[0001] This invention relates to a color photographic silver halide recording material.
In particular, the invention relates to an improved photographic recording material
comprising a dye image-forming coupler compound.
[0002] Color photographic recording materials generally contain silver halide emulsion layers
sensitized to each of the blue, green and red regions of the visible spectrum, with
each layer having associated therewith a color-forming compound which, respectively,
yields a yellow, magenta or cyan dye. The quality of the resulting color image is
primarily based on the dye hues obtained from the respective color-forming compounds.
[0003] Dye image-forming coupler compounds are frequently employed to provide desired color
images. A problem encountered with such couplers is that the spectral absorption characteristics
of dyes obtained therefrom may not be in the particular narrow region where absorption
is most desired. Frequently, the hue which is obtained may be as little as several
nanometers removed from the optimum desired absorption value, and therefore be rejected
for commercial use notwithstanding this slight difference. Conversely, a resulting
dye may have an absorption maximum which is considerably shorter than a desired value.
[0004] Attempts to alter absorption characteristics of dyes obtained from dye image-forming
coupler compounds are usually focused on alterations of the structures of coupler
compounds. This approach, while enjoying some measure of success, is not only time
consuming, but also involves the expense of highly focused research programs. Success
with such programs is not predictable so that improvements in final hue values have
been elusive, even after concentrated research efforts.
[0005] Some coupler solvents are known to cause shifts in absorption values of dyes. For
example, U. S. Patent 3,676,137 describes use of a phosphate ester of a high boiling
coupler solvent to shift absorption of a cyan dye to a shorter wavelength in order
to reduce excessive red wavelength absorption. Alternatively, shifting absorption
of a pyrazolone azomethine dye to a longer wavelength by use of a phenolic compound
is known from
Journal of the American Chemical Society,
73 919 (1951).
[0006] Japanese Patent Publication No. 59(1984) - 204041 describes use of sulfamide compounds
with cyan dye image-forming couplers to improve light fastness, to reduce unwanted
green absorption and to reduce loss of density caused by bleach operations in dyes
obtained from such couplers. This publication also suggests addition of other compounds
that form dyes by oxidative coupling with primary amine color developing agents, such
as magenta and yellow coupler compounds. However, there is no teaching or suggestion
in this publication that a sulfonamide compound can be used to alter absorption characteristics
of dyes derived from dye image-forming couplers or that particular compounds employed
in this invention would be useful for this purpose.
[0007] Accordingly, the object of the present invention is to provide a color photographic
silver halide recording material having the capability of imparting slight as well
as relatively large alterations in the absorption properties of a dye to obtain a
desired spectral absorption which is different from the inherent absorption characteristics
of the dye.
[0008] This object is achieved with a color photographic recording material which comprises
a support having thereon a light-sensitive silver halide emulsion layer, a dye image-forming
coupler capable of forming a dye by reaction with oxidized color developing agent
and associated with the coupler, a sulfonamide compound which is capable of altering
the spectral absorption of a dye formed from the coupler, said sulfonamide compound
having the structural formula:
R¹SO₂NHR²
wherein:
R¹ and R² are substituted or unsubstituted alkyl having from 1 to 20 carbon atoms
or phenyl which may be substituted with alkyl having from 1 to 4 carbon atoms or with
sulfamoyl having the formula - SO₂NHR³ wherein R³ is alkyl of from 1 to 12 carbon
atoms, or with halogen, wherein at least one of R¹ or R² is phenyl.
This invention also relates to a color photographic record comprising a dye formed
by a coupling reaction between a dye image-forming coupler and oxidized silver halide
developing agent, which recording material comprises, in association with the dye,
a sulfonamide compound having the structural formula:
R¹SO₂NHR²
wherein;
R¹ is an alkyl or an aryl group; and
R² is hydrogen or as defined for R¹.
Alkyl groups which are represented by R¹ and R² preferably have from about 1 to about
12 carbon atoms. The carbon chain can be straight or branched and can be substituted.
[0009] The type of substituents which can be present on the alkyl groups include hydroxy,
halogen atoms, particularly chlorine and bromine or - SO₂R³ wherein R³ is as described
above.
[0010] Chlorine is a preferred halogen substituent on a phenyl group inasmuch as it provides
good stability properties and is least expensive to manufacture.
[0011] The described sulfonamide compounds are readily synthesized by reacting a sulfonyl
chloride compound of the formula R¹SO₂Cl with ammonia or with a primary amine compound
of the formula R²NH₂, according to procedures well known in the art. R¹ and R² have
the meanings as described above.
[0012] There are no particular restrictions on the quantity of a sulfonamide compound which
can be employed with a dye image-forming coupler either alone or in combination with
known coupler solvents. Generally, it is desirable that the quantity of sulfonamide
compound, with respect to each part by weight of coupler, be from about 0.05 to about
10 parts, preferably from about 0.2 to about 3 parts by weight of coupler compound.
As the amount of sulfonamide compound increases, relative to the amount of coupler
compound employed, there is usually a detectable increase in the extent of hue shift
in the dye. However, the particular choice of coupler, of sulfonamide compound or
the presence of one or more coupler solvents, all tend to influence the type and the
extent of spectral absorption change in the resulting dye.
[0013] When the coupler compound is added to a silver halide emulsion, conventional procedures
may be employed. For example, the coupler can first be dissolved in one or more known
coupler solvents, such as di-n-butyl phthalate (DBP), and then be mixed with a sulfonamide
compound as described herein. If desired, the coupler compound can be mixed with a
sulfonamide compound, where these compounds are sufficiently compatible, so that known
coupler solvents may not be needed. The resulting mixture or solution is then dispersed
in aqueous gelatin, preferably containing a surfactant, and the dispersion is added
to a silver halide emulsion which can then be coated by known techniques.
[0014] Specific sulfonamide compounds which are useful for shifting absorption values of
dyes obtained by the reaction of dye image-forming coupler compounds with oxidized
color developing agents include the following:

[0015] Couplers which form cyan dyes upon reaction with oxidized color developing agents
are described in such representative patents and publications as U. S. Patent Nos.
2,474,293; 2,772,162, 2,801,171; 2,895,826; 3,002,836; 3,419,390; 3,476,563; 3,779,763;
3,996,253; 4,124,396; 4,248,962; 4,254,212; 4,296,200; 4,333,999; 4,443,536; 4,457,559;
4,500,635 and 4,526,864, the disclosures of which are incorporated herein by reference.
[0016] Preferred cyan coupler structures are phenols and naphthols which form cyan dyes
on reaction with oxidized color developing agent. These preferred structures include
the following moieties:

where R⁴ represents a ballast group, R⁵ represents one or more halogen atoms (e.g.,
chloro, fluoro), lower alkyl (e.g., methyl, ethyl, butyl) or lower alkoxy (e.g., methoxy,
ethoxy, butoxy) groups and X is hydrogen or a coupling off group. An especially preferred
R⁴ group on a C-3 type structure is

as described in U.S. Patent 4,333,999.
[0017] Couplers which form magenta dyes upon reaction with oxidized color developing agents
are described in such representative patents and publications as: U.S. Patent Nos.
1,969,479; 2,311,082; 2,343,703; 2,369,489; 2,600,788; 2,908,573; 3,061,432; 3,062,653;
3,152,896; 3,519,429; 3,725,067; 4,120,723; 4,500,630; 4,540,654 and 4,581,326; and
European Patent Publication Nos. 170,164 and 177,765; and copending U.S. Application
Serial Numbers 23,517 of S. Normandin et al; 23,518 of R. Romanet et al; 23,519 of
A. Bowne et al and 23,520 of A. Bowne et al, all filed March 9, 1987, the disclosures
of which are incorporated herein by reference.
[0018] Preferred magenta couplers include pyrazolones compounds having the structural formulae:

pyrazolotriazole compounds having the structural formulae:

pyrazolobenzimidazole compounds having the structural formulae:

and indazole compounds having the structural formula:

wherein
X is as defined above;
R⁴ is a ballast group;
R⁶ is halogen (e.g., chloro, fluoro), alkyl or alkoxy having from 1 to 4 carbon atoms,
phenyl or substituted phenyl (e.g., 2,4,6-trihalophenyl);
R⁷ is hydrogen or a monovalent organic radical, for example a saturated or unsaturated
alkyl group having from 1 to about 20 carbon atoms (methyl, ethyl, propyl, butyl,
decyl, dodecyl, heptadecyl, octadecyl); a cycloalkyl group (e.g. cyclohexyl); an aralkyl
group (e.g. benzyl); an aryl group (e.g. phenyl, alkoxyphenyl in which the alkyl or
alkoxy radical has from 1 to about 20 carbon atoms, nitrophenyl, aminophenyl, acylaminophenyl,
alkylaminophenyl, naphthyl, diphenyl, diphenylether, diphenylthioether); a heterocyclic
group (e.g. α-furyl, α-benzofuryl, α-pyridyl); an amino, hydroxy or carboxylic acid
group, it being possible for the hydrogen atoms of these groups to be substituted,
for instance by a mono- or dialkylamino group in which the alkyl groups have from
1 to about 20 carbon atoms; a cycloalkylamino group; an amino group in which one hydrogen
atom is replaced by a pyrazolo-[1,5-a]-benzimidazolyl radical which is bonded in 3-
position to said nitrogen atom so that couplers result in which two pyrazolo-[1,5-a]-benzimidazolyl
radicals are connected by an amino group, and in which the remaining hydrogen atom
may be replaced by a substituent such as an alkyl-, aryl-, aralkyl- or acyl- radical;
an acylamino group in which the acyl radical is derived from an aliphatic, aromatic
or heterocyclic carboxylic acid; a carboxylic acid group which is esterified by means
of an aliphatic, cycloaliphatic or aromatic alcohol or by an aromatic compound having
a phenolic hydroxy group; or a carboxyamido group in which the amido group may be
substituted for example by a saturated or unsaturated alkyl, aralkyl, aryl or heterocyclic
group;
R⁸ represents a hydrogen atom, a sulphonic acid or a carboxylic acid group; a halogen
atom (e.g. chlorine or bromine); or an azo radical -N=NR¹³, wherein R¹³ can be an
aromatic or heterocyclic radical (phenyl, naphthyl, diphenyl, diphenylether, benzthiazolyl,
pyridyl, quinolyl or pyrazolyl) which may be substituted such as by an alkyl group
having from 1 to about 20 carbon atoms, hydroxy, alkoxy, halogen, amino, substituted
amino, nitro, sulphonic acid or carboxylic acid groups;
R⁸ represents a divalent radical such as

wherein R¹⁰ can be alkyl, aralkyl, especially phenyl, phenyl substituted preferably
in the p-position by a tertiary amino group such as a dialkylamino group in which
at least one of the alkyl groups is substituted by carboxy, sulpho, hydroxy, alkoxy,
carboxylalkyl, cyano or the divalent radical

wherein R¹¹ and R¹² represent aliphatic, aromatic, araliphatic or heterocyclic radicals.
[0020] Couplers which form yellow dyes upon reaction with oxidized color developing agent
are described in such representative U. S. Patents as Nos. 2,298,443; 2,875,057; 2,407,210;
3,265,506; 3,384,657; 3,408,194; 3,415,652; 3,447,928; 3,542,840; 4,046,575; 3,894,875;
4,095,983; 4,182,630; 4,203,768; 4,221,860; 4,326,024; 4,401,752; 4,443,536; 4,529,691;
4,587,205; 4,587,207 and 4,617,256 the disclosures of which are incorporated herein
by reference.
[0021] Preferred yellow dye image-forming couplers are acylacetamides, such as benzoylacetanilides
and pivalylacetanilides. Structures of such preferred coupler moieties are:

where R¹³ is as defined above, R¹⁴ is hydrogen or one or more halogen, lower alkyl
(e.g. methyl, ethyl) or a ballast (e.g. alkoxy of 16 to 20 carbon atoms) group and
X is a coupling off group.
[0022] Photographic elements in which the photographic couplers of this invention are incorporated
can be simple elements comprising a support and a single silver halide emulsion layer,
or they can be multilayer, multicolor elements. The coupler compounds of this invention
can be incorporated in the silver halide emulsion layer or in another layer, such
as an adjacent layer, where they will come into reactive association with oxidized
color developing agent which has developed silver halide in the emulsion layer. The
silver halide emulsion layer can contain, or have associated therewith other photographic
coupler compounds, such as color forming couplers, colored masking couplers, etc.
These other photographic coupler compounds can form dyes of the same or different
color and hue as the photographic coupler compounds of this invention. Additionally,
the silver halide emulsion layer can contain addenda conventionally contained in such
layers.
[0023] A typical multilayer, multicolor photographic element according to this invention
comprises a support having thereon a red-sensitive silver halide emulsion layer have
associated therewith a cyan dye image-forming coupler compound, a green-sensitive
silver halide emulsion layer having associated therewith a magenta dye image-forming
coupler compound and a blue-sensitive silver halide emulsion layer having associated
therewith a yellow dye image-forming coupler compound, wherein at least one of the
dye image-forming coupler compounds has associated therewith a sulfonamide compound
as described herein. Each silver halide emulsion layer can be composed of one or more
layers and the layers can be arranged in different locations with respect to one another.
Typical arrangements are described in U.S. Patent Nos. 3,227,554; 3,620,747; 3,843,369;
and 4,400,463 and in U.K. Patent No. 923,045.
[0024] The light sensitive silver halide emulsions can include coarse, regular or fine grain
silver halide crystals or mixtures thereof and can be comprised of such silver halides
as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver
chloroiodide, silver chlorobromoiodide and mixtures thereof. The emulsions can be
negative-working or direct-positive emulsions. They can form latent images predominantly
on the surface of the silver halide grains or predominantly on the interior of the
silver halide grains. They can be chemically and spectrally sensitized. The emulsions
typically will be gelatin emulsions although other hydrophilic colloids can be used
in accordance with usual practice.
[0025] The support can be of any suitable material used with photographic elements. Typically,
a flexible support is employed, such as a polymeric film or paper support. Such supports
include cellulose nitrate, cellulose acetate, polyvinylacetal, polyethylene terephthalate,
polycarbonate and resinous materials as well as glass, paper or metal. Paper supports
can be acetylated or coated with baryta and/or an α-olefin polymer, particularly a
polymer of an α-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene
or ethylene-butene copolymers.
[0026] Further details regarding silver halide emulsions and elements, and addenda incorporated
therein can be found in
Research Disclosure, December 1971, Item 9232, Paragraphs I through XVIII.
Research Disclosure is published by Industrial Opportunities Ltd., Homewell, Havant, Hampshire, P09 1EF,
United Kingdom.
[0027] The terms "in association" or "associated with" are intended to mean that materials
can be in either the same or different layers, so long as the materials are accessible
to one another.
[0028] The following examples further illustrate the invention. Unless otherwise indicated
all parts, percents and ratios are by weight.
EXAMPLE I
[0029] Photographic elements employing coupler chemistry to show hue shifting with a 1-aryl-3-anilino-5-pyrazolone
coupler and various sulfonamide compounds were prepared by coating on a paper support
