U.S. patent application number 10/661119 was filed with the patent office on 2005-03-24 for photographic element containing improved pyrazolotriazole coupler.
Invention is credited to Crawley, Michael W., Fischer, Susan M., Romanet, Robert F..
Application Number | 20050064349 10/661119 |
Document ID | / |
Family ID | 34312722 |
Filed Date | 2005-03-24 |
United States Patent
Application |
20050064349 |
Kind Code |
A1 |
Romanet, Robert F. ; et
al. |
March 24, 2005 |
Photographic element containing improved pyrazolotriazole
coupler
Abstract
Disclosed is photographic element comprising a light-sensitive
silver halide emulsion layer containing a
1H-pyrazolo[1,5-b][1,2,4]triazole containing in the 6-position a
fully substituted methyl group, in the 7-position a hydrogen atom
or halogen atom, and in the 2-position a phenyl group substituted
in the meta position with a sulfonamide group free of amide,
sulfonamide, ureido or ester groups and bearing at least 9
(cyclo)aliphatic carbon atoms. The element exhibits improved
resistance to coupler crystallization.
Inventors: |
Romanet, Robert F.;
(Rochester, NY) ; Crawley, Michael W.; (Watford,
GB) ; Fischer, Susan M.; (Rochester, NY) |
Correspondence
Address: |
Paul A. Leipold
Patent Legal Staff
Eastman Kodak Company
343 State Street
Rochester
NY
14650-2201
US
|
Family ID: |
34312722 |
Appl. No.: |
10/661119 |
Filed: |
September 12, 2003 |
Current U.S.
Class: |
430/502 |
Current CPC
Class: |
G03C 7/3835 20130101;
C09B 55/009 20130101 |
Class at
Publication: |
430/502 |
International
Class: |
G03C 001/46 |
Claims
What is claimed is:
1. A photographic element comprising a light-sensitive silver
halide emulsion layer containing a
1H-pyrazolo[1,5-b][1,2,4]triazole containing in the 6-position a
fully substituted methyl group, in the 7-position a hydrogen atom
or halogen atom, and in the 2-position a phenyl group substituted
in the meta position with a sulfonamide group free of amide,
sulfonamide, ureido or ester groups and bearing at least 9
(cyclo)aliphatic carbon atoms.
2. The element of claim 1 wherein the sulphonamide group contains
an unsubstituted alkyl group.
3. The element of claim 1 wherein the sulphonamide group contains
an alkyl group substituted with an ether group.
4. The element of claim 1 containing a chloro in the
7-position.
5. The element of claim 1 wherein R.sub.1, R.sub.2, and R.sub.3 are
methyl groups.
6. The element of claim 1 wherein the coupler does not have a
melting point of 140.degree. C. or higher.
7. The element of claim 1 wherein the coupler is represented by
structure (I): 21wherein R.sub.1, R.sub.2, and R.sub.3 are
independently selected unsubstituted alkyl groups comprising of 3
or less carbons with the proviso that one or more of the R.sub.1,
R.sub.2, and R.sub.3 groups can be joined to form a ring; R is a
straight, cyclic or branched aliphatic carbon chain or carbocyclic
group unsubstituted with amide, sulfonamide, ureido, or ester
groups, and containing at least 9 aliphatic carbon atoms; each R'
is an independently selected alkyl or halogen substituent and n is
0 to 4; and X is hydrogen or halogen.
8. The element of claim 7 wherein R.sub.1, R.sub.2, and R.sub.3 are
methyl groups.
9. The element of claim 7 wherein X is Cl.
10. The element of claim 7 wherein R is an unbranched alkyl
group.
11. The element of claim 7 wherein R is a branched alkyl group.
12. The element of claim 7 wherein R is a cycloalkyl group.
13. The element of claim 7 wherein n is 0.
14. The element of claim 7 wherein n is 1 and R' is not an ether
group.
15. The element of claim 1 provided on a reflective support.
16. The element of claim 1 wherein the silver halide is primarily a
silver chloride.
