Compositions comprising ethane dioic acid hydrazide compounds and derivatives useful as dot-promoting agents

Disclosed are novel compounds of the formula: ##STR1## wherein: X=--NR.sub.5 R.sub.6, or --OR.sub.7 ; PA1 R.sub.1 and R.sub.2 are independently hydrogen, substituted or unsubstituted alkyl, haloalkyl, hydroxyalkyl alkoxyalkyl, alkylaminoalkyl or arylalkyl having up to 18 carbons; cycloalkyl; phenyl or naphthyl; alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituents. PA1 R.sub.3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl, provided that if neither R.sub.1 nor R.sub.2 is hydrogen, then R.sub.3 is hydrogen. PA1 R.sub.4 is a divalent aromatic group which is substituted or unsubstituted. PA1 R.sub.5, R.sub.6, and R.sub.7 are independently hydrogen, alkyl, hydroxyalkyl, haloalkyl, alkoxyalkyl, alkylaminoalkyl, acylaminoalkyl, aminoalkyl or phenylalkyl having up to 12 carbons; a cycloalkyl substituent; phenyl or naphthyl; an alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituent. Furthermore, either R.sub.1 and R.sub.3 or R.sub.1 and R.sub.2 can be linked to form a heterocyclic ring system containing 3-10 atoms. Additionally, R.sub.5 and R.sub.6 can be linked to form a heterocyclic ring system containing 3-10 atoms. Y is an oxygen or sulfur atom. If Y is sulfur then n-1, if Y is oxygen then n=0 or 1. These compounds are useful as high-quality dot promoting agents in negative-working photographic systems. Disclosed as well are radiation-sensitive compositions and elements containing such dot promoting agents in combination with silver halide grains. These exposed compositions and elements when processed in a developer containing a dihydroxybenzene developing agent, a substituted benzotriazole, a sulfite preservative and an amine compound provide a method for the production of halftone dots possessing high image quality.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
One aspect of the present invention relates to a process for forming a 
photographic image using a silver halide light-sensitive material. More 
particularly, it relates to a process for forming a high-contrast negative 
image which simultaneously permits the production of dots possessing high 
image quality as is necessary in the field of graphic arts. Another aspect 
of the present invention relates to novel ethanedioic acid hydrazide 
compounds and compositions containing such compounds, said compounds and 
compositions being useful as dot-promoting agents in negative-working 
image systems. 
2. Description of the Prior Art 
In letterpress and offset lithography, tones cannot be reproduced by 
varying the amount of ink. A printing press can print only a solid color 
in the image areas, while leaving the non-image areas free of ink. In 
order to reproduce pictures in varying tones, graphic-arts photography 
uses a halftone screen. Halftone photography makes the printing of 
continuous-tone photographs possible by converting the continuous-tone 
image into a pattern of small and clearly defined dots ranging in size 
from 80 to 200 or more dots per inch according to the different amounts of 
light that are reflected from the different tones of the original. 
All halftone dots have a fringe area surrounding them. When a printing 
plate is made of the halftone with a wide fringe area, the fringe around 
the dot is also partially exposed. Although it may not be apparent on the 
plate (i.e., the dot may appear to be of the correct size), once the plate 
is run on the press, the fringe area may eventually take ink which will 
fill in the shadow detail. Improvements in dot quality especially in 
regard to high-edge sharpness and minimal fringe (i.e., a "hard" dot) are 
therefore extremely important to the printing industry. 
Traditionally, the production of high quality dot images was obtained with 
the use of "lith" films and chemistry. These films, used for making 
halftone or line images, were capable of producing extremely high contrast 
and good image sharpness. In the case of halftone images, such properties 
contribute to high "dot quality", i.e., the production of halftone dots of 
high density and sharpness. Sharpness is quantified in terms of "edge 
gradient" which is the ratio of change in density to distance at the 
boundary between the darkened part and the undarkened part of the 
photographic image. In general, the higher the edge gradient, the sharper 
the image (i.e. the "harder" the dot). 
Those skilled in the art attribute the formation of hard dots produced with 
lith materials to the high contrast obtained from infectious development 
as described by Yule, J. Frank. Inst. 239 221 (1945). In fact, high 
contrast has come to be synonymous with high edge gradient. However, 
applicant has observed that a photographic element possessing high 
contrast is necessary but by no means sufficient to produce a hard dot. In 
addition, as Hirano (U.S. Pat. No. 4,429,036) states: "for use in the 
application of plate-making using a contact screen, such images having 
only the photographic characteristics of high contrast wherein the 
gradient is 10 or more are inferior in dot quality, are of too high 
contrast in screen range and therefore are not satisfactory." Thus, the 
high contrast of the element in and of itself may actually produce a 
screen range which is unacceptably short. 
The photographic element must possess a wide screen range which allows good 
tone reproduction. This is obtained when the darkest area of the subject 
prints on the press as a solid and the lightest area prints with no 
evidence of a screen. The films may have very small unprintable dots in 
these areas which close up in the shadows and disappear in the highlights 
during printing; however, no loss of intermediate tones due to high 
contrast is allowable. Conversely, low contrast causes shadows to appear 
as 80-90% dots and 10-20% in the highlights; this, also, is unacceptable 
if a faithful reproduction is to be obtained. 
Thus, although the dot quality derived from lith materials is excellent, 
the lith system suffers from serious deficiencies which restrict its 
utility. 
As practitioners of the art recognize, the deficiencies of the lith system 
include a shortened useful life for the processing chemistry (due to the 
lack of sulfite) and a lower sensitivity for the lith photographic 
compositions (because it is necessary to use chloride or chlorobromide 
emulsions). Other problems inherent in the lith system include pepper 
spots, drag streaks, narrow screen range, and differences in sensitivity 
and gradation depending upon the manner in which materials are processed 
(tray vs. automatic processor). 
Mifune (U.S. Pat. No. 4,323,643) discloses an alternative method for 
producing high quality dot images that solves some of the problems 
inherent in the lith system. The method involves the use of 
ureidophenylformyl hydrazide derivatives as additives to negative-working 
emulsions for the purpose of providing good dot quality. The mechanism by 
which the preferred agents operate is not mentioned. Mifune presents 
comparative data showing that various analogs (shown below in Table 1) do 
not produce acceptable dot quality as is required for the printing 
industry. Nevertheless, these same agents are reported in the prior art to 
produce high contrast negative images. 
TABLE A 
______________________________________ 
##STR2## 
##STR3## 
NH.sub.2 NH.sub.22HCl 
##STR4## 
##STR5## 
______________________________________ 
Many examples in the prior art disclose the use of hydrazine derivatives as 
contrast-promoting agents but the Mifune patent is the only one known to 
applicant in disclosing a select family of hydrazides that also produce 
good dot quality. 
