CA2065106A1 - Silver halide photographic light-sensitive material and photographic product for film-making process - Google Patents

Abstract

Abstract A silver halide photographic light-sensitive material is disclosed. The material comprises a support and provided thereon, a silver halide emulsion layer and layers adjacent to the emulsion layer. The emulsion is subject to desalinization comprising using denatured gelatin in the process of preparation thereof. At least one of the layers contains a compound selected from the group consisting of those represented by the following formulas I, II, and III and a hydrazine compound;
formula I

formula II

formula III

Description

20651~6 SILVER HALIDE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL AND
PHOTOGRAPHIC PRODUCT FOR FILM-MAKING PROCESS

FIELD OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material and photographic product for film-making process which can be used to form a photographic image with very high contrast, more specifically a silver halide photographic light-sensitive material and photographic product for film-making process which can be used to form a dot image with high contrast and which are very useful in the field of film-making process.

~ACKGROUND OF THE INVENTION
The film-making process includes a process in which an original with continuous gradation is converted to a dot image or the density change in continuous gradation is 2~651~6 converted to a group of dots having an area in proportion to that density.
This process is based on a photographic technology making it possible to reproduce an image with very high contrast, by which the original is subjected to exposure via a cross-line screen or contact screen, followed by infections development to form a dot image.
Lith-typed silver halide photographic light-sensitive materials, used for infections development, does not offer sufficient contrast unless processed with a infections developer (lith developer). For example, when processed with an MQ developer or PQ developer, they have a gamma value of at most S to 6, and are significantly affected by the occurrence of fringe, which is the most undesirable in forming dots. For these reasons, they should be used in combination with infections developers, which are poor in preservability.
With this background, there have been developed some methods of forming an image with very high contrast comparable to that obtained by infections development using a developer which has a high sulfite ion concentration and good preservability and permits rapid processing, including the known method disclosed in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I.

20S~

~ 3 --Publication) No. 106299/1981. In this method, a compound known as a contrast increasing agent is added to a silver halide photographic light-sensitive material or used in combination with specific silver halide grains and other photographic additives in order to show a contrast increasing effect.
The use of such a silver halide photographic light-sensitive material makes it possible to obtain a photographic image with very high contrast even when it is processed with a highly preservable, rapidly processable developer. However, it has a drawback that sand-like or pin-like fogging, namely Pepper fog, occurs in dots during formation of dot image, which adversely affects the dot image quality. To solve this problem, various attempts have been made in which various stabilizers or inhibitors having a hetero atom were added, but none of them reach a solution to this problem.
In addition, this type of silver halide photographic light-sensitive material is also faulty that it is likely to undergo silver image deterioration and discoloration over time.
SUMMARY OF THE INVENTION
The present invention has been made in order to solve the above-described problems.

206~

It is an object of the invention to provide a silver halide photographic light-sensitive material which can give a high contrast photographic image without lowering of sensitivity and the occurrence of pepper fog in non-image area of dot images.
It is an another object of the invention to provide a photographic product for film-making process with excellent photographic properties which is free of deterioration over time after development.
The objects described above are accomplished by a silver halide photographic light-sensitive material comprising a support and provided thereon, a silver halide emulsion layer and layers adjacent to the emulsion layer, wherein the emulsion is subject to desalinization treatment to remove impurities dissolved therein in the process of preparation thereof, said desalinization treatment comprising using denatured gelatin, and at least one of the emulsion layer and the layers adjacent to the emulsion layer contains a hydrazine compound and a compound represented by the following formula I or II;
Formula I
ffl ~ H
A-- (cH2)n--S--C
\N H I~ , 20651~6 wherein A represents - O H~ - S 0 ~3 or N~ ;
~ 2 represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, a substituted alkyl group or a substituted or unsubstituted phenyl group; R2 represents an alkyl group with 1 to 5 carbon atoms or substituted alkyl group;
X~) .
represents an anlon; X represents a halogen atom or p-toluene sulfonate; n represents an integer of 2 to 5.

~ / 2 When A represents - N~ , it includes HX salt.

FormuIa II

N--( C H ,)n- S - C - N

, wherein~R3 represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, a substituted alkyl group or a ; :~ substituted or unsubstituted aryl group; R4 represents an alkyl group with 1 to S carbon atoms, a substituted alkyl group or a substituted or unsubstituted phenyl group; n ': ~'' ' ~ :
.
~ .

, 20651~6 represents an integer of 2 to 5, provided that it includes a salt with a halogen ion or a p-toluenesulfonate ion.
The objects described above are accomplished by a silver halide photographic ligh-sesitive material comprising a support and privided thereon, a silver halide emulsion layer and layers adjacent to the emulsion layer, wherin the emulsion is subject to disalinization treatment to remove impurities dessolved therein in the process of preparation thereof, said desalinization treatment comprising using denatured gelatin, and at least one of the emulsion layer and the layers adjacent to the emulsion layer contains a hydrazine compound and a compound represented by the following formula III;
Formula III
Q'"
~--S M
"N~

wherein Q represents a group of atoms necessary to form a 5-or 6-membered a heterocyclic ring which may be condensed with a benzene ring or a heterocyclic ring; M represents a hydrogen atom, an alkyl metal atom, an ammonium group or an organic amine residue.
The objects of the invention are also accomplished by a photographic product for film-making process obtained by 20651~6 developing a silver halide photographlc llght-sensltlve material having at least one silver halide photographic emulsion layer on the support, whereln desalinization to remove the dissolved impurities in the silver halide emulsion in said silver halide emulsion layer is achieved by coagulation precipitation with denatured gelatin, and said silver halide emulsion layer or at least one of the adjolning layers contains a hydrazine derivative and a layer containing the compound represented by Formula I or II is formed on the support after developing said silver halide photographic light-sensitive material.
The objects described above are accomplished by a photographic product for film-making process obtained by developing a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on the support wherein desalinization to remove the dissolved impurities in the silver halide emulsion in said silver halide emulsion layer is achieved by coagulation precipitation with denatured gelatin, and said silver halide emulsion layer or at least one of the adjoining layers contains a hydrazine derivative and a layer containing the compound represented by Formula III
is formed on the support after developing said silver halide photographic light-sensitive material.

2~6~

DETAILED DESCRIPTION OF THE INVENTION

The present invention is hereinafter described in detail. Examples of the aryl group represented by R3 in Formula II include a propenyl group, a butenyl group and a phenyl group. With respect to Formula I or II, each group may have a substituent. Examples of the substituent include alkyl groups, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy and p-chlorophenoxy, a heterocyclic oxy groups such as pyridyloxy, mercapto gro~ps, alkylthio groups such as methylthio and ethylthio, arylthio groups such as phenylthio and p-chlorophenylthio, heterocyclic thio groups such as pyridylthio, pyrimidylthio and thiadiazolylthio, alkylsulfonyl groups such as methanesulfonyl and butanesulfonyl, arylsulfonyl groups such as benzenesulfonyl, heterocyclic sulfonyl groups such as pyridylsulfonyl and morpholinosulfonyl, acyl groups such as acetyl and benzoyl, a cyano group, a chloro group, a bromo group, alkoxycarbonyl groups such as ethoxycarbonyl and methoxycarbonyl, aryloxycarbonyl groups such as phenoxycarbonyl, a carboxyl group, a carbamoyl group, alkylcarbamoyl groups such as N-methylcarbamoyl and N,N-dimethylcarbamoyl, an arylcarbamoyl group such as N-phenylcarbamoyl, amino groups, alkylamino groups such as methylamino and N,N-dimethylamino, arylamino groups such , - . . . :

' . : .- ~: :
. .
::

. ~ ' ' 206~

as phenylamino and naphthylamino, acylamino groups such as acetylamino and benzoylamino, alkoxycarbonylamino groups such as ethoxycarbonylamino, aryloxycarbonylamino groups such as phenoxycarbonylamino, acyloxy groups such as acetyloxy and benzoyloxy, alkylaminocarbonyloxy groups such as methylaminocarbonyloxy, arylaminocarbonyloxy groups such as phenylaminocarbonyloxy, a sulfo group, sulfamoyl groups, alkylsulfamoyl groups such as methylsulfamoyl and arylsulfamoyl groups such as phenylsulfamoyl.
Examples of the compound represented by Formula I
(hereinafter referred to as the compound I of the present invention) and those of the compound represented by Formula-II (hereinafter referred to as the compound II of the present invention) are given below, but the invention i~ not by any means limited to them.

