The present invention relates to a color photographic element containing
a phenolic cyan coupler having a specific sulfone ballast group.
Background of the Invention
A typical photographic element contains multiple layers of light-sensitive
photographic silver halide emulsions with one or more of these layers being spectrally
sensitized to each of blue light, green light and red light. The blue, green and
red light-sensitive layers typically contain yellow, magenta, and cyan dye-forming
For forming color photographic images, the color photographic material
is exposed imagewise and processed in a color developer bath containing an aromatic
primary amine color developing agent. Image dyes are formed by the coupling reaction
of these couplers with the oxidized product of the color developing agent.
Generally, image couplers are selected according to their ability
to couple efficiently with oxidized color developer, thus minimizing the necessary
amounts of coupler and silver halide emulsion in the photographic element; to
provide image dyes whose hues are appropriate for the particular photographic application
in which they are used; to provide image dyes whose absorption spectra have low
unwanted side absorptions and thus lead to good color reproduction; to provide
image dyes with good stability to heat, light, and ferrous ions which are present
in the bleaching solution; and to provide good physical and chemical properties
such as good solubility in coupler solvents, and good dispersibility in gelatin.
In recent years, a great deal of study has been conducted to improve
dye-forming couplers for silver halide photosensitive materials in terms of improved
color reproducibility and image dye stability. However, further improvements are
needed, particularly in the area of cyan couplers.
The couplers used to form cyan image dyes are generally derived from
naphthols and phenols, as described, for example, in U.S. Patents 2,367,351, 2,423,730,
2,474,293, 2,772,161, 2,772,162, 2,895,826, 2,920,961, 3,002,836, 3,466,622, 3,476,563,
3,552,962, 3,758,308, 3,779,763, 3,839,044, 3,880,661, 3,998,642, 4,333,999, 4,990,436,
4,960,685, and 5,476,757; in French patents 1,478,188 and 1,479,043; and in British
patent 2,070,000. These types of couplers can be used either by being incorporated
in the photographic silver halide emulsion layers or externally in the processing
baths. In the former case the couplers must have ballast substituents built into
the molecule to prevent the couplers from migrating from one layer into another.
Although these couplers have been used extensively in color photographic film and
paper products, the dyes derived from them still suffer from poor stability to
heat, humidity or light, low coupling efficiency or optical density, and in particular
from undesirable blue and green absorptions which cause considerable reduction
in color reproduction and color saturation.
The hue of a dye is a function of both the shape and the position
of its spectral absorption band. Traditionally, the cyan dyes used in color photographic
papers have had nearly symmetrical absorption bands centered in the region of 620
to 680 nm, preferably 630 to 660 nm, and more preferably 635 to 655 nm. Such dyes
have rather large amounts of unwanted absorption in the green and blue regions
of the spectrum.
More desirable would be a dye whose absorption band is asymmetrical
in nature and biased towards the green region, that is, with a steep slope on the
short wavelength side. Such a dye would suitably peak at a shorter wavelength than
a dye with symmetrical absorption band, but the exact position of the desired peak
depends on several factors including the degree of asymmetry and the shapes and
positions of the absorption bands of the magenta and yellow dyes with which it
Cyan couplers which have been recently proposed to overcome some of
these problems are 2,5-diacylaminophenols containing a sulfone, sulfonamido or
sulfate moiety in the ballasts at the 5-position, as disclosed in U.S. Patents
4,609,619, 4,775,616, 4,849,328, 5,008,180, 5,045,442, and 5,183,729; and Japanese
patent applications JP02035450 A2, JP01253742 A2, JP04163448 A2, JP04212152 A2,
and JP05204110 A2. Even though cyan image dyes formed from these couplers show
improved stability to heat and humidity, enhanced optical density and resistance
to reduction by ferrous ions in the bleach bath, the dye absorption maxima (λmax)
are too bathochromically shifted (that is, shifted to the red end of the visible
spectrum) and the absorption spectra are too broad with considerable amounts of
undesirable blue and green absorptions. Thus, these couplers are not practical
for use in color papers.
JP59-111645 discloses certain phenolic couplers possessing a 2-arylsulfonamido
group and a 5-sulfonylmethylsulfonamido group. None of the couplers disclosed provide
the desired narrow bandwidth on the short wavelength side. EP 234 742 provides
a much broader description of couplers of all types but, again, the cyan couplers
disclosed do not provide the desired narrow bandwidth on the short wavelength side.
Although the use of sulfone (-SO2-) groups in the ballast
moieties of phenolic cyan couplers has been described in various publications cited
above, the coupler structures disclosed therein do not possess the combination
of essential moieties in the ballasts that can provide the desired reduction in
unwanted green and blue absorption, which would result in improved color reproduction
and color saturation in color photographic papers.
Accordingly, there has been a need to provide a photographic element
containing cyan dye-forming couplers which do not have the inherent disadvantages
of the known couplers. It is therefore an object of this invention to provide a
cyan dye-forming coupler which exhibits excellent photographic properties such
as coupling efficiency, and whose dye has excellent stability to heat and light
and exhibits improved color reproduction and saturation.
Summary of the Invention
A photographic element comprises a light sensitive silver halide
emulsion layer having associated therewith a cyan dye forming coupler having Formula
R1 represents hydrogen or an alkyl group selected from methyl,
ethyl, n-propyl, isopropyl, and butyl;
R2 represents an aryl group unsubstituted or
substituted by halogen, a cyano group, a carbonyl group, a carbonamido group, a
sulfonamido group, a carboxy group, a sulfo group, an alkyl group, an aryl group,
an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an
n represents 1, 2, or 3;
each X is located at a position of the phenyl
ring meta or para to the sulfon group and is independently selected from the group
consisting of alkyl, alkenyl, alkoxy, aryloxy, acyloxy, acylamino, sulfonyloxy,
sulfamoylamino, sulfonamido, ureido, oxycarbonyl, oxycarbonylamino, and carbamoyl
Z represents a hydrogen atom or a group which can be split off
by the reaction of the coupler with an oxidized color developing agent
provided that when R1 is an alkyl group of 4 carbon
atoms, R2 is a phenyl group which has an electron withdrawing group having a Hammett's
Sigma value greater than 0 in a position meta or para to the amido group and has
no group having a Hammett's Sigma value greater than 0 in a position ortho to the
The element forms a dye upon development which has improved color
reproduction and saturation.
Brief Description of the Drawings
Figure 1 shows the absorption spectra of the image dyes from couplers
IC-3 (solid line) and C-1 (broken line), both dispersed in solvent S-1. Figure
2 shows the absorption spectra of the image dyes from coupler IC-7 in solvent S-2
(solid line) and coupler C-8 in solvent S-1 (broken line). Both drawings illustrate
the lower unwanted green and blue absorption of the inventive elements.
Detailed Description of the Invention
The Summary of the Invention describes a photographic element containing
a cyan dye-forming coupler which upon processing in the conventional manner forms
in the exposed areas, a cyan dye whose absorption spectrum is hypsochromically
shifted (that is, shifted toward the blue end of the spectrum) and sharp-cutting
on its short wavelength side. The former is particularly necessary for prints obtained
in accordance with conventional printing processes, and the latter improves color
reproduction and provides high color saturation.
