JPS63271339A - Photosensitive material - Google Patents

Abstract

PURPOSE:To improve the preservation stability of the titled material by incorporating a specified compd. in a binder in a fine particle state. CONSTITUTION:The titled material contains the compd. shown by formula I in the binder in the fine particle state. In formula I, N is a nitrogen atom, X is -O-, -S- or -N(R3)- group, R1, R2 and R3 are each a group except hydrogen atom or a single bond, EAG is an electron receiving group, Time is a group capable of releasing the group PUG after releasing the group (Time)t-PUG through the following reaction, (t) is 0 or 1, PUG is a photographic usable group as the group PUG or the group (Time)t-PUG, the group (Time)t-PUG bonds with at least one of groups R1, R2, R3 and EAG. Thus, the preservation stability of the titled material contg. a positive responsible type compd. is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photosensitive material, and particularly to a silver halide photosensitive material with improved storage stability.

(Prior Art) Compounds that provide photographically useful compounds that bind photographic reagents that are essentially immobile in photographic light-sensitive materials, or that are ballast stabilized or whose active sites are blocked are , Belgian Patent No. 810,195, U.S. Patent No. 4,199.354, U.S. Patent No. 3,980.47
No. 9, U.S. Patent No. 4,139.379, Japanese Unexamined Patent Publication No. 1983-1
No. 30゜927, No. 56-164342, No. 57-1
19345, US Pat. No. 4,564.577, and the like. Although such compounds are immobile or photographically inert, they can undergo intramolecular nucleophilic substitution reactions or intramolecular electron transfer reactions to release mobile, photographically useful groups.

However, many of these known positive-acting compounds have the disadvantage that they tend to release photographic reagents from areas other than those where they should be released (in many cases, even from areas where silver halide development is occurring). there were.

In response, new positive-responsive compounds have recently been developed. It is a compound that accepts or takes electrons, triggering a reaction in which a single bond between a nitrogen atom and an oxygen, sulfur, or nitrogen atom is cleaved, releasing a photographically useful group. This compound is a positive-responsive compound in the sense that it responds inversely to the development of silver halide, accepts electrons from the surviving reducing agent, and releases photographically useful groups. Such a new positive-responsive compound has been disclosed in Japanese Patent Application No. 1986-8 by the present applicant.
No. 8625, No. 61-87721, No. 62-3495
No. 4, No. 62-34953.

However, although this new positive-responsive compound is more stable than conventional compounds, it still has problems that need to be improved in terms of deterioration that occurs during long-term storage.

(Object of the Invention) The object of the present invention is to improve the storage stability of a photosensitive material containing a novel positive-responsive compound.

(Structure of the Invention) The object of the present invention has been achieved by a photosensitive material characterized by containing a compound represented by the following general formula (I) in the form of fine particles in a binder.

General formula (I) In the formula, N represents a nitrogen atom, and X represents -0-1-S-1 or -N(R3)-. Rt, Rz, Rs represent a group other than a hydrogen atom or a simple bond, EAG represents an electron-accepting group, Time is released as t-PUG, and then PUG is released through a subsequent reaction. t represents O or 1, PUG represents PU
G or (Time)t-PUG represents a photographically useful group, (Ti■e)t-PUG is R,,
R,, R3, and EAG (both bond to one).

An example will be given in which Rt, Rz, and R3 are groups other than hydrogen atoms.

(Optionally substituted alkyl group, aralkyl group 0) For example, methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group , aminomethyl group, acetylaminomethyl group, ethyl group, 2-(4-dodecanoylaminophenyl)ethyl group, carboxyethyl group, allyl group, 3,3.3-trichloropropyl group,
n-propyl group, 1so-propyl group, n-butyl group,
1so-butyl group, 5ec-butyl group, t-butyl group,
n-pentyl group, 5eC-pentyl group, 1-pentyl group, cyclopentyl group, n-hexyl group, 5ec-hexyl group, t-hexyl group, cyclohexyl group, n-octyl group, 5ec-octyl group, t-octyl group , n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group,
5ec-hexadecyl group, t-hexadecyl group, n-octadecyl group, t-octadecyl group, etc.) 1A → Sanhi (optionally substituted alkenyl group).

For example, vinyl group, 2-chlorovinyl group, 1-methylvinyl group, 2-cyanovinyl group, cyclohexen-1-yl group, etc.) Ezudo Ohdomasu (optionally substituted alkynyl group).

For example, ethynyl group, 1-propynyl group, 2-ethoxycarbonylmethyl group, etc.)
-chlorophenyl group, 4-acetylaminophenyl group,
4-hexadecanesulfonylaminophenyl group, 2-methanesulfonyl-'4-nitrophenyl group, 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group 3.2
゜4-dimethylphenyl group, 4-tetradecyloxyphenyl group, etc.), MJLMN (optionally substituted heterocyclic group, for example, 1-
imidazolyl group, 2-furyl group, 2-pyridyl group, 5-
Nitro-2-pyridyl group, 3-pyridyl group, 3.5-dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2-benzimidazolyl group, 2- benzoxacylyl group, 2-oxazolin-2-yl group, morpholino group, etc.), ヱ-,ztbK (acyl group which may be substituted with W. For example, acetyl group, propionyl group, butyroyl group, 1
so-butyroyl group, 2,2-dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group, 3-
acetylamino-4-methoxybenzoyl group, 4-methylbenzoyl group, 4-methoxy-3-sulfobenzoyl group, etc.), Sudo Soo Odoki (optionally substituted sulfonyl group).

For example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, n-octanesulfonyl group, n-dodecanesulfonyl 3, n-hexadecanesulfonyl group, benzenesulfonyl group, 4-toluenesulfonyl group , 4-
n-dodecyloxybenzenesulfonyl group, etc.), upper left corner (optionally substituted carbamoyl group 0, for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis-(2-methoxyethyl)carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, di-n-octylcarbamyl group, 3-
λ" ≦] Nirin Sanki (il
! Optionally substituted sulfamoyl group 0 For example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, diethylsulfamoyl group, bis-(2-methoxyethyl)sulfamoyl group, di-n-butylsulfamoyl group group, methyl-n-octylsulfamoyl group, n-hexadecylmethylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-N-methylsulfamoyl group, 4-decyloxyphenyl sulfamoyl group, methyloctadecylsulfamoyl group, etc.).

R1 and R1 are substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups,
An acyl group, a sulfonyl group, etc. are preferred. R1 and R
The number of carbon atoms in 1 is preferably 1 to 40.

R2 is preferably a substituted or unsubstituted acyl group or sulfonyl group. Examples are the same as the acyl group and sulfonyl group mentioned for R1 and R3.

(The number of carbon atoms is preferably 1 to 40) -R+, Ri, R1 and EAC may be bonded to each other to form a ring.

EAG will be described later.

Furthermore, in order to achieve the object of the present invention, among the compounds represented by the general formula (I), those represented by the general formula CI+) are preferable.

General formula (n) (Tli+e)t-PUG binds to at least one of R4 and EAG.

Y is a divalent linking group, preferably -(C-0)- or -5Ot-, and X has the same meaning as above.

R4 represents an atomic group that combines with X and Y to form a 5- to 6-membered monocyclic or condensed heterocycle including a nitrogen atom.

Preferred specific examples of the portion corresponding to this heterocycle are described below.

EAG EAG
EAGl! ! AG EAG EAG EAG EAG
[EAG COR'R'
R'RAG
EAGEAG EAG
EAGEAG EAG [EAGEAG
RAG EAGEAG
EAG
EAGEAG
EAG EAGEAG [EAG BAG[
EAG [EAG
In EAGAG, :,, :, R', R'', R', R'' are hydrogen atoms or substituents, and R5, R&, R? As R8, a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group is preferred, and as R8, an acyl group, a sulfonyl group, etc. are preferred.

More particularly preferred examples are listed below, including the bonding position of (Time+t PU G).

However, the compounds of the present invention are not limited thereto.

ivy [! AG AG C1 old.

■ AG AG AG AG CH=CH1 ■ ― AG CH! +Time÷tpuc AG AG ■ AG AG A.C. ■ EAG AG AG ■ AG Cabinet AG [A.G. ■ AG AG AG AG AG AG More details will be described later regarding specific compounds.

EAG represents an aromatic group that accepts or takes electrons from a reducing substance and is bonded to a nitrogen atom. EAG is preferably a group represented by the linear general formula (A).

General Formula (A) In the general formula (A), v and 1 represent an atomic group that forms a king or six-membered aromatic compound together with Z+ and Zz, and n represents an integer from 3 to 3.

V, ;-Z3-1V4; Zs Za-1■.

i Zz 24 2%-1Vh: Zs Z4
-2%-Z, -1V,; Zs-Za Zs Z
b-Z, -1 Vai Zs Za Zs Zb
27-Z, -.

Sub 5ub I Sub represents -0-1-S-1 or -SO-1, and each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Sub may be the same or different, or may be bonded to each other to form a king to six-membered saturated or unsaturated carbocycle or heterocycle.

In general formula (A), the sum of the Hammett substituent constant sigma para of the substituents is +0.50 or more, more preferably +0.
Select Sub so that it is 70 or more, most preferably +0.85 or more.

EAG will be described in more detail.

