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| Publication Date |
May 8, 1990 |
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| Parent Case |
This is a continuation in part of U.S. patent application Ser. No. 184,526
filed Apr. 21, 1988, now abandoned.
This invention relates to a photographic element, and in particular to a
color photographic element containing a scavenger compound for oxidized
developing agent.
It is known in the art to add a scavenger to a photographic element in
order for the scavenger to interact with oxidized developing agent to
prevent it from reacting within the element at an undesired location or at
an undesired point in time. The presence of oxidized developing agent at
an unwanted location can cause stain or fog and thereby affect the quality
of the color images obtained.
Known scavengers for oxidized developing agents include ballasted
hydroquinone compounds as described in U.S. Pat. No. 3,700,453 wherein the
ballasting groups are secondary alkyl substituents having from 9 to 20
carbon atoms. Also known are ballasted sulfonamidophenols such as
described in U.S. Pat. No. 4,205,987 and in Research Disclosure, February
1979, Item No. 17842. (Research Disclosure is published by Kenneth Mason
Publications, Ltd., The Old Harbourmaster's, 8 North Street, Emsworth,
Hampshire P010 7DD, ENGLAND, and is referred to hereinafter simply as
"RD"). However, none of these references suggests use of hydrazide type
compounds as scavenging agents for oxidized developer moieties.
U.S. Pat. No. 4,684,604 relates to compounds capable of releasing
photographically useful groups (PUG). The compounds comprise a hydrazide
moiety which is capable of being oxidized to an azo group. The azo group
then causes release of the desired PUG. The hydrazide moiety is attached
to a heteroatom of a moiety containing the PUG, the attachment being
through a link which comprises an acidic group or an active methylene
group positioned adjacent to an acidic group. Compounds of the instant
invention do not release photographically useful groups; these compounds
are therefore more stable, simpler in structure and easier to prepare.
Moreover, this patent does not disclose or suggest the use of hydrazide
compounds for scavaging oxidized developer moieties.
U.S. Pat. No. 4,224,401 discloses a process for producing high contrast
negative silver images utilizing high sensitivity silver bromide or silver
bromoiodide emulsions and hydrazide compounds. The hydrazide compounds
function as nucleating agents and can comprise substituted phenyl groups.
Moreover, the compounds of the '401 patent, whether ballasted or
unballasted, do not function as effective scavenger compounds for oxidized
developing agents as shown below by comparative data. This U.S. Patent
neither discloses nor suggests the use of such hydrazide compounds as
scavengers for oxidized developing agents in color photographic elements.
Accordingly, it is desirable to reduce, or to eliminate, oxidized
developing agent remaining in color photographic elements. Prior art
hydrazine compounds have not been used or suggested for this purpose.
In accordance with the present invention there is provided a color
photographic element which comprises a support, at least one silver halide
emulsion layer and a scavenger compound for oxidized developing agent
wherein the scavenger compound is a hydrazide having the structural
formula:
##STR1##
wherein: R.sup.1, represents an electron donating group;
R.sup.2 represents hydrogen or alkyl, alkoxy, aryl, aryloxy, aralkyl or
amino of the formula --NHR.sup.3, where R.sup.3 is phenyl or benzyl; with
the proviso that at least one of R.sup.1 and R.sup.2 (a) represents a
ballast group of sufficient size as to render the hydrazide compound non
diffusible in the photographic element prior to development in alkaline
processing solution and (b) comprises a polar group, and
n is 1 or 2.
R.sup.1 substituents, which are electron donating groups, include alkyl,
which can be substituted or unsubstituted, straight or branched chain,
having from 1 to about 20 carbon atoms, preferably from about 8 to about
16 carbon atoms; alkoxy, which can be substituted or an unsubstituted,
straight or branched chain, having from 1 to about 20 carbon atoms,
preferably from about 8 to about 16 carbon atoms; carboxy, carbonamido
having the formula NR.sup.4 COR.sup.5 ; sulfonamido having the NR.sup.4
SO.sub.2 R.sup.5 ; or amino having the formula --NR.sup.4 R.sup.5 where
R.sup.4 is hydrogen or alkyl having from 1 to about 8 carbon atoms and
R.sup.5 is as defined for R.sup.4 or is a benzyl or a phenyl group which
may be substituted.