-- 2 0 ~

Exemplified compounds ~N--(CHz)2--S--~ C~3 CH~ N H2 1--2 ) ~, C2Hs ,,N H2 ~N--(CH2)2--S--~ CQ~3 C2Hs N H2 C I--3 ~ ~3 C H~ ~ H2 ~N--(CHz)~--S-- (~ CQ
CH~ N H2 I--4 ~ ~3 HO--(CH2)2--S--C~ CQ~

--5 ~ E) H O--(CH2)2--S--C\C2Hs ~Q~
N H

...... .
: .

--, .

2065~

CHj l~ /CH~
/N--(CH2),--S--C--N\
CHs CH3 1~ 2 ~
CH~ l~ CzHs /N--(CH2)2--S ~C--N\
CH~ C2Hs /
~N--(CH2)2--S--C--N

( 11--4 ~

C2Hs 1~ /C2Hs /N--(CH%)2--S--C--N\
C2Hs C2Hs t n-s ) ~N--( C H ~ S--C--N~

.. ,. - :

.

206~1~6 The heterocyclic compound having a mercapto group, represented by Formula III, is described below.
With respect to Formula III, the heterocyclic ring for Q which may be condensed with a benzene ring or heterocyclic ring includes rings such as imidazole, thiazole, oxazole, triazole, tetrazole, selenazole, benzimidazole, benzothiazole, benzoxazole, benzoselenazole, thiadiazole, oxadiazole, pyrimidine, triazine, quinoline and tetrazaindene. These heterocyclic rings may have a substituent. Examples of the substituent include the same substituents as those exemplified for Formula I or II.
Examples of the compound represented by Formula III
(hereinafter referred to as the compound III of the present invention) are given below.

206510~

m-l m-2 ¢N~S H ¢ ~SH

m-3 m-~

N a O J S~ N~ ~ N~

m-s m-6 C~H7~o~S H H2N~,S~S H
N N N--N

m 7 m-8 CH[3 C:~5 ~ I~S H H~N~N~S H
N--N N--N

_ 9 ~--10 N--N
N H S 0 2~ N`N~S H
~N~S H [~3 N N

--" 2 0 ~

m 1l m-lz ,~HN~ C H ~r~N ~

1~N~ N ~HN, m-13 H S~ S S H [~;3 N--N H S ~ N~S H
N--N
~ .
m-ls m-~s C H ,J~N'~
OH
, :
: m-l7 m-ls S ~H ~ ~ S ~ I

,m~-ls ~ ~ m -20 H
C H ~y o - S H ~ N
N ~N~

:,:, , ,, ,,~,, .,, ~ . , .. . . ~
.. . ~ .
` ~ , ~ , - , .

.

2~651~6 `m-2l C2Hs m-2z H S ~ H ~ S ~, S~,S C H 2 C O O H
N N N- N

nl--23 m--24 N--N
CH~ N`N~S H

~ ~ ~ N H C O C~

These compounds can easily be synthesized by, or in accordance with, the methods described in US ~atent Nos.
2,271,229, 2,324,123, 2,384,593, 2,496,940, 3,082,088, 3,137,578, 3,473,924, 3,575,699, 3,615,501 and 3,687,660, British Patent Nos. 1,141,773 and 1,376,600, "Dai Yuki Kagaku", edlted by Fujio Kotake, published by Asakura Shoten, 1971, the Chemistry of Heterocyclic Compounds, by A.Weissberger, published by Interscience, pp. 1950-1964.
The amount of the compounds I through III of the present invention used is preferably 5 to 300 mg, more preferably 10 to 200 mg per mol of silver. The amount of less than 5 mg has no effect; the amount exceeding 300 mg results in sensitivity reduction.

;..................................................................... :

-, 2~5106 In the silver halide photographic light-sensitive material of the present invention, at least one of compounds represented by Formula I, II or III should be contained in the silver halide photographic emulsion layer or at least one of the adjoining layers. In the present invention, silver image preservability can also be improved by adding these compounds to developer, fixer or washing solution.
The silver halide photographic light-sensitive material of the present invention contains a hydrazine derlvatlve in its silver halide photographic emulsion layer or at least one of the adjoining layers, preferably in the silver halide photographic emulsion layer. The hydrazlne derivative preferably used for the present invention is represented by the following Formula H.
Formula H

R I ~ - N - N - Gll- R12 I I
l~

wherein R11 represents an aliphatic group, an aromatic group or a heterocyclic group; R12 represents a hydrogen , .

~ atom, a substituted or unsubstituted alkyl group, an aryl . ~ :
~ group, an alkoxy group, an oxy group, an amino group, a , ,~ ., . ~, . .. . .
' :

-- .
, ..

2 ~

~ 17 -heterocyclic group, a carbamoyl group, an oxycarbonyl group or a -O-R13 group (Rl3 represents an alkyl group or a saturated heterocyclic group). G1l represents a carbonyl group, a sulfonyl group, a sulfoxy group, .- 11 an oxalyl group, a - P - group or an iminomethylene I

~ 12 group; A11 and A12 independently represent a hydrogen atom, an acyl group or a sulfinic acid group.
In the present invention, more preference is given to the compound represented by the following Formula H-A or H-B.
Formula H-A

Pl P2 R2l- N - N - C - C - R22 wherein R21 represents an aliphatic group, an aromatic group or a heterocyclic group; R22 represents a hydrogen atom, a substituted or unsubstituted alkoxy group, a heterocyclic ring, an oxy group, an amino group or an .. , ~ .

2~651~6 aryloxy group; P1 and P2 independently represent a hydrogen atom, an acyl group or a sulfinic acid group.
Formula H-B

Il A r - N H N H - C - R3l wherein Ar represents an aryl group containing at least one non-diffusible group or a silver halide adsorption promoting group; R31 represents a substituted or unsubstltuted alkyl group, an alkoxy group or an amino group.
The aliphatic group represented by R21 in Formula H-A
preferably has~not less than 6 carbon atoms, and is `
preferably a linear, a branched or cyclic alkyl group havlng 8 to 50 carbon atoms. The branched alkyl group may , have been cycllzed to form a saturated heterocyclic rinq .
containing one or more hetero atom therein. The alkyl group may have a~substituent such as an aryl group, an alkoxy~qroup or a sulfoxy qroup.
The aromatic group represented by R21 is preferably a monocyclic or dicyclic aryl group or an unsaturated heterocycllc group. The~unsaturated heterocyclic group may~condense with a~ dicyclic aryl qroup to form a hetero acyl group. .: ~

, , , ~
:

2~5106 Examples of such aromatic groups include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring and a benzothiazole ring, with preference given to a benzene ring.
R21 is preferably an aryl group.

The aryl group or unsaturated heterocyclic group represented by R21 may have been substituted. Typical examples of the substituent include a linear, branched or cycllc alkyl group, preferably a monocyclic or dicyclic alkyl group having 1 to 20 carbon atoms in the alkyl moiety, alkoxy groups, preferably those having 1 to 20 carbon atoms, substituted amino groups, preferably those substltuted by an alkyl group having 1 to 20 carbon atoms, acylamino groups, preferably those havlng 2 to 30 carbon atoms, su1fonamide groups, preferably those havlng 1 to 30 carbon atoms and ureide groups, preferably those having 1 t~o 30 carbon aeoms.

The substituted or unsubstituted alkoxy group ~
représented by R22 preferably has 1 to 20 carbon atoms, and may have been substituted by a halogen atom, aryl group~or another substituent.
The~substituted or unsubstituted aryloxy group or heterocyclic oxy group is preferably monocyclic. Examples : ,:

~, , , , ,, ~. , . , ~, ~:
',., ' ' ' ~ , ~ - :

-" 20~51~6 of the substituent include halogen atoms, alkyl groups, alkoxy groups and cyano groups.
In the present invention, the group represented by R22 is preferably a substituted or unsubstituted alkoxy group or an amino group.
When the group represented by R22 is an amino group, ~Al it is represented by a - N group, wherein Al and A2 independently represent a substituted or unsubstituted alkyl group or an alkoxy group or a cyclic structure containing a -O-, -S- or -N- bond. R22 is never a hydrazine group.