EAG represents a group that accepts or takes electrons from a reducing substance, and is bonded to a nitrogen atom. EAG is preferably an aryl group or a heterocyclic group substituted with at least one electron-withdrawing group. A substituent bonded to the 71-nol group or heterocyclic group of EAG can be used to adjust the physical properties of the entire compound. Examples of physical properties of the entire compound include ease of accepting electrons, water solubility, oil solubility, diffusibility, sublimation, melting point, dispersibility with binders such as gelatin, and reaction with nucleophilic groups. It can be used to adjust the properties, reactivity toward electrophilic groups, etc.

Next, a specific example of EAG will be given.

Examples of aryl groups substituted with at least one electron-withdrawing group include 4-nitrophenyl group, 2-nitrophenyl group, 2-nitro-4-N-methyl-N-n-butylsulfur group, Famoylphenyl group, 2-nitro-4-N-methyl-N-n-octylsulfamoylphenyl group, 2-nitro-4-N-methyl-N-n-
dodecylsulfamoylphenyl group, 2-nitro-4-
N-methyl-N-n-hexadecylsulfamoylphenyl group, 2-nitro-4-N-methyl-N-〇-octadecylsulfamoylphenyl group, 2-nitro-4-N
-Methyl-N-(3-carboxypropyl)sulfamoylphenyl group, 2-nitro-4-N-ethyl-N=(
2-Sulfoethyl)sulfamoylphenyl group, 2-nitro-4-N-hexadecyl-N-(3-sulfopropyl)sulfamoylphenyl group, 2-nitro-4-
N-(2-cyanoethyl)-N-((2-hydroxyethoxy)ethyl)sulfamoylphenyl group, 2-nitro-4-diethylsulfamoylphenyl group, 2-nitro-4-di-n-butylsulf famoylphenyl group, 2
-nitro-4-di-n-octylsulfamoylphenyl group, 2-nitro-4-di-n-octadecylsulfamoylphenyl group, 2-nitro-4-methylsulfamoylphenyl group, 2-nitro- 4-n-hexadecylsulfamoylphenyl group, 2-nitro-4-N-methyl-N-(4-dodecylsulfonylphenyl)sulfamoylphenyl group, 2-nitro-4-(3-methylsulfamoyl phenyl) sulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-butylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-octylsulfamoylphenyl group, 4-nitro-2-N
-Methyl-N-n-dodecylsulfamoylphenyl group, 4-, nitro-2-N-methyl-N-n-hexadecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n -octadecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-(3-carboxypropyl)sulfamoylphenyl group, 4-nitro-2
-N-ethyl-N-(2-sulfoethyl)sulfamoylphenyl group, 4-nitro-2-N-n-hexadecyl-N-(3-sulfopropyl)sulfamoylphenyl group, 4-nitro-2- N-(2-cyanoethyl”) −
N-((2-hydroxyethoxyethyl)sulfamoylphenyl group, 4-nitro-2-diethylsulfamoylphenyl group, 4-nitro-2-di-n-butylsulfamoylphenyl group, 4-nitro- 2-di-n-octylsulfamoylphenyl group, 4-nitro-2-di-n
-octadecylsulfamoylphenyl group, 4-nitro 2-methylsulfamoylphenyl group, 4-nitro-
2-n-hexadecylsulfamoylphenyl group, 4-
Nitro-2-N-methyl-N-(4-dodecylsulfonylphenyl)sulfamoylphenyl group, 4-nitro-
2-(3-methylsulfamoylphenyl)sulfamoylphenyl group, 4-nitro-2-chlorophenyl group,
2-nitro-4-chlorophenyl group, 2-nitro-4-
N-methyl-N-n-butylcarbamoylphenyl group,
2-nitro-4-N-methyl-N-n-octylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-
n-dodecylcarbamoylphenyl group, 2-nitro-4
-N-methyl-N-n-hexadecylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-n-octadecylcarbamoylphenyl group, 2-nitro-4-N-
)-1-N-(3-carboxypropyl)carbamoylphenyl group, 2-nitro-4-N-ethyl-N-(
2-sulfoethyl)carbamoylphenyl group, 2-nitro-4-N-n-hexadecyl-N-(3-sulfopropyl)carbamoylphenyl group, 2-nitro-4-N-
(2-cyanoethyl)-N-((2-hydroxyethoxy)ethyl)carbamoylphenyl group, 2-nitro-4
-diethylcarbamoylphenyl group, 2-nitro-4-
di-n-butylcarbamoylphenyl group, 2-nitro-
4-di-n-octylcarbamoylphenyl group, 2-nitro-4-di-n-octadecylcarbamoylphenyl group, 2-nitro-4-methylcarbamoylphenyl group,
2-nitro-4-n-hexadecylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-(4-dodecylsulfonylphenyl)carbamoylphenyl group, 2-
Nitro-4-(3-methylsulfamoylphenyl)carbamoylphenyl group, 4-nitro-2-N-)thyl-
N-n-butylcarbamoylphenyl group, 4-nitro-
2-N-methyl-N-n-octylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-n-dodecylcarbamoylphenyl group, 4-nitro-2-N-methyl-Nn-hexadecy carbamoylphenyl group, 4-
Nitro-2-N-methyl-N-n-octadecylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-
(3-carboxypropyl)carbamoylphenyl group,
4-nitro-2-N-ethyl-N-(2-sulfoethyl)carbamoylphenyl group, 4-nitro-2-N-n-
Hexadecyl-N-(3-sulfopropyl)carbamoylphenyl L 4-nitro-2-N-(2-cyanoethyl) -N-((2-hydroxyethoxy)ethyl)carbamoylphenyl group, 4-nitro-2-diethylcarbamoyl Phenyl group, 4-nitro-2-di-n-butylcarbamoylphenyl group, 4-nitro-2-di-n-
Octylcarbamoylphenyl group, 4-nitro-2-di-n-octadecylcarbamoylphenyl group, 4-nitro-2-methylcarbamoylphenyl group, 4-nitro-
2-n-hexadecylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-(4-dodecylsulfonylphenyl)carbamoylphenyl group, 4-nitro-2-
(3-methylsulfamoylphenyl)carbamoylphenyl group, 2,4-dimethanesulfonylphenyl group, 2
-methanesulfonyl-4-benzenesulfonylphenyl &, 2-n-octanesulfonyl-4-methanesulfo-
Nylphenyl group, 2-n-tetradecanesulfonyl-4
-methanesulfonylphenyl &, 2-n-hexadecanesulfonyl-4-methanesulfonylphenyl L2.4-
Di-n-dodecanesulfonylphenyl 275.2. 4
-') V decanesulfonyl-5-trifluoromethylphenyl group, 2-n-decanesulfonyl-4-cyano-5
-trifluoromethylphenyl group, 2-cyano-4-methanesulfonylphenyl L 2,4゜6-dolycyanophenyl group, 2,4-dicyanophenyl group, 2-nitro-
4-methanesulfonylphenyl group, 2-nitro-4-n
-dodecanesulfonylphenyl group, 2-nitro-4-(
2-Sulfoethylsulfonyl) phenyl group, 2-nitro-4-carboxymethylsulfonylphenyl L2-nitro-4-carboxyphenyl group, 2-nitro-4-ethoxycarbonyl-5-n-butoxyphenyl group, 2 -nitro-4-ethoxyrobonyl-5-n-hexadecyloxyphenyl group, 2-nitro-4-diethylcarbamoyl-5-n-hexadecyloxyphenyl group, 2-nitro-4-cyano-5-n-dodecyl group phenyl group, 2,
4-dinitrophenyl group, 2-nitro-4-n-decylthiophenyl L3.5-dinitrophenyl group, 2-nitro-3,5-dimethyl-4-n-hexadecanesulfonyl group, 4-methanesulfonyl-2= Benzenesulfonylphenyl group, 4-n-octanesulfonyl-2-methanesulfonylphenyl group, 4-n-tetradecanesulfonyl-2-methanesulfonylphenyl 1.4-n-hexadecanesulfonyl-2-methanesulfonylphenyl group,
2.5-Cytodecanesulfonyl-4-trifluoromethylphenyl! , 4-n-decanesulfonyl-2-cyano-5-trifluoromethylphenyl group, 4-cyano-2
-Methanesulfonylphenyl group, 4-nitro-2-methanesulfonylphenyl group, 4-nitro-2-n-dodecanesulfonylphenyl group, 4-nitro-2-(2-sulfoethylsulfonyl)phenyl group, 4-nitro 2-carboxymethylsulfonylphenyl group, 4-nitro-2
-carboxyphenyl group, 4-nitro-2-ethoxycarbonyl-5-n-butoxyphenyl group, 4-nitro-
2-ethoxykawabonyl-5-n-hexadecyloxyphenyl group, 4-nitro-2-diethylcarbamoyl-
5-n-hexadecyloxyphenyl group, 4-nitro-
2-cyano-5-n-dodecyl phenyl group, 4-nitro-2-n-decylthiophenyl group, 4-nitro-3゜5
-dimethyl-2-n-hexadecanesulfonyl group, 4-
Nitronaphthyl group, 2,4-dinitronaphthyl group, 4-
Nitro-2-n-octadecylcarbamoylnaphthyl group, 4-nitro-2-dioctylcarbamoyl-5-(3
-sulfobenzenesulfonylamino) naphthyl group, 2.
3.4,5゜6-pentafluorophenyl group, 2-nitro-4=benzoylphenyl group, 2,4-diacetylphenyl group, 2-nitro-4-trifluoromethylphenyl group, 4-nitro-2- Trifluoromethylphenyl group, 4-nitro-3-trifluoromethylphenyl group, 2
, 4.5-tricyanophenyl group, 3.4-dicyanophenyl group, 2-chloro-4,5-dicyanophenyl group,
2-promo 4゜5-dicyanophenyl group, 4-methanesulfonyl group% 4-n-hexadecanesulfonylphenyl group, 2-decanesulfonyl-5-trifluoromethylphenyl group, 2-nitro-5-methylphenyl group, 2 −
Nitro-5-n-octadecyloxyphenyl group, 2-
Nitro-4-N-(vinylsulfonylethyl)-N-methylsulfamoylphenyl group, 2-methyl-6-nidropenzoxazol-5-yl group, etc.