R.sup.2 substituents which are alkyl or alkoxy can be as defined for these
same substituents in R.sup.1, or R.sup.2 can be aryl or aryloxy having
from 6 to about 10 ring carbon atoms, such as phenyl, phenoxy, naphthyl or
naphthoxy.
When R.sup.2 represents phenyl or phenoxy it is preferred that the aryl
ring have a hydrogen bonding substituent in a position ortho to the point
of attachment of the carbonyl group to a hydrazide nitrogen atom.
Preferred hydrogen bonding groups include hydroxy, primary or secondary
amino groups of the formula --NR.sup.4 R.sup.5, sulfonamido of the formula
-NHSO.sub.2 R.sup.4, carbonamido of the formula -NR.sup.4 COR.sup.5 and
ureido of the formula -NHCONHR.sup.4 where R.sup.4 and R.sup.5 can be
hydrogen or alkyl of from 1 to about 8 carbon atoms and R.sup.5 is as
defined for R.sup.4 or a benzyl or phenyl group.
These groups can also be present as substituents on R.sup.2 alkyl groups.
A polar group which can represent R.sup.1 or R.sup.2 can be a single group
or a combination of groups which have a .pi. constant which is more
negative than -1.0. The .pi. constant is defined by C. Hansch, A. Leo, S.
Unger, K. Hwan Kim, D. Nikaitani and E. T. Lien, in JOURNAL OF ORGANIC
CHEMISTRY, 11, 1973 (pp. 1207-1216). The R.sup.1 or R.sup.2 polar group or
groups include, but are not limited to,
##STR2##
These groups tend to increase the surfactant nature of the hydrazine
during alkaline processing.
The alkyl, alkoxy, aryl, aryloxy, aralkyl and benzyl groups which are
represented by one or more of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 can be substituted with halogen atoms, for example chlorine, or
with haloalkyl groups, for example trifluoromethyl, or with
##STR3##
Typical compounds which fall within the above-presented structural formula
include:
##STR4##
The compounds of the present invention are either known per se or are
structurally similar to known compounds. Their preparation can be
accomplished using existing technology. For example, Compound No. 1 is
prepared according to the following procedure:
SYNTHESIS OF COMPOUND NO. 1
##STR5##
p-methoxyphenylhydrazide hydrochloride (5.0 g) was dissolved in
acetonitrile (200 ml) treated with N,N dimethylaniline (10 g) and cooled
to <10.degree. C. under nitrogen. The
2-(4-(4-acetoxyphenylsulfonyl)-phenoxy)dodecyl chloride was dissolved in
tetrahydrofuran (THF) (50 ml) and added dropwise over a 15 minute period.
The reaction mixture was allowed to warm to room temperature while
stirring for 2 hours. The reaction was partitioned with ethyl acetate
(EtOAc) and 10% HCl. The organic layer was washed again with 10% HCl,
dried with MgSO.sub.4 and concentrated to a thick oil.
The thick oil was dissolved in 100 ml of methanol and treated with 5 ml of
conc HCl and stirred overnight at room temperature. The solution was
partitioned between EtOAC and water and the organic layer was washed with
water, separated, dried with MgSO.sub.4 and concentrated to a thick oil.
This oil was dissolved in dichloromethane and concentrated (twice) and
finally dissolved in 20 ml of dichloromethane and allowed to stand
overnight to crystallize. The solid was collected by filtration and washed
with cold methylene chloride and air dried to yield 15 g (48%) of the
desired product (mp 148.degree.-150.degree. C.).
SYNTHESIS OF COMPOUND NO. 21
##STR6##
Lauroyl chloride (72.2 g) and pivalic acid (33.7 g) were dissolved in 300
ml of acetonitrile and treated with triethylamine (33.4 g). The reaction
mixture was stirred at room temperature for 3 hours. 5-aminosalicyclic
acid was added to the reaction mixture and the reaction was stirred at
room temperature overnight. The solid which formed was filtered off and
washed first with acetonitrile, and then with 10% HCl solution. The
resulting product was recrystallized from methanol and dried overnight in
the vacuum oven at room temperature.