The coupler useful in the invention is a 2,5-diacylaminophenol cyan
coupler in which the 5-acylamino moiety is an amide of a carboxylic acid which
is substituted in the alpha position by a particular sulfone (-SO2-)
group. The sulfone moiety must be an arylsulfone and cannot be an alkylsulfone,
and must be substituted only at the meta or para position of the aryl ring. In
addition, the 2-acylamino moiety must be an amide (-NHCO-) of a carboxylic acid,
and cannot be a ureido (-NHCONH-) group. The result of this unique combination
of sulfone-containing amide group at the 5-position and amide group at the 2-position
is a class of cyan dye-forming couplers which form H-aggregated image dyes having
very sharp-cutting dye hues on the short wavelength side of the absorption curves
and absorption maxima (λmax) generally in the range of 620-645 nanometers,
which is ideally suited for producing excellent color reproduction and high color
saturation in color photographic papers.
Referring to formula (I), R1 represents hydrogen or a methyl,
ethyl, n-propyl, isopropyl or butyl group, and most suitably an ethyl group.
R2 represents an aryl. Such groups include groups such
as a substituted or unsubstituted aryl group typically having 6 to 30 carbon atoms,
which may be substituted by, for example, halogen a cyano group, a carbonyl group,
a carbonamido group, a sulfonamido group, a carboxy group, a sulfo group, an alkyl
group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an
arylthio group, or an arylsulfonyl group. Suitably, R2 represents a 4-chlorophenyl
group, a 3,4-dichlorophenyl group, a 4-cyanophenyl group, a 3-chloro-4-cyanophenyl
group, a pentafluorophenyl group, a 4-carbonamidophenyl group, or a 4-sulfonamidophenyl
It is provided that when R1 is an alkyl group of 4 carbon
atoms, R2 is a phenyl group which has an electron withdrawing group
having a Hammett's Sigma value greater than 0 in a position meta or para to the
amido group and has no group having a Hammett's Sigma value greater than 0 in a
position ortho to the amido group. The data has shown that as the length of an
alkyl chain of R1 is increased, the leftside of the absorption curve
is undesirably shifted to the left and broadened. This is overcome if the R2
group is a phenyl group having an electron withdrawing group located as indicated.
In formula (I), each X is located at the meta or para position of
the phenyl ring, and each independently represents a linear or branched, saturated
or unsaturated alkyl or alkenyl group such as methyl, t-butyl, dodecyl, pentadecyl
or octadecyl; an alkoxy group such as methoxy, t-butoxy or tetradecyloxy; an aryloxy
group such as phenoxy, 4-t-butylphenoxy or 4-dodecylphenoxy; an alkyl or aryl acyloxy
group such as acetoxy or dodecanoyloxy; an alkyl or aryl acylamino group such as
acetamido, benzamido, or hexadecanamido; an alkyl or aryl sulfonyloxy group such
as methylsulfonyloxy, dodecylsulfonyloxy, or 4-methylphenylsulfonyloxy; an alkyl
or aryl sulfamoylamino group such as N-butylsulfamoylamino, or N-4-t-butylphenylsulfamoylamino;
an alkyl or aryl sulfonamido group such as methanesulfonamido, 4-chlorophenylsulfonamido
or hexadecanesulfonamido; a ureido group such as methylureido or phenylureido;
an alkoxycarbonyl or aryloxycarbonylamino group such as methoxycarbonylamino or
phenoxycarbonylamo; a carbamoyl group such as N-butylcarbamoyl or N-methyl-N-dodecylcarbamoyl;
or a perfluoroalkyl group such as trifluoromethyl or heptafluoropropyl. Suitably
X represents the above groups having 1 to 30 carbon atoms, more preferably 8 to
20 linear carbon atoms. Most typically, X represents a linear alkyl group of 12
to 18 carbon atoms such as dodecyl, pentadecyl or octadecyl. It has been found
that unbranched alkyl groups provide results superior to branched alkyl groups.
"n" represents 1, 2, or 3; if n is 2 or 3, then the substituents X
may be the same or different.
Z represents a hydrogen atom or a group which can be split off by
the reaction of the coupler with an oxidized color developing agent, known in the
photographic art as a "coupling-off group."
The presence or absence of such groups determines the chemical equivalency
of the coupler, i.e., whether it is a 2-equivalent or 4-equivalent coupler, and
its particular identity can modify the reactivity of the coupler. Such groups can
advantageously affect the layer in which the coupler is coated, or other layers
in the photographic recording material, by performing, after release from the coupler,
functions such as dye formation, dye hue adjustment, development acceleration or
inhibition, bleach acceleration or inhibition, electron transfer facilitation or
Representative classes of such coupling-off groups include, for example,
halogen, alkoxy, aryloxy, heterocyclyloxy, sulfonyloxy, acyloxy, acyl, heterocyclyl,
sulfonamido, heterocyclylthio, benzothiazolyl, phosophonyloxy, alkylthio, arylthio,
and arylazo. These coupling-off groups are described in the art, for example, in
U.S. Patent Nos. 2,455,169, 3,227,551, 3,432,521, 3,467,563, 3,617,291, 3,880,661,
4,052,212, and 4,134,766; and in U.K. Patent Nos. and published applications 1,466,728,
1,531,927, 1,533,039, 2,066,755A, and 2,017,704A. Halogen, alkoxy and aryloxy groups
are most suitable.
Examples of specific coupling-off groups are -Cl, -F, -Br, -SCN,
-OCH3, -OC6H5, -OCH2C(=O)NHCH2CH2OH,
Typically, the coupling-off group is a chlorine atom.
It is essential that the substituent groups R1, R2,
X, and Z be selected so as to adequately ballast the coupler and the resulting
dye in the organic solvent in which the coupler is dispersed. The ballasting may
be accomplished by providing hydrophobic substituent groups in one or more of the
substituent groups R1, R2, X, and Z. Generally a ballast group is an
organic radical of such size and configuration as to confer on the coupler molecule
sufficient bulk and aqueous insolubility as to render the coupler substantially
nondiffusible from the layer in which it is coated in a photographic element. Thus
the combination of substituent groups R1, R2, X, and Z in
formula (I) are suitably chosen to meet these criteria. To be effective, the ballast
must contain at least 8 carbon atoms and typically contains 10 to 30 carbon atoms.
Suitable ballasting may also be accomplished by providing a plurality of groups
which in combination meet these criteria. In the preferred embodiments of the invention
R1 in formula (I) is a small alkyl group. Therefore, in these embodiments
the ballast would be primarily located as part of groups R2, X, and
Z. Furthermore, even if the coupling-off group Z contains a ballast it is often
necessary to ballast the other substituents as well, since Z is eliminated from
the molecule upon coupling; thus, the ballast is most advantageously provided as
part of groups R2 and X.
The following examples further illustrate the invention. It is not
to be construed that the present invention is limited to these examples.
Unless otherwise specifically stated, substituent groups which may
be substituted on molecules herein include any groups, whether substituted or
unsubstituted, which do not destroy properties necessary for photographic utility.