Examples of heterocyclic groups include, for example, 2-pyridyl group, 3-
Pyridyl group, 4-pyridyl group, 5-nitro-2-pyridyl group, 5-nitro-N-hexadecylcarbamoyl-2
-pyridyl group, 3,5-dicyano-2-pyridyl group, 5
-dodecanesulfonyl-2-pyridyl group, 5-cyano-
2-pyrazyl group, 4-nitrothiophen-2-yl group,
5-nitro-1,2-dimethylimidazol-4-yl group, 3.5-diacetyl-2-pyridyl group, 1-dodecyl-5-carbamoylpyridinium-2-yl group, 5-
Nitro-2-furyl group, 5-nitropentthiazole-
2-yl group, etc.

Time is 1! without causing cleavage of nitrogen-oxygen, nitrogen-nitrogen, or nitrogen-sulfur bonds. represents a group that releases PUG through a subsequent reaction.

Various groups represented by Ti+ee are known, for example, JP-A-61-147244, pages (5)-(6), JP-A-61-147244, pages 61-
No. 236549 (8) page-041, patent application 1988-88
Examples include the groups described in No. 625, pages (36) to (44).

PUG represents a photographically useful group as Time-PUG or PUG.

Photographically useful groups include, for example, development inhibitors, development accelerators, nucleating agents, couplers, diffusible or non-diffusible dyes, desilvering promoters, desilvering inhibitors, halogenated radical solvents, competing compounds, developer, auxiliary developer, fixing accelerator, fixing inhibitor,
Image stabilizers, color toning agents, processing-dependent improvers, halftone improvers, color image stabilizers, photographic dyes, surfactants, hardeners, desensitizers, contrast agents, chelating agents, Represents optical brighteners, ultraviolet absorbers, etc., or their precursors.

Since these photographically useful groups often overlap in terms of usefulness, representative examples will be specifically explained below.

Examples of development inhibitors include halogen atoms (bromine, iodine, etc.), compounds having a mercapto group bonded to a heterocycle, such as substituted or unsubstituted mercaptoazoles (specifically l-phenyl-5-mercaptotetrazole,
1-(4-carboxyphenyl)-5-mercaptotetrazole, 1-(3-hydroxyphenyl)-5-mercaptotetrazole, 1-(4-sulfophenyl)-5
-Mercaptotetrazole, 1-(3-sulfamoylphenyl)-5-mercaptotetrazole, 1-(4-sulfamoylphenyl)-5-mercaptotetrazole, ■-
(3-hexanoylaminophenyl)-5-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, ■-(2-carboxyethyl)-5-mercaptotetrazole, 2-methylthio-5-mercapto-1,3
゜4-thiadiazole, 2-(2-carboxyethylthio)-5-mercapto-1,3,4-thiadiazole,
3-methyl-4-phenyl-5-mercapto-1,2,
4-1-Riazole, 2-(2-dimethylaminoethylthio)-5-mercapto-1,3,4-thiadiazole, 1(4-n-hexylcarbamoylphenyl)-2
-mercaptoimidazole, 3-acetylamino-4-
Methyl-5-mercapto-1,2,4-triazole,
2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole,
2-Mercapto-6-nitro-1°3-benzoxazole, 1-(I-naphthyl)-5-mercaptotetrazole, 2-phenyl-5-mercapto-1,3,4-oxazole, 1-(3-( 3-methylureido)phenyl)-5-mercaptotetrazole, 1-(4-nitrophenyl)-5-mercaptotetrazole, 5-(2
-ethylhexanoylamino)-2-mercaptobenzimidazole, etc.), substituted or unsubstituted mercaptoazaindene (specifically, 6-methyl-4-mercapto-1,3,3a-7-tetrazaindene, 6-methyl-2-benzyl-4-mercapto-1,3,3a,7
-tetrazaindene, 6-phenyl, -4-mercaptotetrazaindene, 4,6-dimethyl-2-mercapto-1,3,3a, 7-tetrazaindene, etc.), substituted or unsubstituted mercaptopyrimidines (specifically Target is 2
Heterocyclic compounds capable of producing iminosilver, such as substituted or unsubstituted benzotriazoles ( Specifically, benzotriazole, 5
-Nitrobenzotriazole, 5-methylbenzotriazole, 5,6-dichlorobenzotriazole, 5-bromobenzotriazole, 5-methoxybenzotriazole, 5-acetylaminobenzotriazole, 5-n
Substituted or unsubstituted indazoles (specifically, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole, 3-cyanoindazole, 3-n-butylcarbamoylindazole, 5-nitro-3-methanesulfonylindazole, etc.), substituted or unsubstituted. Substituted benzimidazole M (specifically, 5-nitrobenzimidazole, 4-nitropenzimidazole, 5,6-dichlorobenzimidazole, 5-cyano-6-chlorobenzimidazole, 5-trifluoromethyl-6= chlorpenzimidazole, etc.). In addition, the development inhibitor is released from the redox core of general formula (f) by the reaction following the redox reaction in the development process, and then becomes a compound that has development inhibiting properties, and furthermore, it substantially inhibits development. It may be a compound that has no or significantly reduced properties.

Specifically, 1-(3-phenoxycarbonylphenyl)
-5-mercaptotetrazole, 1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole,
1-(3-maleinimidophenyl)5-mercaptotetrazole, 5-(phenoxycarbonyl)benzotriazole, 5-(p-cyanophenoxycarbonyl)benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4 -thiadiazole, 5
-nitro-3-phenoxycarbonylindazole, 5
-Phenoxycarbonyl-2-mercaptobenzimidazole, 5-(2,3-dichloropropyloxycarbonyl)benzotriazole, 5-benzyloxycarbonylbenzotriazole, 5-(butylcarbamoylmethoxycarbonyl)benzotriazole, 5-(butoxycarbonyl) methoxycarbonyl)benzotriazole, 1-(4-benzoyloxyphenyl)-5-mercaptotetrazole, 5-(2-methanesulfonylethoxycarbonyl)-2-mercaptobenzothiazole, 1
- +4- (2-chloroethoxycarbonyl)phenyl)-2-mercaptoimidazole, 2- C3-(thiophen-2-ylcarbonyl)propylcothio-5-
Mercap)-1,3,4-thiadiazole, 5-cinnamoylaminobenzotriazole, 1-<3-vinylcarbonylphenyl)-5-mercaptotetrazole, 5
-succinimidomethylbenzotriazole, 2-(4
-succinimidophenyl)-5-mercapto-1,3
,4-oxadiazole,3-(4-(benzo-1,
2-isothiazole-3-oxo-1,1-dioxy-
2-yl)phenyl)-5-mercapto-4-methyl-
Examples include 1,2°4-triazole and 6-phenoxycarbonyl-2-mercaptobenzoxazole.

When PUG is a diffusible or non-diffusible dye, the dye may include an azo dye, an azomethine dye, an azopyrazolone dye, an indoaniline dye, an indophenol dye,
Examples include anthraquinone dyes, triarylmethane dyes, alizarin, nitro dyes, quinoline dyes, indigo dyes, and phthalocyanine dyes. Also included are their leuco forms, those with temporarily shifted absorption wavelengths, and dye precursors such as tetrazolium salts. Additionally, these dyes may form chelate dyes with appropriate metals, as described, for example, in U.S. Pat. No. 3,880,658; U.S. Pat. No. 3,931.
No. 144 - No. 3,932.380; No. 3,932
, No. 381 and No. 3,942,987.

Preferred dyes and dye precursors are Abu dyes, azomethine dyes, indoaniline dyes, and dye precursors thereof. Specific examples of preferred dyes and dye precursors are shown below.

H 0tNHz 0■ D-4 H OCR(CH3)t D-13 0H H ■ H 0C7Hts(n) H 0■ H Hs H H ■ D-23 0H 〇 〇〇婁0-C-0-C-0J! 0JHz 0)1 0H 0■ SO! NH! S(h calls\, / CIIzCHzSOJa■ 0CH(CHs)z υN D-42 Shi! 0zl1 CH, /ゝC1l□CHJH5(hclIt〇
Examples of the case where PUG is a silver halide solvent include JP-A No. 60-163042 and U.S. Patent No. 4゜003.91.
0, U.S. Patent No. 4,378,424, etc., mercaptoazoles or azolethiones having an amino group as a substituent described in JP-A-57-202531, etc., and more. Specifically, those described in Japanese Patent Application No. 1988-71768 can be mentioned.

