JPS63254451A - Direct positive color image forming method - Google Patents

Abstract

PURPOSE:To rapidly form an image having the low min. density and the high max. density by using a specified sensitizing dye for a photosensitive material, thereby processing said material with a color developer having a low pH. CONSTITUTION:The photosensitive material contains an inner latent type emulsion which does no substantially contain silver iodide and is composed of a silver chlorobromide emulsion, and substantially a nondiffusion coupler and one or more of the sensitizing dyes shown by formulas I-III. And, the titled image is formed by image-wisely exposing the photosensitive material and then, by developing the obtd. material with a surface color developer which contains an aromatic primary amine color developer and has <=11.5pH in the presence of a nucleus forming agent, followed by effecting a bleach-fix processing. In the formula, Z1-Z3 are each an atomic group necessary for forming a 5-6 membered nitrogen-contg. heterocyclic ring, R1-R6 are each alkyl group, etc., L1-L7 are each methine group, X1<->-X3<-> are each an anionic ion, (l2)-(l3) are each 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for forming direct positive color images using internal latent image type silver halide emulsions.

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

Various techniques have been known for directly forming positive images using internal latent image type silver halide emulsions, such as U.S. Pat. No. 2,592.250;
466.9ri No. 7, same No. 2゜497.875, same No. 2
．． No. 588.982, No. 3.317.322, No. 3. 761. No. 266, No. 3.761,276, No. 3.796.577 and British Patent No. 1. 1
51. No. 363, No. 1.150.553 (No. 1,
No. 011.062) The main ones are those described in each specification etc.

In a direct positive color image forming method using such an internal latent image type silver halide emulsion, the processing time is longer because the fog development speed is slower than in the case of a normal negative type. Lowering the pH of the developer is generally undesirable because lowering the pH further increases the processing time.

Therefore, it is difficult to obtain a direct positive image with a high maximum image density and a low minimum image density using a low pH developer. Methods have been taken to shorten processing time.

(Problems to be Solved by the Invention) However, there is a problem in that the minimum image density of the direct positive image obtained generally increases when the pH is high. Also high pH
Under these conditions, the developing agent is likely to deteriorate due to air oxidation, and there is a problem in that its imaging activity is significantly reduced.

To solve these problems, compounds that exhibit a nucleation effect even at pH 12 or lower have been proposed in Japanese Patent Application Laid-Open No. 52-69613, U.S. Patent No. 3,615,615, and U.S. Pat. No. 3,850,638, etc., but even with these compounds, the minimum image density There was a problem that the image density increased, and the maximum image density was also insufficient.

On the other hand, U.S. Pat. No. 4,306,016 describes that the maximum image density is increased by using a specific cyanine-based sensitizing dye in an internal latent image type silver halide emulsion, but the extent of this increase is limited. It has not been satisfactory and has never been satisfactory in terms of obtaining low minimum image densities.

Furthermore, if a silver chlorobromide emulsion that does not substantially contain silver iodide is used as a direct positive silver halide emulsion, the maximum density will be high and rapid processing will be possible. There is a problem in that the concentration tends to increase.

Furthermore, when the internal latent image type direct positive color photosensitive material is developed for a long time, there is a problem in that the resulting image tends to have soft tones.

The present invention is intended to solve the above problems.

It is therefore an object of the present invention to process an unfogged internal latent image type silver halide photosensitive material with a low pH color developing solution to rapidly produce direct positive color images with low minimum density and excellent maximum color density. The objective is to provide a method for forming

Another object of the present invention is to provide a direct positive color image forming method that can effectively suppress softening of the toe portion that may occur when such an internal latent image type photosensitive material is developed.

(Means for Solving the Problems) The above-mentioned object of the present invention is to provide a photosensitive material containing on a support at least one internal latent image type silver halide emulsion layer that is not prefogged and a color image-forming coupler. After imagewise exposure, in the method of directly forming a positive color image by developing, bleaching and fixing with a surface color developer containing an aromatic primary amine color developer in the presence of a nucleating agent, The OpH value of the developer is 11.5 or less, the internal latent image type silver halide emulsion is a silver chlorobromide emulsion that does not substantially contain silver iodide, and the color image forming coupler is a silver halide emulsion that is substantially free of silver iodide. It is a compound that is diffusible and generates or releases a dye upon oxidative coupling with the developer, and the photosensitive material has the following general formula [I], general formula [■], and general formula (I [] It has been found that this can be achieved by a direct positive color imaging method characterized in that it contains at least one of the following sensitizing dyes.

General Formula CI] (In Formula [I), Zl represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle.

R1 and R2 may be the same or different and represent a substituted or unsubstituted alkyl group, which may form a salt with a metal atom or other organic compound.

Ll represents a substituted or unsubstituted methine group.

xl represents an anion, 11 represents 0 or 1, and is 0 when the dye forms an inner salt. ) general formula [1
1] In (Formula CII), z2 represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle.

Rs and R= may be the same or different and represent a substituted or unsubstituted alkyl group, which may form a salt with a metal atom or other organic compound.

L2. L3 and R represent a substituted or unsubstituted methine group.

X2- represents an anion, 12 represents 0 or l,
It is 0 when the dye forms an inner salt. ) General formula [
111] (In the formula [■], Z3 represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle.

Rs and Rt; may be the same or different and represent a substituted or unsubstituted alkyl group, which may form a salt with a metal atom or other organic compound.

Ls, Ls and R represent a substituted or unsubstituted methine group.

X" represents an anion, I!3 represents 0 or 1,
It is 0 when the dye forms an inner salt. ) General formula C
I], CU] and [■] will be explained in more detail.