This compound (10 g) was treated with 50 ml of thionyl chloride and stirred
at room temperature for 3 hours and concentrated to a thick oil. The thick
oil was dissolved in 50 ml of tetrahydrofuran and added dropwise to a
solution of phenylhydrazine (3.2 g) and N,N dimethaniline (3.6 g) in
tetrahydrofuran cooled by a dry ice acetone bath. The resulting reaction
mixture was kept cold and stirring for three hours. A solution of aqueous
10% HCl (200 ml) was added and the reaction mixture was brought to room
temperature. The reaction mixture was partitioned with ethyl acetate. The
organic layer was washed with 10% HCl solution (200 ml), dried with
magnesium sulfate and concentrated. The product was purified by column
chromatography on silica gel to yield 9 g (70%) of the desired product mp
(153.degree. C).
SYNTHESIS OF COMPOUND NO. 27
##STR7##
To a round bottom flask containing methoxyethoxyethanol was added phosgene
in toluene. This reaction mixture was stirred under nitrogen at room
temperature overnight and the reaction was concentrated to one third
volume. This solution was added dropwise to a solution of p-nitrophenyl
hydrazine hydrochloride (32.2 g) and N,N dimethyl aniline (41.2 g) in
acetonitrile (300 ml) and the reaction was stirred at room temperature for
3 hours. The reaction mixture was partitioned with ethyl acetate and 10%
HCl solution. The organic layer was washed with 10% HCl solution, dried
with magnesium sulfate and then concentrated to a solid. This material (15
g) was taken up in tetrahydrofuran (50 ml) and treated with 2 g of 10%
palladium on :carbon and shaken with hydrogen at 40 psi overnight. The
reaction was treated with hexadecylsulfonylchloride (16.2 g) and
triethylamine (5.1 g) and stirred at room temperature for 3 hours.
The reaction mixture was filtered through super cell, and then partitioned
with ethyl acetate and 10% HCl. The organic layer was washed with 10% HCl,
dried with magnesium sulfate and concentrated down.
The product was purified with column chromatography using a 30% ethyl
acetate/70% dichloromethane solvent system to yield 19 g (68%) of the
desired product (mp 82.degree. C.).
The scavengers of this invention can be used in the ways and for the
purposes that scavengers for oxidized developing agent are employed in the
art. For example, they can be incorporated in an interlayer between silver
halide emulsion layers sensitive to different regions of the visible
spectrum. Alternatively, they can be in a layer comprising a color forming
material or in a layer comprising other photographic addenda, such as for
example, a layer containing a filter dye or a reflecting agent or a
mordant. When incorporated in a separate layer, such layer can also be an
undercoat layer positioned between all of the silver halide emulsion
layers and a support. The separate layer can also be an overcoat layer
positioned above all of the silver halide emulsion layers.
The amount of scavenger compound employed will depend upon the particular
purpose for which the scavenger is to be used and the degree of scavenging
desired. Typically useful results are obtained when the scavenger is
employed in an amount of between about 5 to about 2000 mg/meter.sub.2.
The scavenger can be incorporated in photographic elements by techniques
known in the art. In certain embodiments, the scavenger can be dissolved
in a high boiling solvent, such as a water insoluble coupler solvent, and
then dispersed either in a silver halide emulsion layer or in a separate
vehicle such as gelatin. Typical useful coupler solvents are moderately
polar solvents such as tritolylphosphate, di-n-butylphthalate, diethyl
lauramide and 2,4-dipentylphenol. Typical vehicles are gelatin and other
hydrophilic colloids commonly employed in silver halide photographic
elements. These vehicles are described in RD, December 1978, Item No.
17643, Section IX. The scavengers can be introduced into the element in a
polymeric latex. Suitable techniques for dispersing the scavengers in a
latex are described in U.S. Pat. Nos. 4,203,716 and 4,214,047 and in RD,
July 1977, Item 15930 and July 1980, Item 19551.
Multicolor photographic elements employed in this invention contain dye
image forming units sensitive to each of the three primary regions of the
spectrum. Each unit can be comprised of a single emulsion layer or of
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 order as is known in the art. In an alternative
format, the emulsion or emulsion layers can be disposed as one or more
segmented layers, e.g., as by the use of microvessels or microcells, as
described in U.S. Pat. No. 4,362,806.