R21 and R22 may each have therein a ballast group in common use as an immobile photographic additive. The ballast group is a group which has not less than 8 aarbon atoms and which is relatively inert on the photographic properties. It can be selected from alkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups and alkylphenoxy groups, for instance.

; R21 and R22 may each have therein a group which enhances adsorption to the surface of silver halide grains. Examples of such adsorbent groups include a .
thiourea group, a heterocyclic thioamide group, a mercapto ....

2~651 a~

heterocyclic group, a triazole group and other groups described in US Patent No.4,355,105.
Formula H-B is described below.
In Formula H-B, Ar represents an aryl group containing at least one non-diffusible group or silver halide adsorption promoting group, and the non-diffusible group is preferably a ballast group in common use for couplers and other immobile photographic additives. The ballast group is a group whicn has not less than 8 carbon atoms and which is relatively inert on the photographic properties. It can be selected from the group comprising alkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups and alkylphenoxy groups, for lnstance.
Examples of the silver halide adsorption promotlng group include a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, a triazole group and other groups described in US
Patent No. 4,385,108.

The substituted or unsubstituted alkyl group represented by R31 is a linear, branched or cyclic alkyl group, including methyl, ethyl, propyl, butyl, isopropyl, pentyl and cyclohexyl groups.
Examples of the substituent include alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy 2 0 ~ 6 and p-chlorophenoxy, heterocyclic oxy groups such as pyridyloxy, mercapto groups, alkylthio groups such as methylthio and ethylthio, arylthio groups such as phenylthio and p-chlorophenylthio, heterocyclic thio groups such as pyridylthio, pyrimidylthio and thiadlazolylthlo, alkylsulfonyl groups such as methanesulfonyl and butanesulfonyl, arylsulfonyl groups such as benzenesulfonyl, heterocyclic sulfonyl groups such as pyridylsulfonyl and morpholinosulfonyl, acyl groups ; ~such as acetyl and benzoyl, cyano groups, chloro groups, bromo groups, alkoxycarbonyl groups such as ethoxycarbonyl - and methoxycarbonyl, aryloxycarbonyl groups such as phenoxycarbonyl, carboxyl groups, carbamoyl groups, alkylcarbamoyl groups such as N-methylcarbamoyl and N,N-dimethylcarbamoyl, arylcarbamoyl groups auch as N-phenylcarbamoyl, amlno groups, alkylamino groups such as :; ~methylamlno and N,N-dimethylamino, arylamino groups such :aa phenylamino and naphthylamino, acylamino groups such aa acetyl:amino and~benzoylamino, alkoxycarbonylamino groups auch as ethoxycarbonylamino, aryloxycarbonylamino groups such~as phenoxycarbonylamino, acyloxy groups such as :acetyloxy and benzoyloxy,~al~kylaminocarbonyloxy groups such~as methylaminocarbonyloxy, arylaminocarbonyloxy ;groups such a~s phenylamlnocarbonyloxy, sulfo groups, sulfamoyl groups, alkylsulfamoyl groups such as ".. ~.. . .

:

2~6~1~6 methylsulfamoyl and arylsulfamoyl groups such as phenylsulfamoyl.
The hydrogen atom of hydrazine may have been substituted by a sulfonyl group such as a methanesulfonyl or toluenesulfonyl, an acyl group such as an acetyl or a trifiuoroacetyl group, an oxalyl group such as ethoxyoxalyl or another substituent.
In the present invention, more preference is given to the compound represented by the following Formula H-a or H-b.
Formula H-a Y O O
Il 11 11 R23(N R2~)nCN~R2,--L~R27--NHNHC--C--E~z~
R2s wherein R23 and R24 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group such as a methyl group, an ethyl group, a butyl group, a dodecyl group, a 2-hydroxypropyl group, a 2-cyanoethyl group or a 2-chloroethyl group, a substituted or unsubstituted phenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group, a pyrrolidyl group such as a phenyl group, a p-methylphenyl group, a naphthyl group, an a-hydroxynaphthyl group, a cyclohexyl group, a p-methylcyclohexyl group, a ;,.: ..

2~631~

pyridyl group, a 4-propyl-2-pyridyl group, or a 9-methyl-2-pyrrolidyl group; R23 preferably represents a substituted alkyl group; R25 represents a hydrogen atom, a substituted or unsubstituted benzyl group, an alkoxy group or an alkyl group such as a benzyl group, a p-methylbenzyl group, a methoxy group, an ethoxy group, an ethyl group or a butyl group; R26 and R27 independently represent a divalent aromatic group such as a phenylene group or a naphthylene group; Y represents a sulfur atom or an oxygen atom; L represents a divalent bonding group such as -S02CH2CH2NH-, -S02NH-, -OCH2S02NH-, -O- or -CH=N-; R28 represents -NR'R" or -OR29; R', R" and R29 wherein independently represent a hydrogen atom, a substituted or unsubstituted alkyl group such as a methyl group, an ethyl group or a dodecyl group, a phenyl group such as a phenyl group, a p-methylphenyl group or a p-methoxyphenyl group, a naphthyl group such as an a-naphthyl group or ~-naphthyl group or a heterocyclic group such as an unsatuvated heterocyctic group, i.e., a pyridine, thiophene, furan or a saturated heterocyclic group, i.e., a tetrahydrofuran, or sulfolane; Provided that R' and R" may bond each other with a nitrogen atom to form a heterocyclic ring such as piperidine, piperazine or morpholine.

206~1~6 m and n independently represent O or 1. Preferably, m is 1 and n is O or m is O and n is 1. When R28 represents -OR29, Y preferably represents a sulfur atom.
Formula H-b ~,5 Z O
~ N--I --C--NH-- Rs--NHN~IC--Rg R 1~. ' wherein R5, R6 and R7 independently represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a 3-aryloxypropyl group, a substituted or unsubstituted phenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group, a pyrrolidyl group, a substituted or unsubstituted alkoxy group such as a methoxy group, ethoxy group or butoxy group or a substituted or unsubstituted aryloxy group such as a phenoxy group or 4-methylphenoxy group.
In the present invention, R5 and R6 are each preferably a substituted alkyl group (the substituent is an alkoxy group or aryl group); R7 ls preferably a hydrogen atom or an alkyl group.
R8 represents a divalent aromatic group such as a phenylene group or a naphthylene group; Z represents a sulfur atom or àn oxygen atom.

- : - . , .

2 0 ~ 6 Rg represents a substituted or unsubstituted alkyl group, an alkoxy group or an amino group, whose substituent includes an alkoxy group, a cyano group and an aryl group.
The hydrazine derivative can easily be synthesized by known methods such as those described in Japanese Patent O.P.I. Publication Nos. 214850/1990, 47646/1990 and 12237/1990.
Examples of hydrazine derivatives preferably used for the present invention include Exemplified Compounds III-1 through III-4, III-6 through III-36 and III-38 given in Japanese Patent O.P.I. Publication No. 214850/1990, pp.12-14, Exemplified Compounds III-1 through III-11, III-13 through III-38, III-40 through III-42 and III-44 through III-50 given in Japanese Patent Application No.83333/1990, Exemplified Compounds II-1 through II-4, II-6 through II-56 and II-58 through II-62 given in Japanese Patent Application No. 83339/1990 and the following compounds, but the invention is not limited thereto.