The nuclei formed by z, Sz, i and Z3 are each independently a thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenyl). thiazole), benzothiazole nucleus (e.g.
Benzothiazole, 4-chlorobenzothiazole, 5-
Chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzo Thiazole, 5
-Phenylbenzothiazole, 5-methoxybenzothiazole, 6-ethoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carpoxypenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5゜6-
dimethylbenzothiazole, 5,6-simethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazonopetetrahydrobenzothiazole, 4-phenylbenzothiazole, etc.), naphthothiazole core (e.g.
naphtho(2,1-d]thiazole, naphtho[:'1.2
-d]thiazole, naphthoC2,3-d)thiazole,
5-methoxynaphtho[:1.2-d]thiasheetpearethoxynaphthoC2,1-d]thiazonope8-methoxynaphthoC2,1-d)thiazole, 5-methoxynaphtho(2,3-d:]thiazole, etc. ), thiazoline core (e.g., thiazoline, 4-methylthiazoline, 4
-nitrothiazoline, etc.), oxazole nucleus [oxazole nucleus (e.g. oxazo-)pe4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, etc. ), benzoxazole core (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole,
5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-)IJ fluoromethylbenzoxazole,
5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6
-chlorobenzoxazole, 6-nitrobenzoxazole, 6-ethoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-
ethoxybenzoxazole, etc.), naphthoxazole core (e.g., naphtho('2.1-d)oxazole,
naphtho[1°2-d]oxazole, naphtho(2,3-
d]oxazole, 5-nitronaphthoC2,1-d]oxazole, etc.), oxazoline nuclei (e.g., 4
．． 4-dimethyloxazoline, etc.), selenazole core (
selenazole core (e.g., 4-methylselenazole, 4
-nitroselenazole, 4-phenylselenazole, etc.), benzoselenazole core (e.g., benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-
hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole, etc.), naphthoselenazole nucleus (e.g. naph) C2,' 1-d )
selenazole, naphtho[1,2-d]selenazole, etc.), selenazoline core (e.g., selenazoline, 4
- methylselenazoline, etc.), telllazole core (e.g., tellurazole, 4-methylthiazoline, 4-7enyltelllazole, etc.), penzotelllazole nucleus (e.g., penzotelllazole, 5-chloropenzotellazoline, etc.), sol, 5-methylbenzotellurazole, 5,
6-dimethylbenzotelllazole, 6-medoxybenzotelllazole, etc.), naphthotellazole core (e.g.,
Naphtho[2,1-d) Tellurazole, Naphtho[1,2-
d) telllazoline etc.), tellazoline core (e.g. telllazoline, 4-methylselenazoline etc.), 3
．． 3-dialkylindolenine core (e.g., 3゜3-dimethylindolenine, 3.3-diethylindolenine,
3.3-dimethyl-5-cyanoindolenine, 3.3-
Dimethyl-6-ditroindolenine, 3.3-dimethyl-5-ditroindolenine, 3.3-dimethyl-5-methoxyindolenine, 3,3.5-)diethylindolenine, 3゜3-dimethyl -5-chloroindolenine, etc.), imidazole nucleus (e.g., 1-alkylimitasol, l-alkyl-4-phenylimidazole, etc.), benzimidazoline nucleus (e.g., 1-
Alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl- 5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimitazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-
Trifluoromethylpenzimitasole, 1-allyl-
5,6-dichlorobenzimidazole, 1-allyl-5
-Chlorobenzo.

Imidazolepe 1-aryl imidazole nucleus, 1-arylbenzimidazole, 1-aryl-5-chlorobenzothiazole, 1-aryl-5,6-dichlorobenzimidazole, l-aryl-5-methoxybenzimidazole % 1-aryl-5-cyanobenzimidazole), naphthoimidazole core (e.g. 1-
alkylnaphtho(1,2-d:]imidazole, 1-arylnaphtho(1,2-d)imidazole, etc.), wherein the aforementioned alkyl group is one having 1 to 8 carbon atoms, such as methyl, ethyl, propyl , unsubstituted alkyl groups such as impropinopeptyl, hydroxyalkyl groups (e.g. 2-hydroxyalkyl, 3-hydroxypropyl, etc.), etc. are particularly preferred. Methyl groups and ethyl groups are particularly preferred. pyridine nucleus (e.g. 2-pyridine,
5-methyl-2-pyridine, etc.), quinoline nucleus (e.g., 2-quinoline, 3-methyl-2-quinoline, 1.5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro -2-quinoline, 8-fluoro-2
-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, etc.)
, isoquinoline nuclei (e.g., 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline, etc.), imidazo (4,5
-b) Quinoxaline core (e.g. 1,3-diethylimidazoC4,5-b) Quinoxaline, 6-chloro-1,3
- diallylimidazo(4,5b)quinoxaline, etc.),
Examples include oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

However, Z2 does not contain a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoterlazole nucleus, or a naphthoimidazole nucleus.

zl is preferably a thiazole nucleus (thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus), oxazole nucleus (oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus), more preferably a benzothiazole nucleus (e.g. benzothiazole nucleus, 5 -chlorobenzothiazole nucleus, 5-methoxybenzothiazole nucleus, etc.)
It is.

Z2 is preferably a thiazole nucleus (thiazole nucleus, benzothiazole nucleus), an oxazole nucleus (oxazole nucleus,
benzoxazole nucleus, naphthoxazole nucleus), more preferably benzoxazole nucleus (e.g. benzoxazole nucleus, 5-chlorobenzoxazole L).
5-phenylbenzoxazole nucleus, etc.).

Z3 is preferably a thiazole nucleus (thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus), more preferably a benzothiazole nucleus (for example, 5-chlorobenzothiazole, etc.) or a naphthothiazole nucleus (for example, naphtho(1,2- dl thiazole nucleus, naphtho[2,1-C
D thiazole nucleus, etc.).

R+, R2, R3, R4, Rs and R6 each independently represent an unsubstituted alkyl group having 18 or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
octyl group, decyl group, dodecyl group, octadecyl group, etc.) or substituted alkyl group (substituents such as carboxy group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group,
Alkoxycarbonyl groups having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group) ), monocyclic aryloxy groups having 10 or less carbon atoms (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy groups having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), carbon atoms 8 or less acyl group (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N, N
-dimethylcarbamoyl group, morpholinocarbonyl group,
piperidinocarbonyl group), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), aryl group having 10 or less carbon atoms (e.g. phenyl group, -chlorophenyl L 4-methylphenyl group,
An alkyl group having 18 or less carbon atoms substituted with an α-naphthyl group, etc.) is preferred.

In particular, R+, R2, R3, Ra, Rs, and R6 are preferably alkyl groups substituted with sulfo groups (eg, sulfoethyl group, sulfopropyl group, sulfobutyl group, etc.).

Also, metal atoms that can form salts with R, , R2 are:
Particularly preferred are alkali metals, and as the organic compound capable of forming a salt with R2, pyridines, amines, etc. are preferred.

L+, L2, La, L, 4. Ls,
Ls and R are methine groups (unsubstituted or substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, etc.), substituted or unsubstituted aryl groups (e.g., phenyl groups, etc.), or halogen atoms (e.g., chlorine atoms). , bromine atom, etc.). It can also form a ring with an auxochrome. Preferably, L l + L2 + L4 *L5 and L
7 is an unsubstituted methine group, and La and L6 are methine groups substituted with an unsubstituted alkyl group (eg, methyl group, ethyl group, etc.).

Specifically, each of X, , X2- and x3- may be an inorganic anion or an organic anion, such as a halogen anion (e.g. fluorine ion, chlorine ion, bromide ion, iodide ion, etc.) , substituted arylsulfonate ions (e.g. p-)luenesulfonate ion, p-chlorobenzenesulfonate ion, etc.),
Aryl disulfonate ion (e.g., tli'1.3-
benzene disulfonate ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion, etc.), alkyl sulfate ion (e.g. methyl sulfate ion, etc.), sulfate ion, thiocyanate ion, neon perchlorate, tetrafluoro Examples include borate ion, picrate ion, and acetate ion.

Preferred are p-toluenesulfonic acid ion and iodine ion.

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

(X,-)β1 %ll l l l l l l l l l-111Xl
I l l l l l
l l-111 key 111111111 111-1 XI = 8 8 de Q x Mushiko Yue
1.

%1 1 1 1 l-1=l l
1=11＾Quantity adventure! = 〒8000 yo --
111111- M l l l 1- Zeng>:! : Ya === ≧ C/) (1) Q φ yoto=ri= 〈α 1ll11 , y , ++−x ++ Typical examples of the compound represented by the general formula [n] are listed below. The present invention is not limited to this.