17. A coupler compound represented by formula (I): 22wherein
R.sub.1, R.sub.2, and R.sub.3 are independently selected
unsubstituted alkyl groups comprising of 3 or less carbons with the
proviso that one or more of the R.sub.1, R.sub.2, and R.sub.3
groups can be joined to form a ring; R is a straight, cyclic or
branched aliphatic carbon chain or carbocyclic group unsubstituted
with amide, sulfonamide, ureido, or ester groups, and containing at
least 9 aliphatic carbon atoms; each R' is an independently
selected alkyl or halogen substituent and n is 0 to 4; and X is
hydrogen or halogen.
18. A dye compound obtained by the reaction of a coupler of claim
17 and a paraphenylenediamine developer compound.
19. The dye of claim 18 wherein the para-phenylenediamine compound
is selected from the group consisting of 4-amino-N,N-diethylaniline
hydrochloride, 4-amino-3-methyl-N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl)aniline
sesquisulfate hydrate,
4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline sulfate,
4-amino-3-(2-methanesulfonamidoethyl)-N,N-diethylaniline
hydrochloride, and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine
di-p-toluene sulfonic acid.
Description
FIELD OF THE INVENTION
[0001] This invention relates to novel bicyclic pyrazolo
dye-forming couplers, to photographic silver halide materials and
processes using such couplers and to the dyes formed there from.
The couplers contain a fully substituted carbon at the 6-position,
hydrogen or a chlorine group at the 7-position, and a phenyl group
at the 2-position substituted with a meta aliphatic or alicyclic
sulfonamide substituent of more than eight carbon atoms.
BACKGROUND OF THE INVENTION
[0002] Color images are customarily obtained in the photographic
art by reaction between an oxidation product of a silver halide
developing agent and a dye-forming coupler. Pyrazolone couplers are
useful for forming magenta dye images; however, such couplers have
shortcomings with respect to color reproduction in that the
unwanted absorption around 430 nm causes color turbidity. Bicyclic
pyrazolo couplers, particularly pyrazolotriazole couplers,
represent another class of couplers for this purpose. Examples of
pyrazoloazole couplers are described in, for example, U.S. Pat. No.
4,443,536; U.S. Pat. Nos. 1,247, 493; 1,252,418; and 1,398,979; and
U.S. Pat. Nos. 4,665,015; 4,514, 490; 4,621,046, 4,540,654;
4,590,153; 4,822,730 and European Patents 177, 765 and 119,860. One
class of pyrazolotriazole couplers includes
1H-pyrazolo[3,2-c][1,2,4]triazole couplers and another includes
1H-pyrazolo[1,5-b][1,2,4]triazole couplers, such as described in
European Patent 177765.
[0003] Pyrazoloazole couplers containing a t-butyl group at the
6-position are described in U.S. Pat. No. 4,882,266. and impart
greater light stability to the resulting dyes.
1H-pyrazolo[1,5-b][1,2,4]triazole couplers with a fully substituted
group in the 6-position and a phenyl substituent in the 2-position
are described in EP 0571,959. U.S. Pat. No. 5,605,788 describes
these types of couplers with aromatic sulfonamides on the 2-phenyl
group. Similar couplers with aromatic and some aliphatic
sulfonamides on the 2-phenyl ring are described in U.S. Pat. No.
6,232,055 and JP 08 146,575. While these sulfonamide substituted
2-phenyl substituted couplers have the advantage of light stability
and hue, they are high melting solids and hard to disperse in
common coupler solvents. In order for a coupler to be useful it
must be soluble in the appropriate coupler solvents and not
crystallize therefrom. When such crystallization occurs, loss in
density and activity occurs and in the extreme case no dye is
formed at all. Couplers with very high melting points of
140.degree. C. or higher often show limited solubility in common
coupler solvents. A problem to be solved is to provide couplers
with the desirable sulfonamide substitution which have a reduced
tendency to crystallize from the solvents they are dispersed
in.