An example of a case where F'LJG is a nucleating agent is disclosed in JP-A-59
-170840 No. i3! ψ is the part of the leaving group released from a certain coupler.

Crying, groaning, soul ψ −−−N ν
Yen=mouth size ro
4 啼 υ
,C+
B~
To-N's ■
cry
1M of
cQ11
(Ju cry
-Q's 0-mouth's 4's ψ
ψ taste
co
B:e
+6 e′u l = rate 00
■Totoro -Co
O0 The compound of the present invention can be used in a wide range. The preferred amount used varies depending on the type of PUG. For example, when PUG is a diffusive dye, it depends on the extinction coefficient of the dye, but 0.05
mmol/rrl to 50 mmol/d, preferably 0.
It is used at 1 mmol/rrr to 5 mmol/d. lXl per mole of silver halide if it is a development inhibitor.
It is preferable to use 0-' mol to IX 10-' mol, particularly preferably 1X10-''mol-1X10-'.In addition, when PUG is a development accelerator and a nucleating agent, the above-mentioned development inhibitor A similar addition amount is preferred, if PUG is a silver halide solvent, I x 10-' mole to 1 x 10°3 per 111 moles of halide.
It is preferably used in a molar range, particularly preferably in a molar range of 1X10-' to IX10-'.

The photosensitive material of the present invention contains the compound of general formula (I) in the form of fine particles.

The fine particles referred to here have an average particle size of 0.01 to 50.
Particles are meant in the range .mu.m, preferably between 0.05 and 5 .mu.m.

By doing this, the compound of general formula (I) is locally present in the binder, and as a result, it does not decompose to release active groups or deteriorate during storage of the photosensitive material. The dependence of the photosensitive material is improved.

In order to add the compound of the present invention into a film, it is preferable to make an aqueous dispersion of fine particles of the compound of the present invention and add it to the coating solution, but it is also possible to add the fine particles as they are to the solution. Alternatively, it may be added in the form of the above dispersion from which water has been removed.

In order to make an aqueous dispersion of fine particles of the compound of the present invention, it is effective to grind a hydrophobic photographic reagent into fine particles and disperse them in water. Usually carried out in a suitable mill, the shear force must be sufficient to reduce the material to the required particle size within a reasonable time.

Examples of mills (pulverizer 11F) suitable for the present invention are listed below.

1. Be Forras, Maschinenfabriken Cologne (
P, Vollrath, Maschinenfab
Sand mill (Sand 5) manufactured by Riken Koln
ill) 2, Drarswerke Gs+bH8Nan
Bead mill (bead mill) 3, manufactured by nheim), W Ny Batiffen, Maschinenfabriken, Bachofen (-2^, Bachofen).

Masc hinenfabriken, Ba5el
) Dyno Mill (Dyno mill) 4, Masap AG Matzendorf Sc
Masap m1ll manufactured by hweiz
) 5, Nippon Seiki's new homogenizer (homog)
enlzar) Processing methods and suitable mills are described in U.S. Pat. No. 2,581°414.
No. 2.855.156 and JP-A-52-11
It is also described in the specification of No. 0012.

The processing method will be briefly explained below.

The crushing container is housed in a cooling jacket and is cooled with a cooling liquid during crushing. The amount of cooling fluid (eg running water) is generally sufficient to virtually completely remove the heat generated by the grinding and to ensure that the temperature of the material being ground does not rise above 40°C.

The average particle size of the grinding elements (eg glass beads) used will depend on the particle size of the compound of the invention to be ground.

The average particle size of the compound of the present invention to be crushed is preferably 2/3 or less of the particle size of the crushing element.

If the compound of the invention to be milled has a particle size larger than this, it is desirable to first reduce its size by conventional methods.

Also, the amount of grinding elements should be at least about 3 to 4 times the amount of the compound of the invention to be ground. As the crushing element, in addition to glass peas, quartz sand, silicon carbide sand, etc. can be used. The aqueous dispersion of positive response compound fine particles used in the present invention is prepared, for example, as follows.

20 g of the compound of the present invention to be ground is mixed with glass beads [for example, Mahlkorper MK-3GX (Mahlkorper M 3Gx) 0.5-0.
75 m diameter] and ground with 50 cc of water and 10 cc of 10% dispersant. The flow rate of the cooling water is adjusted to maintain the internal temperature of the mill below 40°C.The entire contents of the mill are filtered through a filter with appropriate pore size to separate the glass beads.

Wetting agents and/or binders can be added as necessary during grinding in a mill or to the filtrate (aqueous dispersion) after grinding or filtration.

Next, we will discuss how to make an aqueous dispersion without using a grinder such as a mill.

Dissolve the compound of the present invention to be dispersed in an organic solvent that is miscible with water, such as alcohol, and gradually add the organic solution while stirring the water containing a surfactant. 0. Dissolve the compound of the present invention in the form of fine particles in water. A stable aqueous dispersion can also be obtained by precipitating and removing the organic solvent from this solution using an evaporator, ultrafiltration membrane, etc.

However, this method cannot be used if the compound of the present invention is insoluble in the organic solvent, and it takes time and effort to remove the organic solvent afterwards to obtain a stable aqueous dispersion. More preferable is a method of pulverizing into fine particles (solid dispersion method).

The above aqueous dispersion preferably contains a dispersant; useful dispersants include urea and thiourea derivatives described in JP-A-53-102733; saturated and unsaturated mono- and di-carbon Acid amides; Lactams; Acid imides or their derivatives; Oximes; Saturated and unsaturated 5= or 6-membered heterocyclic compounds containing O,
with S, CO and NH and optionally OH, NH
I, substituted with a halogen atom, an alkyl group (preferably one having 1 to 4 carbon atoms), a phenyl group, or a hydroxyalkyl group (preferably one having 1 to 3 carbon atoms); at least divalent aliphatic or Aromatic alcohols; polyalkylene glycols; carbamate esters; benzene derivatives; monomeric, oligomeric and polymeric alkyl-aryl sulfonates having at least 18 carbon atoms as described in JP-A-52-110012; etc.

The amount of dispersant used is preferably 80% by weight or less of the aqueous dispersion.

The aqueous dispersion preferably contains a wetting agent. Useful wetting agents include alkyl polyglycol ethers, alkylphenyl polyglycol ethers, and fatty acid polyglycol ester acids described in JP-A-53-102733. Nonionic surfactants such as; carbon number 8-1
Sulfuric acid cylinder 1 or secondary aliphatic alcohols with 8, sulfated unsaturated fatty acids, sulfated fatty acid amides, sulfated alkyleneoxy adducts, sulfated partially esterified polyhydric alcohols, alkyl sulfonates, naphthenes Sulfonates, olefin sulfonates, marzlates,
Sodium dialkyl sulfosuccinates, taurides, alkylaryl sulfonates, mono- and dialkylnaphthalene sulfonates, condensation products of naphthalene sulfonic acid and formaldehyde, lignin sulfonates, oxylignin sulfonates, polycarboxylic acid esters and sulfonates of polycarboxylic acid amides, condensation products of fatty acids and aminoalkyl sulfonates, and anionic surfactants such as phosphorylated surfactants.

In addition, surfactant science series
No. 1 Nonionifuku Surfactant (Surfa)
ctant 5science 5eries volo
a+e I.

Non1onic 5urfactants) (Martin Jay Schickli (Edited by
Marten J, 5chick), Marcel Dekker Inc. 19
67) Surface Active Ethy
lene OxideAdducts) (Schoufeldt.

Written by Pergamon (Perga+won)
Also useful are nonionic surfactants, such as those described in publications such as J.D. Press, 19693.

The amount of wetting agent used is preferably 50 percent by weight or less of the aqueous dispersion.

The aqueous dispersion used in the invention preferably contains a binder; useful binders are hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, cellulose derivatives, and polysaccharides such as starch, gum acacia, etc. These include natural substances, water-soluble polyvinyl compounds such as polyvinylpyrrolidone, acrylamide polymers, and dispersed vinyl compounds in the form of latex.

Particularly preferred is gelatin. The amount of binder used is preferably 10 percent by weight or less of the aqueous dispersion.

As for the method and apparatus for removing or drying water from the aqueous dispersion used in the present invention, known methods can be used. Freeze drying method can be applied.

In the present invention, a reducing substance is used, but the reducing substance may be incorporated into the processing solution from outside the color light-sensitive material of the present invention, or may be incorporated in advance into the photosensitive material. Alternatively, the reducing substance may be contained in the sensitive material in advance and then the same or different reducing substance may be applied from the processing solution.

The reducing substance may be an inorganic compound or an organic compound, but its oxidation potential is preferably lower than the standard oxidation-reduction potential of silver ions/silver, 0.8 .

Examples of inorganic compounds include metals with an oxidation potential of 0.80 V or less, such as Mn, Ti, St, Zn, Cr, Fe, and Co.

Mo, Sn+ Pb, W, H,, Sb, Cut
Hg.

etc., ions with an oxidation potential of 0.8v or less or their complex compounds,
For example, Cr", V", Cu", Fe", MnO4"'+1-
, Co (CN)&'-, Fe (CN)6'-
1(Fe-EDTA)"-, metal hydrides with an oxidation potential of 0.8 V or less, such as NaH,
LiH, KH, NaBHa, LiBH4゜L
i A l (Ot CnHv)sHlL t A 1
Sulfur or phosphorus compounds with an oxidation potential of 0.8v or less, such as (OCH3)3H, such as NazSOz+ NaH5+ Na1lSOs+ Hs
Examples include P, IIzS+ NaxS, NagSz, etc.