A preferred photographic element according to this invention comprises a
support bearing at least one blue sensitive silver halide emulsion layer
having associated therewith a yellow image dye-providing material, at
least one green sensitive silver halide emulsion layer having associated
therewith a magenta image dye providing material and at least one red
sensitive silver halide emulsion layer having associated therewith a cyan
image dye providing material, the element also containing a scavenger of
this invention.
The elements of the present invention can contain additional layers
conventional in photographic elements, such as overcoat layers, spacer
layers, filter layers, antihalation layers, PH lowering layers (sometimes
referred to as acid layers), neutralizing layers, timing layers, opaque
reflecting layers and opaque light absorbing layers. The support can be of
any material known to be suitable for use with photographic elements.
Typical supports include polymeric films, paper (including polymer coated
paper), metal or glass. Details regarding supports and other layers of the
photographic elements useful in this this invention are contained in RD,
December 1978, Item 17643, referred to above.
The light sensitive silver halide emulsions employed in the photographic
elements of this invention 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, for example, tabular grain light
sensitive silver halide emulsions. 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 in the interior of the silver
halide grains. They can be chemically and spectrally sensitized in
accordance with usual practices. The emulsions typically will be gelatin
emulsions although other hydrophilic colloids can be used in accordance
with usual practice. Details regarding the silver halide emulsions are
contained in RD, Item 17643, December, 1978 and the references listed
therein.
The photographic silver halide emulsions can contain other addenda
conventional in the photographic art. Useful addenda are described, for
example, in RD, December 1978, Item 17643. Useful addenda include spectral
sensitizing dyes and desentizers, antifoggants, masking couplers, DIR
couplers, DIR compounds, anti stain agents, image dye stabilizers,
absorbing materials such as filter dyes and UV absorbers, light scattering
materials, coating aids, plasticizers and lubricants, and the like.
Depending upon the dye image providing material employed in the
photographic element, such addenda can be incorporated in the silver
halide emulsion layer or in a separate layer associated with the emulsion
layer. The dye image providing material can be any of a number known in
the art, such as dye forming couplers, bleachable dyes, dye developers and
redox dye releasers. The particular material employed will depend on the
nature of the element and the type of image desired.
Dye image providing materials employed with conventional color materials
designed for processing with separate solutions are preferably dye forming
couplers; i.e., compounds which couple with oxidized developing agent to
form a dye. Preferred couplers which form :cyan dye images are phenols and
napthols. Preferred couplers which form magenta dye images are pyrazolones
and pyrazolotriazoles. Preferred couplers which form yellow dye images are
benzoylacetanilides and pivalylacetanilides.
The developing agents which can be used to develop the photographic
elements of this invention, the oxidized form of which can be reduced by
the scavengers of this invention, include hydroquinones, aminophenols,
3-pyrazolidones and phenylenediamines. Some of these developing agents,
when used for certain applications, are referred to in the art as electron
transfer agents. The particular developing agent employed will depend on
the particular type of photographic element to be processed. For example,
phenylenediamines are the developers of choice for use with color
photographic elements containing dye forming couplers, while
3-pyrazolidones are frequently used with image transfer materials
containing redox dye releasers.
Representative developing agents include: hydroquinone,
N-methylaminophenol; 1-phenyl-3-pyrazolidone;
1-phenyl-4,4-dimethyl-3-pyrazolidone;
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone;
N,N-diethyl-p-phenylenediamine;-3-methyl-N,N-diethyl-p-phenylenediamine;
3-methoxy-N,N-diethyl-p-phenylenediamine; and
N,N,N',N'-tetramethyl-p-phenylenediamine.
The term "non-diffusible" used herein has the meaning commonly applied to
the term in photography and denotes materials that for all practical
purposes do not migrate or wander through organic colloid layers of a
photographic element, such as gelatin, when the element is processed in an
alkaline medium, preferably when processed in a medium having a pH of 10
or greater. The term "diffusible" has the converse meaning and denotes the
materials having the property of diffusing effectively through the colloid
layers of photographic elements in an alkaline medium.
The term "associated therewith" as used herein is intended to mean that the
materials can be in either the same or different layers so long as the
materials are accessible to one another during processing. |
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