleating agent represented by the following general formula (C) is preferred.

General formula (C) , , =-Z. (In the formula, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, and 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.

R1 and R2 may be substituted with a substituent.

Further, R2 may further be combined with a heterocycle completed by Z to form a ring. However, at least one of the groups represented by R', R'' 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, and dihydro Forms a pyridinium skeleton.

Further, one or more of the substituents of R1, R1 and Z may have an adsorption promoting group to silver halide. Y is a counter ion for charge balance, and n is O or 1.
It is. ) Examples of heterocycles completed with Z include quinolinium,
Mention may be made of benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium 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 groups, hydroxy groups,
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,
Examples include carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate group, hydrazine group, hydrazone group, and imino group.

The substituent of Z may be provided via a suitable linking group.

The aliphatic groups of R1 and R2 preferably have 1-18 carbon atoms.
unsubstituted alkyl groups and alkyl moieties have 1 carbon number
~18 substituted alkyl groups.

The aromatic group represented by R2 preferably has 6 to 20 carbon atoms.
For example, phenyl group, naphthyl group, etc.

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

The thioamide group is preferably an acyclic thioamide group (
For example, thiourethane group, thioureido group, etc.).

Examples of mercapto groups include especially peterocyclic mercapto groups (e.g. 5-mercaptotetrazole, 3-mercapto-1
,2,4-) lyazole, 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 one that produces iminosilver, such as benzotriazole and aminothiatriazole.

These adsorption-promoting groups to silver halide may be via a linking group. Examples of the linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and 0--HN=02NH1HCNHNH8O2NH-.

R2 is preferably an aliphatic group, most preferably a methyl group, a substituted methyl group, or a ring formed by bonding with a heterocycle completed by Z.

It is preferable that at least one of the groups or substituents on the ring represented by R1, R2 and Z is an alkynyl group or an acyl group, or that R1 and R1 are linked to form a dihydropyridinium skeleton, and Preferably it 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, perchlorate ion,
Examples include trifluoromethanesulfonate ion, thiocyanate ion, boron tetrafluoride ion, and phosphorus hexafluoride ion.

Specific examples of the compound represented by the general formula [C] are listed below, but the invention is not limited thereto.

(C-1) 5-ethoxy-2-methyl-1-propargylquinolinium bromide (C-2) 2,4-dimethyl-1-propargylquinolinium bromide (C-3) 3,4-dimethyl-dihydropyride C2
,1-b) Benzothiazolium bromide ((,-4) 6-nitoxythiocarbonylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfo(C-5) (C-6) 7) (C-8) (C-9) (C-10) Nato 6-(5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate 6-(5-mercaptotetrazole-1- yl)-2-methyl-1-propargylquinolinium iosito6-nitoxythiocarponylamino-2- (2-methyl-1-propenyl)l-propargylquinolinium trifluoromethanesulfonate lO-propargyl-1,2 ,3゜4-tetrahydroacridinium trifluoromethanesulfonate 7-nitoxythiocarbonylamino-10-propargyl-1,2,3゜4-tetrahydroacridinium trifluoromethanesulfonate? -(3-(5-mercaptotetra 11) 12) (C-13) (C-14) sol-1-yl)benzamide] l-lopropargyl-1,2,3,4 tetrahydroacridinium benchlorate 7-( 5-Mercaptotetrazol-1-yl)-9-methyl-IO-propargyl-1,2,3,4-tetrahydroacridinium Promide 7-nitoxythiocarponylamino-10-propalkyl-1,2-dihydroacridinium Trifluoromethanesulfonate IO-propargyl-7-(3- (+, 2. 3. 4-thiatriazol-5-ylamino)benzamide]- 1,2,,3,4-tetrahydroacridinium perchlorate 7-(3- cyclohexylmethoxythiocarbonylaminobenzamide) 10-propargyl-], 2.3゜4-tetrahydroacridinium trifluoromethanesulfonate 15) 7-(3-methoxythiocarbonylaminobenzamide)-IO-propargyl-1,2 ,3,4-tetrahydroacridinium trifluoromethanesulfonate 7-[3-(3-ethoxythiocarbonylaminophenyl)ureido] 10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate 7 -(3-ethoxythiocarbonylaminobenzenesulfonamide)-1 0-propargyl-1,2,3,4- tetrahydroacridinium trifluoromethanesulfonate 7- [3-f3- [3-(5-mercaptotetrazole- 1-yl)phenylthureido)benzamide]-1 16) (C-17) (C-18) (C 0-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate 19) 7 -(3-(5-mercapto-1°3.4
-thiadiazol-1-ylamino)benzamide 10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate 7- (3-(3-butylthioureido)benzamide]-IO-propargyl-1, 2,3,4-tetrahydroacridinium trifluoromethanesulfonate 6-(3-ethoxythiocarbonylaminobenzamide)-1-propargyl-2,3-)rimethylenequinolinium trifluoromethanesulfonate As a dorazine compound , for example, the above glue (C-21
) (C-20) Search Disclosure Magazine Nα15.162 (19
Published in November 1976, pp. 76-77) and the same magazine N (L23
, 510 (published 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, for example, US Pat. No. 4,030,925;
Same No. 4゜080.207, Same No. 4,031,127, Same No. 3,718,470, Same No. 4. 269. 9
No. 29, No. 4,276.364, No. 4,278.
No. 748, No. 4,385,108, No. 4,459
, 347, British Patent No. 2,011゜391B, Japanese Patent Application Publication No. 54-74,729, Japanese Patent Application Publication No. 55-163,533,
No. 55-74,536 and No. 60-179,734
No. 63-231441.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86,829, U.S. Pat. No. 4,560.638,
4,478,928, and 2,563,7
Examples include the compounds described in No. 85 and No. 2,588°982.