U.S. Pat. No. 2,419,975 teaches that high-contrast negative photographic 
characteristics can be obtained by adding a hydrazine compound to a silver 
halide photographic emulsion. The compounds listed in this patent are 
hydrazine derivatives that vary considerably in structure, but the quality 
of the screen dots obtained using these agents is not characterized. In 
general, large quantities of the disclosed agents are necessary to produce 
the desired high-contrast effect. 
Recent patents teach that the most efficient hydrazines employ a 
combination of substituents to balance activity and stability. The 
stability of hydrazines was shown to be further increased by attaching 
directly to one of the nitrogen atoms a tertiary carbon atom (e.g., a 
carbon atom located in an aromatic ring). The art has long recognized that 
the activity of these stabilized hydrazines can be increased by the direct 
attachment of an acyl group to the remaining nitrogen. Presently, only a 
few substituents attached to the acyl carbonyl functionality have 
demonstrated utility in a negative-working, high-contrast system. These 
substituents include hydrogen (most preferred), unsubstituted alkyl (the 
activity of which dramatically falls as the chain length is increased) 
and, less desirably, aryl which is preferrably substituted with 
electron-donating substituents (electron withdrawing substituents reduce 
the activity of the phenyl benzoic acid hydrazide). For example, Simson 
and Jordan (Canadian Patent No. 1,146,001 pp 15 line 16-24) state: 
"Although the hydrazine compounds intended for use in the practice of this 
invention each contain a formyl moiety, it is appreciated that otherwise 
comparable hydrazine compounds containing a benzoyl moiety substituted 
with a highly electron-withdrawing substituent such as a cyano group are 
operative. Such compounds have, however, been found to be inferior to the 
hydrazine compounds containing a formyl group." 
Thus, the most commonly employed hydrazines are aryl formyl hydrazides. The 
more soluble agents of this class can be incorporated into the processing 
solution, but if they are to be incorporated into the photographic 
element, their mobility is preferably reduced. This can be achieved by 
incorporating either a ballast group or a functionality that promotes 
adsorption to the silver halide grain surface. The selection of an 
adsorption-promoting substituent for a phenyl hydrazide is limited in that 
"Tightly adsorbed aryl hydrazides are not usually efficient in increasing 
the contrast in negative-working silver halide emulsions. It is believed 
that contrast is increased by infectious development and that undue 
restriction of mobility interferes with the ability of the aryl hydrazides 
to promote infectious development" Parton, U.S. Pat. No. 4,459,347. The 
delicate balance necessary to provide adsorptivity to the silver halide 
grain while still providing adequate solubility, as well as the 
requirement for stability and inherent activity, place serious constraints 
upon the design of new aryl hydrazide contrast-enhancing agents. 
When groups such as thiourea, thioamide, heterocyclic rings, or urea are 
used as adsorption-promoting functionalities, the molar concentration of 
the hydrazide can be reduced by an order of magnitude without loss of 
activity. This is a significant advantage over the use of mobile 
hydrazines because, at the high concentrations necessary to exhibit 
contrast enhancement in a negative emulsion, these mobile hydrazines 
release sufficient nitrogen to disrupt the ordered array of the 
photographic element and thereby deteriorate the image quality. 
Furthermore, diffusion of the mobile hydrazines into the processing 
chemistry alters the properties of the chemistry with time. Finally, the 
adsorption-promoting hydrazides are said to be less sensitive to the 
degree of stirring and temperature variation in the processing chemistry. 
This is a significant factor in reducing the differences in photographic 
speed and contrast found between tray and automatic developing for a given 
photographic emulsion. 
Significantly, although both the mobile hydrazides and the 
adsorption-promoting hydrazides substantially increase the contrast of a 
photographic emulsion, only a select few of the latter class also improve 
dot quality. Undoubtedly, the dual constraints on controlled adsorptivity 
of the hydrazide and the printing parameters, which require tight control 
on screen range, severely limit the initially large number of choices of 
hydrazide derivatives that produce high contrast; it follows then that 
these constraints also limit the number of agents that can produce high 
quality dots since high contrast is a necessary factor in producing 
high-quality dots. 
Despite the many advantages of photographic elements containing 
non-diffusable aryl hydrazides of the type found in U.S. Pat. No. 
4,323,643, several defects still remain. 
One such defect is that elements containing the nondiffusing hydrazides of 
the prior art have an even narrower screen range than that found in lith 
systems. This deficiency makes it increasingly difficult to accurately 
record all the detail in both the shadow and highlight areas of the 
continuous tone original. In general, the narrower the screen range, the 
harder (steeper) the dot gradation and hence the higher the contrast. 
Because the contrast of a silver halide emulsion containing an aryl 
hydrazide is dependent upon the particular aryl hydrazide, it would be 
most desirable to obtain contrast-enhancing agents producing a wider 
(softer) screen range. 
Aryl hydrazides of the prior art have a tendency to produce dark spots on 
portions of the image that have not been (or have been only partially) 
exposed. These spots are known as "pepper grain". This phenomenon is 
observed as the concentration of the aryl hydrazide is increased and its 
onset generally coincides with the concentration necessary to produce 
contrast enhancement. As the processing chemistry becomes oxidized, on 
prolonged exposure to the air, pepper grain becomes more frequent and more 
pronounced. 
A third and perhaps most serious defect associated with the use of the 
nondiffusing hydrazides of the prior art is their dependence on processing 
chemistry temperature. Attempts to solve this problem have included 
combining a nondiffusing hydrazide having a positive temperature 
dependency with other hydrazine derivatives that have a negative 
temperature dependency. U.S. Pat. No. 4,416,969 teaches the use of 
benzotriazole phenyl hydrazides in combination with thiourea-substituted 
phenyl hydrazides for the purpose of improving this temperature 
dependency. 
In regard to the prior art relating to the present invention, Trivelli 
(U.S. Pat. No. 2,419,975) discusses the use of oxalyl hydrazide as a 
contrast- and speed-enhancing agent in a negative-working emulsion whereas 
Whitmore (U.S. Pat. No. 3,227,552) discusses the use of ethoxalyl-2-phenyl 
hydrazide in a direct-positive emulsion. Neither patent discloses the use 
of these agents for the production of high edge-quality dots. Considering 
Mifune's results with the thioureidophenyl formyl hydrazide, there would 
be no reason for those skilled in the art to expect that oxalyl hydrazides 
substituted with adsorption-promoting functionalities (such as thioureido) 
would afford any benefit or advantage in producing high edge quality dots. 