Wisdom-1+1 II 1 > = = Li e e U QN-1
111111 Satoshi-1111111 Qllllllll X-1111111 Ichini〇 x XI l l l l l
l! l ≧ Snake Mushi 5 Power ω ■ Nikki … … # … … … … c@1l11- 11II 1llll- c-h l -l l l --m l , L l”1
---11
111111 -! :! Yoyoyoyo c+II 1 11111;n = Yes
4 days days days white General formulas (I), (■), and (I
The sensitizing dyes represented by [I] are F, M, Hamer (
Heterocyclic Compound (F., M. Hamer)
nds-Cyamine Dyes and Re1a
ted Compounds-)Chapter
ter) II, page 32-76 Chapter m, page
) 77-85 Chapter IV, page 86-115 Chapter
er) V, pages 116-147
Chapter VT, Page (Ima)
ge) 147-199 Published by John Wiley and Sons (
1964) D, M, Star? -(D, M, St
urmer), Heterocyclic Compounds - Special Topics in Heterocyclic Compounds
Chemistry (Heterocyclic Co.
mpounds-3specialTopics in
Heterocyclic Chemistry Chapter ■, sec, IV, pages 482-515゜John Wile & Sons
It can be easily synthesized based on the method described in E31 and 5ons) (1977).

The sensitizing dyes of general formulas (I) to (III) are preferably contained in the silver halide emulsion layer, and the content thereof is generally I x 10-' to I x 10-'' mol per mol of silver, preferably 1 x 10-5 to 1 x 10'''' 3 mol, more preferably 5 x 10-' to 8 x 10-' mol.

The sensitizing dyes of the general formulas (1) to (III) of the present invention may be used in combination of two or more, and/or the sensitizing dyes of the general formula (1)
-(III) Any two or more types may be used in combination. It may also be used in combination with other meloncyanine, cyanine, polymethine dyes, etc.

In the present invention, by further incorporating a specific pyrazoloazole magenta coupler of the following general formula CIV) into the light-sensitive material, the magenta hue becomes clearer due to less secondary absorption when coloring occurs, and the coloring Surprisingly, while maintaining the effect of being able to achieve high density with a small amount of coated silver because of its good properties, the lowermost image density decreased due to the development inhibiting properties of the pyrazoloazole magenta coupler. Contrary to this trend, it has been found that it is possible to prevent the toe from softening when the development time becomes longer, while maintaining the bottom image density.

The pyrazoloazole type magenta coupler that can be used in the present invention is represented by the following general formula (IV).

(In the formula, R7 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb and Zc are methine, Substituted methine, =N- or -NH-
, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, cases in which R7 or X forms a dimer or more multimer are also included. Also, ZaSZb
Alternatively, when Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is also included. ) In the general formula (IVI), a multimer means one having two or more groups represented by the general formula (rV) in one molecule, and bis forms and polymer couplers are also included therein. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula (IV) (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic-class amine. Copolymers may be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of the developer.

The compound represented by the general formula [IV] is a 5-membered ring-5-membered ring nitrogen heterocyclic coupler, and its chromogenic nucleus exhibits isoelectronic aromaticity with naphthalene, and is generally referred to as azapentalene. It has a structure. Among the couplers represented by the general formula (rV), preferred compounds are IH-imidazo[1,2-b]pyrazoles, IH-pyrazolo[
1,5-b] pyrazoles, IH-pyrazolo (5,1-
c] (1,2,4,1) lyazoles, IH-pyrazolo(1,5-bl[:1.2.41) lyazoles, IH-pyrazoloC1,5-d]tetrazoles and IH-pyrazolo I "1. 5-a] Benzimidazoles, each having the general formula (V] CVII C■)
[■] Represented by [■] and [X]. Among these, compounds represented by the general formulas [■], [■] and [■] are preferred, and particularly preferred compounds are [■] and [■].

[■] [■] [■] [■] [IX] [X] General formula [■
] to [X) are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy group,
Silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group , a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, a carboxy group, or an oxygen atom, a nitrogen atom, or a sulfur atom. Represents a group that is bonded to the carbon at the coupling position via an atom and is decoupled.

The case where R'', R9, R'' or x becomes a divalent group and forms a bis body is also included. In addition, the general formula [■] ~ [X
] When the moiety represented by ] is in the vinyl monomer,
R11, R9 or R'' represents a simple bond or linking group, through which the moiety represented by the general formulas [■] to [X] and the vinyl group are bonded.

When R', R9, R'' or -NHCO-R''-CONH- group (R
IG' represents a substituted or unsubstituted alkylene group or phenylene group. ) etc.

When those represented by general formulas [V] to [X] are present in the vinyl monomer, the linking group represented by R11, R9 or RIG is a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenylene group, group, -NHCO-1-CONH
-1-0-1OCO- and aralkylene groups are included.

In addition, the vinyl group in the vinyl monomer has the general formula [V] ~
It also includes cases in which it has a substituent other than those represented by [X]. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α
-Chloroacrylic acid, α-alacrylic acid, and esters or amides derived from these acrylic acids, methylene dibisacrylamide, vinylester acrylonitrile, methacrylonitrile, aromatic vinyl compounds, itaconic acid, citraconic acid, croton Acid, vinylidene chloride, vinyl alkyl ether, maleic acid, maleic anhydride, maleic ester, N-vinyl-
Examples include 2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of couplers represented by the above general formulas [V] to CXI are described in the documents listed below.

The compound of general formula CrV) is disclosed in Japanese Patent Application No. 58-23434, and the compound of general formula CVI) is disclosed in Japanese Patent Application No. 58-1513.
54 etc., the compound of the general formula [■] is
411 etc., the compound of the general formula [■] is
5512 and 59-27745, etc., the general formula [■]
The compound represented by formula [X] is described in Japanese Patent Application No. 142801/1983, and the compound represented by formula [X] is described in US Patent No. 3,061.432.

Also, Japanese Patent Application Publication No. 58-42045, Japanese Patent Application No. 58-8894
The highly color-forming palaste group described in JP 0, JP 58-52923, JP 58-52924 and JP JP 58-52927 is applicable to any of the compounds of the above general formulas [■] to [X].

For details of the pyrazoloazole coupler of general formula CV) that can be used in the present invention, please refer to Japanese Patent Application No. 61-16
No. 1712, pages 17-28, and specific compounds include (M-1) to (M-1) on pages 30-80 of the same book.
M-104) can be mentioned.

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, patent application No. 1988-25371 filed on October 27, 1986
Specification No. 6 (Applicant Fuji Photo Film Co., Ltd.) No. 28
Examples include the emulsions described on page 18, line 31 to page 31, line 2.

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 the silver halide includes silver chloride, silver bromide mixed silver halide, etc. The silver halide used in the present invention does not contain silver iodide or even if it contains it, it is less than 5 mol%, preferably 1. The salt is (iodine)silver bromide, (iodine)silver chloride or (iodine)silver bromide in a mole % or less.

More preferably, it does not contain any silver iodide.

According to the present invention, it is possible to solve the problem of softening of the toe area and increasing the minimum density caused by using a silver chlorobromide emulsion that does not substantially contain silver iodide, and to achieve an excellent maximum density. This enables rapid processing.

Further, the use of a silver chlorobromide core/shell emulsion substantially free of silver iodide allows for even more rapid processing, and it is also preferred to dope the interior (core) and/or surface of the emulsion with a metal.