When the term "group" is applied to the identification of a substituent containing
a substitutable hydrogen, it is intended to encompass not only the substituent's
unsubstituted form, but also its form further substituted with any group or groups
as herein mentioned. Suitably, the group may be halogen or may be bonded to the
remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous,
or sulfur. The substituent may be, for example, halogen, such as chlorine, bromine
or fluorine; nitro; hydroxyl; cyano; carboxyl; or groups which may be further substituted,
such as alkyl, including straight or branched chain alkyl, such as methyl, trifluoromethyl,
ethyl, t-butyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl; alkenyl,
such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy,
sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy,
and 2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl,
naphthyl; aryloxy, such as phenoxy, 2-methylphenoxy, alpha- or beta-naphthyloxy,
and 4-tolyloxy; carbonamido, such as acetamido, benzamido, butyramido, tetradecanamido,
2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl, N-methyltetradecanamido,
N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl,
and N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino,
hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino,
p-toluylcarbonylamino, N-methylureido, N,N-dimethylureido, N-methyl-N-dodecylureido,
N-hexadecylureido, N,N-dioctadecylureido, N,N-dioctyl-N'-ethylureido, N-phenylureido,
N,N-diphenylureido, N-phenyl-N-p-toluylureido, N-(m-hexadecylphenyl)ureido,
N,N-(2,5-di-t-pentylphenyl)-N'-ethylureido, and t-butylcarbonamido;
sulfonamido, such as methylsulfonamido, benzenesulfonamido, p-toluylsulfonamido,
p-dodecylbenzenesulfonamido, N-methyltetradecylsulfonamido, N,N-dipropyl-sulfamoylamino,
and hexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl, N-ethylsulfamoyl,
N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl, N,N-dimethylsulfamoyl; N-[3-(dodecyloxy)propyl]sulfamoyl,
and N-dodecylsulfamoyl; carbamoyl, such as N-methylcarbamoyl, N,N-dibutylcarbamoyl,
N-octadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl, N-methyl-N-tetradecylcarbamoyl,
and N,N-dioctylcarbamoyl; acyl, such as acetyl, (2,4-di-t-amylphenoxy)acetyl,
phenoxycarbonyl, p-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl,
tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3-pentadecyloxycarbonyl,
and dodecyloxycarbonyl; sulfonyl, such as methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl,
2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl,
methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl,
phenylsulfonyl, 4-nonylphenylsulfonyl, and p-toluylsulfonyl; sulfonyloxy,
such as dodecylsulfonyloxy, and hexadecylsulfonyloxy; sulfinyl, such as methylsulfinyl,
octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl,
4-nonylphenylsulfinyl, and p-toluylsulfinyl; thio, such as ethylthio, octylthio,
benzylthio, tetradecylthio, 2-(2,4-di-t
2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such as acetyloxy,
benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy, N-phenylcarbamoyloxy,
N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy; amine, such as phenylanilino, 2-chloroanilino,
diethylamine, dodecylamine; imino, such as 1 (N-phenylimido)ethyl, N-succinimido
or 3-benzylhydantoinyl; phosphate, such as dimethylphosphate and ethylbutylphosphate;
phosphite, such as diethyl and dihexylphosphite; a heterocyclic group, a heterocyclic
oxy group or a heterocyclic thio group, each of which may be substituted and which
contain a 3 to 7 membered heterocyclic ring composed of carbon atoms and at least
one hetero atom selected from the group consisting of oxygen, nitrogen and sulfur,
such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or 2-benzothiazolyl; quaternary
ammonium, such as triethylammonium; and silyloxy, such as trimethylsilyloxy.
If desired, the substituents may themselves be further substituted
one or more times with the described substituent groups. The particular substituents
used may be selected by those skilled in the art to attain the desired photographic
properties for a specific application and can include, for example, hydrophobic
groups, solubilizing groups, blocking groups, releasing or releasable groups. Generally,
the above groups and substituents thereof may include those having up to 48 carbon
atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but
greater numbers are possible depending on the particular substituents selected.
The materials of the invention can be used in any of the ways and
in any of the combinations known in the art. Typically, the materials useful in
the invention are incorporated in a silver halide emulsion and the emulsion coated
as a layer on a support to form part of a photographic element. Alternatively,
unless provided otherwise, they can be incorporated at a location adjacent to the
silver halide emulsion layer where, during development, they will be in reactive
association with development products such as oxidized color developing agent.
Thus, as used herein, the term "associated" signifies that the compound is in the
silver halide emulsion layer or in an adjacent location where, during processing,
it is capable of reacting with silver halide development products.
Representative substituents on ballast groups include alkyl, aryl,
alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxcarbonyl,
carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbamoyl, alkylsulfonyl,
arylsulfonyl, sulfonamido, and sulfamoyl groups wherein the substituents typically
contain 1 to 42 carbon atoms. Such substituents can also be further substituted.
The photographic elements can be single color elements or multicolor
elements. Multicolor elements contain image dye-forming units sensitive to each
of the three primary regions of the spectrum. Each unit can comprise a single emulsion
layer or multiple emulsion layers sensitive to a given region of the spectrum.
The layers of the element, including the layers of the image-forming units, can
be arranged in various orders as known in the art. In an alternative format, the
emulsions sensitive to each of the three primary regions of the spectrum can be
disposed as a single segmented layer.
A typical multicolor photographic element comprises a support bearing
a cyan dye image-forming unit comprised of at least one red-sensitive silver halide
emulsion layer having associated therewith at least one cyan dye-forming coupler,
a magenta dye image-forming unit comprising at least one green-sensitive silver
halide emulsion layer having associated therewith at least one magenta dye-forming
coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive
silver halide emulsion layer having associated therewith at least one yellow dye-forming
coupler. The element can contain additional layers, such as filter layers, interlayers,
overcoat layers or subbing layers.
If desired, the photographic element can be used in conjunction with
an applied magnetic layer as described in Research Disclosure, November
1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a
North Street, Emsworth, Hampshire P010 7DQ, ENGLAND, and as described in Hatsumi
Kyoukai Koukai Gihou No. 94-6023, published March 15, 1994, available from the
Japanese Patent Office. When it is desired to employ the inventive materials in
a small format film, Research Disclosure, June 1994, Item 36230, provides
In the following discussion of suitable materials for use in the
emulsions and elements of this invention, reference will be made to Research
Disclosure, September 1994, Item 36544, available as described above, which
will be identified hereafter by the term "Research Disclosure". The Sections hereafter
identified are sections of the Research Disclosure.
Except as provided, the silver halide emulsion containing elements
employed in this invention can be either negative-working or positive-working as
indicated by the type of processing instructions (i.e. color negative, reversal,
or direct positive processing) provided with the element. Suitable emulsions and
their preparation as well as methods of chemical and spectral sensitization are
described in Sections I through V. Various additives such as UV dyes, brighteners,
antifoggants, stabilizers, light absorbing and scattering materials, and physical
property modifying addenda such as hardeners, coating aids, plasticizers, lubricants
and matting agents are described, for example, in Sections II and VI through VIII.
Color materials are described in Sections X through XIII. Scan facilitating is
described in Section XIV. Supports, exposure, development systems, and processing
methods and agents are described in Sections XV to XX. Certain desirable photographic
elements and processing steps, particularly those useful in conjunction with color
reflective prints, are described in Research Disclosure, Item 37038, February
Cyan image dye-forming couplers may be included in the element besides
the coupler useful in the invention. These couplers may be located in the same
layer as the coupler useful in the invention or in a different layer.