It has now been unexpectedly discovered that oxalyl hydrazides substituted 
with a variety of substituents (e.g., thioureas, ureas, amides and 
heterocycles) attached to the phenyl ring impart excellent dot quality 
properties. Moreover, unlike the ureidophenyl formyl hydrazide series that 
apparently allows substitution on all sites of the phenyl ring, the 
compounds of the present invention require that the adsorption-promoting 
group be attached on the phenyl ring either ortho- or para- relative to 
the oxalyl hydrazide to produce the desired properties. Placement of an 
adsorption-promoting moiety (such as the thioureido group) either on the 
meta-position of the phenyl ring (compound II-3), directly onto the oxalyl 
moiety (compound II-5), or indirectly onto the oxalyl moiety (compound 
II-6) converts these compounds into desensitizing agents. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide novel contrast-enhancing 
agents that can be used in photographic elements to produce high-contrast 
negative images. 
Another object of the present invention is to provide a method by which 
high-contrast silver halide photographic elements can be formed using a 
stable developer. 
A third object of the present invention is to provide a photographic 
element that will generate high quality screen dots. 
A fourth object of the present invention is to provide a photographic 
element that will possess a sufficiently wide screen range so as to 
accurately reproduce, in dot form, the contrast range of the original 
subject. 
Yet another object of the present invention is to provide a photographic 
element containing less pepper grain. 
Still another object of this invention is to provide a method such that the 
above objects can be obtained with little variation in sensitivity and 
unevenness of development due to changes in processing conditions (such as 
stirring rate) or equipment, or changes in processing temperature. 
Other objects of the present invention will become apparent from the 
following detailed description, examples, and claims. 
One aspect of the present invention relates to a method of forming a 
photographic image which comprises providing a developer solution, said 
solution containing a dihydroxybenzene derivative, a substituted 
benzotriazole, a sulfite preservative and an amine compound; processing in 
said solution a silver halide photographic light-sensitive material said 
material comprising a support having thereon at least one surface-latent 
image type silver halide emulsion layer, and containing in at least one 
layer selected from a silver halide emulsion layer and another hydrophilic 
colloid layer a substituted oxalyl compound represented by the formula 
(I): 
##STR6## 
wherein: X=--NR.sub.5 R.sub.6, or --OR.sub.7 ; 
R.sub.1 and R.sub.2 are independently hydrogen, alkyl, haloalkyl, 
hydroxyalkyl, alkoxyalkyl, alkylaminoalkyl or arylalkyl having up to 18 
carbons; cycloalkyl; phenyl or naphthyl; alkylphenyl, cyanophenyl, 
halophenyl or alkoxyphenyl substituents; 
R.sub.3 is hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl, 
except if neither R.sub.1 nor R.sub.2 are hydrogen then R.sub.3 must be 
hydrogen; 
R.sub.4 is a substituted or unsubstituted divalent aromatic group; 
R.sub.5, R.sub.6 and R.sub.7 are independently hydrogen, alkyl, 
hydroxyalkyl, haloalkyl, alkoxyalkyl, alkylaminoalkyl, acylaminoalkyl, 
aminoalkyl or phenylalkyl having up to 12 carbons; a cycloalkyl 
substituent; phenyl or naphthyl; an alkylphenyl, cyanophenyl, halophenyl 
or alkoxyphenyl substituent; 
R.sub.1 and R.sub.3 or R.sub.1 and R.sub.2 can be linked to form a 
heterocyclic ring system containing three to ten atoms; 
R.sub.5 and R.sub.6 can be linked to form a heterocyclic ring system 
containing 3-10 atoms; Y is an oxygen or sulfur atom; n=0,1 but if Y is 
sulfur then n=1. 
Another aspect of the present invention relates to the above-identified 
compounds and their use as high quality dot-producing agenfts of the class 
described above. 
Yet another aspect of the present invention relates to a silver halide 
photographic emulsion comprising a binder, radiation-sensitive silver 
halide grains, and a dot-promoting amount of at least one of the above 
compounds as a fogging agent. 
Another aspect of the invention relates to a radiation-sensitive 
photographic element comprising a support having thereon a layer 
comprising the above-described silver halide photographic emulsion. 
Still another aspect of the invention relates to a method for the formation 
of high quality dot images via the processing of the described 
photographic element in a developing chemistry containing a composition of 
a dihydroxybenzene derivative, a substituted benzotriazole, a sulfite 
preservative and an amine compound. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
In the general formula (I) described above, R.sub.1 represents a hydrogen 
atom, an unsubstituted or substituted alkyl group (suitable substituents 
include halo, alkoxy, alkylamino or aryl), an unsubstituted or substituted 
aryl group (suitable substituents include alkyl, cyano, halo, or alkoxy), 
a cycloalkyl group or an arylsulfonyl group. The total number of carbon 
atoms in R.sub.1 can be up to 18 but, preferably, should be less than 12. 
Most preferably, R.sub.1 is unsubstituted alkyl or cycloalkyl containing 
1-6 carbon atoms. 
R.sub.2 is independently chosen from the group representing R.sub.1 ; 
preferably, however, the total number of carbon atoms between R.sub.1 and 
R.sub.2 should not exceed 12. 
R.sub.3 represents a hydrogen atom, an unsubstituted or substituted benzyl 
group (suitable substituents include alkoxy, halo or alkyl). If neither 
R.sub.1 nor R.sub.2 is hydrogen, then R.sub.3 must be hydrogen. Most 
preferably, R.sub.3 is hydrogen. 
Y represents an oxygen or a sulfur atom. In the preferred case, Y is a 
sulfur atom. 
n=0 or 1. If Y is a sulfur atom then n=1. In the most preferred case n=1. 
R.sup.4 represents either an unsubstituted or substituted divalent aromatic 
group. Suitable substituents include alkyl, alkoxy, halo, or acylamino 
functionalities. In the most preferred case R.sub.4 is phenylene with the 
thioamido or amido group in the ortho- or para-position relative to the 
hydrazino group. Furthermore, it is preferred that any suitable 
substituent as described herein be attached at the remaining, unoccupied 
ortho- or para-position relative to the hydrazine group. 
R.sub.5 represents either a hydrogen atom, an unsubstituted or substituted 
alkyl group (suitable substituents include hydroxy, halo, alkoxy, 
alkylamino, acylamino, amino and aryl), a cycloalkyl group, an 
unsubstituted or substituted aryl group (suitable substituents include 
alkyl, cyano, halo or alkoxy) or an unsubstituted or substituted amine. 
The total number of carbon atoms in R.sub.5 should be up to 12. 
Preferably, R.sub.5 is alkyl, cycloalkyl, dialkylaminoalkyl or 
acylaminoalkyl each containing 1-6 carbon atoms. 
R.sub.6 and R.sub.7 are independently chosen from the group representing 
R.sub.5 ; preferably, however, the total number of carbon atoms between 
R.sub.5 and R.sub.6 should not exceed 12. In addition, R.sub.5 and R.sub.6 
preferably do not contain amino functionalities that are directly linked 
to the nitrogen atom of X. 
