Note: Descriptions are shown in the official language in which they were submitted.
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
/ 2
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.
R2
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
-- 7
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 ~
-- 10 --
Exemplified compounds
CHJ NH2
~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
N H2
HO--(CH2)2--S--C~ CQ~
N H 2
--5 ~ E)
H O--(CH2)2--S--C\C2Hs ~Q~
N H
C2H5
...... .
: .
--, .
2065~
-- 11 --
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
- 12 -
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~
-- 13 --
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
- 16 -
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
I 1 11 11
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
- 18 -
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
- 20 -
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
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
- 22 -
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
- 23 -
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~
- 24 -
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
-- 25 --
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
- 26 -
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
H--93
00
(t)C5HI~O (CH2)3_SO2NH~3NHNHCCOCI2H25
(t)C5H ~ I C FJ
H--145
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
- 28 -
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)
R42
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
- 30 -
Exemplified Compounds
G~ 2
--COC~H,(t) --C:OCH,
G--3 (~--~
C O O H
-co~3 -co ~3
G--S G--6
C 1~
--CO~COOH --CO~COOH
--7 G--8
--CO~ CONH~
H2
G--9 G--10
CC)OH
--C O N H~ --C O N H ~C O O H
G--11 G--12
--CON~) --CONHCH~
C 2 H s
2~6~10~
- 31 -
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.
'
2065106
- 32 -
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
- 33 -
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
- 34 -
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
2065106
- 35 -
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
- 36 -
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
- 37 -
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
- 3B -
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
- 39 -
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
- 40 -
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
2065106
- 41 -
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
- 42 -
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
- 43 -
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
- 44 -
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~
45 -
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
- 46 -
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
-- 47 --
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
- 48 -
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
- 49 -
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
- 50 -
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~
-- 51 --
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
- 54 -
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~
- 55 -
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
-- 57 --
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
-- 58 --
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
59
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
- 60 -
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
- 61 -
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.
