JPS63271443A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obviate degradation in sensitivity and to prevent an increase in fogging density as well as to change the color tones of silver images by providing at least one silver halide emulsion layer on a base and incorporating a specific compd. therein. CONSTITUTION:This photosensitive material is constituted by providing at least one silver halide emulsion layer on the base and incorporating the compd. expressed by the formula therein. In the formula, EAG denotes an electron acceptive group; N denotes a nitrogen atom, and X denotes an atomic group contg. O or O or N, respectively. R<1>, R<2> denote a mere coupler or group except a hydrogen atom, and TD denotes a group which becomes a dye having high solubility in water after releasing, respectively. Time denotes a group which releases TD via the ensuing reaction that takes place by being triggered by the cleavage of an N-X bond, and (t) denotes 0 or 1 integer. Solid lines denote bonds and at least one of broken lines denote bonds. The degradation in the sensitivity is, therefore, obviated and the increase in the fogging density is prevented; in addition, the color tones of the silver images are changeable.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material for observing silver images, and more particularly to a silver halide photographic material with excellent color tone.

Prior Art and its Problems Conventionally, compounds containing sulfur atoms and easily adsorbed to silver (for example, mercapto compounds) have been well-known as methods for controlling the color tone of silver images. However, since these compounds are also easily adsorbed to silver halide, they have drawbacks such as hindering the adsorption of sensitizing dyes, lowering sensitivity, and accelerating yellowing of images upon storage. Furthermore, the color tone tends to change due to development processing, and it is not always possible to obtain a constant color tone. Furthermore, as described in JP-A No. 61-285445, there is a method of uniformly incorporating a dye that does not dissolve during processing into a silver halide photographic light-sensitive material, but this method requires a minimum density (Dmin), that is, a fog density. This has the drawback of significantly degrading the image quality.

■Object of the Invention The object of the present invention is to provide a silver halide that does not reduce sensitivity when obtaining a silver image, prevents changes in the image due to storage and increases in fog density, and can change the tone of the silver image. Our objective is to provide photographic materials.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, the present invention is a silver halide photographic light-sensitive material characterized by having at least one silver halide emulsion layer on a support and containing a compound represented by the following general formula (I). .

General Formula (I) [In the above general formula (I), EAG represents an electron-accepting group.

N represents a nitrogen atom, and X represents an oxygen atom (0), a sulfur atom (S), or an atomic group containing a nitrogen atom (N-R3).

)jl, R2 and R3 each represent a simple bond or a group other than a hydrogen atom. After TD is released,
Represents a group that becomes a highly water-soluble pigment.

R', R2, R', and EAG may be linked to each other to form a ring.

Time represents a group that releases TD through a subsequent reaction triggered by cleavage of the N-X bond in the formula, and t represents an integer of 0 or 1.

When 1=0, Time represents a simple bond.

In the formula, a solid line represents a bond, and a broken line represents at least one bond. ) ■Specific structure of the invention The specific structure of the present invention will be explained in detail below.

In the color image forming method of the present invention, the photosensitive material contains a compound represented by the general formula (I).

In the general formula (I), EAG represents an electron-accepting group. N represents a nitrogen atom, and X represents an oxygen atom (0), a sulfur atom (S), or a nitrogen-containing group (N-R3
).

R1, R2 and R3 each represent a simple bond or a group other than a hydrogen atom.

R1, R2, R3 and EAG may be bonded to each other to form a ring. Time represents a group that releases TD through the subsequent reaction triggered by the cleavage of the N-X bond in the formula.

TD represents a highly water-soluble dye residue.

t represents a positive integer of 0 or 1; when 0, T
ime represents a simple bond.

Further, a solid line in the formula represents a bond, and a broken line represents a bond at least one of them. In addition, when X is a nitrogen-containing group, N takes a positive charge and may be a substituted ammonio group. The group further bonded to N in this case is the same as R3.

In the general formula (I), groups other than hydrogen atoms represented by R1 and R3 include substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, carbamoyl groups or sulfamoyl groups, A sulfonyl group into which a substituted or unsubstituted alkyl group or aryl group is introduced is preferred. The number of carbon atoms in R1 and R3 is preferably 1 to 40.

Examples of these are listed below.

1 or alkyl comethyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, aminomethyl group, acetylaminomethyl group, ethyl group, 2-(4-dodeca noylaminophenyl)
Ethyl group, carboxyethyl group, allyl group, 3°3.3
-) Lichloropropyl 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, t-pentyl group, cyclopentyl group, n-hexyl Ms%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.

alkenyl group vinyl group, 2-chlorovinyl group, 1-methylvinyl group,
2-cyanovinyl group, cyclohexen-1-yl group, etc.

an alkynyl group and an ethynyl group,
1-propynyl group, 2-ethoxycarbonylethynyl group, etc.

8N or aryl group phenyl group, naphthyl group, 3-hydroxyphenyl group,
3-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, 2
．． 4-dimethylphenyl group, 4-tetradecyloxyphenyl group, etc.

1-5, group 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-benzoxasilyl group, 2-xacillin-2-yl group, morpholino group, etc.