20651~6 Exemplified Compounds (t)C5HI~O (CH2)3_SO2NH~3NHNHCCOCI2H25 (t)C5H ~ I C FJ

t--C5HII O l t~CsH,r~O(CH2).,NHgNH~NHNHCCNH--*
Cl13 *~CH~

C H
H ~ 151 CH
~SO2N~I~NHNHC;OCON~ H
Ç3--SCH2CON H C H 3 tCsHtl CH3 tCsHIl~() (CH2hSO2NH~NHNHCOCON~N H
~CH~
C~

2065~06 In the present invention, the hydrazine derivative content preferably ranges from 5 x 10-7 to S x 10~1 mol, more preferably 5 x 10-6 to 1 x Io-2 mol per mol of silver halide.
Desalting of the silver halide emulsion of the present invention to remove the dissolved matters therein is achieved by coagulation precipitation using denatured gelatin. In other words, denatured gelatin coagulants are used for the present invention. Denatured gelatin is a polymeric coagulant capable of coagulating ~ilver halide grains along with protective colloid, especially denatured gelatin which has not less than 50% of an amino group having a substituent based on the total amino group contained in the gelatin molecule. Examples of the substltuent for the amino group of gelatin include those described in US Patent Nos. 2,691,582, 2,614,928 and 2,525,753.
Examples of substituents which serve well for the present invention include:
(1) acyl groups such as alkylacyl/ arylacyl, acetyl and substituted or unsubstituted benzoyl groups, ~2) carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl groups, ~3) sulfonyl groups such as alkylsulfonyl and arylsulfonyl groups, --206~106 ~ 29 -(4) thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl groups, (5) linear or branched alkyl groups having 1 to 18 carbon atoms, and (6) aromatic heterocyclic aryl groups such as substituted or unsubstituted phenyl, naphthyl and pyridyl and furyl groups.
The substituent is preferably an acyl group (-COR41) I

or a carbamoyl group (- C O N R4l) .
The group for R41 is a substituted or unsubstituted aliphatic group such as an alkyl group having 1 to 18 carbon atoms or an allyl group, an aryl group or an aralkyl group such as a phenethyl group; R42 is a hydrogen atom, an aliphatic group, an aryl group or an aralkyl group.
Preference is given to the case where R41 is an aryl group and R42 is a hydrogen atom.

Examples of denatured gelatin coagulants preferably used for the present invention are given by means of a substituent below, but the invention is not limited thereto.

. : -' ' : :
--20~5106 Exemplified Compounds G~ 2 --COC~H,(t) --C:OCH, G--3 (~--~
C O O H
-co~3 -co ~3 C 1~
--CO~COOH --CO~COOH

--CO~ CONH~

CC)OH
--C O N H~ --C O N H ~C O O H

--CON~) --CONHCH~
C 2 H s 2~6~10~

Although the denatured gelatin coagulant can be used at any time during production of silver halide photographic emulsion, it is preferable to use it during or after the desalinization process, more preferably during the desalinization process, since it is more effective on photographic performance that contrast degradation does not occur. Although the amount of its addition is not subject to limitation, the amount i9 preferably 0.1 to 10 times, more preferably 0.2 to 5 times by weight greater than the amount of the substance (preferably gelatin) contained as protective colloid, after desalting, when it is used in the desalting process.
The denatured gelatin coagulant acts to coagulate silver halide grains along with protective colloid, and can be allowed to coagulate the silver halide emulsion by ad~usting the pH after its addition. The pH at coagulation is not more than 5.5, preferably 4.8 to 2.
Although any acid can be used for pH adjustment with no limitation, organic acids such as acetic acid, citric acid and salicylic acid and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid are preferably used. The denatured gelatin coagulant may be used in combination with heavy metal ions such as magnes.ium ion, cadmium ion, lead ion and zirconium ion.

' Removal of dissolved substances (desalting) may be performed once or in several cycles. When it is performed in several cycles, the denatured gelatin coagulant may be added at every removal or only once at the initial.
For producing the silver halide photographic emulsion relating to the present invention, gelatin is normally used as a binder or protective colloid, but other substances can also be used for this purpose, including gelatin derivatives, graft polymers of gelatin and another polymer, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, sugar derivatives such as agar, sodium alginate and starch derivatives, various synthetic hydrophilic homopolymers and copolymers such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylimide, polyvinylimidazole and polyvinylpyrazole.
The silver halide used in the silver halide photographic light-sensitive material of the present invention is described below. The silver halide may have any composition, including silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide and silver iodobromide. The average grain size of the silver halide grains is preferably in the range from 0.05 to 0.5 ~m, more preferably 0.10 to 0.40 ~m.

2~6~6 Although the silver halide grains for the present invention may have any grain size distribution, it is preferably 1 to 30, more preferably 5 to 20 in terms of the degree of monodispersion as defined below.
Here, the degree of monodispersion is defined as the figure obtained by dividing the standard deviation of grain size by average grain size and multiplying the quotient by a factor of 100. For convenience, the grain size of silver halide grains is expressed by the length of ridge for cubic grains or by the square root of projected area for other types of grains such as octadecahedral and tetradecahedral grains.
In the present invention, it is possible to use silver halide grains having at least two laminated layers.
For example, silver iodobromide grains comprising silver iodobromide in the core and silver bromide in the shell can be used. In this case, iodine can be contained in any layer at contents of not more than 5 mol%.
The silver halide grains in silver halide emulsion may contain therein and/or thereon metal elements by adding metal ions using at least one of cadmium salt, zinc salt~ lead salt, thallium salt, iridium salt (including complex salts thereof), rhodium salts (including complex salts thereof) and iron salts (including complex salts thereof) during formation and/or growth of grains. They 206~1~6 may also have a reduction sensitizing nucleus therein and/or thereon by keeping them in appropriate reducing atmosphere.
The silver halide may also be sensitized with various chemical sensitizers. Examples of sensitizers include active gelatin, sulfur sensitizers such as sodium thiosulfate, allyl thiocarbamide, thiourea and allyl isothiocyanate, selenium sensitizers such as N,N-dimethylselenourea and selenourea, reduction sensitizers such as triethylenetetramine and stannous chloride and various noble metal sensitizers such as potassium chloroaurate, potassium aurothiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methylchloride, ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladate. These sensitizers may be used single or in combination. When using a gold sensitizer, rhodan ammonium may be used as an auxiliary.
The silver halide grains for the present invention can be improved in their performance by processing with the chemical sensitizers described above, because they are preferably silver halide grains offering negative images, namely grains wherein the surface sensitivity is higher than the inside sensitivity.
The silver halide grains for the present invention can be stabilized or made to have an antifogging effect by the use of mercapto compounds such as l~phenyl-5-mercaptotetrazole and 2-mercaptobenzothiazole, benzotriazoles such as 5-bromobenzotriazole and 5-methylbenzotriazole and benzimidazoles such as 6-nitrobenzimidazole.
The silver halide photographic light-sensitive material of the present invention is processed with a developer containing the compound represented by Formula IV.
~ With respect:to Formula IV, the alkyl group or hydroxyalkyl group having 1 to 10 carbon atoms, represented by Rl' or R2', may be linear or branched, :including methyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 1,2-dihydroxypropyl group and 1-hydroxybutyl group.

, In the present invention, it is particularly preferable that at least one of R1' and R2' be a , , : ~
hydrosyalkyl group having 2 to 9 carbon atoms.

The alkyl group represented by R3' may be linear or branched, includlng methyl group, ethyl group, n-propyl group~ isopropyl group, n-butyl group, t-butyl group, n-p~éntyl group, t-pentyl group and n-hexyl group.

20~o6 group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, t-pentyl group and n-hexyl group.
Examples of the amino compound represented by Formula IV include diethylethanolamine, n-butyldiethanolamine, n-propyldiethanolamine, 2-di-isopropylaminoethanol, N,N-di-n-butylethanolamine, 3-diethylamino-1,2-propanediol and 3-di-propylamino-1,2-propanediol.
The amount of the amino compound represented by Formula-IV used is preferably 0.01 to 0.30 mol, more preferably 0.01 to 0.2 mol per liter of developer.
In the present invention, to process the silver halide photographic light-sensitive material, the following developing agents, for instance, are used.
Typical examples of developing agents of the HO-(CH=CH)n-OH type include hydroquinone, catechol and pyrogallol.
Typical examples of developing agents of the HO-(CH=CH)n-NH2 type include ortho- or para- aminophenols and aminopyrazolones such as N-methyl-p-aminophenol, N-~-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid and 2-aminonaphthol.
Examples of developing agents of the heterocyclic type include pyrazolidones such as 1-phenyl-3-206~106 Developing agents which can be used for the present invention are described in "the Theory of Photographic Process", 4th edition, by T. H. James, pp. 291-334, and the Journal of the American Chemical Society, Vol. 73, p.
3100 (1951).
Although developing agents for the present invention may be used singly or in combination, as long as they contain the compound of Formula IV, it is preferable to use two or more of them in combination. The developer may incorporate a sulfite such as sodium sulfite or potassium sulfite as a preservative, and may also incorporate hydroxylamine, a hydrazide compound or others as a developing accelerator. Their addition amount is ~preferably 5 to 500 g, more preferably 20 to 200 g per liter of developer.