SUMMARY OF THE INVENTION
[0004] The invention provides a photographic element comprising a
light-sensitive silver halide emulsion layer containing a
1H-pyrazolo[1,5-b][1,2,4]triazole containing in the 6-position a
fully substituted methyl group, in the 7-position a hydrogen atom
or halogen atom, and in the 2-position a phenyl group substituted
in the meta position with a sulfonamide group free of amide,
sulfonamide, ureido or ester groups and bearing at least 9
(cyclo)aliphatic carbon atoms. The invention also provides a
coupler compound and a dye compound.
[0005] The element exhibits improved resistance to coupler
crystallization.
DETAILED DESCRIPTION OF THE INVENTION
[0006] The invention is generally described above. The couplers
useful in the invention are represented by the following structure
(I): 1
[0007] wherein R.sub.1, R.sub.2, and R.sub.3 are independently
selected unsubstituted alkyl groups comprising of 3 or less carbons
with the proviso that one or more of the R.sub.1, R.sub.2, and
R.sub.3 groups can be joined to form a mono- or bicyclic ring.
R.sub.1, R.sub.2, and R.sub.3 can be methyl, ethyl, propyl and any
two R.sub.1, R.sub.2, or R.sub.3 groups can be joined to form a
cyclohexyl, cyclopentyl, or cyclopropyl ring and all three R.sub.1,
R.sub.2, and R.sub.3 groups can be joined to form a [2.2.2]-bicyclo
ring system. Preferably the R.sub.1, R.sub.2, and R.sub.3 groups
are methyl or are joined to form a [2.2.2]-bicyclo ring system.
Most preferably the R.sub.1, R.sub.2, and R.sub.3 groups are each
methyl. The group represented by R is a straight, cyclic or
branched aliphatic carbon chain or carbocyclic group unsubstituted
with amide, sulfonamide, ureido, or ester groups, and comprising
more than 8 carbon atoms. Preferably, there is no substitution on R
or substitution with ethers, halogens, or sulfones. Preferably the
R group contains 9 to 25 carbons and more preferably 10 to 18 and
most preferably 12 to 16. When present, the R' group is an alkyl or
halogen substituent and is more preferably, chlorine, or an alkyl
group with less than 4 carbons and is most preferably methyl. n is
0, 1, 2, 3, or 4 but preferably 0 or 1 and most preferably 0. X is
hydrogen or halogen. Preferably X is hydrogen or chloro and most
preferably X is chloro.
[0008] Representative couplers of the invention are as follows:
23
[0009] Typically, couplers are incorporated in a silver halide
emulsion layer in a mole ratio to silver of 0.05 to 1.0 and
generally 0.1 to 0.5. Usually the couplers are dispersed in a
high-boiling organic solvent in a weight ratio of solvent to
coupler of 0.1 to 10.0 and typically 0.1 to 2.0 although
dispersions using no permanent coupler solvent are sometimes
employed.
[0010] Unless otherwise specifically stated, use of the term
"substituted" or "substituent" means any group or atom other than
hydrogen. Unless otherwise provided, when a group, compound or
formula containing a substitutable hydrogen is referred to, it is
also intended to encompass not only the unsubstituted form, but
also form further substituted with any substituent group or groups
as herein mentioned, so long as the substituent does not destroy
properties necessary for utility. Suitably, a substituent 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 chloro, bromo
or fluoro; nitro; hydroxyl; cyano; carboxyl; or groups which may be
further substituted, such as alkyl, including straight or branched
chain or cyclic alkyl, such as methyl, trifluoromethyl, ethyl,
t-butyl, 3-(2,4-di-t-pentylphenoxy)propyl, cyclohexyl, 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)ethox- y, 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,
alpha-(2,4-di-t-pentyl-phenoxy)acetamido,
alpha-(2,4-di-t-pentylphenoxy)b- utyramido,
alpha-(3-pentadecylphenoxy)-hexanamido, alpha-(4-hydroxy-3-t-bu-
tylphenoxy)-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, 2,5-(di-t-pentylphenyl)carbonyl amino,
p-dodecyl-phenylcarbonyl amino, p-tolylcarbonylamino,
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-tolylureido, N-(m-hexadecylphenyl)ureido,
N,N-(2,5-di-t-pentylphenyl)-N'-ethylureido, and t-butylcarbonamido;
sulfonamido, such as methylsulfonamido, benzenesulfonamido,
p-tolylsulfonamido, p-dodecylbenzenesulfonamido,
N-methyltetradecylsulfon- amido, 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]sulf- amoyl,
N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl,
N-methyl-N-tetradecylsulfamoyl, 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-tetradecylcarbam- oyl, and N,N-dioctylcarbamoyl; acyl,
such as acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl,
p-dodecyloxyphenoxycarbony- l 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-tolylsulfonyl;
sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy;
sulfinyl, such as methylsulfinyl, octylsulfinyl,
2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl,
phenylsulfinyl, 4-nonylphenylsulfinyl, and p-tolylsulfinyl; thio,
such as ethylthio, octylthio, benzylthio, tetradecylthio,
2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio,
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.