Couplers that form magenta dyes upon reaction with oxidized color
developing agent are described in such representative patents and publications
as: U.S. Pat. Nos. 2,311,082, 2,343,703, 2,369,489, 2,600,788, 2,908,573, 3,062,653,
3,152,896, 3,519,429, 3,758,309, 4,540,654, and "Farbkuppler-eine Literature Ubersicht,"
published in Agfa Mitteilungen, Band III, pp. 126-156 (1961). Preferably such couplers
are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that form magenta
dyes upon reaction with oxidized color developing agents.
Couplers that form yellow dyes upon reaction with oxidized color
developing agent are described in such representative patents and publications as:
U.S. Pat. Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, 3,447,928,
4,022,620, 4,443,536, and "Farbkuppler-eine Literature Ubersicht," published in
Agfa Mitteilungen, Band III, pp. 112-126 (1961). Such couplers are typically open
chain ketomethylene compounds.
Couplers that form colorless products upon reaction with oxidized
color developing agent are described in such representative patents as: U.K. Patent
No. 861,138; U.S. Patent Nos. 3,632,345, 3,928,041, 3,958,993 and 3,961,959. Typically
such couplers are cyclic carbonyl containing compounds that form colorless products
on reaction with an oxidized color developing agent.
Couplers that form black dyes upon reaction with oxidized color developing
agent are described in such representative patents as U.S. Patent Nos. 1,939,231;
2,181,944; 2,333,106; and 4,126,461; German OLS No. 2,644,194 and German OLS No.
2,650,764. Typically, such couplers are resorcinols or m-aminophenols that form
black or neutral products on reaction with oxidized color developing agent.
In addition to the foregoing, so-called "universal" or "washout"
couplers may be employed. These couplers do not contribute to image dye-formation.
Thus, for example, a naphthol having an unsubstituted carbamoyl or one substituted
with a low molecular weight substituent at the 2- or 3- position may be employed.
Couplers of this type are described, for example, in U.S. Patent Nos. 5,026,628,
5,151,343, and 5,234,800.
It may be useful to use a combination of couplers any of which may
contain known ballasts or coupling-off groups such as those described in U.S.
Patent 4,301,235; U.S. Patent 4,853,319 and U.S. Patent 4,351,897. The coupler
may contain solubilizing groups such as described in U.S. Patent 4,482,629. The
coupler may also be used in association with "wrong" colored couplers (e.g. to
adjust levels of interlayer correction) and, in color negative applications, with
masking couplers such as those described in EP 213.490; Japanese Published Application
58-172,647; U.S. Patent Nos. 2,983,608; 4,070,191; and 4,273,861; German Applications
DE 2,706,117 and DE 2,643,965; UK. Patent 1,530,272; and Japanese Application 58-113935.
The masking couplers may be shifted or blocked, if desired.
The materials useful in the invention may be used in association
with materials that accelerate or otherwise modify the processing steps e.g. of
bleaching or fixing to improve the quality of the image. Bleach accelerator releasing
couplers such as those described in EP 193,389; EP 301,477; U.S. 4,163,669; U.S.
4,865,956; and U.S. 4,923,784, may be useful. Also contemplated is use of the compositions
in association with nucleating agents, development accelerators or their precursors
(UK Patent 2,097,140; UK. Patent 2,131,188); electron transfer agents (U.S. 4,859,578;
U.S. 4,912,025); antifogging and anti color-mixing agents such as derivatives of
hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides;
sulfonamidophenols; and non color-forming couplers.
The materials useful in the invention may also be used in combination
with filter dye layers comprising colloidal silver sol or yellow, cyan, and/or
magenta filter dyes, either as oil-in-water dispersions, latex dispersions or as
solid particle dispersions. Additionally, they may be used with "smearing" couplers
(e.g. as described in U.S. 4,366,237; EP 96,570; U.S. 4,420,556; and U.S. 4,543,323.)
Also, the compositions may be blocked or coated in protected form as described,
for example, in Japanese Application 61/258,249 or U.S. 5,019,492.
The materials useful in the invention may further be used in combination
with image-modifying compounds such as "Developer Inhibitor-Releasing" compounds
(DIR's). DIR's useful in conjunction with the compositions of the invention are
known in the art and examples are described in U.S. Patent Nos. 3,137,578; 3,148,022;
3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783;
3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962;
4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 4,579,816;
4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959;
4,880,342; 4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299;
4,966,835; 4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662;
GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 3,644,416
as well as the following European Patent Publications: 272,573; 335,319; 336,411;
346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670;
396,486; 401,612; 401,613.
Such compounds are also disclosed in "Developer-Inhibitor-Releasing (DIR) Couplers
for Color Photography," C.R. Barr, J.R. Thirtle and P.W. Vittum in Photographic
Science and Engineering, Vol. 13, p. 174 (1969). Generally, the developer inhibitor-releasing
(DIR) couplers include a coupler moiety and an inhibitor coupling-off moiety (IN).
The inhibitor-releasing couplers may be of the time-delayed type (DIAR couplers)
which also include a timing moiety or chemical switch which produces a delayed
release of inhibitor. Examples of typical inhibitor moieties are: oxazoles, thiazoles,
diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles,
tetrazoles, benzimidazoles, indazoles, isoindazoles, mercaptotetrazoles, selenotetrazoles,
mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles,
mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles, mercaptooxazoles,
mercaptothiadiazoles, mercaptothiazoles, mercaptotriazoles, mercaptooxadiazoles,
mercaptodiazoles, mercaptooxathiazoles, telleurotetrazoles or benzisodiazoles.
In a preferred embodiment, the inhibitor moiety or group is selected from the following
wherein RI is selected from the group consisting of straight and branched
alkyls of from 1 to about 8 carbon atoms, benzyl, phenyl, and alkoxy groups and
such groups containing none, one or more than one such substituent; RII
is selected from RI and -SRI; RIII is a straight or branched
alkyl group of from 1 to 5 carbon atoms and m is from 1 to 3; and RIV
is selected from the group consisting of hydrogen, halogens and alkoxy, phenyl
and carbonamido groups, -COORV and -NHCOORV wherein RV
is selected from substituted and unsubstituted alkyl and aryl groups.
Although it is typical that the coupler moiety included in the developer
inhibitor-releasing coupler forms an image dye corresponding to the layer in which
it is located, it may also form a different color as one associated. with a different
film layer. It may also be useful that the coupler moiety included in the developer
inhibitor-releasing coupler forms colorless products and/or products that wash
out of the photographic material during processing (so-called "universal" couplers).
As mentioned, the developer inhibitor-releasing coupler may include
a timing group, which produces the time-delayed release of the inhibitor group
such as groups utilizing the cleavage reaction of a hemiacetal (U.S. 4,146,396,
Japanese Applications 60-249148; 60-249149); groups using an intramolecular nucleophilic
substitution reaction (U.S. 4,248,962); groups utilizing an electron transfer reaction
along a conjugated system (U.S. 4,409,323; 4,421,845; Japanese Applications 57-188035;
58-98728; 58-209736; 58-209738) groups utilizing ester hydrolysis (German Patent
Application (OLS) No. 2,626,315); groups utilizing the cleavage of imino ketals
(U.S. 4,546,073); groups that function as a coupler or reducing agent after the
coupler reaction (U.S. 4,438,193; U.S. 4,618,571) and groups that combine the features
describe above. It is typical that the timing group or moiety is of one of the
wherein IN is the inhibitor moiety, Z is selected from the group consisting of nitro,
cyano, alkylsulfonyl; sulfamoyl (-SO2NR2); and sulfonamido
(-NRSO2R) groups; n is 0 or 1; and RVI is selected from the
group consisting of substituted and unsubstituted alkyl and phenyl groups. The
oxygen atom of each timing group is bonded to the coupling-off position of the
respective coupler moiety of the DIAR.