,, It is also possible to add caustic alkali, carbonic ~ ~ ~a~lkall or amlne to adjust the pH and offer buffering - ~ ~ function as in ordinary black-and-white developers, and to add~inorganic~developing~inhibitors such as bromopotassium, organic developlng inhibitors such as 5-, -methylbenzotriazole, 5-methylbenzimidazole, 5-- nitroindazole, adenine, guanine and 1-phenyl-5-mercaptoeetrazQ1e, sequestering agents such as gold ethylenediaminetetraacetate, developing accelerators such as methanol,~ethanol, benzyl alcohol and polyalkylene , , .
. . :' `
- , .
.

2~65106 oxide, surfactants such as natural saponin, sugars or alkyl esters of the above-mentioned compounds, hardeners such as glutaraldehyde, formalin and glyoxal, and ionic strength regulators such as sodium sulfate. The developer may also contain organic solvents, specifically alkanolamines such as dlethanolamine and triethanolamine and glycols such as diethylene glycol and triethylene glycol. Alkylamino alcohols such as diethylamino-1,2-propanediol and butylamino propanol are especially preferably used.
These organic solvents may be used singly or in combination.
The photographic light-sensitive material of the present invention can be processed under variouQ sets of conditions. For example, developing temperature is -, .
preferably under SO C, more preferably about 25 to 40 C.
It~is also possible to carry out washing, stopping, stabilization, fixation, and where necessary pre-hardenlng,~neutralization and other processes, and these processes may be omltted. These processes may be achieved :
~ by~a manual process such as dish development or frame ,, , development or by a mechanical process such as roller development or hunger development.
The light-sens`itive silver halide emulsion layer or ad~oining layers may contain the compounds described in :: ~ : ~: ~ : :

- .

.
:, :
- , .
- .

2065~06 Re~oarch Di~cloJure No. 17463, Paragraph XXI, Terms B
through D for the purpose of improvement in sensitivity and contrast and acceleration of development.
The silver halide emulsion for the present invention may incorporate sensitizing dyes, plasticizers, antistatic agents, surfactants and hardeners.
Although the binder for the hydrophilic colloid layer relating to the present invention is preferably gelatin, other hydrophilic colloids can be used. These hydrophilic binders are preferably coated on both faces of the support at not more than 10 g/m2.

-Examples of supports whlch can be used for the present invention include baryta paper, polyethylene-coated~paper, synthetic polypropylene paper, glass plates, céllulose acetate, cellulose nitrate, and films of , polyesters such as polyethylene terephthalate. These upports are selected as appropriate according to the purpos~ of the use of each silver halide photographic : . :
light-sensitive material.

EXAMPLES
The present invention i9 hereinafter described in more~detall by means of the following examples, but these are not to be construed as limitative on the mode of embodlment of the invention.

...

:~ ,, ' :

`- 20~5106 Example 1 Preparation of silver halide emulsion grains A silver halide emulsion having a silver halide composition of 98 mol% silver bromide and 2 mol% silver iodide was prepared under conditions of 50 C, pAg 7.8 and pH 2Ø Silver ion and halide ion were supplied by the double jet precipitation method while increasing the supply rate in proportion to the surface area with the growth of the silver halide grains formed. Just before completion of grain formation, K2IrCl6 was added at 6 x 10-7 mol per mol of silver, and after completion of grain formation, partial halogen replacement was performed using 0.3 mol per mol of silver of potassium iodide.
The emulsion thus obtained comprised cubic grains with an average grain size of 0.2 ~m and a coefficient of variance of 15%.
Desalting The emulsion was adjusted to a pH of 5.5 with caustic soda and then dispensed to some portions, which were each desalted under the following conditions.
Conditions a (desalting outside the present invention) To 1.0 kg of the emulsion described above (silver content 44 g, ossein gelatin content 4 g) was added 80 ml of a 10% ossein gelatin solution at 40 C. After stirring for 10 minutes, 90 ml of a 5~ polynaphthalenesulfonic acid solution and 90 ml of 20% magnesium sulfate solution were added. After stirring for S minutes, the resulting mixture was kept standing to precipitate the emulsion, and 800 ml of the supernatant was discarded.
Then, 800 ml of pure water at 40 C was added. After stirring for 5 minutes, 30 ml of a 20~ magnesium sulfate solution was added. After stirring for 5 minutes, the mlxture was kept standing, and 800 ml of the supernatant was dlscarded. The same desalting procedure was performed one more time using 30~ml of 20% magnesium sulfate solution.
The emulslon temperature was kept at 40 C throughout this process.
TQ the emulsion thus obtained was added 80 ml of a 10% ossein gelatin solution containing a mixture of the :~ , following compounds A, B and C, followed by re-dispersion at~SS C, to yield the desired silver halide emulsion a.
[A] ~ : ~ r8] tc]

;;N`C H . ~N`C H C Q~N`C H
, 0 o o ;Conditions b (desalting according to the present , "
, invention) :, ' ::
, ,.',. ~,-'' .

2 a ~ 6 To 1.0 kg of the emulsion described above (silver content 44 g, ossein gelatin content 4 g) was added 80 ml of a 10% denatured gelatin solution containing G-8 at 40 C
as shown in Table 1. After stirring for 10 minutes, a 5%
sulfuric acid solution was added to obtain a pH of 4.4.
After stirring for 5 minutes, the mixture was kept standing to precipitate the emulsion, and 800 ml of the supernatant was discarded.
Then, 800 ml of pure water at 40 C was added. After adding 5 % caustic soda to obtain a pH of 5.7, the mixture was stirred for 5 minutes to yield a dispersion.
Subsequently, the same desalting procedure was performed two more times using a sulfuric acid solution and a caustic soda solution.
The emulsian temperature was kept at 40 C throughout this process.
To the emulsion thus obtained wa~ added 80 ml of a 10% ossein gelatin solution containing a mixture of the same compounds A, B and C as with the conditions above, followed by re-dispersion at 55 C to yield the desired silver halide emulsion b.
The emulsions obtained under conditions a and b both had a pAg of 7.6 at 40 C.
Preparation of silver halide photographic light-sensitive material 206~06 On one face of a 100 ~m thick polyethylene terephthalate film having a 0.1 ~m thick undercoat (see Example 1 of Japanese Patent O.P.I. Publication No. 19941/1984) on both faces, a silver halide emulsion layer with the following composition 1 was coated so that the amount of gelatin coated was 2.0 g/m2 and the amount of silver coated was 3.2 g/m2, and further coated with a protective layer with the following composition 2 so that the~amount of gelatin coated was 1.0 g/m2. On the undercoat on the opposite side, a backing coat with the following composition 3 was coated so that the amount of gelatin coated was 2.4 g/m2 and further coated with a protective layer with the following composition 4 so that the amount of gelatin coated was 1.0 g/m2. A sample was thUs obtained.
Composition 1 (silver halide emulsion layer) Gelatin 2.0 g/m2 Silver hallde emulsion ~see Table 1) 3-2 g/m2 (as silver) Antifogging agent: Adenine10 mg/m2 Stabi~lizer: ~4-methyl-6-hydroxy-1,3-3a, 7-tetrazaindene 30 mg/m2 ;Nydrazine derivativeSee Table 1 compound I of the present invention See Table 1 rfactan~: ~SapoAin 0.1 g/m2 :
, . ~ - :

2~65~6 S--1 :
CH2COO(C:H2),CH~
~CHJ
CH2COO(CH~)~CH
\C1~J
S O~N8 8.0 mg/m2 Polyethylene glycol ~molecular weight 4000) 0.1 g/m2 Latex polymer:
~CH--CH~ ~CH~--CH~
COOC~H~ C)COCH~ 0.5 g/m2 Sensitizing dye:
C1H~
C H ~ C ~ C H=~

(CH2)~ (CH~)~
SOJe SO~Na 8mg/m2 Hardener H-1: ~
ON~
N~N
1~N~ 60 mg/m2 , :
.