M or -bi″ acyl-acetyl group, propionyl group, butyroyl group, 1so-
butyroyl group, 2,2-dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group, 3-acetylamino-4-methylbenzoyl group, 4-methylbenzoyl group, 4-methoxy-3-sulfobenzoyl group, etc.

carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis-(2-methoxyethyl)carbamoyl group, diethylcarbasoyl group, cyclohexylcarbamoyl group, di-n-octylcarbamoyl group , 3-dodecylpropylcarbamoyl group, hexadecylcarbamoyl group, 3-(2,4-di-t-pentylphenoxy)
propylcarbamoyl group, 3-octanesulfonylaminophenylcarbamoyl group, di-n-octadecylcarbamoyl group, etc.

I! Sulfamoyl group to 2 negative or -4 sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, diethylsulfamoyl group, bis-(2-methoxyethyl)sulfamoyl group, di-n-butylsulfamoyl group , methyl-n-octylsulfamoyl group,
n-hexadecylmethylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-N
-Methylsulfamoyl group, 4-decyloxyphenylsulfamoyl group, methyloctadecylsulfamoyl group, etc.

Methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, n-octanesulfonyl group, n-dodecanesulfonyl group, n-hexadecanesulfonyl group, benzenesulfonyl group, 4-toluenesulfonyl group, 4 -n-dodecyloxybenzenesulfonyl group, etc.

The group other than the hydrogen atom represented by R2 is preferably a substituted or unsubstituted acyl group, or a sulfonyl group into which a substituted or unsubstituted alkyl group or aryl group is introduced.

Specific examples of these are the same as those described for R1 and R3 above. Similarly, the number of carbon atoms is 1 to
Preferably, it is 40.

The ring formed by combining R1, R2, R3 and EAG with each other is a five- to six-membered ring formed from a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom, or an aromatic ring such as a benzene ring. Examples include fused rings.

In the present invention, among the compounds represented by the general formula (I), those represented by the following general formula (II) are preferred.

General formula (II) In the above general formula (■), (Time)t-TD is R
4. Binds to at least one of EAG.

Y is a divalent linking group, preferably -(C=0)- or -802-. X has the same meaning as in the general formula (I) above.

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

Below is the part corresponding to this heterocycle (Time) 1
Preferred examples will be described, including the bonding position of -TD.

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 following general formula (8).

General formula (8) represents.

Vn represents an atomic group that forms a three- to six-membered aromatic ring together with Zl and 22, and n represents an integer from 3 to 3.

v3;-z3-1v4;-z3-24-.

v5;-z3-24-z5-1Vct;-23-z4
-z5-z6-1v7 ;-Z3-z4-25-z6
-z7-1Va ;-Z3-z4-Z5-26-27
-za-.

-〇-1-S-5 or -5o2-, Sub
Each represents a simple bond (π 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 3- to 6-membered saturated or unsaturated carbocycle or heterocycle.

In general formula (8), Sub
Select.

EAG will be described in more detail.

EAG represents a group that accepts and takes electrons from reducing substances,
Bonds to nitrogen atoms. EAG is preferably an aryl group or a heterocyclic group substituted with at least one electron-withdrawing group. Substituents bonded to the aryl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire compound. Examples of the physical properties of a compound as a whole include adjusting the ease with which it accepts electrons;
For example, it can be used to adjust water solubility, oil solubility, diffusibility, sublimation, melting point, dispersibility with binders such as gelatin, reactivity with nucleophilic groups, reactivity with 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-n-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-FJ -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-butylsulfamoylphenyl 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-methylsulfamoylphenyl)sulfamoylphenyl group, 4-nitro-2-N-methyl-N -n-butylsulfur ylphenyl group, 4-nitro-2-N-methyl-N
-n-octylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-dodecylcarbamoylphenyl 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-
Methyl-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-bitroxyethoxy)
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-methyl-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-N
-n-hexadecylcarbazoylphenyl 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 group, 4-nitro-2-N -(2-cyanoethyl)
-N-((2-hydroxyethoxy)ethyl)carbamoylphenyl group, 4-nitro-2-diethyl carbamoylphenyl 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 group, 2
-n-octanesulfonyl-4-methanesulfonylphenyl group, 2-n-tetradecanesulfonyl-4-methanesulfonylphenyl group, 2-n-hexadecanesulfonyl-4-methanesulfonylphenyl group, 2,4-di-n
-dodecanesulfonylphenyl group, 2,4-cytodecanesulfonyl-5-trifluoromethylphenyl group, 2-
n-decanesulfonyl-4-cyano-5-trifluoromethylphenyl group, 2-cyano-4-methanesulfonylphenyl group, 2°4.6-)dicyanophenyl group, 2,
4-dicyanophenyl group, 2-nitro-4-methanesulfonylphenyl group, 2-nitro-4-n-dodecanesulfonylphenyl group, 2-nitro-4-(2-sulfonidesulfonyl)phenyl group, 2-nitro -4-carboxymethylsulfonylphenyl group, 2-nitro-4-carboxyphenyl group, 2-nitro-4-ethoxycarbonyl-5-n-butoxyphenyl group, 2-nide.