The total halogen composition of the silver chlorobromide is 10 to 10% of silver chloride.
100 mol%, especially 20-80 mol%, even 20-6
Preferably it is 0 mol%.

As the metal doping method, the method described in JP-A-47-32814, pages 10 to 16 can be used.

The average grain size of the silver halide grains is 2μ or less and 0.
It is preferably 1μ or more, particularly preferably 1.4μ or less and 0.15μ or more, and even more preferably 1.1μ or less 0.20μ.
μ 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 or more types of monodisperse silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or in a layered manner.

Regarding the magenta, cyan and yellow couplers that can be used in the present invention, the above-mentioned Japanese Patent Application No. 61-253
It is described in the specification of No. 716, page 33, line 18 to page 40, last line.

In the present invention, a light-sensitive material containing an internal latent image type silver halide emulsion which has not been fogged in advance according to the present invention is
After imagewise exposure, the image is developed in the presence of a nucleating agent with a surface color developer containing an aromatic primary amine color developer, and subjected to bleaching and fixing treatments to directly form a positive color image.

Here, the term "nucleating agent" refers to a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance.

As the nucleating agent used in the present invention, all compounds conventionally developed for the purpose of nucleating endothermic silver halide can be used. An example of this is research disclosure (
Research Disclosure) Magazine N (L22
534 (published in January 1983), pages 50-54. Further, two or more of these compounds may be used in combination.

In the present invention, the following general formulas (N-I) and (N
It is preferable to use the nucleating agent represented by -II) because the maximum density can be increased while maintaining good color reproduction.

General formula [N-I] , , Z l 4. , (wherein, Zll represents a nonmetallic atomic group necessary to form a 5- to 6-membered heterocycle, and Zll may be substituted with a substituent. R" is an aliphatic group, and R+2 is It is a hydrogen atom, an aliphatic group, or an aromatic group.

Rl l and RI2 may be substituted with a substituent.

Furthermore, RI2 may be further combined with the heterocycle completed by 211 to form a ring. However, R1, R12 and Z l 1
At least one of the groups represented by contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R'' and RI2 form a 6-membered ring to form a dihydropyridinium skeleton.

Furthermore, at least one of the substituents Rl 1, Rl 2 and Zll may have a group promoting adsorption to silver halide. Yl is a counterion for charge balance,
n is 0 or l. ) General formula ["N-IN R"-N-N-G-R" R2coR24 (wherein, R21 represents an aliphatic group, aromatic group, or heterocyclic group; R22 represents a hydrogen atom, an alkyl group , represents an aralkyl group, aryl group, alkoxy group, aryloxy group, or amino group; G represents a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (HN=C); R23 and R24 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.However, if G, R'', R24, and hydrazine nitrogen are included, the hydrazone structure <;N-N=
'C) may also be formed. Further, the groups described above may be substituted with a substituent if possible.

Furthermore, at least one of R21 and R22 may have a group that promotes adsorption to silver halide. ) General formula [N=
To explain in more detail the nucleating agent represented by I), the heterocycle completed with Zll is, for example, quinolinium,
Benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridinium, inquinolinium, oxacillium, Examples include naphthoxacillium and benzoxacillium nuclei. Zll may be substituted with a substituent, and examples of the substituent include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, and an alkylthio group. group, AIJ + ruthio group, acyloxy group, acylamino group,
Sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate group, hydrazine group, hydrazone group, or imino group, etc. can give. As the substituent for Z I 1, 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 Zll, a heterocyclic quaternary ammonium group completed with Zll via an appropriate linking group L1 may be included. In this case, it takes a so-called dimer structure.

The heterocycle completed by 211 is preferably quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium,
and inquinolinium nuclei. More preferred are quinolinium and benzothiazolium, and most preferred is quinolinium.

RI+ and R12 may be substituted with a substituent.

The aliphatic groups of R'' and R12 preferably have 1 to 1 carbon atoms.
Eight unsubstituted alkyl groups and a substituted alkyl group in which the alkyl moiety has 1 to 18 carbon atoms.

Examples of the substituent include those described as the substituent for Zll.

The aromatic group represented by Rl 2 preferably has 6 to 6 carbon atoms.
Examples of the 20 groups include phenyl group and naphthyl group. Examples of the substituent include those described as the substituent for Z l 1. R12 is preferably an aliphatic group, most preferably a methyl group, a substituted methyl group,
or further bonded with a heterocycle completed with Zll to form a ring (for example, a 5- to 12-membered ring, with O,
may contain heteroatoms such as N and S).

At least one of the groups represented by Rl, R12 and ZI1 has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or Rl
l and R12 form a 6-membered ring to form a dihydropyridinium core, which may be substituted with the group described above as a substituent for the group represented by Z l l.

When at least one of the substituents to the group or ring represented by R1, R12 and Zl is an almulanyl group or an acyl group, or when R'' and R12 are linked to form a dihydropyridinium core. is preferred, and more preferably contains at least one alkynyl group, most preferably R'' is a propargyl group.

The adsorption promoting group to silver halide that Rl l, RI2 and 2+1 substituents may have is X'-G-L")-m
Those represented by are preferred.

Here, xl is an adsorption promoting group to silver halide, and L
I 1 is a divalent linking group. m is 0 or l. X
Preferred examples of the adsorption-promoting group to silver halide represented by l include a thioamide group, a mercapto group, and a 5- or 6-membered nitrogen-containing heterocyclic group.

These may be substituted with the substituents mentioned for Z I 1 . The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.).

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

The 5- to 6-membered nitrogen-containing heterocycle represented by xl consists of a combination of nitrogen, oxygen, sulfur, and carbon,
Preferred are those that produce iminosilver, such as benzolazole.

The divalent linking group represented by Lll is C1N,
An atom or atomic group containing at least one of S and O. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group -0-1-S-1
-NH-1-N=, -C○-1-3O2- (these groups may have a substituent), etc. alone or in combination.

As the counter ion Y1 for charge balance, for example,
Examples include bromide ion, chloride ion, iodide ion, p-)luenesulfonate ion, ditylsulfonate ion, perchlorate ion, triple olomethanesulfonate ion, and thiocyanate ion.

Among the compounds represented by the general formula [N-1], those having an adsorption-promoting group to silver halide are preferred, and it is particularly preferred that the adsorption-promoting group x1 is a thioamide group or a heterocyclic mercapto group. .

Examples of these compounds and their synthesis methods can be found, for example, in Research Disclosure (Research Disclosure).
1osure) Magazine No. 22.534 (published January 1983, pages 50-54) and magazine No. 23,213 (
Patents cited in 1983, August 1983, pp. 267-270);
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 the general formula [N-1] are listed below, but the present invention is not limited thereto.