, :, 2~651~

The sensitizing dye was adsorbed to silver halide emulsion grains at 60 C for 1 hour.
Composition 2 (emulsion protective layer) Gelatin 0.9 g/m2 Matting agent: Silica having an average grain size of 3.5 ~m 3 mg/m2 Surfactant S-2:
CH2COOCH2(C2Hs)C~H~
CHCOOCH2CH(C2Hs)C~Hs S OJN~
10 mg/m2 Hardener: Formalin 30 mg/m2 " 2~5~1D6 Composition 3 (backing coat) (CH~)2N~C~N(CHJ)2 ~C H 2 S O ~e 40~ 2 CH2S O ~H

l C H J ) 2 N~ C H ~ , H

~0~8/~
S O,K

(CH3)21J~CH=CH--CHl ~ COOH
O N,N

O~N~
30~g/~ 2 Gelatin 2.4 g/m2 Surfactant: Saponln 0.1 mg/m2 206~106 S--1 :
CH2COO(CH2)~CHs ~H~
CH2COO(CH2)2CH~
CH~
S O,N~ 6.0 mg/m2 Composition 4 (backing protective layer) Gelatin 1 g/m2 Matting agent:
Polymethyl methacrylate having an average grain size of 3.0 to 5.0 ~m 50 mg/m2 Surfactant: S-2 10 mg/m2 Hardeners : Glyoxal 25 mg/m2 : H-1 35 mg/m2 The samples thus obtained were tested as directed below. The results are shown in Tables 3 and 4.
Dot quality test The sample was brought into contact with a transparent original comprising a step wedge and a dot screen (150 lines/inch) with 50% dot area, and exposed with xenon lamp for 5 seconds. The expased sample was processed in an automatic rapid developing machlne containing a developer with a developer composition shown in Tables 1 and 2 and a fixer with the following fixer composition under the following conditions.

' ~ :

. . .
, ,'' ~ . .
. .

---` 2~6~ 06 Pepper fog in the dots were observed through a magnifying glass of 100 magnifying power. When no pepper fog occurred in the dots, the sample was rated highest at a rank of "5". The samples were ranked according to the degree of occurrence of pepper fog and under ranks of "4", "3~ 2" and "1". Ranks "1" and "2" are practically undesirable levels because of significant occurrence of pepper fog.
Each sample processed above was subjected to densitometry using the Konica digital densitometer PDP-65.
Sensitivity was expressed as percent ratio relative to the sensitivity of sample No. 1 at a density of 3.0, with the gamma value expressed by the tangent for densities 0.3 and 3Ø
Silver image ~tability test After exposure through a step wedge using a xenon lamp for 5 seconds, the sample was processed in an automatic rapid developing machine containing a developer with a developer composition shown in Tables 1 and 2 and a fixer with the following fixer composition under the following conditions. Each processed sample was kept standing under conditions of 40C and 80~ RH for 3 days.
The silver image formed on the image portion was examined for the degree of deterioration. When the silver image remained unchanged, the sample was rated highest at .

, ~ :

`-` 2 0 ~ 6 a rank of ~5~. The samples were ranked under five ranks of "5", "4", "3", "2" and "1". Ranks "1" and "2" are practically undesirable levels.
Developer composition 1 Disodium ethylenediaminetetraacetate 1 g Sodium sulfite 60 g Hydroquinone 35 g 3-(diethylamino)-1,2-propanediol 30 g Sodium bromide 3.0 g 5-methylbenzotriazole 0.1 g 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.2 g Phenetyl picolium bromide 2.5 g Water was added to make a total quantlty of 1 liter, and sodium hydroxlde was added to obtain a pH of 11.7.
Developer composition 2 Disodium ethylenediaminetetraacetate 1 g Sodium sulfite 60 g Hydroquinone 35 g 3-(diethylamino)-1,2-propanediol 30 g Sodium bromide 3.0 g 5-methylbenzotriazole 0.1 g 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.2 g Phenytyl picolium bromide 2.5 g 1-phenyl-5-mercaptotetrazole 0.08 g .

' 2~g~6 water was added to make a total quantity of 1 liter, and sodium hydroxide was added to obtain a pH of 11.7.
Fixer Composition A
Ammonium thiosulfate (72.5% w/v aqueous solution) 240ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Composition B
Pure water (ion exchange water)17 ml Sulfuric acid (50% w/w aqueous solution) 4.7 g Aluminum sulfate (8.1% w/w Al2O3 aqueous solution) 26.5 g The compositions A and B were dissolved in 500 ml of water in this order and diluted to 1 liter before use as a fixer. Thls fixer was adjusted to a pH of 4.8 with acetic acid.
Processing conditions ProcedureTemperature Time Development 40 C 15 seconds Fixation 35 C 15 seconds Washing 30 C 10 seconds Drying 50 C 10 seconds .
. : ' :
.

` 206~1 0~

Table 1 Compound I or II .
Silver Hvdrazine of the present Sam~le halide i.nvention Developer Remark No. emulslon Amount of _ Amount of composition Kind addition Kind addition (mg/m2) ~mg/m2) 1 _ _ l Comparative 2 b _ _ _ _ 1 Comparative 3 H-5 35 _ Comparative H-14535 _ 1 Comparative H-77 35 _ l Comparative 6 b H-5 35 _ _ 1 Comparative 7 b H-145 35 _ _ 1 Comparative __ a ~ H-77 35 _ Comparative H-5 35 I-2 Comparative 10H-145 35 I-3 1 Comparative 11a H-77 35 I-8 1 Comparative 12 - H-5 35 I-8 5 1 Inventive _ 13 H-5 35 II-2 1 Inventive 14_ H-37 35 I-3 Inventive 15 H-37 35 II-3 Inventive 16_ H-93 35 I-8 Inventive 17 b H-93 35 Il-l Inventlve 18 H-145 35 I-7 1 Inventlve 19 b H-152 35 I-7 5 1 Inventive b H-152 35 II-4 5 1 Inventive 21 H-50 35 I-7 1 Inventive 22 H-50 35 II-l 1 Inventive 23 H-77 35 I-7 1 Inventive 24 b H-77 35 II-2 5 1 Inventive b H-81 35 I-4 5 1 Inventlve 26 b H-81 35 II-l 5 Inventlve , .

:' .

-206~10~

Table 2 Hydrazine Compound III of the Sample Silver deri~ ~tive present 1 ~ventlon Developer No. halide Amount of Amount of composition Remark emulslon Compound addition Compound addition ( mg ~m2 ~ ~ mg /m2 ) 27 a H-S 35 _ _ 1 Comparative 28 _ H-195 35 _ 1 Comparative 29 . H-7735 _ Comparative b H-5 35 _ _ 1 Comparative 31 b H-145 35 Comparative 32 H-77 35 1 Comparative 33 a H-5 35III-3 5 1 Comparative 34 a H-145 35III-10 1 Comparative H-77 35 ~ Comparative 36 b H-5 35III-10 5 1 Inventive 37 H-5 35III-10 Inventive 38 b H-5 35III-17 5 2 Inventive 39 H-37 35III-10 1 Inventive H-37 35III-10 2 Inventive 41 H-37 35III-19 Inventlve 42 b H-93 35III-8 5 2 Inventlve __ 43 H-93 35III-12 Inventive 44 b H-145 35III-10 5 1 Inventive __ b H-145 35III-15 5 2 Inventive 46 H-152 35III-7 Inventive 47 H-152 35III-22 5 2 Inventive 48 H-50 35III-2 Inventive 49 H-50 35III-20 ~ 5 Inventive H-77 35III-10 Inventive 51 H-77 35III-10 2 Inventlve 52 b H-77 35III-24 5 2 Inventive 53 b H-81 35III-10 ~ Inventlve 54 b H-81 35III-20 ~ Inventive " 206~10~

- 53 ~

Table 3 Sample Relative Gamma Pepper Silver No. sensitivity value fog image Remark stability 1 100 9.5_ 5 1 Comparative 2 100 4.5 5 1 Comparative 3 180 11.5 1 1 Comparative 4 200 12.0 2 1 Comparative 200 12.0 2 1 Comparative 6 185 11.5 4 2 Comparative 7 205 12.0 9 2 Comparative .