Rho 4-, :r-)oxycarbonyl-5-n-hexadecyloxyphenyl group, 2-nitro-4-diethylcarbamoyl-5-n-hexadecyloxyphenyl group,
2-nitro-4-cyano-5-n-dodecylphenyl group, 2,4-dinitrophenyl group, 2-nitro-4-n-
Decylthiophenyl group, 3.5-dinitrophenyl group,
2-nitro-3,5-dimethyl-4-n-hexadecanesulfonyl group, 4-methanesulfonyl-2-benzenesulfonylphenyl group, 4-n-octanesulfonyl-2
-methanesulfonylphenyl group, 4-〇-tetradecanesulfonylphenyl-2-methanesulfonylphenyl group, 4-n
-hexadecanesulfonyl-2-methanesulfonylphenyl group, 2,5-cytodecanesulfonyl-4-trifluoromethylphenyl group, 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-ethoxycarbonyl-5-n-hexadecyloxyphenyl group, 4-nitro-2-diethylcarbamoyl-5-n-hexadecyloxyphenyl group, 4-
Nitro-2-cyano-5-n-dodecylphenyl group, 4
-Nitro-2-n-decylthiophenyl group, 4-nitro-3,5-dimethyl-2-n-hexadecanesulfonylphenyl 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, 4-'nitro-2-trifluoromethylphenyl group, 2-nitro-4-trifluoromethylphenyl group, 4-nitro-3-trifluoromethylphenyl group, 2,4.5-tricyano phenyl group,
3.4-dicyanophenyl group, 2-chloro-4,5-dicyanophenyl group, 2-bromo-4,5-dicyanophenyl group, 4-methanesulfonylphenyl group, 4-n-hexadecanesulfonylphenyl group, 2- Zocansulfonyl-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-nidro Pentuoxazole-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-pyridyl 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.

Next, +Time)1-TD will be explained in detail.

Time represents a group that may cause cleavage of a nitrogen-oxygen, nitrogen-nitrogen, or nitrogen-sulfur bond, releasing TD through a subsequent reaction.

Various groups represented by Time are known, for example, in JP-A-61-147244, pages (5)-(6) and 61-147244.
No. 236549, pages (8) to (14), patent application 1986-8
Examples include the groups described in No. 8625, pages (36) to (44).

In the present invention, the water-soluble dye represented by TD has a pKa of 1 after being released from the compound of general formula (I).
It has at least one group of 1 or less (preferably 5<p
Any dye may be used as long as it is a compound (two or more groups with Ka≦11, one or more groups with pKa≦5), but the following are preferable.

For example, arylidene dyes, azomedine dyes, cyanine dyes, hemicyanine dyes, merocyanine dyes, oxonol dyes, azo dyes, anthraquinone dyes, naphthoquinone dyes, triarylmethane dyes, or precursors of these dyes. It's okay.

More specifically, JP-A-58-58543, pages (5) to (11), and JP-A-61-88623, pages 52 to 6.
8 pages, JP-A-57-198458, JP-A No. 57-1798
Examples include the dyes described in No. 40.

Further, the auxochrome may be blocked by a cleavable group to temporarily shorten the wavelength. That is, when the compound of general formula (I) reacts with a reducing agent and cleaves the TD through a series of reactions, the original dye is produced and the color is restored.
For example, in the case of azo dyes, temporary shortening of the wavelength is achieved by blocking auxochromes such as hydroxyl groups, mercapto groups, or amino groups. Examples of dyes shortened by blocking groups include, for example, U.S. Pat. No. 4,234,67
No. 2, No. 4,310.612, No. 3.579,3
No. 34, No. 3,999,991, No. 3,994,
No. 731 or No. 3,230,085.

Specific examples of the compound represented by general formula (I) are listed below.

0 Q helicopter 2 η Oenbej ■ centre ^　　　'104N e:co.

z z (J Z+
1=
= C,)Q 2: − ＾ He ＾
jJ+h S − ～−Ko==Ko=0−(J=U) Akane 01 CFI Go=Erotic;! ;;I;;I;=
Work = 2 Ma 0 Go: l: 0 0-○ ■ ■ し181137 0-Q Work = 0 Work 1 = = Ichinori o-Q C,) 15 N ~ Go Q Q Work Q = ! ■ = 田ζshi; ○:e = :! :Z Free = ♂ 8 Snake = N Q.

(J(1) S″　　　　　　■ S　　　　　　　　-＝ Shi12 r125 O = O ■ 0 ■ O = ul of S -.

〒 〒 工 工 Φ 田 z = S (J 3 :!: ++/ -1 2 rice comb; ri - = = u3 ri groan S
up ≧= ) ↓ ν to × υ w Yamaichi■゛
0 - , :C: , Q Shirisi and 2 Liq
q to C1 ν 0= S − η ; /\ Q ○ E − 0 ・III 802 = = Q ′ = ; 9.

; 0−bej = しIGr133ζshi 2, 8 Eng:! :O; :e:! knee
;, z 2! :0 = = ^ 11! J z ζ shi; 〆)-FIN:! 0 = = ♂ B = 80
Neo
:! :S /\Q υ = = :e η mf') N 8 :! : 0 u12 r125 1' -1○
-2 Engineering II Z ζ; = 0= 0 ζ; The compound of formula (I) is reduced to its N-X
The bond is cleaved, resulting in the release of TD (a water-soluble dye).

In the present invention, the reducing agent develops the silver halide and loses its reducibility in the areas where developable silver halide exists, and the reducing agent in the areas where developable silver halide does not exist. Since the compound of formula (I) is reduced, T
D (a water-soluble dye) is released. This water-soluble dye is then discharged from the system due to its water solubility. Therefore, in the present invention, the general formula (
The compound of I) (having a dye) will be present,
By appropriately selecting the color tone of the compound of general formula (I), the color tone of the silver image can be adjusted as desired.