(N-I-1) 6-nitoxythiocarponylamino-2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-2) 2-methyl-6-(3-phenylthioureido)-1-propargylquinolinium bromide (N-1-3) 6 - (5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-4) 6 [:3 (2-mercaptoethyl)ureido]-2-methyl-1-7' 0pargylquinolinium trifluoromethanesulfonate (N-I-5)6- (3-(3-(5-mercapto-
thiadiazol-2-ylthio)propyl]ureido)
-2-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-6) 6- (5-mercaptotetrazole-
1-yl)-2-methyl-1-propargylquinolinium iosito(N-I-7) 7-nitocythiocarponylaminol
O-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-I-8) 6-nitoxythiocarponylamino 1
-Propargyl-2,3-pentamethylenequinolinium trifluoromethanesulfonate (N-I-9) 7- [3-(5-mercaptotetrazol-1-yl)benzamide-10-propargyl-1,2,3, 4-Tetrahydroacridinium perxerade (N-I-10) 6- (3-(5-mercaptotetrazol-1-yl)benzamide)-1-propargyl-2,3-pentamethylenequinolinium bromide (N-I -11)? -(5-mercaptotetrazole-
Niyl)-9-methyl-10-prohalkyl-1,2
,3,4-tetrahydroacridinium promide (N-1-12)6-(5-mercaptotetrazol-1-yl)-4-methyl-1-propargyl-2,3
-Pentamethylenequinolinium Bromide (N-1-13> 7-C3-(N-C2-(5-mercapto-1,3,4-thiadiazol-2-yl)ethyl]carbamoyl)propanamide-10-propargyl -1,2,3゜4-tetrahydroacridinium iosito(Nl-14)6-nitoisthiocarponylamino-2-(2-methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonyl Nato (N-1-15) 6-nitoxythiocarponylamino-2-methyl-3-propargylbenzothiazolium trifluoromethanesulfonate (N-1-16) 2-methyl-1-propargylquinolinium bromide ( N-I-17) 2-(1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate (N-I-18) 1-propargyl-1,2,3゜4-
Tetrahydroacridinium trifluoromethanesulfonate (N-I-19) 6-nitoxythiocarbonylamino-3-(2-formylethyl)-2-methylbenzothiazolium bromide (N-I~20) 6-ni Toxythiocarbonylamino-3.4-dimethyl-dihydropyrido (2,1-b) benzothiazolium bromide (N-1-21) 6-nitoxythiocarbonylamino-2-methyl-1-(3-C2- (4-methylphenyl)
Hydrazino)butyl)quinolinium iositoTo explain in more detail the nucleating agent represented by the general formula CN-111, R21 may be substituted with a substituent, and examples of the substituent include the following.

These groups may be further substituted. For example, alkyl groups, aralkyl groups, alkoxy groups, alkyl or aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, aryl groups, alkylthio groups, Examples include arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, and carboxyl group.

Among these, ureido groups and sulfonylamino 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 heterocycle, or an aryl-substituted methyl group, and more preferably an aryl group (eg, phenyl group, naphthyl group, etc.).

Among the groups represented by R'', preferred are hydrogen atoms,
Examples include an alkyl group (for example, a methyl group) or an aralkyl group (for example, an 0-hydroxybenzyl group), and a hydrogen atom is particularly preferred.

R22 may have a substituent, and examples of the substituent include the substituents listed for R21, as well as acyl groups, acyloxy groups, alkyl or aryloxycarbonyl groups, alkenyl groups, alkynyl groups, and nitro groups. Also applicable are bases.

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

R21 or R'', in particular R21 may contain a diffusion-resistant group such as a coupler, a so-called ballast group, and is particularly preferably linked with a ureido group or a sulfonylamine group), and is adsorbed on the surface of silver halide grains. may have a group, X 2-(-L' 2)-m2, which promotes ), a mercapto group, or a 5- to 6-membered nitrogen-containing heterocyclic group. L + 2 represents a divalent linking group, and [, +1 of the general formula CN-I']
expresses the same meaning as m2 is 0 or 1.

More preferably, X2 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 l-mercaptothiadiazole group, a 3-mercapto-1
, 2,4-) lyazole group, 5-mercaptotetrazole group, 2-mercapH,3,4,-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or nitrogen-containing heterocyclic group (e.g., benzo ) IJ azole group,
(benzimidazole group, indazole group, etc.).

The most preferable x2 varies depending on the photosensitive material used. For example, when using a coloring material (so-called coupler) that forms a dye through a coupling reaction with an oxidized form of a p-phinidine diamine developer in a color sensitive material, x2 is a mercapto-substituted nitrogen-containing heterocyclic ring. , or a nitrogen-containing heterocycle forming iminosilver.

Hydrogen atoms are most preferred as R23 and R24.

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

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

The compounds represented by the general formulas [N to (2)] are most preferably those having a group that promotes adsorption to silver halide, and particularly preferably have a peterocyclic mercapto group as the adsorption promoting group x2.

Examples of these compounds and their synthesis methods are described in US Patent No. 4. 030. No. 925, No. 4.0
80.207, 4,031.127, 3.
No. 718,470, No. 4.269.929, No. 4.276.34, No. 4,278.748, No. 4,385°108, No. 4,459,347 , 4°478.928, 4,560.638, British Patent No. 2,011,391B, and Japanese Patent Application Laid-open No. 1974-74.
No. 7'29, 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, US Pat. No. 4.560.638, US Pat. No. 4.478, and US Pat. No. 2.563.785 and US Pat.

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

(N-m-1)1-formyl-2-(4-(3-(5-
Mercaptotetrazol-1-yl)benzamido]phenyl)hydrazine (N-n-2)1-formyl-2-C4-(3-(3-
(5-Mercaptotetrazol-1-yl)phenylthureido)phenyl]hydrazine (N-n-3)1-formyl-2-C4-(3-CN'
-<5-mercapto-4-methyl-1゜2.4-)'l
azol-3-yl)carnoimoyl]propanamido)phenyl]hydrazine (NII4)1-formyl-2-(4-(3-(N-C
4-(3-Mercapto-1,2,4-)1777'-4-yl)phenyl]carbamoyl)-propanamido]phenyl)hydrazine (N-n-5)1-formyl-2-C4-(3 -[N-
(5-mercapto-1,3,4-thiadiazole-2-
yl)carbamoyl]propanamido)phenylcouhydrazine(N-n-6)2-(4-(benzotriazole-5
-carboxamide) phenyl-1-formylhydrazine (N-11-7) 1-formyl-2-(4-[3-(5
-mercaptotetrazol-1-yl)benzenesulfonamido]phenyl)hydrazine (N-n-8)1-formyl-2-(4-[3-(3-
[:3- (5-mercaptotetrazol-1-yl)
phenylthureido) benzenesulfonamide] phanyl) hydrazine (N-n-9) 1-formyl-2-(4
-[3-(3-phenylthioureido)benzamide]
phenyl)hydrazine(N-II-10)1-formyl-2-(4-(3-hexylureido)phenyl)hydrazine(N-I[-1
1) 1-formyl-2-[4-[:3-(2-methoxyphenyl)ureido]-phenyl)hydrazine (N-I[-12)1-formyl-2-(4-[3-(
3-[:3-(2,4-di-tert-pentylphenoxy)propyl]ureido)phenylsulfonylaminoco-phenyl)hydrazine The nucleating agent used in the present invention is contained in the sensitive material or in the processing solution for the sensitive material. Preferably, it can be incorporated into the photosensitive material.

When incorporated into a 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 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 H pre-bath.