As a highly active hydrazine compound, JP-A-63-23
No. 1441, No. 234244, No. 234245, No. 234246, No. 204256, Patent Application No. 1983-16
Examples include compounds described in No. 7773 and No. 63-200189.

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-1yl)benzamido]phenyl)hydrazine (B-3) 1-formyl-2-[4-(3[3-(
As the nucleating agent for 5-mercaptotetrazol-1-yl)phenylthureido 1phenyl]hydrazine, quaternary heterocyclic compounds are preferable since they greatly exhibit the effects of the present invention. A quaternary heterocyclic compound and a hydrazine compound may be used in combination.

When the nucleating agent is added to the processing solution, it may be contained in the developer solution or a low pH prebath as described in JP-A-58-178350.

When a nucleating agent is added to the treatment liquid, the amount used is preferably 10-1 to 10-3 mol, more preferably 10-7 to 10-' mol per 11 mol.

In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is preferably contained in the silver halide emulsion layer.

The amount added varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent, and the development conditions, so it can vary over a wide range, but it is about 1x per mole of silver in the silver halide emulsion. A range of 10 moles to about 1X10-' moles is useful in practice, with a preferred range of about 1X10-' to about 1X10-' moles per mole of silver.

When using a nucleating agent, it is preferable to use a nucleating promoter to promote the action of the nucleating agent.

A nucleation accelerator is a substance that does not substantially function as a nucleating agent, but is necessary to promote the action of the nucleating agent to increase the maximum density of a direct positive image and/or to obtain a constant direct positive image density. A substance that works to speed up the development time.

Such nucleation accelerators include tetrazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group;
Triazaindenes, pentazaindenes, and the compounds described in JP-A-63-106656, pages 5 to 16 can be mentioned. Also, JP-A-63-226652
No. 63-106656 and No. 63-8740.

Specific examples of nucleation accelerators are given below.

-1 -2 -6- 7 (CH2)2 N(C3H7 (n))2 (CH.).

The N(CH.)2 nucleation accelerator can be contained in the light-sensitive material or in the processing solution. or a protective layer). Particularly preferred is a layer in or adjacent to a silver halide emulsion.

The amount of nucleation accelerator added is lO-6 per mole of silver halide.
~1O-2 mol is preferred, more preferably 10-5~
IO-2 moles.

When the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, it is preferably added in an amount of 10 to 10@-3 mol, more preferably 10 to 10@-1 mol per 11 mol.

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

Known photographic additives that can be used in the present invention include the aforementioned Research Disclosure Nα17643 (January 1978).
(February) and Nα18716 (It month, 1979), and the relevant parts are summarized in the table below.

Additive type RD17643 1 Chemical sensitizer 2 Sensitivity enhancer 23 pages RD18716 648 pages Right column Same as above 4 Brighteners 24 pages Dye image stabilizer Hardener Binder Plasticizer, lubricant 25 pages 26 pages 26 pages 27 pages 651 pages Left column Same as above, page 650 Right column 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 glass, ceramic, metal, etc., which are commonly used in photographic light-sensitive materials. applied to a rigid support. Useful flexible supports include films made of semi-synthetic or synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, or a layer of a lighter or α- Paper coated with or laminated with an olefin polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods can be used, such as a dip coating method, a roller coating method, a curtain coating method, and an extrusion coating method.

In addition, as necessary, US Patent Nos. 2,681,294, 2,761,791, 3,526,528,
Multiple layers may be applied simultaneously by methods such as those described in No. 08947.

The internal temperature type emulsion-containing light-sensitive material of the present invention can directly produce a positive image by developing with 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.

The color developer used for surface development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl N- [β−
(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl -N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl N-β-
Ethoxyethylaniline D-114-amino-3-methyl-N=ethyl N-β-
Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred are exemplary compounds D-2, D-4, D-5 and D-6.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per developer IA'.
, more preferably at a concentration of about 0.5 g to 10 g.

In addition, the color developer requires sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and the carbonyl compound sulfite adduct of the present invention as a preservative. It can be added depending on the situation.

The preferable addition amount is 0.5 g to 142 color developer.
10g, more preferably 1g to 5g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines described in No. 61-170756, hydrazines, No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-18
It is preferable to add various saccharides described in No. 0616. In addition, in combination with the above compounds, patent application No. 61-1471323
No. 61-166674, No. 61-165621, No. 61-164515, No. 61-170789,
and monoamines described in No. 61-168159, etc.
Diamines described in No. 61-173595, No. 61-164515, No. 61-186560, etc., No. 61-186560, etc.
165621 and polyamines described in 61-169789, polyamines described in 61-188619, nitroxy radicals described in 61-197760, 61-186561, and 61-197419
It is preferable to use the alcohols described in No. 61-198987, the oximes described in No. 61-198987, and the tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary. Particularly preferred is the addition of aromatic polyhydroxy compounds, especially those of the following general formula (A)
It is preferable to add a compound represented by:

(In the formula, L represents an optionally substituted alkylene group, and A
1 is a hydrogen atom, a carboxy group, a sulfo group, a phosphono group,
phosphinic acid residue, hydroxy group, amino group which may be substituted with alkyl, ammonio group which may be substituted with alkyl,
Carbamoyl group which may be substituted with alkyl: represents a sulfamoyl group which may be substituted with alkyl, and RA represents a hydrogen atom or an alkyl group which may be substituted. ) General formula (A) will be explained in detail below.