Suitable developer inhibitor-releasing couplers for use in the present
invention include, but are not limited to, the following:
It is also contemplated that the concepts of the present invention
may be employed to obtain reflection color prints as described in Research
Disclosure, November 1979, Item 18716, available from Kenneth Mason Publications,
Ltd, Dudley Annex, 12a North Street, Emsworth, Hampshire P0101 7DQ, England. Materials
of the invention may be coated on pH adjusted support as described in U.S. 4,917,994;
on a support with reduced oxygen permeability (EP 553,339); with epoxy solvents
(EP 164,961); with nickel complex stabilizers (U.S. 4,346,165; U.S. 4,540,653 and
U.S. 4,906,559 for example); with ballasted chelating agents such as those in U.S.
4,994,359 to reduce sensitivity to polyvalent cations such as calcium; and with
stain reducing compounds such as described in U.S. 5,068,171. Other compounds
useful in combination with the invention are disclosed in Japanese Published Applications
described in Derwent Abstracts having accession numbers as follows: 90-072,629,
90-072,630; 90-072,631; 90-072,632; 90-072,633; 90-072,634; 90-077,822; 90-078,229;
90-078,230; 90-079,336; 90-079,337; 90-079,338; 90-079,690; 90-079,691; 90-080,487;
90-080,488; 90-080,489; 90-080,490; 90-080,491; 90-080,492; 90-080,494; 90-085,928;
90-086,669; 90-086,670; 90-087,360; 90-087,361; 90-087,362; 90-087,363; 90-087,364;
90-088,097; 90-093,662; 90-093,663; 90-093,664; 90-093,665; 90-093,666; 90-093,668;
90-094,055; 90-094,056; 90-103,409; 83-62,586; 83-09,959.
Especially useful in this invention are tabular grain silver halide
emulsions. Specifically contemplated tabular grain emulsions are those in which
greater than 50 percent of the total projected area of the emulsion grains are
accounted for by tabular grains having a thickness of less than 0.3 micrometer
(micron) (0.5 micrometer (micron) for blue sensitive emulsion) and an average
tabularity (T) of greater than 25 (preferably greater than 100), where the term
"tabularity" is employed in its art recognized usage as
T = ECD/t2
ECD is the average equivalent circular diameter of the tabular grains in micrometers
t is the average thickness in micrometers of the tabular grains.
The average useful ECD of photographic emulsions can range up to
10 micrometers, although in practice emulsion ECDs seldom exceed 4 micrometers.
Since both photographic speed and granularity increase with increasing ECDs, it
is generally preferred to employ the smallest tabular grain ECDs compatible with
achieving aim speed requirements.
Emulsion tabularity increases markedly with reductions in tabular
grain thickness. It is generally preferred that aim tabular grain projected areas
be satisfied by thin (t < 0.2 micrometer) tabular grains. To achieve the lowest
levels of granularity it is preferred that aim tabular grain projected areas be
satisfied with ultrathin (t < 0.06 micrometer) tabular grains. Tabular grain
thicknesses typically range down to 0.02 micrometer. However, still lower tabular
grain thicknesses are contemplated. For example, Daubendiek et al U.S. Patent 4,672,027
reports a 3 mole percent iodide tabular grain silver bromoiodide emulsion having
a grain thickness of 0.017 micrometer. Ultrathin tabular grain high chloride emulsions
are disclosed by Maskasky U.S. 5,217,858.
As noted above tabular grains of less than the specified thickness
account for at least 50 percent of the total grain projected area of the emulsion.
To maximize the advantages of high tabularity it is generally preferred that tabular
grains satisfying the stated thickness criterion account for the highest conveniently
attainable percentage of the total grain projected area of the emulsion. For example,
in preferred emulsions, tabular grains satisfying the stated thickness criteria
above account for at least 70 percent of the total grain projected area. In the
highest performance tabular grain emulsions, tabular grains satisfying the thickness
criteria above account for at least 90 percent of total grain projected area.
Suitable tabular grain emulsions can be selected from among a variety
of conventional teachings, such as those of the following: Research Disclosure,
Item 22534, January 1983, published by Kenneth Mason Publications, Ltd., Emsworth,
Hampshire P010 7DD, England; U.S. Patent Nos. 4,439,520; 4,414,310; 4,433,048;
4,643,966; 4,647,528; 4,665,012; 4,672,027; 4,678,745; 4,693,964; 4,713,320; 4,722,886;
4,755,456; 4,775,617; 4,797,354; 4,801,522; 4,806,461; 4,835,095; 4,853,322; 4,914,014;
4,962,015; 4,985,350; 5,061,069 and 5,061,616.
The emulsions can be surface-sensitive emulsions, i.e., emulsions
that form latent images primarily on the surfaces of the silver halide grains,
or the emulsions can form internal latent images predominantly in the interior
of the silver halide grains. The emulsions can be negative-working emulsions, such
as surface-sensitive emulsions or unfogged internal latent image-forming emulsions,
or direct-positive emulsions of the unfogged, internal latent image-forming type,
which are positive-working when development is conducted with uniform light exposure
or in the presence of a nucleating agent.
Photographic elements can be exposed to actinic radiation, typically
in the visible region of the spectrum, to form a latent image and can then be processed
to form a visible dye image. Processing to form a visible dye image includes the
step of contacting the element with a color developing agent to reduce developable
silver halide and oxidize the color developing agent. Oxidized color developing
agent in turn reacts with the coupler to yield a dye.
With negative-working silver halide, the processing step described
above provides a negative image. The described elements can be processed in the
known Kodak C-41™ color process as described in The British Journal of Photography
Annual of 1988, pages 191-198. Where applicable, the element may be processed in
accordance with color print processes such as the RA-4™ process of Eastman
Kodak Company as described in the British Journal of Photography Annual of 1988,
Pp 198-199. Such negative working emulsions are typically sold with instructions
to process using a color negative method such as the mentioned C-41 or RA-4 process.
To provide a positive (or reversal) image, the color development step can be preceded
by development with a non-chromogenic developing agent to develop exposed silver
halide, but not form dye, and followed by uniformly fogging the element to render
unexposed silver halide developable. Such reversal emulsions are typically sold
with instructions to process using a color reversal process such as E-6™.
Alternatively, a direct positive emulsion can be employed to obtain a positive
Preferred color developing agents are p-phenylenediamines such as:
Development is usually followed by the conventional steps of bleaching,
fixing, or bleach-fixing, to remove silver or silver halide, washing, and drying.
The cyan couplers of this invention can be prepared by reacting alkyl
or aryl acid chlorides with an appropriate aminophenol, such as 2-amino-5-nitrophenol
or 2-amino-4-chloro-5-nitrophenol to form the 2-carbonamido coupler intermediates.
The nitro group of the coupler intermediate can then be reduced and a separately
prepared sulfone-containing ballast can be attached thereto by conventional procedures.
The synthesis of coupler compound IC-3 will further illustrate the invention.