When the nucleating agent is contained in the sensitive material, the amount used is preferably 10-'' to 10-2 mol per 1 mol of silver halide.
More preferably, it is lo-7 to 10-3 mol.

In addition, when adding a nucleating agent to the processing solution, the amount used is 1
It is preferably 10-' to 10-1 mol, more preferably 10-4 to 10''2 mol per β.

Regarding the nucleation accelerator that can be used in the present invention, please refer to the above-mentioned Japanese Patent Application No. 61-253716, page 68, line 11 to page 71, line 3.
In particular, as a specific example,
It is preferable to use (A-1) to A-13) described on pages 9 to 70.

The color developer used in the development of the light-sensitive material of the present invention is described in the same specification from page 71, line 4 to page 72, line 9, and in particular aromatic primary amine color developer. As specific examples, p-ph, enylenediamine type compounds are preferable, and representative examples thereof include 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 3-methyl- Examples include 4-amino-N-ethyl-N-(β-hydroxyethyl)aniline, 3-methyl-4-amino-N-ethyl-N-methoxyethylaniline, and salts thereof such as sulfates and hydrochlorides. can. In addition, the development treatment of the present invention has a pH of 11.5 or lower,
It is preferably carried out at a pH of 11.0 to 9.8. Furthermore,
The color developing solution of the present invention preferably does not substantially contain benzyl alcohol, but may contain it.

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

Bleaching and fixing treatment means that bleaching treatment may be carried out simultaneously with fixing treatment in a one-bath bleach-fixing process, or may be carried out separately. In order to further speed up processing,
A method may be employed in which a bleaching treatment is followed by a bleach-fixing treatment, or a method in which a fixing treatment is followed by a bleach-fixing treatment. An aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or bleach-fixing solution of the present invention. Additives used in the bleaching solution or bleach-fixing solution of the present invention include Japanese Patent Application No. 61-32
Various compounds described in No. 462, pages 22 to 30 can be used. After the desilvering step (bleach-fixing or fixing), treatments such as water washing and/or stabilization are performed.

It is preferable to use softened water as the washing water or stabilizing liquid. As a method of water softening treatment,
Examples include a method using an ion exchange resin or a reverse osmosis device described in Japanese Patent No. 131,632. As a specific method for these, it is preferable to carry out the method described in Japanese Patent Application No. 131632/1982.

Further, as additives used in the water washing and stabilization steps, various compounds described on pages 30 to 36 of Japanese Patent Application No. 61-32462 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.

In the present invention, the following compounds (2) to (15) can be described as preferred nucleating agents.

(2) Nucleating agent N-I according to claim (4).

When N-II has a group promoting adsorption to silver halide as a substituent.

(3) In the nucleating agent N-1 of item (2), the adsorption-promoting group to silver halide represented by xl is composed of a thioamide group, a peterocyclic mercapto group, or a nitrogen-containing heterocycle that forms iminosilver. case.

(4) Nucleating agent N-11 of item (3): Oite, Zl
When the heterocycle completed by l is quinolinium, isoquinolinium, naphtopyridinium, benzothiazolium.

(5) In the nucleating agent N-I of item (3), if the heterocycle completed with Zl is quinolinium (6)
) Item R in the nucleating agent N-I.

When R'2 or Z l l has an alkynyl group as a substituent.

(7) In the nucleating agent N-I of item (6), when R11 is a propargyl group.

(8) In the nucleating agent N-I of item (7), Rl 2
When is combined with the heterocycle completed by 211 to form a ring.

(9) When the nucleating agent N-I of item (3) is a thiourethane group as the thioamide group of xl and a mercaptotetrazole as the heterocyclic mercapto group of xl.

(10) Nucleating agent N-n1 of item (2). :Oiite, x2
When the adsorption-promoting group to yellow silver halide represented by is a heterocyclic mercapto group or a nitrogen-containing heterocycle forming imino silver.

(11) In the nucleating agent N-11 of item (10), G
When the group represented by R22 is a formyl group, in (12) the nucleating agent N-n of item (11), R23 and R24
If is a hydrogen atom.

(13) In the nucleating agent N-n of item (11), when R'' is an aromatic group.

(14) In the nucleating agent N-n of item (13), when R'' has a sulfonamide group or a urea group as a substituent.

(15) In the nucleating agent N-ff in paragraph (10), x2
When the heterocyclic mercapto group is 5-mercaptotellurazole or 5-mercapto-1,2°4-triazole.

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

Example 1 Sample 101, which is a multilayer color photosensitive material having the layer structure shown below, was prepared on a paper support laminated on both sides with polyethylene.

Table 1 (Layer composition) The composition of each layer is shown below. The numbers represent the coating amount per m'' in g. For silver halide emulsions and colloidal silver, the coating amount in terms of silver is expressed in g, and for the spectral sensitizing dye, the amount added per mol of silver halide is expressed in moles.

Support polyethylene laminate paper [white pigment (T 102) on polyethylene on the E1 layer side]
and a bluish dye (ulmarine blue)] 61st layer silver halide emulsion A 0.26 Spectral sensitizing dye (ExSS-1) 1. 6x1o-' gelatin
1.11 Cyan Turnip 5- (
ExCC-1) 0.21 cyan coupler (Ex
CC-2) 0.26 ultraviolet absorber (ExUV
-1) 0.17 solvent (ExS-1)
0. 23 Development control agent (ExGC-1
) 0.02 Stabilizer (ExA-1) 0.00
6 Nucleation accelerator (ExZS-1) 3.0XIO-'
its jjE agent (N-I-1> 8.0XIO-
'E2nd layer gelatin 1.41 Color mixture prevention agent (ExKB-1) 0.09 Solvent
(ExS-1) 0. 10 Solvent (ExS-2>0. 10th E3
Layered silver halide emulsion A 0.23 spectral enhancing g dye (ExSS=2)3. OXI O'gelatin
1.05 Magenta Cub 5- (
ExMC-1) 0. 16 color image stabilizer (ExSA
-1) 0.20 solvent (ExS-3)
0. 25 Development control agent (ExGC-1
) 0.02 Stabilizer (ExA-1) 0.00
6 Nucleation accelerator (ExZS-1) 2.7xlO-'&
Nucleating agent (N-I-1) 1.4X10-5 E4 layer gelatin 0.47 Color mixing inhibitor (ExKB-1) 0.03 Solvent
(ExS-1) 0.03 solvent
(ExS-2) 0.03 E5 layer colloidal silver 0.09 Gelatin 0.49 Color mixing prevention agent (
ExKB-1) 0.03 solvent (
ExS-1) 0. 03 solvent
(ExS-2) 0. 03 E6 layer Same as 84th layer E7 layer Silver halide emulsion A 0.40 Spectral sensitizing dye (ExSS-3) 4. 2xto-'gelatin
2.1 Yellow coupler (
ExYC71) 0.51 solvent (Ex
S-2) 0. 20 solvent (E
xS-4) 0. 20 Development regulator (E
xGC-1) 0.06 stabilizer (ExA-1)
0.001 Nucleation accelerator (ExZS-1)5. ox
t Q-4 nucleating agent (N-I-1) i, 2X10-6
E8th layer gelatin 0.54 Ultraviolet absorber (ExUV-2) 0. 21 Solvent (E
xS-4> 0.08 E9 layer gelatin 1.28 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Latex particles of polymethyl methacrylate (average particle size 2.8 μm >0.05 81st layer gelatin 8.70 82nd layer Same as E9 layer, in addition to the above composition, gelatin hardening agent ExGK-1
and surfactant were added.