In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms and which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene,
Propylene is mentioned as a preferred example. Examples of substituents include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, and alkyl (preferably 1 to 5 carbon atoms) optionally substituted ammonio groups; , hydroxy group is mentioned as a preferable example. A1 is a hydrogen atom, a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an optionally substituted amino group with alkyl (preferably 1 to 5 carbon atoms), and an alkyl group (preferably 1 to 5 carbon atoms). An optionally substituted ammonio group, an alkyl (preferably 1 to 5 carbon atoms) optionally substituted carbamoyl group, an alkyl (
Preferably, it represents an optionally substituted sulfamoyl group (having 1 to 5 carbon atoms), and preferable examples thereof include an ethyl group, a carboxy group, a sulfo group, a hydroxy group, a phosphono group, and a carbamoyl group that may be substituted with an alkyl group. -L-A,
Preferred examples include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group. Particularly preferred examples include a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. RA represents a hydrogen atom or a linear or branched optionally substituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Examples of substituents include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, and an alkyl group. Represents an optionally substituted sulfamoyl group. There may be two or more substituents. RA as hydrogen atom, ethyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group,
Preferred examples include a phosphonoethyl group and a hydroxyethyl group, and particularly preferred examples include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. L and RA may be linked to form a ring.

Specific examples of the compounds of the present invention are listed below, but the present invention is not limited thereto.

(A-1) CH.

(A-5) (A-6) (A-7) 2H5 C,H.

C4H- CH3 CH.

CH (A 9) (A-1 0) CH.

(A 1 3) (A-14) (A-1 5) (A 6) (A-1 7) (A-18) NH (A-19) HO-NH-CH,C02H (A-20) HO NH CH, CH, CO, H (A-21) HO-NH-CH, CH, 5OIH The content of these compounds in the color developer is preferably 085 g to 50 g per 147 color developer, more preferably , 1.0g to 30g, particularly preferably 1
．． It is 5g to 20g.

These compounds may be present in the photosensitive material. In addition, color developing agents that are present in each solution (such as brought in from the color developer), not only in color developers, but also in bleach and bleach-fix solutions, washing with water, or washing substitute stabilizers, It can act on the oxidant to give good performance.

The compound represented by the general formula (A) can be obtained by converting commercially available hydroxylamines into alkylation reactions (nucleophilic substitution reactions,
addition reaction, Mannich reaction). West German Patent No. 1159634 "Inorganic force, chemical force, acta J"
a Chimica Acta), 93, (1984
) 101-108, etc., and the specific method is described below.

Synthesis Example Synthesis of Exemplified Compound (A-7) 11.5 g of sodium hydroxide and 96 g of sodium chloroethanesulfonate were added to 200 kg of an aqueous solution of 20 g of hydroxylamine hydrochloride, and the mixture was kept at 60°C and 40 Trl of an aqueous solution of 23 g of sodium hydroxide was added for 1 hour. I added it slowly. Further, the temperature was kept at 60°C for 3 hours, the reaction solution was concentrated under reduced pressure, 200°C of agricultural hydrochloric acid was added, and the mixture was heated to 50°C. Insoluble materials were filtered, and 500 g of methanol was added to the filtrate to obtain the desired compound (exemplified compound (A-7)) as crystals of monosodium salt.

41g (yield 53%) The color developer used in the present invention preferably has a pH of 9.
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate,
Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate,
Sodium 0-hydroxybenzoate (sodium satylylate), potassium 0-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalycylate), potassium 5-sulfo-2-hydroxybenzoate (5- potassium sulfosalicylate) and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/j
It is preferably 7 or more, especially 0.1 mol/I! ~
Particularly preferred is 0.4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-t-rimethylenephosphonic acid, ethylenediamine-N,N.

N', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, ■, 2-diaminopropanetetraacetic acid, droxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1 ,2,4-
Tricarboxylic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, and two or more of these chelating agents may be used in combination as necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means that the developer contains 2 or less, preferably not at all, per 11 parts of the developer.

Other development accelerators include Japanese Patent Publications No. 37-15088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho. 44- 30074, JP-A-56-156826 and JP-A-52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2,
No. 494,903, No. 3,128゜182, No. 4,2
No. 30,796, No. 3,253.919, Special Publication No. 1977
-11431, U.S. Patent No. 2,482,546, 2. 596. 926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, and U.S. Patent No. 3. 128.
No. 183, Special Publication No. 41-11431, No. 42-238
Polyalkylene oxides such as those disclosed in No. 83 and US Pat. No. 3,532.501, 1-phenyl-3-pyrazolidones, imidazoles, etc. may be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Thiazolylmethyl-
Representative examples include nitrogen-containing heterocyclic compounds such as benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent brightener. As the fluorescent brightener, 4°4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/II, preferably 0.1 g to 4 g.
/II.

Further, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although it is preferable that the replenishment amount be small, it is 100 to 1,507 d, preferably 100 to 800 d per 1-photosensitive material. More preferably 100WI
~4001d.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing steps for the silver halide color light-sensitive material of the present invention will be explained.

After exposure, the color photosensitive material of the present invention is subjected to a color development process, a desilvering process, and a water washing process.

As the desilvering step, instead of the bleaching step using a bleaching solution and the processing step using a fixing solution, a bleach-fixing step may be performed using a bleach-fixing solution, or a bleaching step, a fixing step, The bleach-fixing treatment steps may be combined arbitrarily.

Examples of the desilvering step of the present invention include, but are not limited to, the following steps.

■ Bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-washing constant-fixing ■ Bleach-constant fixing ■ Bleach-fixing ■ Bleach-fixing - bleach-fixing The color photosensitive material of the present invention is subjected to bleaching treatment or bleaching treatment after color development. Bleach-fixing processing is performed, but these processings may be performed immediately after color development without going through other processing steps, or
In order to prevent unnecessary post-development and air fog, and to reduce the carry-over of color developer into the desilvering process, it is also impregnated into sensitive material components such as sensitizing dyes and dyes contained in photographic light-sensitive materials and in photographic light-sensitive materials. In order to wash out the color developing agent and render it harmless, the color developing agent may be subjected to processing steps such as stopping, adjusting, and washing with water, and then subjected to a bleaching treatment or a bleach-fixing treatment.