[0011] 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 desirable properties for a
specific application and can include, for example, hydrophobic
groups, solubilizing groups, blocking groups, and releasing or
releasable groups. When a molecule may have two or more
substituents, the substituents may be joined together to form a
ring such as a fused ring unless otherwise provided. 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.
[0012] The materials useful in the invention can be used in any of
the ways and in any of the combinations known in the art.
Typically, the invention materials are incorporated in a melt and
coated as a layer described herein on a support to form part of a
photographic element. When the term "associated" is employed, it
signifies that a reactive compound is in or adjacent to a specified
layer where, during processing, it is capable of reacting with
other components.
[0013] To control the migration of various components, it may be
desirable to include a high molecular weight hydrophobe or
"ballast" group in coupler molecules. Representative ballast groups
include substituted or unsubstituted alkyl or aryl groups
containing 8 to 48 carbon atoms. Representative substituents on
such 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.
[0014] 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.
[0015] A typical multicolor photographic element comprises a
support bearing a cyan dye image-forming unit comprising one or
more red-sensitive silver halide emulsion layers, each layer having
associated therewith or preferably containing a cyan dye-forming
coupler, a magenta dye image-forming unit comprising one or more
green-sensitive silver halide emulsion layers, each layer having
associated therewith or preferably containing a magenta dye-forming
coupler, and a yellow dye image-forming unit comprising one or more
blue-sensitive silver halide emulsion layers, each layer having
associated therewith or preferrably containing a yellow dye-forming
coupler. The element can contain additional layers, such as filter
layers, interlayers, overcoat layers, and subbing layers.
[0016] 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 1996, Item 38957, available
as described above, which is referred to herein by the term
"Research Disclosure". The Sections hereinafter referred to are
Sections of the Research Disclosure.
[0017] 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. Suitable methods for incorporating
couplers and dyes, including dispersions in organic solvents, are
described in Section X(E). Scan facilitating is described in
Section XIV. Supports, exposure, development systems, and
processing methods and agents are described in Sections XV to XX.
The information contained in the September 1994 Research
Disclosure, Item No. 36544 referenced above, is updated in the
September 1996 Research Disclosure, Item No. 38957. Certain
desirable photographic elements and processing steps, including
those useful in conjunction with color reflective prints, are
described in Research Disclosure, Item 37038, February 1995.
[0018] Coupling-off groups are well known in the art. Such groups
can determine the chemical equivalency of a coupler, i.e., whether
it is a 2-equivalent or a 4-equivalent coupler, or 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, and color
correction.
[0019] The presence of hydrogen at the coupling site provides a
4-equivalent coupler, and the presence of another coupling-off
group usually provides a 2-equivalent coupler. Representative
classes of such coupling-off groups include, for example, chloro,
alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, acyl,
heterocyclyl, sulfonamido, mercaptotetrazole, benzothiazole,
mercaptopropionic acid, phosphonyloxy, arylthio, and arylazo. These
coupling-off groups are described in the art, for example, in U.S.