The compound represented by general formula (I) in the present invention may be contained in any layer (e.g., emulsion layer, protective layer, intermediate layer, etc.) in the light-sensitive material, but it is particularly preferably contained in the emulsion layer. .

In this case, the amount added is 5xlO-'~1.0x10°g/
Go, preferably 5X10-' to 1. O×10-'g/m
” is better.

Methods for adding the compound of the present invention to a photosensitive material include a method in which it is directly made into an aqueous solution and introduced into a hydrophilic colloid;
and various known dispersion methods. Examples of high boiling point organic solvents used in the oil-in-water dispersion method are U.S. Pat.
It is described in No. 322゜027, etc. The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.
S) No. 2,541,274 and No. 2.541,2
It is described in issue 30 etc. In addition, both the Fischer dispersion method and the solid dispersion method can be used.

The reducing substance used in the present invention may be an inorganic compound or an organic compound with a deviation of 't71, and its oxidation potential is preferably lower than the standard oxidation-reduction potential of silver ion/silver, 0.80V.

In inorganic compounds, total flexion with an oxidation potential of 0.8v or less,
For example, Mn, Ti, Si, Zn, Cr, Fe, Co, M
o, Sn, Pb, W.

Examples include H2, Sb, Cu, and Hg. In addition, ions with an oxidation potential of 0.8v or less or complex compounds thereof, such as Cr2+, V2÷, Cu,
F e 24 , M n
0 4 2- , do , GO(
CN)6'-1Fe (CN)6'-1 or (F
e-EDT8) 2-, etc. Furthermore, metal hydrides with an oxidation potential of 0.8 V or less, such as HaH
H% NaB114 to lLiH1, Li[lH
4.Li/j! (0-C4tl g-L) 3 I
Examples include f or Li8 (OC113), 3H, and the like. In addition, sulfur or phosphorus compounds with an oxidation potential of 0.8 V or less, such as Na2 S03, NaH5,
Examples include Na11SO3, H3P%H2S, Na2S, or Na2S2.

Examples of reducing substances for organic compounds include organic nitrogen compounds such as aliphatic amines or aromatic amines, organic sulfur compounds such as aliphatic thiols or aromatic thiols,
Alternatively, organophosphorus compounds such as aliphatic or aromatic phosphines are also suitable, but preferably
dal-PGI type 1 (T.H. James (T.
, 1 Tatami, James), The Theory of the Photographic Process
of the photographic processes
s) 4 th, cd, page 299).

Examples of compounds that can be used as reducing substances in the present invention include inorganic reducing agents such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane-amine complexes, hydroquinones, Aminophenols, catechols, p-phenylenediamines, 3-pyrazolidinones, droxytetronic acid, ascorbic acid, 4-
In addition to amino-5-pyrazolones and the like, reducing agents described in the book by T.H. James, pages 291 to 334, can also be used. Also, JP-A-56-138,736, JP-A No. 57-4
Reducing agent precursors such as those described in US Pat. No. 0,245 and US Pat. No. 4,330,617 can also be used.

Examples of more preferable reducing agents include the following.

3-pyrazolidones and their precursors [e.g. 1
-Phenyl-3-pyrazolidone, 1-phenyl-4,4
-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, l-
m-tolyl-3-pyrazolidone, 1-p-tolyl-3-
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-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-birazolitone, 1-(4-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-
) lyl)-4-methyl-3-pyrazolidone, 1-(2-
tolyl)-4-methyl-3-pyrazolidone, 1-(4-
tolyl)-3-pyrazolidone, 1-(3-tolyl)-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, 1-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, sodium 5-pentadecylhydroquinone-2-sulfonate, p-benzoyloxyphenol, 2-methyl-4-benzoyloxyphenol, 2-t-butyl-4-(4 -chlorobenzoyloxy)phenol, hydroquinone Sodium disulfonate, 2-(3,S-bis(2-hexyldecanamido)benzamide)hydroquinone, 2-(3-hexadecanamido)benzamidehydroquinone, 2-(
2-hexyldecanamido) hydroquinone], color developers of paraphenylenediamines (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
-butoxyethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline).

As a reducing agent for aminophenols, 4-amino-2
, 6-dichlorophenol, 4-amino-2,6-dibromophenol, 4-amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, 4-amino-2,6-dichlorophenol hydrochloride, etc. There is. Furthermore, Research Disclosure Magazine No. 151, No. 1510B, U.S. Patent No. 4
．． No. 021.240 describes 2,6-dichloro-4-substituted sulfonamidophenol% 2,6-dipromo 4-substituted sulfonamidophenol, JP-A-59-11674
No. 0 lists p-(N,N-dialkylaminophenyl)sulfamine and the like, which are useful. In addition to the phenolic reducing agents described above, naphthol reducing agents such as 4-amino-naphthol derivatives and 4-substituted sulfonamide naphthol derivatives are also useful.