A stabilization treatment step may be performed after the water washing step, if necessary, or a stabilization treatment step may be performed instead of the water washing step. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, etc. may be performed. A washing step and a rinsing step may be optionally provided between these steps.

In addition, as a replenishment method for the desilvering step, it is common to replenish each processing bath with the corresponding replenisher and discard the overflow liquid as waste. A forward flow replenishment system or a countercurrent replenishment system in which the overflow liquid of the subsequent bath is led to the preceding bath can also be implemented. For example, the wash water or overflow liquid of the stabilizing bath can be conducted to a fixing bath or a bleach-fixing bath.

In the present invention, the bleach-fix solution or the fix solution contains thiosulfate and carbonyl bisulfite adduct.

It may be contained in both the bleach-fix solution and the fix solution.

Thiosulfate is used as a fixing agent.

Examples of thiosulfates that can be used in the present invention include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate, and magnesium thiosulfate. Ammonium thiosulfate is preferred. The amount of thiosulfuric acid added is O.1 mol/l-3 mol/l, preferably 0.3 mol/p to 2 mol/Il.

In addition to the above-mentioned thiosulfate, thiocyanic acid compounds (particularly ammonium salts), thiourea, thioether, urea, etc. can be used as a fixing agent or a fixing accelerator for the bleach-fixing solution and/or fixing solution of the present invention. The concentration of these auxiliary fixing agents or fixing accelerators, including the thiosulfate, is 1.11 to 3.0 mol/l, preferably 1.4 to 2.8 mol/l.

Next, the carbonyl compound bisulfite adduct of the present invention will be explained.

The carbonyl compound is preferably an aliphatic carbonyl compound having 8 or less carbon atoms and containing 1 to 3 carbonyl groups in the aliphatic carbonyl compound.

Specifically, the following compounds or salts thereof are preferable as the carbonyl bisulfite adduct of the present invention.

(1) Acetaldehyde bisulfite adduct (2) Propionaldehyde bisulfite adduct (3) n-butyraldehyde bisulfite adduct (4) 1so-butyraldehyde bisulfite adduct (5) Glutaraldehyde bisulfite adduct ( 6) Succinic aldehyde bis-bisulfite adduct (7) Malonic aldehyde bis-bisulfite adduct (8)
Maleic aldehyde bisulfite adduct (9) Beta-methylglutaraldehyde bisulfite adduct 0ω Glycolaldehyde bisulfite adduct OD Glyoxylic acid bisulfite adduct (D) Pyruvaldehyde bisulfite adduct (131D-Glyceraldehyde bisulfite adduct Product (14) L-Glyceraldehyde bisulfite adduct (Is Formic acid bisulfite adduct (151 Chloroacetaldehyde bisulfite adduct (1?)
) Bromoacetaldehyde bisulfite adduct (glue) Acetone bisulfite adduct (19 Dihydroxyacetone bisulfite adduct (20 Hydroxyacetone bisulfite adduct (21) Pyruvate bisulfite adduct (22 N-acetylaminoacetic acid bisulfite adduct (233)
-Acetylpropionic acid bisulfite adduct (24) 4
- Acetylpropatur bisulfite adduct (25) 4
-Acetyl butyric acid bisulfite adduct (26) Methyl acetoacetate methyl bisulfite adduct (27) Ethyl acetoacetate bisulfite adduct (28) Methyl ethyl ketone bisulfite adduct (29) Acetylacetone bisulfite adduct (30) Ethyl acetoacetate bisulfite adduct Sulfite adductsThese compounds are
The carbonyl compound and the bisulfite or sulfite salt may be added separately to the bleach-fix solution or the fix solution, or may be added in the form of the above-mentioned bisulfite adduct.

When the carbonyl compound bisulfite adduct is added to the bleach-fixing solution or fixing solution of the present invention, the molar ratio of the carbonyl compound and bisulfite or sulfite is 30:1.
It can be used in a ratio of 1:30 to 1:30, preferably 5:1 to 1:10, particularly 1:1 to 1:5. Further, the amount of the carbonyl compound bisulfite adduct added to the bleach-fix solution/fixer of the present invention can be used in the range of 1×10-' mol to 10 mol/l per bleach-fix solution or fixer iz, and 1×10-s The ratio is preferably mol/1-5, particularly lXl0-2 mol/l-1 mol/1.

All of these carbonyl compounds are commercially available,
It can be easily obtained.

As the bleaching agent used in the bleach solution and/or the bleach-fix solution, ferric complex salts of aminopolycarboxylic acids, peroxides (eg, sodium persulfate), etc. can be used, but ferric complex salts of aminopolycarboxylic acids are preferred.

As the above aminopolycarboxylic acid, it is preferable to use a compound represented by the following general formula (III) in addition to ethylenediaminetetraacetic acid.

General formula (B) In the formula, is an oxygen atom, a sulfur atom, Alkyre R32,
R 11SRs+ each represents a hydrogen atom or an alkyl group, and R 3 1 and R +2 or R11 and R 1
2 may be connected to each other to form a cycloalkylene ring. k, II, m, and n each represent an integer of 0 to 4; a represents an integer of 1 to 3; however, the sum of R12, m, and n is 2 or more. However, if a is 1 and Rs+
, R12, R33, and R11 are each a hydrogen atom,
The sum of k, 1, m, and n is never 2.

General formula (B) will be explained in more detail.

In general formula (B), is an oxygen atom, a sulfur atom,
Alkylene groups having 6 or less carbon atoms are preferred, and in the case of alkylene groups, particularly methylene groups, ethylene groups, propylene groups,
Butylene groups are preferred. R8I, R12, R$1, R8
Regarding 4, a hydrogen atom and an alkyl group having 6 or less carbon atoms are preferable, and in the case of an alkyl group, a methyl group, an ethyl group, an n-propyl group, and a 1so-propyl group are particularly preferable.