Pat. Nos. 2,455,169, 3,227,551, 3,432,521, 3,476,563, 3,617,291,
3,880,661, 4,052,212 and 4,134,766; and in UK. Patents and
published application Nos. 1,466,728, 1,531,927, 1,533,039,
2,006,755A and 2,017,704A.
[0020] Image dye-forming couplers may be included in the element
such as couplers that form cyan dyes upon reaction with oxidized
color developing agents which are described in such representative
patents and publications as: "Farbkuppler-eine Literature
Ubersicht," published in Agfa Mitteilungen, Band III, pp. 156-175
(1961) as well as in U.S. Pat. Nos. 2,367,531; 2,423,730;
2,474,293; 2,772,162; 2,895,826; 3,002,836; 3,034,892; 3,041,236;
4,333,999; 4,746,602; 4,753,871; 4,770,988; 4,775,616; 4,818,667;
4,818,672; 4,822,729; 4,839,267; 4,840,883; 4,849,328; 4,865,961;
4,873,183; 4,883,746; 4,900,656; 4,904,575; 4,916,051; 4,921,783;
4,923,791; 4,950,585; 4,971,898; 4,990,436; 4,996,139; 5,008,180;
5,015,565; 5,011,765; 5,011,766; 5,017,467; 5,045,442; 5,051,347;
5,061,613; 5,071,737; 5,075,207; 5,091,297; 5,094,938; 5,104,783;
5,178,993; 5,813,729; 5,187,057; 5,192,651; 5,200,305 5,202,224;
5,206,130; 5,208,141; 5,210,011; 5,215,871; 5,223,386; 5,227,287;
5,256,526; 5,258,270; 5,272,051; 5,306,610; 5,326,682; 5,366,856;
5,378,596; 5,380,638; 5,382,502; 5,384,236; 5,397,691; 5,415,990;
5,434,034; 5,441,863; EPO 0 246 616; EPO 0 250 201; EPO 0 271 323;
EPO 0 295 632; EPO 0 307 927; EPO 0 333 185; EPO 0 378 898; EPO 0
389 817; EPO 0 487 111; EPO 0 488 248; EPO 0 539 034; EPO 0 545
300; EPO 0 556 700; EPO 0 556 777; EPO 0 556 858; EPO 0 569 979;
EPO 0 608 133; EPO 0 636 936; EPO 0 651 286; EPO 0 690 344; German
OLS 4,026,903; German OLS 3,624,777. and German OLS 3,823,049.
Typically such couplers are phenols, naphthols, or
pyrazoloazoles.
[0021] Couplers that form magenta dyes upon reaction with oxidized
color developing agent are described in such representative patents
and publications as: "Farbkuppler-eine Literature Ubersicht,"
published in Agfa Mitteilungen, Band III, pp. 126-156 (1961) as
well as U.S. Pat. Nos. 2,311,082 and 2,369,489; 2,343,701;
2,600,788; 2,908,573; 3,062,653; 3,152,896; 3,519,429; 3,758,309;
3,935,015; 4,540,654; 4,745,052; 4,762,775; 4,791,052; 4,812,576;
4,835,094; 4,840,877; 4,845,022; 4,853,319; 4,868,099; 4,865,960;
4,871,652; 4,876,182; 4,892,805; 4,900,657; 4,910,124; 4,914,013;
4,921,968; 4,929,540; 4,933,465; 4,942,116; 4,942,117; 4,942,118;
U.S. Pat. Nos. 4,959,480; 4,968,594; 4,988,614; 4,992,361;
5,002,864; 5,021,325; 5,066,575; 5,068,171; 5,071,739; 5,100,772;
5,110,942; 5,116,990; 5,118,812; 5,134,059; 5,155,016; 5,183,728;
5,234,805; 5,235,058; 5,250,400; 5,254,446; 5,262,292; 5,300,407;
5,302,496; 5,336,593; 5,350,667; 5,395,968; 5,354,826; 5,358,829;
5,368,998; 5,378,587; 5,409,808; 5,411,841; 5,418,123; 5,424,179;
EPO 0 257 854; EPO 0 284 240; EPO 0 341 204; EPO 347,235; EPO
365,252; EPO 0 422 595; EPO 0 428 899; EPO 0 428 902; EPO 0 459331;
EPO 0 467 327; EPO 0 476 949; EPO 0487 081; EPO 0 489 333; EPO 0
512 304; EPO 0 515 128; EPO 0 534 703; EPO 0 554 778; EPO 0 558
145; EPO 0 571 959; EPO 0 583 832; EPO 0 583 834; EPO 0 584 793;
EPO 0 602 748; EPO 0 602 749; EPO 0 605 918; EPO 0 622 672; EPO 0
622 673; EPO 0 629 912; EPO 0 646 841, EPO 0656 561; EPO 0 660 177;
EPO 0 686 872; WO 90/10253; WO 92/09010; WO 92/10788; WO 92/12464;
WO 93/01523; WO 93/02392; WO 93/02393; WO 93/07534; UK Application
2,244,053; Japanese Application 03192-350; German OLS 3,624,103;
German OLS 3,912,265; and German OLS 40 08 067. Typically such
couplers are pyrazolones, pyrazoloazoles, or pyrazolobenzimidazoles
that form magenta dyes upon reaction with oxidized color developing
agents.