Preparation of Emulsion A A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate are added to an aqueous gelatin solution to which 0.5 g of 3°4-dimethyl-1,3-thiazoline-2-thione per mole of Ag is added while stirring vigorously. It took about 5 minutes at 55°C to add the particles simultaneously, and the average particle size was about 0.2 μm (silver bromide content: 4
A monodisperse silver chlorobromide emulsion of 0 mol %) was obtained. This emulsion contains 35 mg of sodium thiosulfate and 20 mg of sodium thiosulfate per mole of silver.
A chemical sensitization treatment was performed by adding chloroauric acid (tetrahydrate) and heating at 55° C. for 60 minutes.

Using the thus obtained silver chlorobromide particles as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and finally a monodisperse core/shell salt odor with an average particle diameter of 0°4μ... A silver oxide emulsion was obtained. The coefficient of variation in particle size was approximately 10%.

To this emulsion were added 3 mg of sodium thiosulfate and 3.5 mg of chloroauric acid (tetrahydrate) per mole of silver, and
A chemical sensitization treatment was performed by heating at °C for 50 minutes to obtain an internal latent image type silver halide emulsion A.

Compound used to prepare the sample (ExCC-’l) Cyan coupler (ExCC-2) Cyan coupler (ExMC-1) Magenta coupler C-L7 (ExYC-1>Yellow coupler (ExSS-1) Spectral sensitizing dye (ExSS-2) Spectral sensitizing dye (ExSS-3) Spectral sensitizing dye ■ SO,- (ExS-1) Solvent <ExS-2) Solvent (ExS-3) Solvent 1:l mixture (volume ratio) of (ExS-4) Solvent (ExUV-1) Ultraviolet absorber " CH, CH, C00C, H, t C41-Is(t).

CnHs(t) (1): (2): (3) 5:8:9 mixture (weight ratio) (ExUV-2) Ultraviolet absorber 2:Q of the above (1): (2): (3) :8 mixture (weighted) (ExSA-1) Color image stabilizer (ExKB-1) Color mixing inhibitor (ExGC-1) Development regulator (ExA-1) Stabilizer 4-hydroxy-5,6-)limethylene- 1°3.3a
,? -Tetrazaindene (EXZS-1) Nucleation accelerator 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazol'-hydrochloride (ExGK-1) Gelatin hardening agent 1- Oxy-3,5-dichloro-8-triazine sodium salt Next, Samples 102 to 109 were prepared in which the spectral sensitizing dye shown in Table 2 below was added instead of the spectral sensitizing dye ExSS-1 added to the E1 layer. Created.

The sample thus obtained was subjected to wet exposure (1/10 second, I
After applying the following processing step [A), the maximum color density and minimum color density of the cyan image were measured. The results are shown in Table 21.

Processing process CA) Time Temperature color development 80 seconds 38℃ bleach fixing
Wash with water at 38℃ for 30 seconds ■ 3
The replenishment method for water in the 38°C water bottle for 0 seconds was a so-called countercurrent replenishment method, in which the water in the water bottle was replenished into the washing bath (2) and the overflow liquid from the water bath (2) was led to the washing bath (2).

[Color developer]

Mother liquor Diethylenetriaminepentaacetic acid 0.5 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.5 g Diethylene glycol 8.0 g Benzyl alcohol 10.0 g Sodium bromide
0.5g sodium chloride
0.7g sodium sulfite 2
．． 0g N,N-diethylhydroxylamine 3.5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline 6.0g Potassium carbonate 30.0g Fluorescent brightener (stilbene type) Added 1.0 g of pure water to 1,000 ml of pH 1O, 5Q. The pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

- Mother liquor Ammonium thiosulfate 110 g Sodium hydrogen sulfite 10 g Iron(I) ethylenediaminetetraacetate Ammonium dihydrate 40 g Ethylenediaminetetraacetic acid disodium dihydrate 5 g 2-Mercapto-1,3,4- Add pure water 1000mApH7,
O pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water]

Pure water was used.

Here, pure water is water in which the concentrations of all cations other than hydrogen ions and all anions other than hydroxide ions in water ditch water are removed to 1 ppm or less by ion exchange treatment.

Table-2 *1: The amount added is 1 per mole of silver halide in the E1 layer.
．． 6 x 10-' moles.

*2: Indicated by the above compound number.

Spectral sensitization color;! I (A) Spectral sensitizing dye (B) From the results in Table 2, samples 104 to 109 of the present invention have a high maximum color density (Dmax,) and a minimum color density (p
It is clear that the value of min, ) is low and excellent.

Example 2 Samples 202 to 209 were prepared by adding the spectral sensitizing dye shown in Table 3 instead of the spectral sensitizing dye ExSS-2 in the E3 layer of sample 101 obtained in Example 1.

The sample thus obtained was exposed to wedge light (1×10 seconds, 1
0 CMS), the same treatment steps as in Example 1 [A
], and the maximum color density and minimum color density of the magenta color image were measured. The results are shown in Table-3.

Table-3 *3: Addition amount is 3 per mole of silver halide in the E3 layer
．． 0x10-' mol.

*4: Indicated by the above compound number.

Spectral sensitizing color g (C) Spectral sensitizing dye (D) As is clear from the results in Table 3, sample 204 of the present invention
-209 is excellent in that Dmax is high and Dmin is low.

In addition, when processing was performed in which the color development time in processing step (A) was changed to 120 seconds, samples 204-2 of the present invention were obtained.
09 has Dm compared to comparative sample 1'01.202-203.
The increase in in was significantly small, which was preferable.

Example 3 For samples 101 and 202-209, Example 1.
After applying wedge exposure similar to 2, the following processing step C
B) was applied and the maximum color density and minimum color density of the magenta color image were measured, and the same results as in Example 2 were obtained.

Processing step CB] Time Temperature color development 90 seconds 40℃ bleach fixing
40 seconds 38℃ water washing ■ 3
0 seconds 38℃ water washing ■ 30 seconds 38
°C [Color developer] Mother solution Ethylenediaminetetraacetic acid disodium dihydrate 1.0g Sodium sulfite 2.0g Sodium bromide
0.3g hydroxylamine sulfate
2.6g sodium chloride
3.2g 3-Methyl-4-amino-N-ethyl-N-hydroxyeylaniline 7.0g Potassium carbonate 30.0g Add pure water
1000 mf pH 10.50 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 110 g Sodium hydrogen sulfite 10 g Iron ethylenediaminetetraacetate (I[[) Ammonium dihydrate 40 g Ethylenediaminetetraacetic acid 2 Add pure water 100 Qmf, H6
, 5 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water]

Example 4 Same as treatment step [A] of Example 1 For samples 101 and 202 to 209, Example 1.
After applying the same wet exposure as in 2, the following processing steps [
C''l was applied and the maximum color density and minimum color density of the magenta color image were measured, and the same results as in Example 2 were obtained.