Furthermore, R.sub.5 and R.sub.6 can be linked to form a heterocyclic ring 
system containing 3-10 atoms. 
Additionally, either R.sub.1 and R.sub.3 or R.sub.1 and R.sub.2 can be 
linked to form a heterocyclic ring system containing 3-10 atoms. 
The preferred compounds represented by the general formula (I) are those 
represented by the general formula (Ia). 
##STR7## 
In this formula, Y=S or O; Z=O or NH; R.sub.8 and R.sub.9 have the same 
meaning as R.sub.1 and R.sub.5 respectively for the above described 
general formula (I). Most preferably R.sub.8 is ethyl, n-butyl or 
cyclohexyl, R.sub.9 is hydrogen, methyl, ethyl, dimethylaminoethyl or 
acetylaminoethyl, Z=NH, and Y=S. 
Specific examples of the compounds represented by the general formula (I) 
are given below in Table I, but the present invention is not limited to 
these examples. 
TABLE I 
__________________________________________________________________________ 
##STR8## I-1 
##STR9## I-2 
##STR10## I-3 
##STR11## I-4 
##STR12## I-5 
##STR13## I-6 
##STR14## I-7 
##STR15## I-8 
##STR16## I-9 
##STR17## I-10 
##STR18## I-11 
##STR19## I-12 
##STR20## I-13 
##STR21## I-14 
##STR22## I-15 
##STR23## I-16 
##STR24## I-17 
##STR25## I-18 
##STR26## I-19 
##STR27## I-20 
##STR28## I-21 
##STR29## I-22 
##STR30## I-23 
##STR31## I-24 
##STR32## I-25 
##STR33## I-26 
##STR34## I-27 
##STR35## I-28 
##STR36## I-29 
__________________________________________________________________________ 
The compounds in Table II, below, are set forth here for comparison: 
##STR37## 
The amount of the compound of formula (I) added to the silver halide 
emulsion layer or hydrophilic colloidal layer(s) is such that the compound 
does not appreciably function as a developer. Typically, amounts from 
10.sup.-8 to 5.times.10.sup.-2 moles/mole Ag and preferably about 
10.sup.-5 to 5.times.10.sup.-3 mole/mole Ag are used. 
The compound can be incorporated in a silver halide emulsion used in the 
photographic element. Alternatively, the ethanedioic acid hydrazide 
compound can be present in a hydrophilic colloid layer of the photographic 
element, preferably a hydrophilic colloid layer which is coated to be 
contiguously adjacent to the emulsion layer in which the effects of the 
compound are desired. The compound of the present invention can, of 
course, be present in the photographic element distributed between or 
among the emulsion and hydrophilic colloid layers, such as undercoating 
layers, interlayers and overcoating layers. 
The ethanedioic acid hydrazide compounds of the present invention are 
employed in combination with negative-working photographic emulsions 
comprising radiation-sensitive silver halide grains capable of forming a 
surface latent image, and a binder. The silver halide emulsions include 
the high-chloride emulsions conventionally employed in forming lith 
photographic elements as well as silver bromide and silver bromiodide 
emulsions, which are recognized in the art to be capable of attaining 
higher photographic speeds. Generally, the iodide content of the silver 
halide emulsions is less than about 10 mole percent silver iodide, based 
on the total amount of silver halide. 
The compound of formula (I) can be incorporated in the photographic element 
by common techniques used for the addition of additives to photographic 
emulsions. The compound is typically dissolved in a solvent selected from 
organic solvents compatible with water, such as alcohols, glycols, 
ketones, esters, amides, and the like which exert no adverse influences on 
the photographic characteristics, and the solution is added to the 
photographic element. Preferred solvents include dimethylformamide (DMF), 
dimethylsulfoxide (DMSO) and N-methyl-2-pyrrolidinone (NMP). 
Alternatively, the compound of formula (I) can be added to the emulsion in 
an oil dispersion by known methods used when water-insoluble (so-called 
oil soluble) couplers are added to emulsions. Preferred oils include 
N-butyl acetanilide, N-methyl formanilide and N,N-diethyl-m-toluamide. 
These oils are all commercially available. Ultrasound can be employed to 
dissolve marginally soluble ethanedioic acid hydrazides. These solutions 
or dispersions can be added to the emulsion at any stage subsequent to the 
precipitation and washing steps. Preferably, these agents should be added 
during chemical ripening or just prior to coating. 
Gelatin is advantageously used as a binder or protective colloid in the 
photographic emulsion, but other hydrophilic colloids can also be used. 
For example, gelatin derivatives, graft polymers of gelatin with other 
high molecular weight materials, proteins such as albumin or casein. 
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl 
cellulose or cellulose sulfate, saccharide derivatives such as sodium 
alginate or starch derivatives, various synthetic hydrophilic high 
molecular weight materials such as homopolymers or copolymers, e.g., 
polyvinyl alcohol, polyvinyl alcohol (partial acetal), poly-N-vinyl 
pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, 
polyvinyl imidazole, polyvinyl pyrazole, etc., can be used. Polyglycoside 
dextrans are preferred. 
Lime-processed gelatin and acid-processed gelatin can be used as the 
gelatin. Hydrolysed or enzyme-decomposed gelatin can also be used. 
Suitable gelatin derivatives are prepared by reacting gelatin with various 
compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic 
acid, alkanesultones, vinylsulfonamides, maleinimide compounds, 
polyalkylene oxides or epoxy compounds and, preferably, with phthalic 
anhydride or succinic anhydride. Specific examples of these gelatin 
derivatives are described in e.g., U.S. Pat. Nos. 2,614,928, 3,132,945, 
3,186,846 and 1,005,784, all incorporated by reference. 
Examples of suitable gelatin graft polymers include those prepared by 
grafting a homopolymer or a copolymer of a vinylic monomer such as acrylic 
acid, methacrylic acid, the derivatives thereof (such as the esters or the 
amides thereof), acrylonitrile or styrene to gelatin. In particular, graft 
polymers prepared from polymers which are compatible with gelatin to some 
degree, such as those of acrylic acid, methacrylamide or a hydroxyalkyl 
methacrylate are preferred. Examples of those polymers are described in, 
e.g., U.S. Pat. Nos. 2,763,625, 2,831,767 and 2,956,884, etc. Typical 
synthetic hydrophilic high molecular weight materials are described in, 
e.g., German Patent Application (OLS) No. 2,312,708, U.S. Pat. Nos. 
3,620,751 and 3,879,205, all incorporated by reference. 