Furthermore, general color developing agents that can be applied include aminohydroxypyrazole derivatives described in U.S. Patent No. 2,895,825, aminopyrazoline derivatives described in U.S. Patent No. 2,892,714, and research Disclosure magazine June 1980 issue 227-230.23
Pages 6-240 (RD-19412, RD-1941
5) describes hydrazone derivatives. These color developers may be used alone or in combination of two or more. Regarding the implementation of the present invention, the functions of the compounds of the present invention in silver halide photographic materials will be explained.

The compound of the present invention is incorporated into a silver halide photographic light-sensitive material by the addition method described below, and is reduced along the electron transfer path represented by the arrow shown in the following formula (1) to release TD.

Formula (1) % Formula % (REOX) Reduced decomposition product of the compound of the present invention 7 In formula (1), the reducing substance (RE) is the above-mentioned inorganic or organic reducing substance and is contained in the processing liquid from the outside. It may be allowed to act by allowing it to act, or it may be made to act by pre-containing it in the photosensitive material, or it may be made to act by including it in the photosensitive material in advance and then the same or different type of reducing substance (RE) is made to act from the processing solution. It's okay.

This reducing substance (RE) is used to reduce silver halide and is consumed depending on the degree of exposure when a commonly used negative silver halide emulsion is used. The reaction requires an amount that corresponds inversely to the degree of exposure, i.e.
Of the supplied reducing substance (RE), only the remaining amount that is not used for reducing silver halide is used.

Therefore, a larger amount of TD is emitted from a portion that is less exposed.

Furthermore, when an autopositive emulsion is used, the reduction of silver halide occurs on the unexposed side, contrary to the case of a negative emulsion, so that reducing substances are consumed on the unexposed side. Therefore, the reaction between the compound of the present invention and the reducing substance occurs in a larger amount in the exposed area, and a larger amount of photographically useful groups is released.

As described above, the compound of the present invention releases a small amount of TD in the developed area (the area where silver halide and a reducing substance react) and a large amount in the non-developed area, but TD is released in the developed area and the non-developed area. For the purpose of adjusting the ratio of amounts (usually to improve this ratio), an electron transfer agent (ET
A reducing substance called A) may be used in combination.

Formula (2) % Formula % ( ) In formula (2), the electron transfer agent (ETA) can be selected from the reducing substances mentioned above, and is preferably selected from organic reducing agents. Further, in order for the electron transfer agent (ETA) to have a more favorable effect, it is desirable that the redox potential is located between that of the reducing substance (RE) and the silver halide.

The method of causing the electron transfer agent (ETA) to interact with the reducing substance (RE) is the same as the method explained for the reducing substance fft(RE) in equation (1).

Ru.

In formula (2), the TD release process described in formula (1) is the same except that the electron transfer agent mediates the transfer of electrons from the reducing substance to silver halide. Formula (2
), if the reducing substance is immobile, the electron transfer from the reducing substance to the silver halide may be slowed down. As understood from formula (1), when the electron transfer from the reducing substance to the silver halide is slowed down, the reaction between the reducing substance and the compound of the present invention occurs preferentially. The difference in the amount of TD released at The electron transfer agent can be used for the purpose of smoothly transferring electrons from the immobile reducing substance to the silver halide and increasing the difference in the amount of TD released between the developed area and the non-developed area. For the above purpose, the electron transfer agent is an immobile reducing substance (
When used in combination with a reducing substance (RE), it is necessary that the mobility is greater than that of the reducing substance (RE). By using an electron transfer agent as shown in formula (2), an immobile reducing substance can be effectively used.

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, aminephenols, and aminonaphthols are particularly preferred. kind,
Examples include 3-pyrazolidinones, saccharin and their precursors, corriniums, and compounds described as electron donors in JP-A-53-110827. .

An example is shown below.

S-3S-4 s-s 56S-7
3-8 S-13S-14 5-15 S-16S
-193-2O S-223-23 S-255-26 S-293-3O S-34 S-35 S-395-40 CH, Co/ \SO2C+eH33 S -46 S -47 S -49 S -50 S - 52 S-53 In the present invention, when the reducing substance for reducing the compound of general formula (I) is contained on the same support, the two positions may be in the same layer or in an adjacent layer. preferable.

On the other hand, reducing substances that can be contained in the processing solution include alkali-soluble reducing substances such as ordinary developing agents, hydroquinones, and inorganic reducing agents. Many of these reducing substances are often used for other functions, but in the present invention, they can also be used to have the function of the reducing substance of general formula (1).

The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention may have regular crystal bodies such as cubic, octahedral, rhombidodecahedral, and tetradecahedral, and may also have spherical, Irregular (ir
It may have a regular crystal form or a composite form of these crystal forms. In addition, Research Disclosure w-(Research Dis
closure) 225 @ pages 20-58 (19
The grains may be tabular grains having an aspect ratio of 5 or more as described in (January 1983).

Further, the particles may have an epitaxial structure, or may have a five-layer structure in which the interior and surface of the particles have different compositions (for example, halogen compositions).

Further, it may be a surface latent image type silver halide in which a latent image is mainly formed on the surface, or an internal latent image type silver halide in which a latent image is mainly formed inside. In the latter case, it is also possible to directly obtain a reversed image using a nucleating agent or optical fog.

Further, it is preferable that the average size of the particles is 0.3 μ or more. More preferably, the average size is 0.3μ or more5.
It is 0μ or less.