Processing process [C] Time Temperature color development") 135 seconds 36℃ bleach fixing 40 seconds 36℃ stability ■
40 seconds Stable at 36℃ ■ 40 seconds
Dry at 36℃ 40 seconds 7
0℃*1) 0.60M542 for 15 seconds from the start of color development
Color development processing was performed at 00''K while performing optical fogging.

[Color developer]

Mother liquor Hydroxyethyliminodiacetic acid 0.5g Monoethylene glycol 9.0g Benzyl alcohol 9.0g Monoethanolamine 2.5g Sodium bromide
0.3g sodium chloride
3.0 g N, N-diethylhydroxylamine 6.3 g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline
3.0 g 3-Methyl-4-amino-N-ethyl-N-hydroxyethylaniline 5.0 g Potassium carbonate 30.0 g Fluorescent brightener (Stilbene type) 1.0 g pH 10,30 pH is potassium hydroxide or hydrochloric acid Adjusted with.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 110 g Sodium hydrogen sulfite 10 g Diethylenetriaminepentaacetic acid iron (III) ammonium 80 g Diethylenetriaminepentaacetic acid 5g 2-Mercapto-5-amino-1,3,4-thiadiazole 0.3g Add pure water to 1000ml pH 6, 80 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother liquor 1-hydroxyethylidene-1゜1-diphosphonic acid 2.7go-phenylphenol 0.2g Potassium chloride
2.5 g bismuth chloride
1.0 g zinc chloride 0
．． 25g Sodium sulfite 0.3g
Ammonium sulfate 4.5 g Pure water was added to 1000 rrl pH 7.2 The pH was adjusted with potassium hydroxide or hydrochloric acid.

Example 5 Samples 502 to 509 were prepared by adding the spectral sensitizing dye shown in Table 4 instead of the spectral sensitizing dye ExSS-3 in the 87th layer of sample 101 obtained in Example 1.

The sample thus obtained was subjected to wedge exposure (1×10 seconds, I
OCMS), the same treatment steps as in Example 1 [A
], and the maximum color density and minimum color density of the yellow color image were measured. The results are shown in Table 4.

Table-4 *5: The amount added is 4 per mole of silver halide in the 87th layer.
．． 2×10-' moles.

*6: Indicated by the above compound number.

Spectral sensitizing dye (E) Spectral sensitizing dye (F) From the results in Table 4, samples 504-5゜9 of the present invention have Dm
It is clear that it is an excellent product with high ax and low Dmin.

Example 6 81st layer of samples 101 and 502-509.

Instead of the nucleating agent (N-I-1) added to the E3 layer and the E7 layer, the nucleating agent (N-I-9) was added to each layer (N-I-9).
Example 5 for the sample replaced with -1-1) in an equimolar amount
When the same test was conducted as in Example 5, the same results as in Example 5 were obtained.

Example 7 No. E of samples 101.202-209 obtained in Example 2
Example 2 was repeated, except that the three-layer magenta coupler (ExMC-1) was changed to the magenta coupler shown below, and the same results as in Example 2 were obtained.

However, in the process in which the color development time in process step CA was changed to 120 seconds, the Dmi of the comparative sample and the present invention sample was
The difference in the degree of increase in n was not as remarkable as in Example 2.

(Magenta coupler) i (Effects of the invention) According to the present invention, an internal latent image type silver halide photosensitive material which has not been fogged in advance is processed with a low pH color developing solution.
Direct positive color images with low minimum density and excellent maximum color density can be rapidly formed.

Further, it is possible to effectively suppress softening of the toe portion that may occur when such an internal latent image type photosensitive material is subjected to development processing.

Representative Patent Attorney (8107) Kiyotaka Sasaki (and 3 others)'
.

Claims (4)

[Claims] (1) After imagewise exposure of a light-sensitive material containing at least one unfogged internal latent image type silver halide emulsion layer and a color image-forming coupler on a support, in the presence of a nucleating agent, In a method of directly forming a positive color image by developing, bleaching and fixing with a surface color developer containing an aromatic primary amine color developer, the pH value of the developer is 1.
1.5 or less, the internal latent image type silver halide emulsion is a silver chlorobromide emulsion containing substantially no silver iodide, and the color image forming coupler is substantially non-diffusible. Moreover, it is a compound that generates or releases a dye upon oxidative coupling with the developer, and the light-sensitive material is a compound that is a sensitizing dye of the following general formula [I], general formula [II], or general formula [III]. A direct positive color image forming method characterized by containing at least one of the following. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula [I], Z_1 represents the atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle. It represents an alkyl group which may be the same or different, and may form a salt with a metal atom or other organic compound. L_1 represents a methine group. X^-_1 represents an anion, l_1 is 0 or 1 and is 0 when the dye forms an inner salt.) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In formula [II], Z_2 is a 5- or 6-membered nitrogen-containing complex Represents a group of atoms necessary to form a ring. R_3 and R_4 may be the same or different and represent an alkyl group, and may form a salt with a metal atom or other organic compound. L_2, L_3 and L_4 represents a methine group. There is It may form a salt with a metal atom or other organic compound. L_5, L_6 and L_7 represent a methine group. When forming, it is 0.) (2) The direct positive color image forming method according to claim (1), wherein the photosensitive material contains a coupler of the following general formula [IV]. General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In formula [IV], R_7 represents a hydrogen atom or a substituent,
X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Z_
a, Z_b and Z_c are methine, substituted methine, =N-
or -NH-, Z_a-Z_b bond and Z_b-
One of the Z_c bonds is a double bond, and the other is a single bond. The case where Z_b-Z_c is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, R_7 or
This also includes the case where a dimer or more multimer is formed. Also, Z
When _a, Z_b or Z_c is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer. ) (3) The internal latent image type silver halide emulsion is a silver chlorobromide core/shell emulsion that does not substantially contain silver iodide, and the interior (core) and/or surface of the emulsion is doped with a metal. A direct positive color image forming method as claimed in claim (1) or (2). (4) After imagewise exposure of the photosensitive material, the following general formula [N-I
] and/or [N-II] in the presence of a nucleating agent, developing, bleaching and fixing with a surface color developer containing an aromatic primary amine color developer. Direct positive color image forming method according to any one of range items (1) to (3). General formula [N- I] ▲ There are mathematical formulas, chemical formulas, tables, etc. Expression, Z^1^
1 may be substituted with a substituent. R^1^1 is an aliphatic group, and R^1^2 is a hydrogen atom, an aliphatic group, or an aromatic group. R^1^1 and R^1^2 may be substituted with a substituent. Also, R^1^2 is further Z^1^1
may be combined with a heterocycle completed by to form a ring. However, at least one of the groups represented by R^1^1, R^1^2 and Z^1^1 contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R
^1^1 and R^1^2 form a 6-membered ring to form a dihydropyridinium skeleton. Y^1 is a counter ion for charge balance, and n is 0 or 1. ) General formula [N-II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula [N-II], R^2^1 is an aliphatic group, an aromatic group,
or represents a heterocyclic group; R^2^2 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; group, or iminomethylene group (HN=C■); R^2^
3 and R^2^4 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group. however,
A hydrazone structure (▲numerical formula, chemical formula, table, etc. available▼) may be formed by including G, R^2^3, R^2^4, and hydrazine nitrogen. )