A. Preparation of the phenolic coupler intermediate
To a stirred solution of 37.7 g (0.20 mol) of 2-amino-4-chloro-5-nitrophenol
(1) and 48.5 g (0.40 mol) of N,N-dimethylaniline in 500 ml THF was added
30.9 g (0.22 mol) of benzoyl chloride (2). After stirring for 3 hours at
room temperature, the reaction mixture was drowned in ice water and 20 ml concentrated
HCl. The solid which precipitated out was collected, washed with water, and recrystallized
from CH3CN to give 54.6 g of the nitro compound (3).
A solution of 8.8 g (0.03 mol) of (3) in 150 ml THF was heated
with a teaspoonful of 10% Pd/C and hydrogenated at room temperature under 3,5 kg/cm2
(50 1b per square inch) hydrogen pressure for 3 hours. The catalyst was filtered
off to give the reduced aminophenol (4) which was stored under a blanket
of nitrogen while the sulfone-containing ballast was being prepared.
B. Preparation of the ballast acid chloride
To a well-stirred solution of 40 g (0.13 mol) m-pentadecylphenylthiol
(5) and 27 g (0.15 mol) of methyl a-bromobutyrate (6) in 500 ml
acetone was added 104 g (0.75 mol) K2CO3. The mixture was
heated on a steam bath and refluxed for 1 hour. After cooling to room temperature
the insolubles were filtered off. The filtrate was poured into water and extracted
with ethyl acetate. The ethyl acetate was removed under reduced pressure and the
residual crude product mixture was dissolved in ligroin. The solution was chromatographed
through a short silica gel column, eluting first with ligroin and finally with
50% ligroin-CH2Cl2 mixture. The fractions containing the pure
product were combined and the solvent was removed to give 43 g of (7) as
a colorless oil.
The ballast intermediate (7) was taken up in 300 ml acetic
acid, cooled to 10-15°C, and treated with 23 ml 30% H2O2.
The mixture was stirred at room temperature for 0.5 hour and then heated on the
steam bath for another hour. Upon standing at room temperature overnight the product
crystallized out. The pure white solid crystals were collected to give 41.5 g of
The sulfone ballast ester (8) was dissolved in 200 ml CH3OH
and 200 ml THF. The solution was then heated with 18 g NaOH dissolved in 150 ml
water. After stirring at room temperature for 1 hour, the mixture was poured into
dilute HCl. The white solid that precipitated out was collected, washed with water
and dried to give 40 g of the sulfone ballast acid (IX) as a white solid.
To a solution of 13.6 g (0.031 mol) of (9) in 100 ml CH2Cl2
was added with stirring 11.4 g (0.09 mol) oxalyl chloride and 5 drops of DMF. After
stirring at room temperature for 2 hours, the mixture was concentrated to give
13.9 g of ballast acid chloride (10) as an oil.
C. Preparation of coupler compound IC-3
To a stirred solution of 7.9 g (0.03 mol) of the aminophenol (4)
in 150 ml THF was added 7.3 g (0.06 mol) of N,N-dimethylaniline and 13.9 g (0.03
mol) of the ballast acid chloride (10). After stirring at room temperature
for 2 hours the reaction mixture was poured into water containing 5 ml concentrated
HCl. The tan colored solid was collected, washed with water, and recrystallized
from CH3CN to give 17.4 g (85%) of crystalline white solid (IC-3). The
structure was confirmed by H1 NMR and elemental analysis.
Calcd. for C38H51C1N2O5SC, 66.79;H, 7.52;N, 4.10 FoundC, 66.61;H, 7.56;N, 4.02
Preparation of Photographic Elements
On a gel-subbed, polyethylene-coated paper support were coated the
An underlayer containing 3.23 grams gelatin per square meter.
A photosensitive layer containing (per square meter) 2.15 grams gelatin,
an amount of red-sensitized silver chloride emulsion containing the amount of silver
(determined by the equivalency of the coupler) indicated in Table 1, 2, or 3; a
dispersion containing 8.61x10-4 mole of the coupler indicated in Table
1, 2, or 3; and 0.043 gram surfactant Alkanol XC (trademark of E. I. Dupont Co.)(in
addition to the Alkanol XC used to prepare the coupler dispersion). The coupler
dispersion contained the coupler, all of the gelatin in the layer except that supplied
by the emulsion, an amount of the coupler solvent indicated in Table 1, 2, or 3
equal to the weight of coupler, and 0.22 gram Alkanol XC.
Comparison couplers C-1 through C-6 are closely related to the couplers
useful in the present invention; they all contain sulfone ballasts, but they do
not satisfy the structural requirements useful in the invention in other respects.
Comparison coupler C-7 is similar to coupler IC-2 useful in the invention except
that is has an oxygen atom replacing the sulfonyl group in the ballast. Comparison
coupler C-8 is a phenolic coupler not closely related to the couplers useful in
the invention, but is one included because it is currently used in many commercially
available color photographic papers.
Preparation of Processed Photographic Examples
Processed samples were prepared by exposing the coatings through a
step wedge and processing as follows:
Process Step Time (min.) Temp. (C) Developer0.7535.0 Bleach-Fix0.7535.0 Water wash1.5035.0
The processing solutions used in the above process had the following compositions
(amounts per liter of solution):
Developer Triethanolamine12.41 g Blankophor REU (trademark of Mobay Corp.)2.30 g Lithium polystyrene sulfonate0.09 g N,N-Diethylhydroxylamine4.59 g Lithium sulfate2.70 g Developing agent Dev-15.00 g 1-Hydroxyethyl-1,1-diphosphonic acid0.49 g Potassium carbonate, anhydrous21.16 g Potassium chloride1.60 g Potassium bromide7.00 mg
pH adjusted to 10.4 at 26.7C
Bleach-Fix Solution of ammonium thiosulfate71.85 g Ammonium sulfite5.10 g Sodium metabisulfite10.00 g Acetic acid10.20 g Ammonium ferric ethylenediaminetetraacetate48.58 g Ethylenediaminetetraacetic acid3.86 g
pH adjusted to 6.7 at 26.7C
The spectra of the resulting dyes were measured and normalized to
a maximum absorption of 1.00. The wavelength of maximum absorption was recorded
as the "λmax." As a measure of the sharpness of the curve on the left (short
wavelength) side of the absorption band the "left bandwidth" (LBW) was obtained
by subtracting the wavelength at the point on the left side of the absorption band
where the normalized density is 0.50 from the λmax. A lower value of LBW
indicates a reduction in the unwanted green absorption and is thus desirable. The
λmax and LBW values are shown in Tables 1, 2 and 3.