As reducing substances for organic compounds, organic nitrogen compounds such as alkylamines or arylamines, organic sulfur compounds such as alkyl mercaptans or aryl mercaptans, or organic phosphorus compounds such as alkyl phosphines or arylphosphines can also be used. Kendal-Pelz formula (Kendal-Pelz formula) described in "The Theory of the Photographic Ink Process" by James, 4th edition (I977), p.299
Silver halide reducing agents according to the following are preferred.

Examples of more preferable reducing agents include the following.

3-pyrazolidones and their precursors [e.g. 1
-phenyl-3-pyrazolidone, -phenyl-4.4
-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-
m-) lilu-3-pyrazolidone, x-p-+-lilu 3
-Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, ■-Phenyl-4.4-bis(hydroxymethyl)-3-pyrazolidone, 1.4-di- Methyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4.4-dimethyl-3-pyrazolidone, 1-(3-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-chlorophenyl)-4- Methyl-3-pyrazolidone, 1-(4
-) lyle) -4-methyl-3-pyrazolidone, 1-(
2-Tolyl)-4-methyl-3-pyrazolidone, 1-(
4-tolyl)-3-pyrazolidone, 1-(3-)lyl)
-3-pyrazolidone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidone, 1-(2-trifluoroethyl)-4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone , 1,5-diphenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-stearoyloxymethyl-3-pyrazolidone, l-phenyl-
4-Methyl-4-lauroyloxymethyl-3-pyrazolidone, 1-phenyl-4,4-bis-(lauroyloxymethyl)-3-pyrazolidone, 1-phenyl-2-
Acetyl-3-pyrazolidone, 1-phenyl-3-acetoxypyrazolidone] hydroquinones and their precursors [e.g., hydroquinone, toluhydroquinone, 2゜6-dimethylhydroquinone, t-butylhydroquinone, 2,5-di-t -butylhydroquinone,
t-octylhydroquinone, 2.5-di-t-octylhydroquinone, pentadecylhydroquinone, 5-
Sodium pentadecylhydroquinone-2-sulfonate, p-benzoyloxyphenol, 2-methyl-4
-benzoyloxyphenol, 2-t-butyl-4-
(4-chlorobenzoyloxy)phenol], another example of a silver halide reducing agent that is also useful is a color developer, which is described in U.S. Pat.
No. 86 describes a p-phenylene color developer represented by N,N-diethyl-3-methyl-p-phenylenediamine.

Additional useful reducing agents include U.S. Pat. No. 3,761.2.
Aminophenol is described in No. 70. Among the aminophenol reducing agents, 4-amino-
2,6-dibromophenol, 4-amino-2,6-dibromophenol, 4-amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, 4-amino-2,6-dichlorophenol hydrochloride and so on. Furthermore, Research Disclosure Magazine No. 151 Na15108, U.S. Patent No. 4.0
No. 21,240 describes 2,6-dichloro-4-W-substituted sulfonamidophenol, 2,6-dipromo-4-substituted sulfonamidophenol, and JP-A-59-116740 describes p-(N,N-dialkyl Aminophenyl) sulfamine and the like have been described and are useful. In addition to the above phenolic reducing agents, naphthol reducing agents, such as 4-amino-naphthol derivatives and
The 4-substituted sulfonamide naphthol derivatives described in No. 0 are particularly useful. Furthermore, as a general color developer that may be applied, U.S. Pat. No. 2,895,825
The aminopyrazoline derivatives described in U.S. Pat.
Monthly issue 227-230. Pages 236-240 (RD-1
9412, RD-19415) describe hydrazone derivatives. These color developers may be used alone or in combination of two or more.

When a light-sensitive material contains a diffusion-resistant reducing substance, an electron transfer agent (ETA) may be used in combination to promote electron transfer between the reducing substance and the developable silver halide emulsion. It is preferable to use

The electron transfer agent (ETA) can be selected from the reducing substances mentioned above. In order for an electron transfer agent (ETA) to have a more favorable effect, it is desirable that its mobility is greater than that of an immobile reducing substance.

In this case, as the reducing substance used in combination with ETA, any reducing agent may be used as long as it does not substantially migrate in the layer of the photosensitive material, but hydroquinones and aminophenols are particularly preferable. , aminonaphthols,
Examples include 3-pyrazolidinones, saccharin and their precursors, picoliniums, and compounds described as electron donors in JP-A-53-110827.

ETA used in combination with these is ETA
Any oxidant can be used as long as it cross-oxidizes with these oxidants, but preferred are 3-pyrazolidinones, aminophenols, phenylenediamines, and reductones, each of which is diffusible.

The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble root salt (for example, nitric acid solution) and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used.

The average grain size of silver halide (grain diameter for spherical or approximately spherical grains, principal grain size for cubic grains, expressed as an average based on projected area) is:
The particle size distribution is preferably 2μ or less, particularly preferably 0.4μ or less.The particle size distribution may be narrow or wide.

The shape of these silver halide grains is cubic, octahedral, mixed crystal, or JP-A-58-127921, JP-A-58-127921.
Any flat plate shape as described in No. 113926 etc. may be used.

Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed.Furthermore, even if the crystal structure of the halide root grains is uniform to the inside, or if the inside and outside are different, Those with a layered structure, British Patent No. 635,841,
It may also be of the so-called conversion type, as described in US Pat. No. 3,622.318. In addition, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particles may be used. In the latter case, a positive image can be directly obtained by using a nucleating agent or optical fogging.

In the silver halide grain formation or physicothermal process, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Although a so-called immature emulsion (primitive emulsion) which is not chemically sensitized may be used as the silver halide emulsion, it is usually chemically sensitized. For chemical sensitization, sulfur sensitization using sulfur-containing compounds (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines) that can react with active gelatin or silver, reducing substances (e.g. Reduction sensitization using tin salts, amines, hydrazine derivatives, formamidine sulfins, silane compounds), noble metal compounds (e.g., gold compounds, complex salts of Group I metals of the periodic table such as platinum, iridium, palladium, etc.) A noble metal sensitization method using a sensitizer can be carried out alone or in combination.

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.

For example, gelatin y: conductors, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugars such as sodium alginate, dextran, and starch derivatives. Derivatives: Various synthetic hydrophilic polymers such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Substances can be used.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.
For example, chromium salts (chromium mitauban, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (
dimethylol urea, methylol dimethylhydantoin, etc.) dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (I,3,5-triacryloyl-hexahydro-5-1-riazine, 1,3-vinylsulfonyl-2) - propatool, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-8-triazine, etc.), mucohalogen ft [(mucochloric acid,
mucophenoxychloric acid, etc.), N-carbamoylpyridinium salts ((I-morpholinocarbonyl-3-pyridinio) methanesulfonate, etc.) and haloamidinium salts 11t (I-(I-chloro-1-pyridinomethylene)
pyrrolidinium, 2-naphthanesulfonate, etc.) can be used alone or in combination.

Among these compounds, active vinyl compounds or active halogen compounds can be preferably used. The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material may contain various additives such as coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization), etc. Various surfactants may be included for this purpose.

The photographic emulsion may be spectrally sensitized with methine dyes or others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Included are holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbyl nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, Polymers containing glycidyl (meth)acrylate, styrene, etc. alone or in combination, and a combination of these and acrylic acid, methacrylic acid, etc. as monomer components can be used.

The photosensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

Various compounds other than the compounds of the present invention can be used in the photographic emulsion for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (e.g. mercapto thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.); Compounds; azaindenes (e.g. triazaindenes, pentaazaindenes, etc.); many compounds known as anti-capri agents or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added.

Photographic light-sensitive materials use color image-forming couplers, that is, aromatic primary amine developers (for example, phenylenediamine Lq 1, aminophenol derivatives, etc.) in color development processing.
It may contain a compound that can develop a color by oxidative camping with. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule, or a polymerized coupler. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also contain a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor during development (so-called DIR coupler), or the product of the coupling reaction is colorless and may contain a development inhibitor. It may also include a colorless DIR coupling compound that releases .

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumaron couplers, open-chain acylacetonitrile couplers, pyrazolotriazole couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivalotriazole couplers, etc.). cyan couplers include naphthol couplers and phenol couplers.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

Couplers can be introduced into the silver halide emulsion layer using known methods, such as those described in US Pat. No. 2,322,027.

A known anti-fading agent can be used in the photographic material. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-
- Oxyphenol derivatives and bisphenols, etc.

The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Search Disclosure Itea/j643 (December 1978) and 1te+w/8716 (November 1979), and the relevant sections are summarized in the table below. Ta.

Additive type RD17643 RD1B716
1 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity increasing agent
Same as above 4 Brightening agent page 24 8 Dye image stabilizer page 25 9 Hardening agent 26 true page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27, page 650, right column For photographic processing of light-sensitive materials, any known method can be used, and known processing liquids can be used. Further, the treatment temperature is usually selected between 18°C and 50°C, but it may be lower than 18°C or higher than 50°C.

Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

The black and white developer contains known developing agents such as dihydroxybenzene (e.g. hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination.