The photographic emulsion used in this invention can be prepared using the 
well-known methods described in, e.g., P. Glafkides, Chimie et Physique 
Photographique, Paul Montel, Paris (1967), G. F. Duffin, Photographic 
Emulsion Chemistry, The Focal Press, London (1966), V. L. Zelikman et al., 
Making and Coating Photographic Emulsions, the Focal Press, London (1964), 
all incorporated by reference. These methods include the acid method, the 
neutral method, the ammonia method and others. Moreover, a soluble silver 
salt can be reacted with a soluble halogen salt using any of the single 
jet method, the double jet method and a combination thereof. The method of 
forming grains in the presence of an excess of silver ions (the so-called 
"reverse mixing method") can also be used. The "controlled double jet 
method" (also called "controlled diffusion method") is preferred. 
According to this method, the pAg of the liquid phase (in which the silver 
halide is to be produced) is kept constant. This method can provide silver 
halide emulsions having a regular crystal form and an almost uniform grain 
size. 
The silver halide grains in the photographic emulsion used in this 
invention can have a relatively wide grain size distribution, but a narrow 
grain size distribution is preferred. In particular, the size of the 
silver halide grains amounting to 90% of the total, based on the weight or 
number of the grains, is preferably within +40% of the average grain size 
(such an emulsion is usually called a monodispersed emulsion). 
The individual reactants can be added to the reaction vessel through 
surface or sub-surface delivery tubes by gravity feed or by delivery 
apparatus for maintaining control of the pH and/or pAg of the reaction 
vessel contents, as illustrated by Culhane et al U.S. Pat. No. 3,821,002, 
and Oliver U.S. Pat. No. 3,031,304, all incorporated by reference. In 
order to obtain rapid distribution of the reactants within the reaction 
vessel, specially constructed mixing devices can be employed, as 
illustrated by Audran U.S. Pat. No. 2,996,287, McCrossen et al U.S. Pat. 
No. 3,342,605, Frame et al U.S. Pat. No. 3,415,650, Porter et al U.S. Pat. 
No. 3,785,777, Saito et al German OLS No. 2,556,885 and Sato et al German 
OLS No. 2,555,364, all incorporated by reference. An enclosed reaction 
vessel can be employed to receive and mix reactants upstream of the main 
reaction vessel, as illustrated by Forster et al U.S. Pat. No. 3,897,935 
and Posse et al U.S. Pat. No. 3,790,386. 
The grain size distribution of the silver halide emulsions can be 
controlled by silver halide grain separation techniques or by blending 
silver halide emulsions of differing grain sizes. The emulsions can 
include ammoniacal emulsions, as illustrated by Glafkides, Photographic 
Chemistry, Vol. 1, Fountain Press, London, 1958, pp. 365-368 and pp. 
301-304; thiocyanate ripened emulsions, as illustrated by Illingsworth 
U.S. Pat. No. 3,320,069; thioether ripened emulsions, as illustrated by 
McBride U.S. Pat. No. 3,271,157, Jones U.S. Pat. No. 3,574,628 and 
Rosecrants et al U.S. Pat. No. 3,737,313 or emulsions containing weak 
silver halide solvents, such as ammonium salts, as illustrated by Perignon 
U.S. Pat. No. 3,784,381 and Research Disclosure, Vol. 134, June 1975, Item 
13452, all incorporated by reference. The method using ammonium salts is 
preferred. 
The crystal form of the silver halide grains in the photographic emulsion 
may be regular (such as cubic or octahedral) or irregular (such as 
spherical or plate-like or a composite of these forms. The grains may 
comprise mixed grains having various crystal forms. 
The interior and the surface layer of the silver halide grains may be 
different or the grains may be uniform throughout. During formation or 
physical ripening of the grains, cadmium salts, zinc salts, lead salts, 
thallium salts, rhodium salts or complex salts thereof, iron salts or iron 
complex salts, and the like can be present, as can mixtures thereof. 
Preferred are rhodium or iridium salts or mixtures thereof. 
Two or more of silver halide emulsions which are separately prepared can be 
mixed and then used, if desired. 
After the formation of the precipitates or after physical ripening, the 
soluble salts are usually removed from the emulsion. For this purpose, the 
well-known noodle washing method may be used. Alternatively, the 
flocculation method may be used. This method employs an inorganic salt 
having a polyvalent anion such as sodium sulfate, an anionic surface 
active agent, an anionic polymer (such as polystyrene sulfonic acid) or a 
gelatin derivative (such as an aliphatic acylated gelatin, an aromatic 
acylated gelatin or an aromatic carbamoylated gelatin). The removal of the 
soluble salts may be omitted, if desired. 
Although the silver halide emulsions used in the present invention do not 
need to be chemically sensitized, chemically sensitized silver halide 
emulsions are preferred. Processes for chemical sensitization, of the 
silver halide emulsions which can be used include known sulfur 
sensitization, reduction sensitization and noble metal sensitization 
processes. In addition to sulfur sensitization, selenium, tellurium, 
rhenium or phosphorus sensitizers or combinations of these sensitizers can 
be used. Chemical ripening can be performed at pAg levels of from 5 to 10, 
pH levels of from 5 to 8 and at temperatures from 30.degree. to 80.degree. 
C. 
These processes are described in references such as P. Glafkides, Chimie et 
Physique Photographique, Paul Montel, Paris (1967) or Zelikmann, Making 
and Coating Photographic Emulsions, The Focal Press, London (1964) or H. 
Frieser, Die Gundlagen der Photographischen Prozesse mit 
Silberhalogeniden, Akademische Verlagsgesellschaft (1968). The disclosure 
of these references is incorporated by reference. In the noble metal 
sensitization processes, a gold sensitization process is a typical process 
where gold compounds or mainly gold complexes are used. 
Complexes of noble group VIII metals other than gold, such as those of 
platinum, palladium, osmium or iridium, etc. can also be used. A reduction 
sensitization process may be used if the process does not generate fog to 
a degree that causes practical difficulties. A particularly preferred 
chemical sensitization process for the present invention is the use of a 
sulfur sensitization process. 
Examples of sulfur sensitizing agents which can be used include not only 
sulfur compounds present in the gelatin per se, but also various sulfur 
compounds such as thiosulfates, thioureas, thiazoles or rhodanines, etc. 
Examples of suitable sulfur compounds are described in U.S. Pat. Nos. 
1,574,994, 2,410,689, 2,278,947, 2,728,668 and 3,656,955, all incorporated 
by reference. Typical examples of suitable reduction-sensitizing agents 
include stannous salts, amines, formamidine sulfinic acid and silane 
compounds, methyldichlorosilane, hydrazine derivatives, aminoboranes, 
thiourea dioxide, hydrogen, cyanoborohydrides, etc. Reduction 
sensitization can also be obtained by low pAg (less than 5) or high pH 
(greater than 8) treatment. 
Specifically contemplated is the combined use of several of the 
aforementioned chemical ripening techniques; in particular, gold-sulfur 
combinations are highly preferred. 
A photographic material used in this invention may contain an anti-foggant. 