Specific examples of the aminopolycarboxylic acid compound represented by general formula (B) are shown below, but the invention is not limited thereto.

B-1: 1.3-diaminopropanetetraacetic acid B-2 = glycol ether diamine tetraacetic acid B-3 = cyclohexanediaminetetraacetic acid B-4: 1,4-diaminobutanetetraacetic acid B-5: 1.2-propylene Diaminetetraacetic acid B-6: Thioglycol ether diaminetetraacetic acid B-7: 1.3-
Butylenediaminetetraacetic acid The amount of the bleaching agent of the present invention added is 0.05 mol to 1 mol, preferably 0.05 mol per 1 liter of bleaching solution or bleach-fixing solution. The amount is 1 mol to 0.5 mol. Further, the above-mentioned ferric aminopolycarboxylic acid complex salt and ferric ethylenediaminetetraacetic acid complex salt can be used in combination as a bleaching agent. In this case, the mixing ratio of both is 1:10 to 10:
1 is preferable, and the total concentration of both iron complex salts is 0.05 mol to 1 mol, preferably 0.1 to 1 mol, per treatment liquid 11.
It is 0.5 mole.

In addition to the above-mentioned aminopolycarboxylic acid iron(III) complex, an aminopolycarboxylic acid or a salt thereof can be added to the bleach solution and/or bleach-fix solution of the invention.

The amount added is preferably 0.0001 mol to 0.1 mol/l, more preferably 0.003 to 0.05 mol/l.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

Further, the bleach solution and/or bleach-fix solution containing the above-mentioned ferric complex salt may contain complex salts of metal ions other than iron, such as cobalt and copper.

Various bleach accelerators can be added to the bleach solution and/or bleach-fix solution of the present invention.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
, 812, British Patent No. 1 138.842, JP-A-53-95630, and Research Disclosure No. 17129 (July 1978 issue). Compounds, thiazolidine derivatives described in JP-A No. 50-140129, thiourea derivatives described in U.S. Pat. No. 3,706.561, iodides described in JP-A-58-16235, German patents Polyethylene oxides described in specification No. 2,748.430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferred is British Patent No. 1.138.
Mercapto compounds such as those described in '842 are preferred.

The amount of bleach accelerator added is 0.0 per 11 liquids with bleaching ability.
The amount is 1 g to 20 g, preferably 0.1 g to 10 g.

In addition to bleaching agents and the above-mentioned compounds, the bleaching solution and/or bleach-fixing solution constituting the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide or chlorides such as potassium chloride, sodium chloride, Rehalogenating agents such as ammonium chloride can be included. The concentration of the rehalogenating agent is 0.00% per 11 parts of the bleaching solution. The amount is 1 to 5 mol, preferably 0.5 to 3 mol. In addition, sodium nitrate,
One or more types of nitrates such as ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. with pH buffering ability Known additives that can be commonly used in bleaching solutions, such as inorganic acids, organic acids, and salts thereof, can be added.

The bleach-fix solution and/or fix solution of the present invention may contain sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, hydroxylamine, hydrazine, and the like. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as a preservative, Japanese Patent Application No. 60-28383
It is preferable to use the sulfinic acid compounds described in Specification No. 1.

Furthermore, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids.

Particularly effective is 1-hydroxyethylidene-1,1-diphosphonic acid. The amount of these additions is 0.01 to 0.
．． 3 mol/1. It is preferably 0.05 to 0.2 mol/l, and is particularly effective in fixing solutions.

The pH of the bleaching solution and/or bleach-fixing solution of the present invention is generally 9 to 1, preferably 7.5 to 1.5, most preferably 7.0 to 2.0.

For bleaching solutions, 5.0 to 2.0 is particularly preferred.

In a preferred pH range, there is little bleaching fog and excellent desilvering performance.

The pH of the fixer of the present invention is generally 9.0 to 5.0, particularly preferably 7.5 to 5.5.

The amount of replenishment of the bleaching solution and/or bleach-fixing solution of the present invention is 50 to 3000 - preferably 1001 d per 1 rd photosensitive material.
~1000-.

The amount of fixer replenishment is preferably from 300 d to 30,004 d per durability of the photosensitive material, more preferably 300 d.
It is 1000- from l.

However, the above-mentioned replenishment amount can be reduced to a smaller amount if, for example, a regeneration treatment is performed, such as oxidation regeneration of the processing solution and silver recovery treatment.

The shorter the total time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 10 minutes, more preferably 1 minute to 6 minutes. In addition, the processing temperature is 25℃ ~
The temperature is 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, U.S. Patent No. 4,758
, 858, a method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, a method of increasing the stirring effect using a rotating means of JP-A-62-183461, and a method of increasing the stirring effect by using a rotating means provided in the liquid. Examples include a method of moving the photosensitive material while bringing the wiper blade into contact with the emulsion surface to create turbulent flow on the emulsion surface to improve the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improvement means is more effective when a bleach accelerator is used, and can significantly increase the acceleration results and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258, No. 60-1912
No. 59, Re5earch DisclosureIt
em N (129118 (July 1988)), preferably has a photosensitive material conveying means described in U.S. Pat. No. 4,758,858.
As described in No. 91257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration in the performance of the processing liquid. The means described in the above RD are also preferable. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

These agitation strengthening means are effective in addition to the desilvering process, and are preferably applied to the water washing process and the developing process to shorten the processing time and reduce the amount of replenishment.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Bactericidal agents and antifungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E
, West.

“Water Quality Cr1teria”,
Phot, Sci, ancl Eng.