Also, the particle size distribution may be broad or narrow. The latter is known as a so-called monodisperse emulsion, and has a dispersion coefficient of 20% or less, more preferably 15% or less (here, the dispersion coefficient is the standard deviation divided by the average grain size).

These photographs 'emulsion by Hato Graffkide (P.

Chimie et Phyaique (Glafkides)
Photographique) (Paul Montel, 1967) G.
Photographic Emulsion Chemistry (Photo by G, F, Duffin)
graphicEmulsion Chemistry
y) (The Focal Press
(Press, 1966), Making of the Book by V. L. Zelikman et al.
Making and Coating Photographic Emulsion
ographic Emulsion) (The Focal Press
s), 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

These photographic emulsions may be any combination of silver chloride, silver bromide, silver iodide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.

At the stage of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, or a complex salt thereof, rhodium salt or complex salt thereof, iron salt or complex salt thereof, etc. may be present.

Binders for the emulsion layer and other layers of the silver halide photographic material of the present invention include proteins such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, dextran sodium alginate, and starch derivatives; It is also possible to use synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives and partial hydrolysates thereof.

Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

Further, the photographic light-sensitive material of the present invention contains an alkyl acrylate latex described in U.S. Pat. No. 3,411,911, U.S. Pat. I can do it.

The emulsion used in the photosensitive silver halide emulsion layer of the present invention is preferably chemically sensitized.

For chemical sensitization, the Glafkides or Zelikman
11, edited by Frleser et al.
rPhotographischen Prozess
e mitSilberhalogeniden) Akademissi J-”Verlagsgesellschaft (Akad
emische Verlagsgesellschaf
t), (196B) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used.

The light-sensitive material of the present invention can contain various compounds as stabilizers. i.e. azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds, such as mercaptothiazoles, mercaptobenzothiazoles; mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyridines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carphoxyl group or a sulfone group. Compounds; thioketone compounds, such as oxazolinthione; azaindenes, such as tetraazaindenes; (especially 4-hydroxy substituted (1,3,3a
, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as stabilizers can be added.

The photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention may contain various additives such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). A surfactant may also be included for this purpose.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols, Non-ionic interfaces such as glycol alkylamides or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator; alkyl carboxylate, alkyl sulfonate,
Alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl tauric acid, sulfosuccinate, sulfoalkyl polyoxyethylene alkylphenyl ether, polyoxyethylene Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as alkyl phosphate esters, diamino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates, or phosphate esters. , amphoteric surfactants such as alkyl betaines, amine oxides: alkyl amine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

Among these surfactants, polyoxyethylene surfactants and fluorine-containing surfactants are particularly preferably used.

The polyoxyethylene surfactant of the present invention is preferably added to a light-sensitive emulsion layer of a photographic light-sensitive material, but it may also be added to a non-light-sensitive layer.

The curing agent may be a polymer curing agent having diffusion resistance as described in JP-A-56-142524, or a low molecular curing agent as shown below. Typical examples include mucochloric acid, mucobromic acid, formaldehyde, dimethylolurea, trimethylolmelamine, glyoxal, 2,3-dihydroxy-5-methyl-1
, 4-dioxane, aldehyde-based compounds such as glutaraldehyde; divinylsulfone, methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-5-)riazine, 1,3.5-triacryloyl- Hexahydro-5-triazine, 1,3゜5-trivinylsulfonyl-hexahydro-S-triazine, bis(vinylsulfonylethyl)ether, 1.3-bis(vinylsulfonyl)-2-propatol, 1.3- Active vinyl compounds such as bis(vinylsulfonylacetylamido)propane; 2,4-dichloro-6-hydroxy-S-triazine sodium salt, 2.4-dichloro-6-nodoxy-S-triazine, 2.4 ~Dichloro-6-(4-sulfoanilino)-5-triazine sodium salt, 2,4-dichloro-6-(2-sulfoethylamino)-s-triazine, N,N'-bis(2-chloroethylcarba Active halogen compounds such as (mil) piperazine; Epoxy compounds such as bis(2,3-epoxypropyl)methylpropylammonium p-toluenesulfonate: 2,4,6-triethyleneimino-S-triazine Ethyleneimine compounds such as; 1
, methane sulfonic acid ester compounds such as 2-di(methanesulfonoxy)ethane; carbodiimide compounds such as dicyclohexylcarbodiimide = 2.5-
Examples include isoxazole compounds such as dimethyl isoxazole/perchlorate; inorganic compounds such as chromium alum and chromium acetate.

Particularly preferred among these compounds are compounds having a vinyl sulfone group and active halogen compounds.

The photographic emulsions of this invention are spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are 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. Namely, pyridine 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
A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiopidantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

The amount of the sensitizing dye used in the present invention is preferably from txto-s to 5.times.10' moles per mole of silver.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above. Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention. An example of a matting agent is a suitable particle size (preferably a particle size of 0.3 to 5 μm or a particle size of at least twice the thickness of the protective layer, particularly at least 4 times the thickness of the protective layer).
Organic compounds such as water-dispersible vinyl polymers such as polymethyl methacrylate, etc., or inorganic compounds such as silver halide, strontium valylum sulfate, etc. are preferably used. Smoothing agents help prevent adhesion failure similar to matting agents, and are particularly effective in improving the frictional properties of motion picture film related to camera compatibility during shooting or projection; specific examples include liquid paraffin, Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, silicones such as polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or their alkylene oxide addition derivatives. etc. are preferably used.