The color developer is generally an alkaline water-soluble color developer containing a color developer, and the color developer is a known primary aromatic amine developer, such as phenylene diamines (e.g. 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, F. A. Meson, “Fetographic Processing Chemistry”, published by Focal Press (I
966), pages 226-229, U.S. Patent No. 2,193,
No. 015, same 2. No. 592゜364, Japanese Unexamined Patent Publication No. 48-6
Those described in No. 4933 may also be used.

The developer may also contain development inhibiting agents such as pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants other than the compounds of this invention. , an antifoggant, and the like. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, U.S. Pat. No. 4,083,7
The polycarboxylic acid chelating agent described in No. 23, the antioxidant described in OLS No. 2,622.950, and the like may be included.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be carried out simultaneously with the fixing process or separately. Examples of bleaching agents include iron (III), cobalt (■), chromium (■), copper (n), etc. Compounds of polyvalent metals, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron (III) or cobal l-([1), such as ethylenediaminetetraacetic acid. , nitrilotriacetic acid, aminopolycarboxylic acids such as 1,3-diamino-2-propatoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, malic acid; persulfates, permanganates; nitrosophenols, etc. Can be used. Of these, potassium ferricyanide, sodium iron(Ill) ethylenediaminetetraacetate, and ammonium iron(III) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (II) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Patent 3,042.52
No. 0, No. 3,241.966, Special Publication No. 45-8506
Bleaching accelerators described in Japanese Patent Publication No. 45-8836, etc.
In addition to the thiol compound described in JP-A-53-65732, various additives can also be added.

The washing process is sometimes carried out in one tank, but in many cases it is carried out in two tanks.
It is carried out using a multi-stage countercurrent water washing method with more than one tank.

The amount of water in the washing process can be set arbitrarily depending on the type and purpose of the color photosensitive material, but for example, the amount of water used in the washing process can be set as desired depending on the type and purpose of the color photosensitive material.
1 WaterFION Rates in Immersing of Motion Picture Film (May issue)
Immersion-Washing of Moti
onPicture Film, S, R, Goldw
It can also be calculated by the method described in J. Asser.

When reducing the amount of water used for washing, the growth of bacteria and mold becomes a problem.
Washing water with reduced calcium and magnesium content, bactericides and antifungal agents described in Specification No. 2, for example, Journal of Antibacterial and Antibacterial Agents (J, Antibact, Anti
fug, Agents) vol, l 1, &5,
Compounds described in p. 207 to 223 (I983) and compounds described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi can be added. In addition, chelating agents such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid can also be added as water softeners.

When reducing the amount of washing water, the amount of water used is usually 10 to 200 M1 per color photosensitive material IM, but in particular, a range of 200 to 1000 M1 is recommended in order to achieve both color image stability and water saving effect. Preferably used.

The pH in the water washing step is usually in the range of 5 to 9.

The photographic elements of this invention are also advantageously used in color imaging processes in which imagewise diffusible dyes are formed or released and then diffused and then fixed.

The above-mentioned color image forming methods include those in which development is performed using a developer at a temperature near room temperature (color diffusion transfer method) (for example, the method described in Belky Patent No. 757,959), and methods in which development is performed using a developer at a temperature near room temperature (for example, the method described in Belky Patent No. 757,959); Developing device [thermal development method]
(For example, European Patent No. 76492A2 and Japanese Unexamined Patent Publication No. 58-79
No. 247, No. 59-218443, Patent Application No. 60-79
No. 709, etc.), and the photographic element of the present invention can be used in any of them.

The dye-providing substance that is advantageous for the above color image forming method includes a compound represented by the general formula (I) in which PUG is a diffusible dye, but it may be replaced by a compound represented by the following formula (V).

Dy-Y (V) Here, Dy represents a dye moiety (or its precursor moiety), and Y represents a functional substrate that changes the diffusivity of the dye-donating substance (presentation) as a result of development.

Here, "the diffusivity changes" means that the +11 dye dye-donating substance V) is originally non-diffusible, and it changes to diffusive, or a diffusible dye is released, or ( 2) This means that the originally diffusible dye-donating substance (stem) changes to non-diffusible.

Further, depending on the nature of Y, this change may occur due to oxidation or reduction of Y.

Examples of "diffusivity changing" due to oxidation of Y include p-sulfonamide naphthols (including p-sulfonamide phenols: JP-A-48-33-826;
53-50.736 and European Patent No. 76.492), O-sulfonamidophenol W
4 (including 0-sulfonamidnaphthols: JP-A-1973
1-113゜624, 56-12642, 56
-16130, 56-16131, 57-40
No. 43, No. 57-650, U, S, 4. 053
゜312, specific examples are described in European Patent No. 76.492), hydroxysulfonamide heterocycles (JP-A No. 5
1-104,343 and European Patent No. 76.492), 3-sulfonamide indoles (
JP-A-51-104.343, JP-A No. 53-46,730
No. 54-130.122, No. 57-85,055
(Specific examples are described in European Patent No. 76.492),
α-Sulfonamide ketones (JP-A-53-3,819
No. 54-48,534, European Patent No. 76°492
For example, the so-called dye-releasing redox substrates can be mentioned.

Another example is JP-A No. 57-20.735, in which Y releases a dye by intramolecular nucleophilic attack after being oxidized.
Examples include intramolecularly assisted substrates described in Japanese Patent Application No. 177148/1982.

Another example is a substrate that releases a dye by an intramolecular ring-closing reaction under basic conditions, but does not substantially release the dye when Y is oxidized (Japanese Patent Laid-Open No. 51 Specific examples are described in No. 63.618), and as a modified version of this, a substrate in which the isoxacilone ring undergoes ring wrapping with a nucleophilic reagent and releases a dye is also useful (Japanese Patent Laid-Open No. 49-111,628). No. 52-481
Specific examples are given in issue 9).

Another example is a substrate in which the dye moiety is released by dissociation of acidic protons under basic conditions, but when Y is oxidized, the dye does not substantially release (
Specific examples are described in JP-A-53-69.033 and JP-A-54-130927).

The image receiving element may be provided on a separate support from the photosensitive element or may be a film unit associated with the photosensitive element.

A typical form of the film unit is a form in which the above image-receiving element and photosensitive element are laminated on one transparent support, and there is no need to separate the photosensitive element from the image-receiving element after the transferred image is completed. It is. More specifically, the image-receiving element comprises at least one mordant layer, and in preferred embodiments of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. , a combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer;
Each of the above-mentioned emulsion layers is composed of a yellow dye-providing substance, a magenta dye-providing substance, and a cyan dye-providing substance, respectively. between the mordant layer and the light-sensitive layer or dye-providing substance-containing layer, titanium oxide, etc. A white reflective layer is provided containing a solid pigment.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. Further, if desired, a peeling layer may be provided at an appropriate position so that all or part of the photosensitive element can be peeled off from the image receiving element. 674.082).

In another form that does not require peeling, the photosensitive element described above is coated on one transparent support, a white reflective layer is coated on it, and an image-receiving layer is further laminated thereon. A mode in which an image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support and the photosensitive element is intentionally peeled off from the image receiving element is described in U.S. Pat. No. 3,730,718. ing.

On the other hand, there are two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports.
One is a peelable type, and the other is a peelable type. To explain these in detail, a preferred embodiment of the peelable film unit has a light-reflecting layer on the back surface of the support, and at least one image-receiving layer coated on the surface thereof. In addition, the photosensitive element is coated on a support having a light-shielding layer, and the surface coated with the photosensitive layer and the mordant layer do not face each other before the end of exposure, but after the end of exposure (for example, during development) the surface coated with the photosensitive layer does not face each other. It is devised so that it turns over and overlaps the surface on which the image-receiving layer is applied. Immediately after the transfer image is completed with the mordant layer, the photosensitive element is peeled off from the image receiving element.

In a preferred embodiment of the peel-free film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-blocking layer, The surface coated with the photosensitive layer and the surface coated with the mordant layer are stacked facing each other.

All of the above-mentioned forms can be applied to both the color diffusion transfer method and the heat development method, but especially in the former case, a container (processing element) containing an alkaline processing liquid and rupturable under pressure is also combined. It's okay. In particular, in a peel-free film unit in which an image-receiving element and a photosensitive element are laminated on one support, the processing element is preferably disposed between the photosensitive element and a cover sheet overlaid thereon.

In addition, in a configuration in which a photosensitive element and an image receiving element are separately coated on two supports, it is preferable that the processing element is placed between the photosensitive element and the image receiving element during the development process. The film preferably contains a light shielding agent (such as carbon black or a dye whose color changes depending on pH) and/or a white pigment (such as titanium oxide) depending on the form of the film unit. - Preferably, in the unit, a neutralization timing mechanism consisting of a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet or in the image receiving element or in the photosensitive element.

On the other hand, in a heat-developable film unit, a support,
A heat-generating layer containing fine metal particles, carbon black, graphite, or other conductive particles is provided at an appropriate position on the photosensitive element or image-receiving element to generate Joule heat when electricity is applied for thermal development or diffusion transfer of dyes. Alternatively, a semiconductive inorganic material (for example, silicon carbide, molybdenum silicide, lanthanum chloride, barium titanate ceramics, tin oxide, zinc oxide, etc.) may be used instead of the conductive particles.