Vol.9. N(L 6, pages 344-359 (
Compounds described in 1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (eg, geltal aldehyde), etc. can be used. Formalin is undesirable in terms of pollution. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and Af, optical brighteners, chelating agents (for example, EDTA 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides,
A fungicide, a hardening agent, a surfactant, etc. can be used. As a fungicide, thiazolone compounds such as 5-chloro-2-methyl-isothiazolin-3-one and 1°2-pentwinthiazolin-3-one are effective.

Further, as the surfactant, a silicone compound represented by the following general formula is preferable because it has an effect of preventing water droplet unevenness and defoaming.

Here, aSb, d, and e are integers of 5 to 30, C is an integer of 2 to 5, or R is an alkyl group having 3 to 6 carbon atoms.

Further, it is preferable to add an alkanolamine to the stabilizing solution in order to prevent thiosulfate ions carried by the photosensitive material from flowing away. The use of alkanolamines is described in US Pat. No. 4,786,583.

Also, - For boat fishing, the stabilizing liquid contains formalin.
It is preferable not to use it in the present invention.

The pH of the stabilizer of the present invention is 3-8, preferably 5-7.

The temperature of the stabilizing liquid is preferably 5°C to 45°C, more preferably 10°C to 40°C.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. Two or more types of stabilizing solutions may be used in multiple stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The shorter the processing time of the water washing and stabilization steps, the more effective the present invention will be.From the viewpoint of rapid processing, the total processing time of the water washing and stabilization steps is preferably 10 to 50 seconds, and the effect is particularly remarkable when the processing time is 10 to 30 seconds.

Furthermore, the smaller the amount of replenishment in the water washing and stabilization steps, the greater the effect of the present invention, and the amount is preferably 50 to 400 per 1 d of light-sensitive material.
In particular, 50-200- is particularly preferred.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have an Mg concentration of 5/1 or less, water that has been sterilized with halogen, an ultraviolet sterilizing lamp, or the like.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

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

For example, color reversal film for slides or television, color reversal paper, instant color film, color hard copy for storing images from full-color copiers and CRTs, etc. can be applied. The present invention also applies to "Research Disclosure" magazine Nα17
123 (published in July 1978), etc., and which utilizes a mixture of three color couplers.

Various exposure means can also be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-burning flashbulbs are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear or planar microshutter arrays using phosphor screens (CRT, etc.), liquid crystals (LCD), and lanthanum-doped lead titanium zirconate (PLZT) emitted from phosphors excited by electron beams, etc. It is also possible to use an exposure means that combines a light source. If necessary, the spectral distribution used for exposure can be adjusted using color filters. Also, Fuji Photo Film Co., Ltd.'s color copy machine AP-
The scanning exposure method used in 5000 can be used.

〔Example〕

The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

〔Example〕

Example 1 - KL: 1. An aqueous solution of potassium bromide and silver nitrate was added simultaneously to an aqueous gelatin solution over a period of 15 minutes at 50°C without vigorous stirring, and the average particle size was 0.20μ. Octahedral silver bromide particles were obtained. In this case, 0.1 g of 3,4-dimethyl-1 per mole of 1M
, 3-thiazoline-2-thione and lead acetate 5.0X10-
'mol/silver mole added. This emulsion contains 5 μm of sodium thiosulfate and 7M of chloroauric acid (tetrahydrate) per mole of silver.
Chemical sensitization treatment was carried out by sequentially adding and heating at 75°C for 80 minutes. The particles obtained in this way are used as cores,
Further growth was performed in the same precipitation environment as the first time, and a final octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.35μ was obtained.The coefficient of variation of the zero grain size was approximately 10%. Ta. To this emulsion were added 1.5 μ of sodium thiosulfate and 1.5 μ of chloroauric acid (tetrahydrate) per mole of silver, and the emulsion was heated to 60°C.
Chemical sensitization was carried out by heating for 0 minutes to obtain an internal latent image type silver halide emulsion.

- Cunning: "] The temperature during the formation of the expanded core particles was changed to 75°C instead of 50°C, and the amount of 3,4-dimethyl-1,3-thiazoline 2-thione added was changed to 0.1g. The average particle size of the core particles was 0.35 μm, and the final average particle size was 0.70 μm.
An internal latent image type silver halide emulsion was obtained in the same manner as EIll except that m was changed.

Internal latent image type silver halide emulsion E was prepared in the same manner as Es-1 except that a palladium compound, potassium thiocyanate and a compound of general formula (I) were used as shown in Table 1 during chemical sensitization of the core grains. Internal latent image type silver halide emulsion E+w-E-H was obtained in the same manner as in (1)-A-D and in E+s-2.

Further, in the same manner, an internal latent image type silver halide emulsion E-1 with an average grain size of 0.90 μm was obtained.

Paper support laminated on both sides with polyethylene (thickness 10
A photographic material was prepared in which the following 1N to 14th layers were coated on the front side of the film (0 micron), and the 15th to 16th layers were coated on the back side. Titanium oxide was added as a white pigment to the polyethylene on the 1st N coating side at a rate of 4g/rd and 0,003g/n.
(The ultramarine blue color is included as a dye.(The chromaticity of the surface of the support is L8a*, bm system, 88.0, -0.20.
, -〇, 75. ).

(Photosensitive JIIl&ll formation) The components and coating amounts (in g/rrf units) are shown below. For silver halide, the coating amounts are shown in terms of silver.

The emulsion used in each layer has a grain size of 0.35μ.
-1 with a particle size of 0.70μ was used as E■-2. However, as the emulsion for the 14th layer, a Lippmann emulsion without surface chemical sensitization was used.