Couplers Dispersed in Solvent S-1 Comparison or Invention Coupler Solvent g Ag per m2λmax nm LBW nm ComparisonC-1S-10.1964983 ComparisonC-2S-10.1964277 ComparisonC-3S-10.1968398 ComparisonC-4S-10.1964683 ComparisonC-5S-10.3968588 ComparisonC-6S-10.3964885 ComparisonC-7S-10.3964181 ComparisonC-8S-10.1966180 InventionIC-3S-10.1962453 InventionIC-5S-10.3962456 InventionIC-6S-10.1963062 InventionIC-7S-10.1962851 InventionIC-8S-10.3962658 InventionIC-9S-10.3963161 InventionIC-10S-10.3962861 InventionIC-15S-10.1963566
Couplers Dispersed in Solvent S-2 Comparison or Invention Coupler Solvent g Ag per m2Imax LBW ComparisonC-3S-20.1968090 ComparisonC-6S-20.1964378 InventionIC- 2S-20.1962056 InventionIC- 3S-20.1962144 InventionIC- 4S-20.1963156 InventionIC- 7S-20.1962643 InventionIC-10S-20.3962454 InventionIC-13S-20.1963562 InventionIC-15S-20.1962854
Couplers Dispersed in Various Solvents Comparison or Invention Coupler Solvent g Ag per m2lmax LBW ComparisonC-1S-10.1964983 ComparisonC-1S-40.1966691 ComparisonC-3S-10.1968398 ComparisonC-3S-20.1968098 InventionIC-3S-10.1962657 InventionIC-3S-20.1962247 InventionIC-3S-30.1963058 InventionIC-3S-40.1962656 InventionIC-3S-50.1962656
The data in Tables 1, 2 and 3 show that all of the cyan image couplers
of the present invention form image dyes that are shifted hypsochromically and
at the same time have spectra that are very sharp cutting on the short wavelength
side of their absorption bands. These sharp-cutting absorption dye curves are
indicated by the unusually smaller values for the left bandwidth (LBW) than those
of the dyes from the comparison couplers. Thus the dyes from the couplers of our
invention have less unwanted green and blue absorption than the dyes from the comparison
couplers, resulting in superior color reproduction and high color saturation. Furthermore,
this advantage is realized even when the couplers are dispersed in a wide variety
of coupler solvents, indicating that the couplers of the present invention have
The superior hue of the dyes generated from the couplers of our invention
are further illustrated in Figures 1 and 2. Figure 1 compares the spectra of the
dyes from coupler IC-3 of our invention and comparison coupler C-1, both dispersed
in coupler solvent S-1. These two couplers both have sulfone-containing ballasts,
but the ballast of coupler C-1 does not conform to the requirements of the invention.
Thus it does not exhibit the desired hue advantages. Figure 2 compares the dyes
from coupler IC-7 of the invention dispersed in coupler solvent S-2, and comparison
coupler C-8 dispersed in solvent S-1. Again, lower unwanted absorption is realized
by the invention. The combination of coupler C-8 and solvent S-1 is used in most
commercially available color photographic papers. In each of these comparisons,
the coupler of our invention yields a dye which has significantly less unwanted
absorption in the region of 400-585 nm, which encompasses nearly all of the blue
and green regions of the visible spectrum.
Sample elements were prepared using oleyl alcohol, processed and
tested as in Example 1. The couplers contained in each of the samples were 4-chlorophenols
substituted as follows:
It is observed that the LBW undesirably increases with increasing
alkyl chain length of R1 but is desirably much narrower using the R2
group comprising a phenyl group with an electron withdrawing substituent para to
the amido group.
Further sample elements were prepared using oleyl alcohol, processed
and tested as in Example 1. The couplers contained in each of the samples were
4-chlorophenols substituted as follows:
As may be observed from the results, the LBW is desirably more narrow
when R2 is a phenyl group containing a para or meta electron withdrawing
group compared to a similar group containing an ortho electron withdrawing group.
Fotografisches Element mit einer lichtempfindlichen Silberhalogenidemulsionsschicht,
der ein blaugrünfarbstoffbildender Kuppler mit folgender Formel (I) zugeordnet
R1 für Wasserstoff oder eine Alkylgruppe steht, die aus Methyl, Ethyl,
n-Propyl, Isopropyl und Butyl auswählbar ist;
R2 für eine Arylgruppe steht, unsubstituiert oder durch Halogen substituiert,
eine Cyanogruppe, eine Carbonylgruppe, eine Carbonamidgruppe, eine Sulfonamidgruppe,
eine Carboxygruppe, eine Sulfogruppe, eine Alkylgruppe, eine Arylgruppe, eine Alkoxygruppe,
eine Aryloxygruppe, eine Alkylthiogruppe, eine Arylthiogruppe oder eine Arylsulfonylgruppe.
n für 1, 2 oder 3 steht;
jedes X sich an dem Phenylring in Meta- oder Parastellung zur Sulfonylgruppe befindet
und unabhängig aus der Gruppe auswählbar ist, die aus Alkyl-, Alkenyl-, Alkoxy-,
Aryloxy-, Acyloxy-, Acylamin-, Sulfonyloxy-, Sulfamoylamino-, Sulfonamido-, Ureido-,
Oxycarbonyl-, Oxycarbonylamino- und Carbamoylgruppen besteht; und
Z für ein Wasserstoffatom oder eine Gruppe steht, die durch Reaktion des Kupplers
mit einem oxidierten Farbentwicklungsmittel abspaltbar ist;
vorausgesetzt, dass wenn R1 eine Alkylgruppe von 4 Kohlenstoffatomen
eine Phenylgruppe ist, die einen Substituenten mit desaktivierender
Wirkung (elektronenentziehende Gruppe) und einem Hammettschen Sigma-Wert von größer
als 0 in einer Meta- oder Para-Stellung zur Amidogruppe besitzt, und die keine
Gruppe mit einem Hammettschen Sigma-Wert von größer als 0 in einer Ortho-Stellung
zur Amidogruppe besitzt.
Fotografisches Element nach Anspruch 1, worin R1 für Wasserstoff
Fotografisches Element nach Anspruch 1 oder 2, worin R2 für eine
Fotografisches Element nach Anspruch 3, worin die Phenylgruppe mit einem Element
substituierbar ist, das aus der Gruppe auswählbar ist, die aus Cyano-, Halogen-,
Carbonyl-, Oxysulfonyl-, Sulfoxid-, Sulfamoyl-, Carboxy-, Sulfonamid- und Carbamoylgruppen
Fotografisches Element nach Anspruch 4, worin R2 aus der Gruppe auswählbar
ist, die aus 4-Chlorophenyl, 3,4-Dichlorophenyl, 4-Cyanophenyl, 3-Chloro-4-Cyanophenyl,
Pentafluorophenyl, 4-Carbonamidophenyl und einer 4-Sulfonamidphenylgruppe besteht.
Fotografisches Element nach Anspruch 1-5, worin mindestens ein X aus der Gruppe
auswählbar ist, die aus Alkyl, Alkoxy, Carboxy, Sulfonamid und Halogen besteht.
Fotografisches Element nach Anspruch 6, worin mindestens ein X für eine lineare
Alkylgruppe mit 12-18 Kohlenstoffatomen steht.
Fotografisches Element nach Anspruch 1, worin R2 eine unsubstituierte
Phenylgruppe oder eine Phenylgruppe ist, die durch eine Halogen-, Cyano- oder eine
Sulfonamidgruppe substituiert ist.
Fotografisches Element nach Anspruch 1, worin Z für Halogen steht.
Fotografisches Element nach Anspruch 1, worin das Element einen reflektierenden
Fotografisches Element nach Anspruch 1, worin R1 eine Methyl-, Ethyl-,
n-Propyl-, Isopropyl- oder Butylgruppe ist.
Fotografisches Element nach Anspruch 1, worin X eine Alkoxygruppe ist.
Fotografisches Element nach Anspruch 1, worin mindestens ein X eine Sulfonylgruppe
Fotografisches Element nach Anspruch 1, worin mindestens ein X in Metastellung
zur Sulfonylgruppe steht.
Fotografisches Element nach Anspruch 1, worin X eine Alkylgruppe ist.