The heat-developable photosensitive materials to which the present invention can be applied include pages 242 to 255 of "Fundamentals of Photographic Engineering" Non-Silver Salt Photography (published by Corona Publishing, 1982), Eizo Information 40, published in April 1978.
Page, Neblets Handbook of Photography and Reprography (Nebletts, 1l.
andbook of Photography an
dReprography) 7th Ed.
Van Nostrand Reinhold Company (
VanNostrand Re1nhold Comp
any), pages 32-33, U.S. Patent No. 3.152,9
No. 04, No. 3,301.678, No. 3,392,
No. 020, No. 3.457,075, British Patent No. 1,
No. 131゜108, No. 1,167.777 and
In addition to the heat-developable photosensitive materials that produce silver images described in Research Disclosure t=t 97s, June issue, pages 9-15 (RD-17029), there are also heat-developable photosensitive materials that produce color images. can also be applied.

Heat-developable photosensitive materials for obtaining this color image are disclosed in U.S. Pat. No. 3,531,286, U.S. Pat. Page, U.S. Patent No. 4,021,240, U.S. Patent No. 4,463.079
No. 4゜474.867, No. 4,478,92
No. 7, No. 4,507,380, No. 4. 500.
No. 626, No. 4,483,914; Japanese Unexamined Patent Publication No. 1983-
No. 149046, No. 58-149047, No. 59-1
No. 52440, No. 59-154445, No. 59-16
No. 5054, No. 59-180'548, No. 59-16
No. 8439, No. 59-174832, No. 59-174
No. 833, No. 59-174834, No. 59-1748
No. 35, etc., U.S. Patent No. 4,499.180, JP-A-59-161.943, European Patent No. 125,521, U.S. Patent No. 4,499,172, JP-A-59-180
．． No. 537, No. 61-84, 640, No. 59-218
．． There are heat-developable color photosensitive materials disclosed in No. 443 and No. 61-238.056, and described in European Patent Publication No. 210.660.

Example 1 The method of making the emulsion for the first layer will be described.

A well-stirred aqueous gelatin solution (20 g of gelatin and 3 g of sodium chloride in water kept at 75 °C) was mixed with an aqueous solution containing sodium chloride and potassium bromide (600 °C) and an aqueous silver nitrate solution ( At the same time, 0,959 moles of silver nitrate dissolved in 600 moles of water were added at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 8
0 mol%) was prepared.

After washing with water and desalting, sodium thiosulfate 5* and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 2
Chemical sensitization was carried out at 60° C. by adding 0.0 μm. The yield of emulsion was 600 g.

Next, we will discuss how to prepare the emulsion for the third layer.

Good < Stirring gelatin aqueous solution (water 10001n!
Contains 20g of gelatin and 3g of sodium chloride at 75°C.
An aqueous solution containing sodium chloride and potassium bromide (600% water) and a silver nitrate aqueous solution (600% water)
(in which 0.59 mol of silver nitrate was dissolved) and the following dye solution (I) were simultaneously added at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol %) was prepared, in which a dye having an average grain size of 0.35 μm was adsorbed.

After washing with water and desalting, sodium thiosulfate 5■ and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 2
Chemical sensitization was carried out at 60° C. by adding 0.0 μm. The yield of emulsion was 600 g.

Dye solution (I) Dye with the following structure: 160 methanol 400 + dNext, the preparation of the emulsion for the 5th N will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin and ammonium dissolved in 1,000 ml of water and kept at 50°C), an aqueous solution containing an iodide column and potassium bromide, and a silver nitrate aqueous solution ( Nitric acid (1 mole dissolved in 1000 g of water) was simultaneously added while maintaining the pA and g. In this way, a monodisperse octahedral silver iodobromide emulsion (iodine 5 mol%) with an average grain size of 0.5 μm was prepared.
) was prepared.

After washing with water and desilvering, gold and sulfur sensitization was performed at 60° C. by adding chloroauric acid (tetrahydrate) and 1 g of sodium thiosulfate. The yield of emulsion was I kg.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

Weighed 180 g of yellow dye-donating substance 05, 9 g of electron donor (ED-1) with the following structure, and 9 g of tricyclohexyl phosphate, added 46 m of cyclohexanone, and heated to approximately 60°C to dissolve. It was made into a solution. This solution was mixed with 100 g of a 10% solution of lime-treated gelatin and 1.5 g of sodium dodecylbenzenesulfonate, and then heated at 1100 g for 10 minutes using a homogenizer.
Dispersed at 00 rpm. This dispersion is called a yellow dye-providing substance dispersion.

Electron donor (ED-1) 0■ "The dispersion of magenta and cyan dye-donating substances is similar to the dispersion of yellow dye-donating substance, and the dispersion of magenta and cyan dye-donating substances is similar to the dispersion of yellow dye-donating substance. Donating substance (
25).

With these, color photosensitive material 1 having a multilayer structure shown in Table 1
I made 01.

Next, a method for dispersing fine particles of a dye-providing substance according to the present invention will be described.

Dye-donating substance Log, the following surfactant + a11, O
100 g of a 1% aqueous gelatin solution was added to the resulting mixture, and the mixture was ground for 20 minutes in a dyno mill using 100 g of glass beads having an average particle size of about 0.6 mm. The glass beads were separated by sieve to obtain an aqueous dispersion (average particle size: 0.6 μm).

Further, a fine particle dispersion of the electron donor (ED-1) was also prepared in the same manner.

Except that in the photographic material 101, a fine particle dispersion of a dye-donating substance and an electron donor prepared by the above method was used instead of a gelatin dispersion of a dye-donating substance, and the high boiling point solvent (tricyclohexyl phosphate) was omitted. A photosensitive material 102 having the same composition as photosensitive material 101 was prepared.

Next, we will discuss how to make the dye fixing material.

63 g of gelatin, 130 g of a mordant having the following structure, and 80 g of guanidine picolinate were dissolved in 1300 d of water, coated on a paper support laminated with polyethylene to a wet film thickness of 45 μm, and then dried.

Mordant OJ Furthermore, on top of this, add 35 g of gelatin, 1.0 g of hardening agent, and 1.05 g of 2-bis(vinylsulfonylacetamido)ethane.
A dye fixing material was prepared by applying and drying a solution dissolved in 0 (ld) water to a wet film thickness of 17 μm.

The multilayered color photosensitive material was exposed to light at 2000 lux for 1 second using a tungsten light bulb through color separation filters of B, G, R, and gray whose densities were continuously changed.

15-/I water was supplied to the emulsion surface of the exposed color light-sensitive material using a wire bar, and then the dye-fixing material and the film surface were superimposed so that they were in contact with each other.

The film was heated for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 85°C.

Next, when the dye-fixing material was peeled off from the light-sensitive material, clear blue, green, red, and gray images were obtained on the dye-fixing material corresponding to the BSG, R, and gray color separation filters.

Table 2 shows the results of measuring the maximum density ([l+*ax) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part.

In addition, these color photosensitive materials were heated at 45°C and relative humidity 60°C.
Table 2 also shows the results of the same treatment after storage for one week under the conditions of %.

Table 2 When the method of the present invention is stored under high temperature conditions, Dmi
It was found that the increase in n was small.

Example 2 A third layer was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper having the layer structure shown in the table was produced. Sample 201 was prepared as a coating liquid as follows.

First layer coating solution preparation Yellow coupler fal 19.1g and color image stabilizer (
b14.4g, ethyl acetate 27.2cc and solvent f'
10% sodium dodecylbenzenesulfonate containing 8 cc of 10% sodium dodecylbenzenesulfonate was added and dissolved.
% gelatin aqueous solution (185 cc). On the other hand, silver chlorobromide emulsion (silver bromide 90.0 mol%, Ag 70 g/kg
Contains 5 blue-sensitizing dyes shown below per 1 mole of silver.
, OX was prepared by adding 10-' moles of OX. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition of the second layer. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-1-riazine sodium salt was used.

The following spectral enhancing dyes were used in each layer.

Blue sensitive emulsion layer (CI aSOs-(CHz) asOzll・N(
Czlls)s (5.OX per 111 moles of halokenide
10-' mol) green-sensitive emulsion layer SO311.N(Cwt!5)s (4.OX per mol of silver halide 10-' mol) SOJN(CzHs) i (7.OX 10 per mol of silver halide) −'mol)
(0.9 x 10-' mol per 1 mol of halogenated S) In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, respectively. Per mole of halogenated 8.5X 10-' mole, 7.7×101 mole, 2
．． 5X 10-' moles were added.

Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a+ 7-tetrazaindene was added at 1.2X 10 per mole of silver halide, respectively.
-"mol, 1.IX 10-"mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

and +a) yellow coupler mountain) color image stabilizer fcl solvent (el magenta coupler (fl color image stabilizer (a) color image stabilizer H (hi solvent 2:1 mixture (volume ratio) (I) '2 of ultraviolet absorber :9:8 mixture (weight ratio) fil Color mixture inhibitor H (g)) Solvent 0=P +0-CJ+w(jso))3 (I1 Cyan coupler I -H to color image stabilizer, (:H, υυl; , 11.1 5:8:9 mixture (weight ratio) (nl Polymer (0) medium (Preparation of samples 202 and 203) The following were added to the first layer, third layer, and fifth layer of sample 201, respectively. Samples 202 and 20 were prepared in exactly the same manner as sample 201 except that compound (86) was added lXl0-'mol/rrr.
3 was prepared. However, in sample 202, compound (86) was dissolved in the solvents fcl, (hl, (0)) of each layer together with the respective couplers, emulsified and dispersed, and added.
In No. 03, Compound (86) was dispersed into fine particles using a Dynomill and added in the same manner as the dye-donating substance of Example 1.