Examples of anti-foggants which can be advantageously used for the 
photographic material used in this invention are 1,2,4-triazole compounds 
substituted with a mercapto group at the 3-position, benzotriazole 
compounds, 2-mercaptobenzimidazole compounds (which do not contain a nitro 
group), 2-mercaptopyrimidines, 2-mercaptothiazoles, 
2-mercaptobenzothiazoles, benzothiazolium compounds (such as 
N-alkylbenzothiazolium halides, nitrobenzindazole, substituted 
triazaindolizines (tetraazaindenes) or N-allylbenzothiazolium halides), 
and 2-mercapto-1,3,4-thiazoles. Antifoggants which are not effective when 
used alone, such as 6-nitrobenzimidazole, however, can be used in 
combination with any of the above advantageous antifoggants. 
It has been observed that both fog reduction and an increase in contrast 
are obtainable by employing benzotriazole antifoggants. When the 
benzotriazole is located in the photographic element concentrations of 
10.sup.-4 to 10.sup.-1, preferably 10.sup.-3 to 3.times.10.sup.-2, mole 
per mole of silver are employed. 
Useful benzotriazoles can be chosen from among conventional benzotriazole 
antifoggants, such as those disclosed by Land U.S. Pat. No. 2,704,721 and 
Rogers et al U.S. Pat. No. 3,265,498, both incorporated by reference. The 
preferred benzotriazoles for use in this invention are benzotriazole (that 
is, the unsubstituted benzotriazole compound), halo-substituted 
benzotriazoles (e.g., 5-chlorobenzotriazole, 4-bromobenzotriazole and 
4-chlorobenzotriazole) and alkyl-substituted benzotriazoles wherein the 
alkyl moiety contains from about 1 to 12 carbon atoms (e.g., 
5-methylbenzotriazole). 5-methyl benzotriazole is most preferred. The use 
of 5-methylbenzotriazole as an antifoggant is illustrated by Baldassari et 
al U.S. Pat. No. 3,925,086, incorporated by reference. 
The effect of this invention is enhanced even more by adding a small amount 
of an iodide salt (such as potassium iodide) to the emulsion after the 
formation of the grains, before chemical ripening, after chemical 
ripening, or before coating. A suitable amount of iodide ranges from about 
10.sup.-4 to about 10.sup.-2 mol/mol Ag. 
The photographic emulsions used in this invention can be spectrally 
sensitized with methine or other dyes. Suitable sensitizing dyes include 
cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine 
dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol 
dyes. Particularly useful dyes are cyanine dyes, merocyanine dyes and 
complex merocyanine dyes. These dyes can contain, as a basic heterocyclic 
nucleus, any of the nuclei which are usually employed in cyanine dyes: a 
pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole 
nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an 
imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; 
one of the above-described nuclei condensed with an alicyclic hydrocarbon 
ring; and one of the above-described nuclei condensed with an aromatic 
hydrocarbon ring, such as an indolenine nucleus, a benzindolenine nucleus, 
an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a 
benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole 
nucleus, a benzimidazole nucleus and a quinoline nucleus. The carbon atoms 
of the above-described nuclei may be substituted. 
The merocyanine dyes or complex merocyanine dyes can contain, as a nucleus 
having a ketomethylene structure, a 5- to 6-membered heterocyclic nucleus 
such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 
2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a 
rhodanine nucleus or a thiobarbituric acid nucleus. 
Useful sensitizing dyes are those described in, e.g., German Pat. No. 
929,080, U.S. Pat. Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 
2,912,329, 3,656,959, 3,672,897 and 3,694,217, and British Pat. No. 
1,242,588, all incorporated by reference. 
These sensitizing dyes may be used individually or in combination. A 
combination of sensitizing dyes is often employed particularly for the 
purpose of supersensitization. Typical examples of such combinations are 
described in, e.g., U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 
3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,679,428, 
3,703,377, 3,769,301, 3,814,609 and 3,837,862, and British Pat. No. 
1,344,281, all incorporated by reference. Preferred sensitizing dye 
combinations are mixtures of cyanine and merocyanine dyes that 
orthochromatically sensitive at wavelengths between 400 and 580 nm. 
The sensitizing dyes may be present in the emulsion together with dyes 
which themselves do not have any spectral sensitizing effects but exhibit 
a supersensitizing effect when used in combination, or with materials 
which do not substantially absorb visible light but exhibit a 
supersensitizing effect when used in combination. For example, 
aminostilbene compounds substituted with a nitrogen-containing 
heterocyclic ring group (e.g., those described in U.S. Pat. Nos. 2,933,390 
and 3,635,721), aromatic organic acid formaldehyde condensates (e.g., 
those described in U.S. Pat. No. 3,743,510), azaindene compounds, and the 
like, can be present. The combinations described in U.S. Pat. Nos. 
3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularly useful. 
(The disclosure of all patents mentioned in this paragraph is incorporated 
by reference.) 
A water-soluble dye may be present in any of the hydrophilic colloid layers 
of the photographic light-sensitive material used in this invention, for 
example, as a filter dye or for prevention of light scattering, or for 
antihalation. Examples of these dyes include oxonol dyes, hemioxonol dyes, 
styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, 
oxonol dyes, hemioxonol dyes and merocyanine dyes are particularly useful. 
Specific examples of dyes which can be used are those described in British 
Pat. Nos. 584,609 and 1,177,429, and U.S. Pat. Nos. 2,274,782, 2,533,472, 
2,956,879, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,604, 
3,653,905 and 3,718,472, all incorporated by reference. 
An inorganic or organic hardener may be present in any of the hydrophilic 
colloid layers in the light-sensitive material used in this invention. 
These hardeners include, for example, chromium salts (such as chrome alum 
or chromium acetate), aldehydes (such as formaldehyde, glyoxal or 
glutaraldehyde), N-methylol compounds (such as dimethylolurea or 
methyloldimethylhydantoin), dioxane derivatives (such as 
2,3-dihydroxydioxane), active vinyl compounds (such as 
1,3,5-triacryloyl-hexahydro-s-triazine or bis(vinylsulfonyl)methyl ether), 
active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), 
mucohalic acids (such as mucochloric acid or mucophenoxychloric acid), 
isooxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin 
and the like can be used individually or in combination. Specific examples 
of these compounds are described, e.g., U.S. Pat. Nos. 1,870,354, 
2,080,019, 2,726,162, 2,870,013, 2,983,611, 2,992,109, 3,047,394, 
3,057,723, 3,103,437, 3,321,313, 3,325,287, 3,362,827, 3,539,664 and 
3,543,292, British Pat. Nos. 676,628, 825,544 and 1,270,578, and German 
Pat. Nos. 872,153 and 1,090,427, all incorporated by reference. A 
preferred hardener is one that will not cause reduction-sensitization 
(formaldehyde, for example, should be avoided). An example of a preferred 
hardener is dichlorohydroxytriazine. 