Fotografisches Element nach Anspruch 1, worin der Wert für die linke Bandbreite
(Left Bandwidth / LBW) des Farbstoffs, der aus dem Kuppeln mit 4-Amino-3-Methyl-N-Ethyl-N-(2-Methansulfonamidethyl)-Anilin-Sesquisulfathydrat
in Di-n-Butyl-Phthalat erzielbar ist, 66 nm oder weniger beträgt.
A photographic element comprising a light sensitive silver halide emulsion
layer having associated therewith a cyan dye forming coupler having Formula (I):
R1 represents hydrogen or an alkyl group selected from methyl, ethyl,
n-propyl, isopropyl, and butyl;
R2 represents an aryl group unsubstituted or substituted
by halogen, a cyano group, a carbonyl group, a carbonamido group, a sulfonamido
group, a carboxy group, a sulfo group, an alkyl group, an aryl group, an alkoxy
group, an aryloxy group, an alkylthio group, an arylthio group or an arylsulfonyl
n represents 1, 2, or 3;
each X is located at a position of the phenyl ring meta or para to the sulfonyl
group and is independently selected from the group consisting of alkyl, alkenyl,
alkoxy, aryloxy, acyloxy, acylamino, sulfonyloxy, sulfamoylamino, sulfonamido,
ureido, oxycarbonyl, oxycarbonylamino, and carbamoyl groups; and
Z represents a hydrogen atom or a group which can be split off by the reaction of
the coupler with an oxidized color developing agent;
provided that when R1 is an alkyl group of 4 carbon
atoms, R2 is a phenyl group which has an electron withdrawing group
having a Hammett's Sigma value greater than 0 in a position meta or para to the
amido group and has no group having a Hammett's Sigma value greater than 0 in a
position ortho to the amido group.
The element of claim 1 wherein R1 is hydrogen.
The element of claim 1 or 2 wherein R2 is a phenyl group.
The element of claim 3 wherein the phenyl group is substituted with a member
selected from the group consisting of cyano, halogen, carbonyl, oxysulfonyl, sulfoxide,
sulfamoyl, carboxy, sulfonamido, and carbamoyl groups.
The element of claim 4 wherein R2 is selected from the group consisting
of a 4-chlorophenyl, 3,4-dichlorophenyl, 4-cyanophenyl, 3-chloro-4-cyanophenyl,
pentafluorophenyl, 4-carbonamidophenyl, and a 4-sulfonamidophenyl group.
The element of claims 1-5 wherein at least one X is selected from the group
consisting of alkyl, alkoxy, carboxy, sulfonamido, and halogen.
The element of claim 6 wherein at least one X represents a linear alkyl group
having 12-18 carbon atoms.
The element of claim 1 wherein R2 is an unsubstituted phenyl group
or a phenyl group substituted by a halogen, cyano, or a sulfonamido group.
The element of claim 1 wherein Z is halogen.
The element of claim 1 wherein the element comprises a reflective support
The element of claim 1 wherein R1 is a methyl, ethyl, n-propyl,
isopropyl or butyl group.
The element of claim 1 wherein X is an alkoxy group.
The element of claim 1 wherein at least one X is para to the sulfonyl group.
The element of claim 1 wherein at least one X is meta to the sulfonyl group.
The element of claim 1 wherein X is an alkyl group.
The element of claim 1 wherein the LBW of the dye obtained upon coupling with
4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl) aniline sesquisulfate hydrate
in di-n-butyl phthalate is 66 nm. or less.
Elément photographique comprenant une couche d'émulsion aux halogénures d'argent
photosensibles à laquelle est associé un coupleur formateur de colorant cyan ayant
la formule (I) :
dans laquelle :
R1 représente un atome d'hydrogène ou un groupe alkyle choisi parmi
les groupes méthyle, éthyle, n-propyle, isopropyle et butyle ;
R2 représente un groupe aryle non substitué ou substitué par un atome d'halogène,
un groupe cyano, un groupe carbonyle, un groupe carbonamido, un groupe sulfonamido,
un groupe carboxy, un groupe sulfo, un groupe alkyle, un groupe aryle, un groupe
alcoxy, un groupe aryloxy, un groupe alkylthio, un groupe arylthio ou un groupe
n est égal à 1, 2 ou 3 ;
chaque substituant X est situé sur le noyau phényle en position méta ou para
par rapport au groupe sulfonyle et est choisi séparément dans le groupe constitué
des groupes alkyle, alcényle, alcoxy, aryloxy, acyloxy, acylamino, sulfonyloxy,
sulfamoylamino, sulfonamido, uréido, oxycarbonyle, oxycarbonylamino et carbamoyle
Z représente un atome d'hydrogène ou un groupe qui peut être séparé par la
réaction du coupleur avec un développateur chromogène oxydé ;
à condition que, lorsque R1 représente un groupe alkyle
ayant 4 atomes de carbone, R2 représente un groupe phényle qui comprend un groupe
attracteur d'électron ayant une valeur a de Hammett supérieure à 0 en position
méta ou para par rapport au groupe amido et qui ne comprend pas de groupe ayant
une valeur σ de Hammett supérieure à 0 en position ortho par rapport au groupe
Elément photographique selon la revendication 1, dans lequel R1 représente
un atome d'hydrogène.
Elément photographique selon la revendication 1 ou 2, dans lequel R2
un groupe phényle.
Elément photographique selon la revendication 3, dans lequel le groupé phényle
est substitué par un élément choisi dans le groupe constitué des groupes cyano,
halogène, carbonyle, oxysulfonyle, sulfoxyde, sulfamoyle, carboxy, sulfonamido
Elément photographique selon la revendication 4, dans lequel R2 est choisi
dans le groupe constitué des groupes 4-chlorophényle, 3,4-dichlorophényle, 4-cyanophényle,
3-chloro-4-cyanophényle, pentafluorophényle, 4-carbonamidophényle et 4-sulfonamidophényle.
Elément photographique selon les revendications 1 à 5, dans lequel au moins
un substituant X est choisi dans le groupe constitué des groupes alkyle, alcoxy,
carboxy, sulfonamido et halogène.
Elément photographique selon la revendication 6, dans lequel au moins un substituant
X représente un groupe alkyle linéaire contenant 12 à 18 atomes de carbone.
Elément photographique selon la revendication 1, dans lequel R2 représente
un groupe phényle non substitué ou un groupe phényle substitué par un atome d'halogène,
un groupe cyano ou un groupe sulfonamido.
Elément photographique selon la revendication 1, dans lequel Z représente un
Elément photographiqùe selon la revendication 1, dans lequel l'élément comprend
un support réfléchissant.
Elément photographique selon la revendication 1, dans lequel R1 représente
un groupe méthyle, éthyle, n-propyle, isopropyle ou butyle.
Elément photographique selon la revendication 1, dans lequel X représente un
Elément photographique selon la revendication 1, dans lequel au moins un substituant
X est en position para par rapport au groupe sulfonyle.
Elément photographique selon la revendication 1, dans lequel au moins un substituant
X est en position méta par rapport au groupe sulfonyle.
Elément photographique selon la revendication 1, dans lequel X représente un
Elément photographique selon la revendication 1, dans lequel la valeur de LBW
du colorant obtenu lors du couplage avec un sesquisulfate hydraté de 4-amino-3-méthyl-N-éthyl-N-(2-méthanesulfonamidoéthyl)
aniline dans du phtalate de di-n-butyle est inférieure ou égale à 66 nm.