These samples 201 to 203 were imagewise exposed and processed by changing only the bleach-fixing time in the following processing steps, and the bleach-fixing speed was measured.

In addition, these samples were stored immediately after preparation and at a temperature of 45°C and a relative humidity of 80% for 7 days, and then developed using the following processing steps, and the minimum density (Dmin) of cyan, magenta, and yellow was measured. . These results are shown in Table 4.

Processing process n Single skin color development 38℃ 1 minute 40 seconds bleach fixing
30-34℃? Rinse■ 30-34℃ Rinse for 20 seconds■
30~34℃ 20 seconds rinse ■ 30~
Dry for 20 seconds at 34℃ 70-80℃
50 seconds (3-tank countercurrent method for rinsing ①-②) The composition of each treatment solution is as follows.

Left i 2nd base Yeongshusui 80 (
ld diethylenetriaminepentaacetic acid 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0g nitrilotriacetic acid 2. OgDABCO5.0g Potassium bromide 0.5g Potassium carbonate 30gN-ethyl-N-(
β-Methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.5g Hydroxylamine sulfate 4.0g Optical brightener (UV [T
EX-CK (manufactured by Ciba Geigi) Add 1.5g water to 1000dpH (25℃)
10.25 Star Wataru i Namizu 400I
R1 Ammonium thiosulfate (70%> 200dSodium sulfite 20gEthylenediaminetetraacetate iron(III) ammonium 60gEthylenediaminetetraacetate disodium 10gAdd water 1000dpH (25℃)
7.00 yl ion-exchanged water (calcium, magnesium 3pp each)
m or less) Example 3 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material #4301 was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/l, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes and couplers, the coating amounts are expressed in moles per mole of silver halide in the same layer.

(Sample 301) 1st layer; antihalation layer black colloid ilo, 18 gelatin 1.40 2nd layer; intermediate layer 2.5-di-t-pentadecylhydroquinone 0.18C-10,
07 C-30,02 Ll-10,08 U-20,08 HBS-10,10 HBS-20,02 Gelatin 1.04 3rd layer; 1st red-glare emulsion layer Silver iodobromide emulsion (silver iodide 6 Mol%, average particle size 0.8μ) silver 0.50, distracting dye 1
6.9X10-' sensitizing dye n
1.8X10-' sensitizing dye m
3.1xlO-'sensitizing dye IV 4
．． 0X10-'C-20,146 HBS-10,005 C-90,0050 Gelatin 1.20 4th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0. 85μ) 1.15 silver 1 5. lX10-S sensitizing dye I+
1.4X10-' sensitizing dye m
2.3XlO-'sensitizing dye TV
３．０ %, average particle size 1.5μ) Silver 1.50 Sensitizing dye 1
5.4xlO-'sensitizing dye n
1.4X10-' sensitizing dye m
2.4xlO-'sensitizing dye TV
3.1xlO-'C-30,003 C-40,40 C-90,003 HBS-10,40 Gelatin 1.63 6th layer; Intermediate layer gelatin 1.06 7th layer; 1st green emulsion layer Silver bromide emulsion (u16 mol% iodide, average grain size 0.8μ) Silver 0.35 sensitizing dye V 3.0X10-' sensitizing dye VI
1.0X10-'sensitizing dye■
3.8X10-'C-50,180 C-10,010 C-60,042 C-70,025 H3B-10,20 Gelatin 0.70 8th layer; 2nd green emulsion layer Silver iodobromide emulsion ( Silver iodide 5 mol%, average grain size 0.85 μ) Silver 0.75 sensitizing dye V 2. lX10-'sensitizing dye V[7
,0X10-' Sensitizing dye■ 2.6X10-'C-50
,035 C-70,004 C-10,002 C-60,015 H3B-10,15 Gelatin 0.80 9th layer; 3rd green-sensitive emulsion layer Silver iodobromide (silver iodide 10 mol%, average grain diameter 1.5μ) Silver 1680 sensitizing dye V
3.5X10-' sensitizing dye Vl
8.0X10-'sensitizing dye■
3.0X10-'C-100,012 G-10,00L HBS-20,69 Gelatin 1.74 10th layer;
Yellow filter single layer C-110,02 2,5-G[-pentadecylhydroquinone 0,03 gelatin
0.95 11th N; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol %, average grain size 0.6 μ) 0.24 Multiplying dye ■
3.5XlO-'C-80,27 C-70,005 HBS-10,28 Gelatin 1.28 12th layer;
Second blue-sensitive emulsion layer Silver iodobromide emulsion (il iodide ¥10 mol%, average grain size 1.0
μ) 0.45 sensitizing dye■
2. lX10-'C-80,098 HBS-10,03 Gelatin 0.46 13th layer;
Third blue emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.8μ) Silver 0.77 sensitizing dye■
2.2X10-'C-80,036 HBS-10,07 Gelatin 0.69 14th layer;
First protective layer iodobromide 1m (silver iodide 1 mol%, average grain size 0.07μ) silver 0. 5U-1
0,11 U-20,17 Butyl p-hydroxybenzoate 0.012H
BS-10,90 Gelatin 0.80 No. 15M;
Second protective layer polymethyl methacrylate particles (diameter approximately 1.5 μm) 0.543-1
0.053-2
0.25 gelatin
0.72 In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer.

(Preparation of Samples 302 to 304) Compound (71) of the present invention (8XI
O-'mol 1 mol Ag) and ED-2 (8X10-4
Sample 302 was prepared in the same manner as Sample 301, except that 1 mol of Ag) was dissolved in HBS-1 together with the coupler, emulsified and dispersed, and added.

In addition, the compound (71) of the present invention was added to the fifth layer of sample 301.
(8X 10-' mol 1 mol Ag) was added by dispersing fine particles with a Dynomill in the same manner as the dye-providing substance in Example 1,
Sample 303 was prepared in the same manner as Sample 301, except that ED-2 (8×10-' mol 1 mol Ag) was dissolved in HBS-1 together with the coupler, emulsified and dispersed, and added.

Furthermore, the compound (71) of the present invention was added to the sixth layer of sample 301.
Sample 304 was prepared in the same manner as Sample 301, except that ED-3 (0.01 g/n?) was added as fine particle dispersion as above, and ED-3 (0.02 g/n?) was also added.

For these samples, use the A light source and set the color temperature to 4 with a filter.
After adjusting the temperature to 800'K and giving imagewise exposure so that the maximum exposure amount was 10 CMS, a color development process was carried out at 38 DEG C. using the following Bleach-A solution.

Furthermore, these samples were stored at a temperature of 45°C and a relative humidity of 80% for 7 days, and then treated in the same way. I asked about it.

These results are shown in Table-5.

(Processing process) Color development 3 minutes 15 seconds Bleach-A 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Safe, fixed, 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,l-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide 1.
Hydroxylamine sulfate 2.4g4-(
Add 4.5g of N-ethyl-N-β-hydroxyethylamino 2-methylaniline sulfate water.
1.0jlpH10.0 Bleach-A solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate
IO, add 0g water
1.0e pH6.0 Fixer ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0d Sodium bisulfite 4.6g Add water
1.0/pH6,6 Stabilized liquid formalin (40%>2.01 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization -10) Add 0.3g water 1.OI!Table-5 *ΔS0 Change rate ΔD after storage at 45°C 80% for 7 days with respect to the value immediately after production of the logarithm value of exposure ME giving a density of .2 cyan density fog + 0.2 density 45 with respect to the value immediately after production of the lowest cyan density Amount of change after storage for 7 days at 80% ℃ I found that it was suppressed.

Structure of the compound used in Example 3 It H H H 0CHxCLSOzCL N 0!1 0■ HBS-1) Liclesyl phosphate HB S-2
Dibutyl phthalate Clh”-CI-Sow-ClbCONHC11zCH
I = CH-Sow cll, collll -C
11! Sensitizing dye (CHI) 5sOs. (CHt) 5sOJa■ (I;rim)3≧υ3Na Js xHs ■ xHs Patent applicant Fuji Photo Film Co., Ltd. Procedural Amendment (
Mr. Gei 1, Director General of the Patent Office, 1/1/1988 Patent Application No. 1 o 6 rra of 1988
No. 2, Title of the invention Photosensitive material 3, Relationship with the case of the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Date of amendment order Items & subject of amendment Description a Contents of the amendment We will submit an engraving (with no changes to the contents).

Claims (1)

[Scope of Claims] A photosensitive material characterized by containing a compound represented by the following general formula (I) in the form of fine particles in a binder. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, N represents a nitrogen atom, and X represents -O-, -S-, or -N(R_3)-. R_1, R_2, and R_3 represent groups other than hydrogen atoms or simple bonds. EAG represents an electron-accepting group. Time is (Time)t-PUG
represents a group that releases PUG through a subsequent reaction after being released as PUG. t represents 0 or 1. PUG is P
Represents a photographically useful group as UG or (Time)t-PUG. (Time) t-PUG is R_1, R_2
, R_3, and EAG.