The silver halide photographic material of the present invention may also be provided with an intermediate layer, a filter layer, etc., if necessary.

Specific examples of the silver halide photographic material of the present invention include X-ray photosensitive materials, Lithium photosensitive materials, black-and-white photographic materials, and black-and-white photographic paper. Preferably, X-ray sensitive materials and black and white photographic paper are used.

In the photographic material of the present invention, various other additives may be used as necessary. For example, development accelerator,
Fluorescent brighteners, color antifoggants, ultraviolet absorbers, etc. Specifically, research disclosure (1
1E S E A It ClIDl5CLOSUII
E) No. 176, pages 28-30 (RD-17643, 1
978) can be used.

Furthermore, regarding the development processing of the photosensitive material of the present invention, RD-1
7643, pages 28 to 30, can be referred to.

Examples of fixing solutions for processing the light-sensitive materials of the present invention include Fuji F, Fuji Fix, Super Fuji Fix, Fuji DP Fix, and Super Fuji Fix DP manufactured by Fuji Photo Film ■, F-6 and KOD^ manufactured by Kodak Company in the United States. Fixer, Conifix manufactured by Rokusha Konishi, Conifix Rabbit, other Orifix, My Fix, Niwa Fix, 8 bit fixer F, 0 bit fixer P, pan fix F, pan fix P, my roll F , Oriental QF, etc.

■Specific effects of the invention According to the present invention, when obtaining a silver image, there is no decrease in sensitivity, it is possible to prevent changes in the image due to storage and increase in fog density, and it is also possible to change the tone of the silver image. A silver halide photographic material is obtained.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in more detail.

Example 1 (1) Preparation of photosensitive silver halide emulsion! ! -A knee 1 water 900 cc
Inside is 20 g of gelatin, 30 g of potassium bromide, and 3.9 g of potassium iodide.
35 g of silver nitrate in the form of an aqueous solution was added over a period of 4 minutes while stirring into a container in which 1 g was added and maintained at 52°C. Further, ammoniacal silver nitrate (165 g as silver nitrate) was simultaneously added to the potassium bromide aqueous solution over a period of 5 minutes using a double jet method. After completion of addition, temperature at 35°C by sedimentation method.
After removing soluble salts, the temperature was raised to 40° C., 100 g of gelatin was added thereto, and the pH was adjusted to 6.7. The resulting emulsion had a potato rod shape, the average diameter of spheres having the same volume as each grain was 0.9 BP, and the silver iodide content was 2 mol %. This emulsion was chemically sensitized using gold and sulfur sensitization to obtain Emulsion A.

J-j'l-H's? - Add 30 g of gelatin and 6 g of potassium bromide to 1 liter of water and make 60
A silver nitrate aqueous solution (5 g as silver nitrate) and a potassium bromide aqueous solution containing 0.15 g of potassium iodide were added by a double jet method over a period of 1 minute into a container maintained at .degree. C. while stirring. Furthermore, silver nitrate aqueous solution (145g as silver nitrate) and potassium iodide 4
．． An aqueous solution of potassium bromide containing 2 g was added by double jet method. The addition flow rate at this time was accelerated so that the flow rate at the end of the incubation was five times that at the start of addition.
After the addition, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, 75 g of gelatin was heated to an appropriate temperature, and p
H was adjusted to 6.7. The resulting emulsion had a projected area diameter of 0.98. In, the tabular grains had an average thickness of 0.138 mm, and the silver iodide content was 3 mol %.

This emulsion was chemically sensitized using gold and sulfur sensitization to obtain emulsion B.

(2) Preparation of coated samples Samples 1 to 7 were prepared by sequentially providing each layer of the following formulation on both sides of a polyethylene terephthalate support from the support side.

<Emulsion layer> Coated silver amount: 2 g/Go Ag/gelatin (weight ratio) = 1. :1 Compound of the present invention 2 Sensitizing dye listed in Table 1: Anhydro 5.5'-di-chloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt 500 mg/1 Mol Ag Carini iodide 200 mg 71 Mol Ag Stabilizer = 4-hydroxy-6-methyl-1,3,3a,
? -Tetrazainan 2,6-bis(hydroxyamino)-4-diethylamino-1°3.5-)riazine Dry antifoggant Nitrimethylolpropane Coating aid:
Thickener Polybotacium p-vinylbenzenesulfonate Hardener: 2,4-dichloro-6-hydroxy-1,3,
5-Triazine color toning agent: Compound -■ Compound -■ (oil-soluble dye: added as an emulsion) <Surface protective layer> Gelatin 0.8g/rn' ■40,000 dextran 0.8g/fluorinated antistatic agent polyethylene Oxide-based surface resistance lowering agent PMMA matting agent Samples 1 to 7 thus prepared were exposed to X-rays using a GRENEX intensifying screen rG-4J manufactured by Fuji Photo Film ■.

After that, Fujifilm's "Fuji X" was developed as an automatic processor.
Ray processor FPM4000 J was used.

The developer and fixer had the following compositions.