The light-sensitive material of this invention may contain various known 
surface active agents for various purposes, e.g., as a coating aid, for 
preventing the generation of static charges, improving slip 
characteristics, improving emulsion dispersion, preventing adhesion, 
improving photographic characteristics (e.g., accelerating development, 
increasing contrast, sensitization), etc. 
Examples of suitable surfactants are: nonionic surface active agents such 
as saponin (steroids), alkylene oxide derivatives (such as polyethylene 
glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene 
glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene 
glycol sorbitan esters, polyalkylene glycol alkylamines or amides or 
silicone/polyethylene oxide adducts), glycidol derivatives (such as 
alkenylsuccinic acid polyglycerides or alkylphenol polyglycerides), 
aliphatic esters of polyhydric alcohols, alkyl esters of sucrose, 
urethanes or ethers; anionic surface active agents containing an acidic 
group such as a carboxy group, a sulfo group, a phospho group, a sulfuric 
acid ester group or a phosphoric acid ester group, such as triterpenoid 
type saponin, alkylcarboxylates, alkylsulfonates, alkylbenzenesulfonates, 
alkylnaphthalenesulfonates, alkyl sulfuric acid esters, alkyl phosphoric 
acid esters, N-acyl-N-alkyltaurines, sulfosuccinates, 
sulfoalkylpolyoxyethylene alkylphenyl ethers or polyoxyethylene 
alkylphosphates; amphoteric surface active agents such as amino acids, 
aminoalkylsulfonic acids, aminoalkylsulfuric acid esters, 
aminoalkylphosphoric acid esters, alkylbetaines, amineimides or amine 
oxides; and cationic surface active agents such as alkylamine salts, 
aliphatic or aromatic quaternary ammonium salts, (such as pyridinium or 
imidazolium salts) or phosphonium or sulfonium salts containing an 
aliphatic or heterocyclic ring. 
Specific examples of these surface active agents are those described in, 
e.g., U.S. Pat. Nos. 2,240,472, 2,831,766, 3,158,484, 3,210,191, 3,294,540 
and 3,507,660, British Pat. Nos. 1,012,495, 1,022,878, 1,179,290 and 
1,198,450, U.S. Pat. Nos. 2,739,891, 2,823,123, 3,068,101, 3,415,649, 
3,666,478 and 3,756,828, British Pat. No. 1,397,218, U.S. Pat. Nos. 
3,133,816, 3,441,413, 3,475,174, 3,545,974, 3,726,683 and 3,843,368. 
Belgium Pat. No. 731,126, British Pat. Nos. 1,138,514, 1,159,825 and 
1,374,780, and U.S. Pat. Nos. 2,271,623, 2,288,226, 2,944,900, 3,253,919, 
3,671,247, 3,772,021, 3,589,906 and 3,754,924, all incorporated by 
reference. Specifically preferred is a mixture of saponin, nonionic 
surfactants such as aliphatic esters of polyhydric alcohols, and an 
anionic surfactant containing a sulfuric acid ester group. 
The photographic emulsion used in this invention can contain a dispersion 
of a synthetic polymer which is insoluble or slightly soluble in water for 
the purpose of improving the dimensional stability, the development and 
the fixing and drying rates. Examples of polymers which can be used 
include polymers composed of one or more alkyl acrylates or methacrylates, 
alkoxyalkyl acrylates or methacrylates, glycidyl acrylates or 
methacrylates, acryl or methacrylamide, vinyl esters (for example, vinyl 
acetate), acrylonitrile, olefins and styrene, etc., and polymers 
comprising a combination of the above described monomers and acrylic acid, 
methacrylic acid, unsaturated dicarboxylic acids, hydroxyalkyl acrylates 
or methacrylates, or styrenesulfonic acid, etc. For example, those 
compounds described in U.S. Pat. Nos. 2,376,005, 2,739,137, 2,853,457, 
3,062,674, 3,411,911, 3,488,708, 3,525,620, 3,607,290, 3,635,715 and 
3,645,740, and British Pat. Nos. 1,186,699 and 1,307,373, all incorporated 
by reference, can be used. A suitable amount of the polymer ranges from 
about 20 to 80% by weight based on the total weight of the binders. Since 
high-contrast emulsions such as that used in this invention are suitable 
for the reproduction of line drawings and the dimensional stability is of 
importance for such a purpose, it is preferred to use the above-described 
polymer dispersion. 
In addition to the components of the photographic emulsions and other 
hydrophilic colloid layers described above, it is appreciated that other 
conventional agents compatible with obtaining relatively high contrast 
images can be present. For example, the photographic elements can contain 
developing agens (described below in connection with the processing 
steps), development modifiers, plasticizers and lubricants, coating aids, 
antistatic materials, matting agents, brighteners and color materials, 
these conventional materials being illustrated in Paragraphs V, VIII, XI, 
XII, and XVI of Research Disclosure, December 1978 Item 17643, all 
incorporated by reference. Preferably, the photographic emulsion also 
contains anti-ageing agents, useful to prolong the shelf life of the 
emulsion. Suitable anti-ageing agents (especially for rhodium-doped 
emulsions) include polyhydroxyspiro-bis-indane as disclosed in U.S. Pat. 
No. 4,346,167 of E. Imatomi and preferably phenidone (up to 2 g/kg of 
emulsion) as disclosed in U.S. Pat. No. 2,751,297 of G. Hood. 
In forming the photographic elements, the layers can be applied on 
photographic supports by various procedures, including immersion or dip 
coating, roller coating, reverse roll coating, air knife coating, doctor 
blade coating, gravure coating, spray coating, extrusion coating, bead 
coating, stretch-flow coating and curtain coating. High speed coating 
using a pressure differential is illustrated by Beguin U.S. Pat. No. 
2,681,294. Controlled variation in the pressure differential to facilitate 
coating starts is illustrated by Johnson U.S. Pat. No. 3,220,877 and to 
minimize splicing disruptions is illustrated by Fowble U.S. Pat. No. 
3,916,043. Coating at reduced pressures to accelerate drying is 
illustrated by Beck U.S. Pat. No. 2,815,307. Very high speed curtain 
coating is illustrated by Greiller U.S. Pat. No. 3,632,374. Two or more 
layers can be coated simultaneously, as illustrated by Russell U.S. Pat. 
No. 2,761,791, Wynn U.S. Pat. No. 2,941,898, Miller et al U.S. Pat. No. 
3,206,323, Bacon et al U.S. Pat. No. 3,425,857, Hughes U.S. Pat. No. 
3,508,947, Herzhoff et al U.K. Pat. No. 1,208,809, Herzhoff et al U.S. 