1st N (Antihaleshitane layer) Black colloidal silver 0.10 Gelatin 0.35 2nd layer (Intermediate layer) Gelatin Red-sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.35μ, size distribution [coefficient of variation] 8χ, octahedral) 0.12 gelatin - −−−−・・−・−・−0,80
Cyan coupler (ExC-1, 2 1:1) -----
-0, 30 anti-fading agent (Cpd-1, 2, 3, 4 equivalents)
0.18 Stain inhibitor (Cpd-5)-・
---0, 03 force puller dispersion medium (Cpd-6) 0, 03 coupler solvent (Solv-1, 2, 3 equivalents) ---0, 12 4th
Layer (high-sensitivity red-sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.70μ, size distribution 15χ, octahedron) -. 0,14 Gelatin ----------・--・-0,8
0 cyan coupler (EXC-1, 2 1:1) ---
...-0,30 anti-fading agent (Cpd-1,2,3,4 equivalent >-----1...-0,18 force puller dispersion medium (Cp
d-6) -1-0,03 coupler solvent (Solv
-1, 2, 3 equivalent)---0, 12 5th layer (intermediate layer) Gelatin------
--0,70 color mixing prevention agent (Cpd-7) ・・---
------0,08 Anti-fading solvent (Cpd-4,5 equivalent) 70.16 Polymer latex (
Cpd-8) - - - - - - - - - - 0, 10 6th layer (low-sensitivity green-sensitive layer) Silver bromide (
Average particle size 0.35 μ, size distribution 8χ, octahedral) -0,10 gelatin - - - - - - - - - - - - -
-------・-・-----1--～--0,70 Magenta coupler (Equivalent amounts of ExM-1, 2, and 3) 0,1 I Ol 15 Antifading agent (Cpd-9, 26) stain inhibitor (Cpd-10, 11, 12, 13 in 10:1:1:I
(in ratio) ・・・・−−−−m−−・−・−・−・−−−
--0,025 force puller dispersion medium (Cpd-6) ---
...--11-------0.05 coupler solvent (S
olv-4,6 equivalent)---= 0. 15 7th layer (high sensitivity green sensitive layer) Silver bromide (
Average particle size 0.70μ, size distribution 16χ, octahedral) Gelatin magenta coupler (equal amounts of ExM-1, 2, 3) 0, 1
0 0, 70 0, 11 Anti-fading agent (Cpd-9,26 equivalent)・------
0,15 stain inhibitor (Cpd-10,11,12,
13 to 10 near:7:1 ratio) 0
．． 025 force puller dispersion medium (Cpd-6) ・
-0,05 coupler solvent (Solv-4,6 etc.ff1)
---0,15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 51W Yellow colloidal silver (particle size 100A) -----
0,12 gelatin −・−−1−−−−−・−0,6
0 Anti-fading agent (Cpd-7) ・−・−・
0.03 Anti-fading agent solvent (Solv-4,5 equivalent) -
111110, 1 O polymer latex (Cpd
-8)-・-0,07 10th layer (intermediate layer) 11th layer (low sensitivity blue sensitive layer) same as 5th layer Brominated spectrally sensitized with blue sensitizing dye (ExS-5,6) Silver (average particle size 0.70μ, size distribution 8χ, octahedral) -0, 21 Gelatin - 1 - 0.70 Yellow coupler (EXY - 1,2 equivalent") - 0, 35 Fading Inhibitor (Cpd-14) 0.1
0 stain prevention wi (Cpd-5,15 at 1:5 ratio)
,,,-,-0,007 Force blur dispersion medium (Cpd-6) 0,
05 coupler solvent (S01 sea 2)-----0,1
0 12th layer (high sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, size distribution 18χ, octahedral) 0° Gelatin 0゜Yellow coupler (ExY-1, 2 equivalents>------
-0, 30 anti-fading agent (Cpd44) ----1--
-------------0, 10 stain prevention 荊 (Cp
d-5,15 in 1=5 ratio)-------------
----------...0.007 Force Blur dispersion medium (Cpd-6) -------0,05 Coupler solvent (Soiv-2) ----1--0, 10 13th layer (ultraviolet absorbing layer) Gelatin---1---0, 80 Ultraviolet absorber (Cpd-2, 4, 16 equivalent)---0
, 50 anti-fading (Cpd-7,17 equivalent) -1
--------・0.03 dispersion medium (Cpd-8)
−−−−−−・・・・・−１−−〜−１−−−・0
．． 02 UV absorber solvent (Solv-2,7 equivalent)-O
, OS irradiation prevention dye (Cpd-18°19
．． 20, 21.27 in 10:10:13:15:20 ratio) −・・−−−・・−−−−−−・−・・
0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol, average size 0.1 μ> -------・・−・−・
...--0,03 Acrylic modified copolymer of polyvinyl alcohol (average molecular weight 50,000) ----〇,0
1 polymethyl methacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) equivalent amount −1,50 gelatin −
111---------
m-------1, 50 gelatin hardener (H-1
, H-2 equivalent) --11110. 18 15th layer (back side) Gelatin -------------2,25 Ultraviolet absorber (Cpd-2,4,16 equivalent) -0,50
Dye (equal amounts of Cpd-18, 19, 20, 21, 27)
−・−・−・−−−−−−−−−−−−−−−11−−
−−−−−−−−−−−−−−・・−〇, 06 No. 16
Layer (backside protective layer) Polymethyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ) in equal amounts ・−・−−−−−−−−・−−−−−−11− −
0.05 Gelatin-----11---------
−−−−・・・−・−−−−1,75 gelatin hardening agent (
H-1, H-2 equivalent) -・-・-0,14 Each photosensitive layer contained ExZK-1 as a nucleating agent at 10-3% by weight based on silver halide, and Cpd as a nucleating accelerator. -22 was used in an amount of 104% by weight. Furthermore, Alkanol XC (Dupon) and sodium alkylbenzenesulfonate were used as emulsification dispersion aids, and succinic acid sulfonic acid and Magefac F-120 (manufactured by Dainippon Ink Co., Ltd.) were used as coating aids. (Cpd-23, 24°25) was used as a stabilizer in the silver halide and colloidal silver containing layers.