8 205 12.0 4 2 Comparative 9 160 11.5 2 3 Comparative 180 12.0 2 4 Comparative 11 180 12.0 2 4 Comparative 12 180 11.5 4 3 Inventive 13 175 11.5 4 4 Inventive 14 185 12.0 9 3 Inventive 185 12.0 4 4 Inventive 16 190 11.5 4 4 Inventive 17 190 11.5 9 4 Inventive 18 200 12.5 5 5 Inventive 19 205 12.5 5 5 Inventive 205 12.5 5 5 Inventive 21 19511.5 4 _ 4 Inventive 22 195`11.5 4 4 Inventive 23 19512.5 5 4 Inventive 24 20513.0 5 5 Inventive 20512.5 5 5 Inventive 26 20512.5 5 5 Inventive 20651~6 Table 4 Sample Relative Gamma Pepper Silver No. sensitivity value fog image Remark stability 27 180 11.5 1 1 Comparative 28 200 12.0 2 1 Comparative 29 200 12.0 2 1 Comparative `30 185 11.5 4 2 Comparative 31 205 12.0 4_ 2 Comparative 32 205 12.0 4 2 Comparative 33 150 11.5 2 3 Comparative 34 170 12.0 2 4 Comparàtive 170 12.0 2 4 Comparative 36 170 11.5 4 3 Inventive _ 37 170 11.5 4 4 Inventive : 38 170 11,5 4 4 Inventive , 39 _ 180 12.0 4 3 Inventive 180 12.0 4 4 Inventive 41 180 12.0 4 4 Inventive 42 190 11.5 4 4 Inventive ~: 43 ~ 190 ~ ~11 5 4 4 Inventive 44 195 12.5 5 Inventive ~45 ~ 195 12.5 5 5 Inventive __ r : 46 ~200 12.5 5 5 Inventive 47 200 12.5 5 5 Inventive ~ ~48 190 11.5 4 . 4 Inventive : ~ 49 190 11.5 4 4 Inventive ~; 195 12.5 5 4 Inventive ~51 200 12.5 5 5 Inventive : ~ 52 ~200 13.0: 5 5 Inventive , ~ : :
53 . 205 12.5 5 5 Inventive 54 205 12.5 5 5 Inventive , ~: .' ' :

2~6~

As is evident from Tables 3 and 4, the samples according to the present invention had high sensitivity and satisfactory levels of gamma value, pepper fog and silver image stability.
Example 2 Silver halide light-sensitive material samples obtained as in Example 1 were processed and evaluated in the same manner as in Example 1 except that developers with the following compositions were used as shown in Table 5 and 6. The results are shown in Tables 7 and 8.
Developer composition 3 Disodium ethylenediaminetetraacetate 1 g Sodium sulfite 60 g Sodium phosphate 12 hydrate 75 g Hydroquinone 22.5 g N,N-diethylethanolamine 15 g Sodium bromide 3 g 5-methylbenzotriazole 0.25 g Metol 0.25 g Water was added to make a total quantity of 1 liter, and sodium hydroxide was added to obtain a pH of 11.7.
Developer composition 4 Disodium ethylenediaminetetraacetate 1 g Sodium sulflte 60 g Sodium phosphate 12 hydrate 75 g -`"` 2 0 ~ 6 Hydroquinone 22.5 g N,N-diethylethanolamine 15 g Sodium bromide 3 g 5-methylbenzotriazole 0.25 g 1-phenyl-5-mercaptotetrazole 0.08 g Metol 0.25 g Water was added to make a total quantity of 1 liter, and sodium hydroxide was added to obtain a pH of 11.7.

2 ~ 0 6 Table 5 _ Compound I or II
Hydrazlne o~ the present Silver derivative Sample halide _ invenl ion Developer Remark No. emulsion Amount of Amount o~ compositlon Kind addition Kind addition (mg/m ) tmq~m ) 1 a _ _ _ _ 3 Comparative 2' b _ ~ = ~ = 3Comparative 3' H-5 35 _ _ Comparative _ _ q' a H-145 35 _ 3 Comparative 5' a H-77 35 _ 3 Comparative 6' b H-5 35 _ _ 3 omparative 7' b H-145 35 _ 3 Comparative 8 b H-77 35 _ 3 Comparative 9' a H-5 35 I-2 5 3 Comparative 10' a H-145 35 I-3 5 3 Comparative 11' a H-77 35 I-8 3 Comparative _ 12 ' b H-5 35 I-8 5 3 Inventive 13' b H-5 35 I-8 5 3 Inventive 14' b H-37 35 I-3 5 3 Inventive 15' H-37 35 II-3 Inventlve 16' H-93 35 I-8 Inventlve __ _ ~
17~ b H-93 35 II-1 5 3 Inventive 18' b H-145 35 I-7 5 3 Inventive _ 19 ' b H-152 35 I-7 5 3 Inventive 20' b H-152 35 II-4 5 3 Inventive 21' b H-50 35 I-7 5 _ 3 Inventive 22' H-50 35 II-l Inventive 23' H-77 35 I-7 Inventlve _ 24 ~ b H-77 35 II-2 5 3 Inventlve 25' b H-81 35 I-q 5 3 Inventlve 26' b H-81 35 II-l 5 3 Inventlve .

.

', .

" 206~106 Table 6 Hydrazlne Compound III of the _ Sample Silver derlvativepresent invention Developer No. hallde _ Amount of _ Amount of composltlon Remark . emulsion Compound addltion Compound addition ~mg/m2 ~ (mg/m2 ) 27 ~ a H-5 35 3 Comparative 28 ' , a H-145 35 3 Comparative 29 l a H-77 35 _ _ 3 Comparative 30 ' b H-S l 35 l 3 __ Comparative 31 ' H-195 35 3 Comparative .
32 ' b H-77 35 3 Comparative 33 ' a H-5 35 III-3 5 3 Comparative __ 34 ' a H-145 35 III-10 5 3 Comparative 35 ~ a H-77 35 III-10 5 3 Comparative 36 ' b H-5 35 III-10 5 3 Inventive 37 l b H-5 35 III-10 5 4 Inventive 38 ' b H-5 35 III-17 _ 4 Inventive 39 ' b H-37 35 III-10 5 3 Inventive 40 ' b H-37 35 III-10 5 9 Inventlve _ 41 ' b H-37 35 III-l9 5 4 Inventive 42 ' ~ ~ b ~ H-93 35 III-8 5 4 Inventlve 43 ' b H - 93 35I I I - 12 4 I nve nt lve 44 ' b H-145 35 III-10 5 3 Inventlve 45' b H-145 35 III-15 5 4 Inventive 46' b H-152 35 III-7 5 4 Inventive 47 ' b H-152 35 III-22 5 4 Inventive 48 ' b H-50 35 III-2 5 4 Inventive 49' b H-50 35 III-20 5 4 Inventive 50, ~b ~ ~ H-77 35 III-10 5 3 Inventive 51 ' b H - 77 35 I I I - 10 4 I n vent ive 52 ' b H-77 35 III-24 5 4 Inventive 53' _ H-81 35 III-10 5 3 Inventive 54 ' b H-al 35 III-20 5 3 Inventive ~` 206~106 Table 7 Sample Relative Gamma Pepper Silver . sensitivity value fog stability Remark 1' 100 4.5 5 1Comparative 2' 100 4.5 5 1Comparative 3 ' 180 11. 5 1 1Comparative 4 ' 200 12.0 2 1Comparative 200 12.0 2 1~Comparative 6' 185 11.5 4 2Comparative 7 ' 205 12.0 4 Comparative 8' 205 12.0 4 2Comparative 9' '60 11.5 2 3Comparative 10 ' 180 12.0 2 9Comparative 11 ' 180 12.0 2 4Comparative 12' 180 11.5 4 3Inventive 13 ' 175 11.5 4 4Inventive 14' 185 12.0 4 3Inventive 15' 185 12.0 4 4Inventive 16 ' 190 11.5 4 4Inventive 17 ' 190 11.5 4 4Inventive 18' 200 12. 5 5 5Inventive 19 ' 205 12.5 S 5Inventive 20 ' 205 12. 5 5 5Inventive 21 ' 19511.5 4 4Inventive 22 ' 19511.5 4 4Inventive 23 ' 19512.5 5 4Inventive .

24 ' 20513.0 5 5Inventive 25 ' 20512.5 5 5Inventive 26 ' 20512.5 5 5Inventive , .

, `` 206~106 Table 8 Sample Relative Gamma Pepper Silver No. sensitivity value fog image Remark.
stability 27' 180 11.5 l 1 Comparative .