(Developer) 1-phenyl-3-pyrazolidone 1.5 g Hydroquinone 30 g 5-Nitroindazole 0.25 g Potassium bromide
:1. Og anhydrous sodium sulfite
50 g potassium hydroxide
30 g boric acid 1
0g Glutaraldehyde Add 5g water to make a total volume of 11 (PL+ was adjusted to 10.20) (Fixer) Ammonium thiosulfate 200.0g Sodium sulfite (anhydrous) 20.0g Boric acid
8.0g disodium ethylenediaminetetraacetate 0.1g aluminum sulfate 15.0g sulfuric acid
2.0g glacial acetic acid
Add 22.0 g water
1.01 (The PL amount was adjusted to 4.20.) (3) Sensitometry These samples were stored at a temperature and humidity of 25° C. and 65% RH for 7 days after coating. Each sample was evaluated using the following method.

The results of photographic properties are shown in Table 1.

Note that the sensitivity is determined by the fog density (D
The comparison was made using the reciprocal of the exposure amount required to obtain a degree of blackening of m1n) value + 1.0, and the sensitivity of sample 1 was set as 100, and the relative value was shown.

Table 1 1 A None None 100 0.17 Cool black tone From Table 1, samples 16 and 17 using the compound of the present invention have high sensitivity, suppressed fog density (D m1n), and have a cool black tone. It can be seen that the condition is good.

Example 2 Preparation of (+) photosensitive silver halide emulsion An aqueous solution consisting of potassium bromide and sodium chloride was added to a silver nitrate solution and an aqueous gelatin solution in an acidic state (pH = 4) by the double jet method while stirring vigorously. Average particle size 0
．． A 4μ cubic monodisperse emulsion (silver bromide 70 mol %, dispersion coefficient 11%) was prepared. Thereafter, it was washed with water by a conventional precipitation method, and then sulfur sensitized to obtain a photosensitive silver chlorobromide emulsion C.

(2) Preparation of coated samples Samples 8 to 11 were prepared by sequentially applying each layer of the following formulation on a paper support laminated on both sides with polyethylene from the support side.

(Emulsion layer) Binder: Gelatin 4.7 g/Coated silver amount: Emulsion C1.5 g/ is sensitizing dye: 0.2 tng/ is optical brightener: 0.1 g/rn' Polymer latex: polyethyl Acrylate 2 g/+n2 colors Preparation: Table 2 (compounds are the same as in Example 1) (Surface protective layer) Binder: Gelatin 1.2 g/rn'
Coating aid Coating aid Nidodecylbenponse sodium 80g/colloidal silica (average 0.05μ) 0.3 g7m'' Hard agent: 4-dichloro-6-hydroxy 1.3°5-triazine sodium salt 0. 08 g/nf (3) Sensitometry These samples were stored for 7 days after coating at a temperature and humidity of 25° C. and 65% RH. Each sample was evaluated by the following method.
The results of photographic properties are shown in Table 2.

(A) Color tone evaluation Samples 8 to 11 were measured using a sensitometer using a tungsten bulb.
While exposing through a continuous wedge, each sample was developed using Fuji Pavitol developer (manufactured by Fuji Photo Film) diluted 1:1 with water at 20°C for 90 seconds, and after stopping,
The color tone was evaluated by fixing with Fuji Fix (manufactured by Fuji Photo Film ■) for 5 minutes, washing with water, and drying.

(B) Measurement of aging deterioration (yellowing) characteristics of silver images The steps from exposure and development to drying were carried out in the same manner as in (A).

Each processed sample is protected by British Patent (Publication) No. 2.019.02.
As described in Specification No. 4A, nitrogen dioxide gas (
3000 ppm) atmosphere for 20 minutes, and then left outdoors (under sunlight) for 2 days. After standing, the degree of deterioration of the silver image that occurred in the image area was observed and evaluated as follows.

O: There is no deterioration of the silver image. Δ: There is some deterioration of the silver image (practical limit). The density was measured, and the relative sensitivity was calculated from the exposure amount that gave a high optical density of fog + 0.1.

Table 2 8 None None 100 Cooling O From Table 2,
It can be seen that Sample 1O111 using the compound of the present invention can have a desired color tone without lowering the sensitivity or impairing the stability of the silver image.

Claims (4)

[Claims] (1) A silver halide photographic material having at least one silver halide emulsion layer on a support and containing a compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above general formula (I), EAG represents an electron-accepting group. N represents a nitrogen atom, and X represents an oxygen atom (O), a sulfur atom (S), or an atomic group (N-R^3) containing a nitrogen atom. R^1, R^2 and R^3 each represent a simple bond or a group other than a hydrogen atom. TD represents a group that becomes a highly water-soluble dye after being released. R^1, R^2, R^3, and EAG may be bonded to each other to form a ring. Time represents a group that releases TD through a subsequent reaction triggered by cleavage of the N-X bond in the formula, and t represents an integer of 0 or 1. When t=0, Time represents a simple bond. In the formula, a solid line represents a bond, and a broken line represents at least one bond. } (2) The silver halide photographic material according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above general formula (II), Y represents a divalent linking group, R^4 is bonded to
Represents a group of atoms forming a member heterocycle. N, X, EAG, Time, t, TD, and solid and broken lines have the same meaning as stated in claim 1. } (3) The silver halide photographic material according to claim 1 or 2, wherein X is an oxygen atom. (4) The silver halide photographic material according to any one of claims 1 to 3, which is used to obtain a silver image as a final image.