Pat. No. 3,645,773 and Dittman et al U.S. Pat. No. 4,001,024. In 
simultaneous multilayer coating varied coating hoppers can be used, as 
illustrated by Russell et al U.S. Pat. No. 2,761,417, Russell U.S. Pat. 
Nos. 2,761,418 and 3,474,758, Mercier et al U.S. Pat. No. 2,761,419, 
Wright U.S. Pat. No. 2,975,754, Padday U.S. Pat. No. 3,005,440, Mercier 
U.S. Pat. No. 3,627,564, Timson U.S. Pat. Nos. 3,749,053 and 3,958,532, 
Jackson U.S. Pat. No. 3,933,019 and Jackson et al U.S. Pat. No. 3,996,885. 
Silver halide layers can also be coated by vacuum evaporation, as 
illustrated by Lu Valle et al U.S. Pat. Nos. 3,219,444 and 3,219,451. (The 
disclosures of all of the patents in this paragraph are incorporated by 
reference.) 
The photographic emulsions are coated on conventional supports which do not 
undergo serious dimensional changes during processing. Typical suitable 
supports are a cellulose acetate film, a polystyrene film, a polyethylene 
terephthalate film, a polycarbonate film, a laminate thereof, paper, 
baryta paper, paper coated on laminated with a hydrophobic polymer such as 
polyethylene, polypropylene, etc. as are commonly used for photographic 
light-sensitive materials. Transparent supports can be employed for 
certain end uses of the light-sensitive material. Also, transparent 
supports may be colored by adding a dye or a pigment thereto as described 
in J. SMPTE, 67, 296 (1958), or Cleare, U.S. Pat. No. 3,822,131 (1984), 
incorporated by reference. Where the adhesion between the support and the 
photographic emulsion layer(s) is insufficient, a subbing layer (an 
adhesive layer) that adheres to both the support and the photographic 
emulsion layer(s) can be employed. Also, in order to improve the adhesion, 
the surface of the support may be subjected to a preliminary processing 
such as corona discharge, irradiation with ultraviolet light, flame 
treatment, etc. A suitable coating amount of silver is about 0.5 g/m.sup.2 
to about 10 g/m.sup.2 of the support. 
The photographic elements can be imagewise exposed with various forms of 
energy, which encompass the ultraviolet and visible (e.g., actinic) and 
infrared regions of the electromagnetic spectrum as well as electron beam 
and beta radiation, gamma ray, X-ray, alpha particle, neutron radiation 
and other forms of corpuscular and wavelike radiant energy in either 
noncoherent (random phase) forms or coherent (in-phase) forms, as produced 
by lasers. Exposures can be monochromatic, orthochromatic or panchromatic. 
Imagewise exposures at ambient, elevated or reduced temperatures and/or 
pressures, including high or low intensity exposures, continuous or 
intermittent exposures, exposure times ranging from minutes to relatively 
short durations in the millisecond to microsecond range and solarizing 
exposures, can be employed within the useful response ranges determined by 
conventional sensitometric techniques, as illustrated by T. H. James, The 
Theory of the Photographic Process, 4th Ed., Macmillan, 1977, Chapters 
4,6, 17, 18 and 23, incorporated by reference. 
The photographic light-sensitive material of this invention can be 
photographically processed using known methods and known processing 
solutions. The processing temperature usually ranges from about 18.degree. 
to about 50.degree. C., but temperatures lower than about 18.degree. C. or 
higher than about 50.degree. C. may be used. This invention is useful for 
the formation of an image by development in which a silver image is formed 
(a black-and-white photographic processing). 
The developers used for black-and-white photographic processing preferably 
contain, as a developing agent, aminophenols (such as 
N-methyl-p-aminophenol), 3-pyrazolidones (such as 
1-phenyl-3-pyrazolidone), 1-phenyl-3-pyrazolines, dihydroxybenzene (such 
as hydroquinone) and other of the aforementioned developing agents. 
Specific examples of the useful developing agents include hydroquinone 
alone, hydroquinone plus N-methyl-p-aminophenol, hydroquinone plus 
1-phenyl-3-pyrazolidone, and hydroquinone plus N-methyl-p-aminophenol plus 
1-phenyl-3-pyrazolidone. Moreover, the developers usually contain a known 
antioxidant, an alkali agent, a pH buffer or the like and, if desired, a 
dissolving aid, a color toning agent, a development accelerator, a surface 
active agent, an anti-foaming agent, a water softener, a hardener, a 
tackifier, etc., may be present. An anti-fogging agent (such as an alkali 
metal halide or benzotriazole) may be present in the developer. 
According to this invention, even when development is carried out using a 
developer containing more than about 0.15 mol/l of sulfite ions, a gamma 
of more than 8 can be obtained. The pH of the developer is preferably 
about 11 to about 12.3. If the pH exceeds about 12.3, the developer is 
unstable even when a high concentration of sulfite ions is present, and it 
is difficult to maintain stable photographic characteristics for more than 
3 days under normal use conditions. 
Fixing solutions having a composition generally employed in the art can be 
used in the present invention. Not only thiosulfates and thiocyanates but 
also organic sulfur compounds known as fixing agents can be used as fixing 
agents in the present invention. 
Preferred examples of fixing agents which can be used in the fixing 
solution include water-soluble thiosulfates such as sodium thiosulfate, 
potassium thiosulfate, ammonium thiosulfate, etc., water-soluble 
thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium 
thiocyanate, etc., water-soluble organic diol fixing agents containing an 
oxygen atom or a sulfur atom such as 3-thio-1,5-pentanediol, 
3,6-dithio-1,8-octanediol, 9-oxo-3,6,12,15-tetrathio-1,17-heptadecanediol, 
etc., water soluble sulfur-containing organic dibasic acids and 
water-soluble salts thereof such as ethylenebisthioglycollic acid and the 
sodium salt thereof, etc., imidazolidinethiones such as 
methylimidazolidinethione, etc. These agents have been described in L. F. 
A. Mason, Photographic Processing Chemistry, pages 187 to 188, Focal Press 
(1966). 
A particularly preferred developing system in accordance with the present 
invention contains a hydroquinone developing agent, a benzotriazole 
antifogging agent (development restrainer), diethylaminopropanediol, 
sodium sulfite, and a pH modifier (preferably NAOH and/or Na.sub.2 
CO.sub.3) to adjust the pH to 11.60.+-.0.5. The most preferred developing 
system is set forth in Example 28. 
The preferred ethanedioic acid hydrazides of the present invention are 
listed in Table I. Among them, the semioxamazides I-1, I-2, I-3 and I-15 
are particularly preferred. 
The compounds of the present invention, "I", are synthesized in accordance 
with the following scheme: 
##STR38## 
The following examples are given to illustrate the present invention in 
more detail. However, the scope of the present invention is not limited to 
these examples.