a silver chlorobromide emulsion layer (15 mole % chloride) comprising green sensitized
0.3 µm grains (0.42 gAg/m²). Each layer also contained gelatin (1.6 g/m²) and the
magenta coupler M-1 (0.52 g/m²) as described above, dispersed in the coupler solvent
di-n-butylphthalate (DBP) (0.52 g/m² when used alone) or in combination with DBP and
a sulfonamide compound (SC), each at 0.26 g/m² as described below in Table I.
[0030] Each coating was exposed imagewise through a graduated-density test object to provide
a maximum density image and was processed at 33°C employing the color developer solution
described below, and then subjected to 1.5 minutes in the bleach-fix bath described
below, washed and dried.
Color Developer (pH 10.08)
[0031] Triethanolamine 11 mL
Benzyl alcohol 14.2 mL
Lithium chloride 2.1 g
Potassium bromide 0.6 g
Hydroxylamine sulfate 3.2 g
Potassium sulfite (45% solution) 2.8 mL
1-Hydroxyethylene-1,1-diphosphoric acid (60%) 0.8 mL
4-Amino-3-methyl-N-ethyl-N-β-methanesulfonamido)ethylaniline sulfate hydrate 4.35
g
Potassium carbonate (anhydrous) 28 g
Water to make 1.0 liter
Bleach-Fix Bath (pH 6.8)
[0032] Ammonium thiosulfate 104 g
Sodium hydrogen sulfite 13 g
Ferric ammonium ethylenediamine tetraacetic acid 65.6 g
Ethylenediamine tetraacetic acid 6.56 g
Ammonium hydroxide (28%) 27.9 mL
Water to make 1 liter
[0033] Transmission density versus wavelength data were obtained to determine the λmax of
the dye in an environment with the addition of different sulfonamide compounds. Results
are recorded in Table I which reflects the coupler: DBP: sulfonamide compound (SC)
ratio used in each test.
Table I
Sulfonamide Compound |
Weight Ratio Coupler:DBP:SC |
λmax, nm |
None(control) |
2 : 2 : 0 |
540 |
1 |
2 : 1 : 1 |
542 |
7 |
2 : 1 : 1 |
542 |
11 |
2 : 1 : 1 |
542 |
14 |
2 : 1 : 1 |
544 |
15 |
2 : 1 : 1 |
543 |
[0034] As is demonstrated by the data in Table I, hue shifts are highly subtle and vary
only a few nanometers from the control when using sulfonamide compounds as described
herein. These variations in wavelength shifts offer a high degree of manipulative
control and provide an excellent, inexpensive means to obtain particularly desired
hue values.
EXAMPLE 2 - Tests using preformed dyes.
[0035] A solution of 6.25% photographic grade gelatin and 0.2% duPont Alkanol XC were added
to each solution of preformed dye in 1ml ethyl acetate with coupler solvent di-n-butylpthalate
(DBP) or sulfonamide compound (SC) or a mixture of DBP and SC. The dyes and the sulfonamide
compounds are described below. The amounts used of each are shown in Table II.
[0036] This mixture was passed five times through a colloid mill and 0.2 ml (10% solution)
Olin Corp. 10G surfactant and 0.05 ml (5.0% solution) formaldehyde were added. The
milled mixture was then coated on a poly(ethyleneterephthalate) support, 100 µm wet
thickness, and dried at 49°C. After 24 hours, the coating was washed for 5 minutes,
dried, and spectrophotometric absorption maxima values were obtained.
[0037] Table II shows that sulfonamide compounds as described herein, are capable of shifting
the absorption maxima of dyes derived from dye-forming couplers to usefully longer
wavelengths. The extent of hue shifting depends upon the specific dye and sulfonamide
compounds used and also varies with the dye: sulfonamide compound ratio. The Table
reflects the Dye:DBP:sulfonamide compound (SC) ratio used in each test.
Table II
Dye Compound* |
Sulfonamide Compound(SC) |
Weight Ratio Dye:DBP:SC |
λ-max, nm |
A |
none(control) |
1 : 3 : 0 |
532 |
A |
1 |
1 : 2 : 1 |
535 |
A |
1 |
1 : 0 : 3 |
539 |
A |
2 |
1 : 2 : 1 |
533 |
B |
none(control) |
1 : 3 : 0 |
533 |
B |
1 |
1 : 0 : 3 |
543 |
C |
none(control) |
1 : 3 : 0 |
639 |
C |
1 |
1 : 2 : 1 |
645 |
C |
1 |
1 : 0 : 3 |
653 |
C |
2 |
1 : 2 : 1 |
644 |
[0038] As is demonstrated by the data in Table II, hue shifts to longer wavelengths, varying
from a few nanometers to as much as 14 nanometers, are possible with sulfonamide compounds
as described herein. These variations in wavelength shifts offer a high degree of
manipulative control and provide an excellent, inexpensive means to obtain particularly
desired hue values with a variety of dye types.