28' 200 12.0 2 1 Comparative 29' 200 12.0 2 1 Comparative 30' 185 11.5 4 2 Comparative 31' 205 12.0 4 2 Comparative :32' ~ 205 12,0 4 2 Comparative 33' 150 11,5 2 3 Comparative 34' 170 12.0 2 4 Comparative 35' 170 12.0 2 4 Comparative 36' 170 11.5 4 3 Inventive 37' 170 11.5 4 4 Inventive 38l 17~0 11.5 4 9 Inventive _ 39' 185 12,0 4 3 Inventive 40' 185 12.0 4 9 Inventive 41' 180 12.0 4 4 Inventive 42' 190 11.5 4 4 Inventive 43' 190 11.5 4 4 Inventive 44' 200 12.5 5 5 Inventive 45l 200 :12.5 5 5 Inventive 46' :205 12.5 : 5 5 Inventive : ~ 47l~ ~ 205 12.5 5 5 Inventive 48' 190 11,5 4 4 Inventive ~: : 49l 190 11,5 4 9 Inventlve 50l ~ 200 12.5 5 4 Inventive : 511 210 12.5 5 5 Inventive :
~52l 210 13.0 5 5 Inventlve :: ~ 53l ~:205 12.5 5 5 Inventive ~ :541 : 205 12.5 5 5 Inventive : - . : '.: ~ ~ :
.

.
.

2~106 As is evident from Tables 7 and 8, the samples according to the present invention had high sensitivity and satisfactory levels of gamma value, Pepper fog and silver image stability.

Claims (9)

1. A silver halide photographic light-sensitive material comprising a support and provided thereon, a silver halide emulsion layer and layers adjacent to the emulsion layer, wherein the emulsion is subject to desalinization comprising using denatured gelatin in the process of preparation thereof, and at least one of the emulsion layer and the layers adjacent to the emulsion layer contains 5 to 300 mg per mol of silver of a compound selected from the group consisting of those represented by the following formulas I, II, and III and 5 x 10-7 to 5 x 10-1 mol per mol of silver halide of a hydrazine compound represented by the following formula H-a or H-b;
formula I

wherein A represents -OH, -SO3-, -N(R2)2 or -NH+(R2)2X-, R1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, R2 represents an alkyl group having 1 to 5 carbon atoms, X- represents an anion, X
represents a halogen atom or p-toluenesulfonate, and n is an integer of 2 to 5.

formula II

wherein R3 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group, R4 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and n is an integer of 2 to 5, provided that it includes a salt with a halogen ion or p-toluenesulfonate ion, formula III

wherein Q represents a group of atoms necessary to form a 5-or 6-membered heterocyclic ring, and M represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic amine residue, provided that the heterocyclic ring may be condensed with a benzene ring or another heterocyclic ring, formula H-a wherein R23 and R24 each represent a hydrogen atom, an alkyl group, a phenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group or a pyrrolidyl group, R25 represents a hydrogen atom, a benzyl group, an alkoxy group or an alkyl group, R26 and R27 each represent a divalent aromatic group, Y represents a sulfur atom or an oxygen atom, L represents a divalent bonding group, R28 represents -NR'R" or -OR29 wherein R', R"
and R29 each represent a hydrogen atom, an alkyl group, a phenyl group, a naphthyl group or a heterocyclic ring, provided that R' and R" may bond each other with a nitrogen atom to form a heterocyclic ring, and m and n each represent O
or 1, formula H-b wherein R5, R6 and R7 each represent a hydrogen atom, an alkyl group, a phenyl group, a naphthyl group, a cyclohexyl group, a pyrldyl group, a pyrrolidyl group, an alkoxy group or an aryloxy group, R8 represents a divalent aromatic group, R9 represents an alkyl group, an alkoxy group or an amino group, and Z represents a sulfur atom or an oxygen atom.

2. The material of claim 1, wherein said compound and said hydrazine compound are contained in the silver halide emulsion layer.

3. The material of claim 1, wherein in said formula I R1 represents a hydrogen atom, a methyl group, an ethyl group or a -CH2=CHCH3 group, A represents a -OH, -N(CH3)2 or -SO3Na group, X represents a halogen ion or a p-toluensulfonate ion, and n represents 2 or 3; in said formula I I R3 and R4 represent a methyl group, an ethyl group or a phenyl group, and n is 2;
in said formula III a heterocyclic ring formed by Q includes imidazole, thiazole, oxazole, triazole, tetrazole, selenazole, oxadiazole, thiadiazole, pyrimidine or triazine; in said formula H-a R23 represents a substituted alkyl group, and m is 1 and n is 0 or m is 0 and n is 1; and in said formula H-b R5 and R6 each represent an alkyl group having an alkoxy group or an aryl group, and R7 represents a hydrogen atom or an alkyl group.

4. The material of claim 2, wherein in said formula I R1 represents a hydrogen atom, a methyl group, an ethyl group or a -CH2=CHCH3 group, A represents a -OH, -N(CH3)2 or -SO3Na group, X represents a halogen ion or a p-toluensulfonate ion, and n represents 2 or 3; in said formula II R3 and R4 represent a methyl group, an ethyl group or a phenyl group, and n is 2;
in said formula III a heterocyclic ring formed by Q includes imidazole, thiazole, oxazole, triazole, tetrazole, selenazole, oxadiazole, thiadiazole, pyrimidine or triazine; in said formula H-a R23 represents a substituted alkyl group, and m is 1 and n is 0 or m is 0 and n is 1; and in said formula H-b R5 and R6 each represent an alkyl group having an alkoxy group or an aryl group, and R7 represents a hydrogen atom or an alkyl group.

5. The material of claim 1, wherein said denatured gelatin has not less than 50 % of an amino group having an acyl group or a carbamoyl group based on the total amino group contained in the gelatin molecule.

6. The material of claim 2, wherein said denatured gelatin has not less than 50 % of an amino group having an acyl group or a carbamoyl group based on the total amino group contained in the gelatin molecule.

7. The material of claim 1, wherein said denatured gelatin has not less than 50 % of an amino group having -COAr or -CONHAr wherein Ar represents an aryl group, based on the total amino group contained in gelatin molecule.

8. The material of claim 2, wherein said denatured gelatin has not less than 50 % of an amino group having -COAr or -CONHAr wherein Ar represents an aryl group, based on the total amino group contained in gelatin molecule.

9. A silver halide photographic light-sensitive material comprising a support and provided thereon, a silver halide emulsion layer and layers adjacent to the emulsion layer, wherein the emulsion is subject to desalinization comprising using denatured gelatin in the process of preparation thereof, and at least one of the emulsion layer and the layers adjacent to the emulsion layer contains 5 to 300 mg per mol of silver of a compound represented by the following formula I or II, and 5 X 10-7 to S X lo-1 mol per mol of silver halide of a hydrazine compound represented by the following formula H-a or H-b;
formula I

wherein A represents -OH, -SO3-, -N(R2)2 or -NH+(R2)2X-, R1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, R2 represents an alkyl group .

having 1 to 5 carbon atoms, X- represents an anion, X
represents a halogen atom or p-toluenesulfonate, and n is an integer of 2 to 5.
formula II

wherein R3 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group, R4 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and n is an integer of 2 to 5, provided that it includes a salt with a halogen ion or p-toluenesulfonate ion, formula H-a wherein R23 and R24 each represent a hydrogen atom, an alkyl group, a phenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group or a pyrrolidyl group, R25 represents a hydrogen atom, a benzyl group, an alkoxy group or an alkyl group, R26 and R27 each represent a divalent aromatic group, Y represents a sulfur atom or an oxygen atom, L represents a divalent bonding group, R28 represents -NR'R" or -OR29 wherein R', R"
and R29 each represent a hydrogen atom, an alkyl group, a phenyl group, a naphthyl group or a heterocyclic ring, provided that R' and R" may bond each other with a nitrogen atom to form a heterocyclic ring, and m and n each represent O
or 1, formula H-b wherein R5, R6 and R7 each represent a hydrogen atom, an alkyl group, a phenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group, a pyrrolidyl group, an alkoxy group or an aryloxy group, R8 represents a divalent aromatic group, R9 represents an alkyl group, an alkoxy group or an amino group, and Z represents a sulfur atom or an oxygen atom.