This sample was designated as floor 1. Internal latent image emulsion E--1,
Samples 1llQ, 2 to 10 were prepared in the same manner as sample 1 except that internal latent image emulsion Em-A-H was used instead of Em-2 as shown in Table 2.

These samples were left at 50°C, 160% RH for 14 days, and then wedge exposed (color temperature 3200K).

Treatment step A, which will be described later, was performed at 100C for 0.1 seconds. The sensitivity of the magenta colored image was determined from the exposure amount giving a density of Dmin+0.1 and is shown in Table 2.

Next, compounds used in Examples will be specifically shown.

xS-1 xS xS-3 xS-4 xS xS O3- 5O3H-N(C!H8)I Cpd-1 Cpd Cpd Cpd-4 Cpd-5 OR H Cpd-6 1←CH.

CH +1 CONHC.

H9 (1) (n=100-1000) Cpd-7 H H Cpd Polyethyl acrylate (M W = 10.000-100.000) Cpd
-9 Cpd-10 CsHz(j) Cpd-11 Cpd-12 Cpd-13 H Cpd-14 Cpd-15 H H Cpd-16 Cpd-17 Cpd-18 Cpd-19 CH υH (jiH*)3S03K (shiNz )35UzK Cpd 0 Cpd Cpd 2 Cpd-23 Cpd 4 Cpd-25 Cpd 6 Cpd 7 CH, C00K CH, C00K xM ExM-2 ExM-3 ExM-2 olv-I 0IV-2 olv-3 olv-4 olv -5 olv-6 olv-7 -1 -2 xZK-1 Di(2-ethylhexyl) sebacate trinonyl phosphate di(3-methylhexyl) phthalate tricresyl phosphate dibutyl phthalate trioctyl phosphate di(2-ethylhexyl) phthalate 1. 2-bis(vinylsulfonylacetamido)ethane 4.6-dichloro-2-hydroxy-1°3.5. -Triazine Na salt 7- (3-(5-mercaptotetrazol-1-yl)benzamide)-10-propargyl 1, 2. 3 4-tetrahydroacridinium perchlorate color development 135 seconds 38°C bleach fixing
40 seconds 33°C water washing (1)
40 seconds 33°C water washing (2)
40 seconds 33°C3080°C The method of replenishing the washing water is to replenish the washing water into the washing bath (2) and
A so-called countercurrent replenishment system was adopted in which the overflow liquid of 2) was led to the washing bath (1). At this time, the amount of bleach-fix solution brought into the washing bath (1) from the bleach-fix bath for photosensitive materials is 3
5d/rrf, and the ratio of the amount of washing replenishment to the amount of bleach-fix solution brought in is 9. It was 1x.

The composition of each treatment liquid was as follows.

D-sorbitol 0.15g Sodium naphthalene sulfonate/formalin condensate 0.15g Ethylenediaminetetrakismethylenephosphonic acid 1.5g Diethylene glycol 12.0Ilf Benzyl alcohol 13.5d Potassium bromide
0.70g benzotriazole
0.003g sodium sulfite 2
．． 4gNN-bis(carboxymethyl)hydrazine 4.0gD-glucose 2.0gtriethanolamine 6.0gN-ethyl-N-(β-
Methanesulfonamidoethyl)-3-methyl 4-aminoaniline sulfate 6.4g Potassium carbonate 30.0g Optical brightener (diaminostilbene type) 1.0gd pH (25°C) 10.25
Ethylenediamine tetraacetic acid, disodium, dihydrate 2.0g Ethylenediaminetetraacetic acid, Fe(III), ammonium, dihydrate 70.0g Ammonium thiosulfate (700g #
! ) 180 mp-sodium toluenesulfinate 4
5.0g Sodium bisulfite 35.0g
5-mercapto-1,3,4-) lyazole 0.5g ammonium nitrate IO, OgPH (25°C)
6.10 Water Supply A hotbed column filled with tap water and an H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite 1 R-400, manufactured by Rohm and Haas). The calcium and magnesium ion concentrations were reduced to below 3/1 by passing water through the solution, and then sodium dichloride isocyanurate 20/l and sodium sulfate 0/1 were added. 15 g/l was added. The pH of this solution is 6.
It was in the range of 5 to 7°5.

Internal latent image type emulsion E+ using the palladium compound of the present invention
- Samples 2 to 10 using A-1 are Comparative Example 1
It was preferable that the decrease in Dmax due to incubation was small and the Da+in was low compared to the above.

In addition, samples containing general formula (1) 2.4.6.1
0 was more preferable because the Dmax decrease was even smaller.

Similar trends were obtained for cyan and yellow color image densities.

Example 2 Example 1 was repeated except that in addition to the nucleating agent ExZ -1, the following ExZK-2 was added to each photosensitive layer at 1.5XIO-' mol per mol of silver halide, and the same results were obtained. However, the effect was rather small.

Niformyl-2-(4-(3-(3-(3-(5-mercaptotetrazol-l-yl)phenyl)ureido)benzenesulfonamido]phenyl)hydrazine

Claims (2)

[Claims] (1) having at least one photographic emulsion layer containing internal latent image type silver halide grains that are not prefogged;
In a direct positive photographic light-sensitive material, the internal latent image type silver halide grains have a core/shell structure, and the core grains are chemically sensitized in the presence of 10^-^4 moles or more of a palladium compound per mole of silver halide. A direct positive photographic material characterized by being (2) Direct positive photographic sensitization according to claim (1), characterized in that the core grains of the internal latent image type silver halide grains are chemically sensitized in the presence of general formula (I). material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, M_1 represents a hydrogen atom, a cation, or a protecting group for a mercapto group that is cleaved with an alkali, and Z is a 5- or 6-membered
represents a group of atoms necessary to form a member heterocycle, and this heterocycle may have a substituent or be fused.