[0022] Couplers that form yellow dyes upon reaction with oxidized
color developing agent are described in such representative patents
and publications as: "Farbkuppler-eine Literature Ubersicht,"
published in Agfa Mitteilungen; Band III; pp. 112-126 (1961); as
well 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; 4,758,501; 4,791,050;
4,824,771; 4,824,773; 4,855,222; 4,978,605; 4,992,360; 4,994,361;
5,021,333; 5,053,325; 5,066,574; 5,066,576; 5,100,773; 5,118,599;
5,143,823; 5,187,055; 5,190,848; 5,213,958; 5,215,877; 5,215,878;
5,217,857; 5,219,716; 5,238,803; 5,283,166; 5,294,531; 5,306,609;
5,328,818; 5,336,591; 5,338,654; 5,358,835; 5,358,838; 5,360,713;
5,362,617; 5,382,506; 5,389,504; 5,399,474; 5,405,737; 5,411,848;
5,427,898; EPO 0 327 976; EPO 0 296 793; EPO 0 365 282; EPO 0 379
309; EPO 0 415 375; EPO 0 437 818; EPO 0 447 969; EPO 0 542 463;
EPO 0 568 037; EPO 0 568 196; EPO 0 568 777; EPO 0 570 006; EPO 0
573 761; EPO 0 608 956; EPO 0 608 957; and EPO 0 628 865. Such
couplers are typically open chain ketomethylene compounds.
[0023] Couplers that form colorless products upon reaction with
oxidized color developing agent are described in such
representative patents as: UK. 861,138; U.S. Pat. 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.
[0024] Couplers that form black dyes upon reaction with oxidized
color developing agent are described in such representative patents
as U.S. Pat. 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.
[0025] 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.
Pat. Nos. 5,026,628, 5,151,343, and 5,234,800.
[0026] 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. Pat. No. 4,301,235; U.S. Pat. No. 4,853,319
and U.S. Pat. No. 4,351,897. The coupler may contain solubilizing
groups such as described in U.S. Pat. No. 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. Pat. 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.
[0027] 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.
Pat. No. 4,366,237; EP 96,570; U.S. Pat. No. 4,420,556; and U.S.
Pat. No. 4,543,323.) Also, the materials useful in the invention
may be blocked or coated in protected form as described, for
example, in Japanese Application 61/258,249 or U.S. Pat. No.
5,019,492.
[0028] It is particularly contemplated that 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 useful in the
invention may be coated on pH adjusted support as described in U.S.
Pat. No. 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. Pat. No. 4,346,165; U.S. Pat. No. 4,540,653 and
U.S. Pat. No. 4,906,559 for example); with ballasted chelating
agents such as those in U.S. Pat. No. 4,994,359 to reduce
sensitivity to polyvalent cations such as calcium; and with stain
reducing compounds such as described in U.S. Pat. No. 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.
[0029] Conventional radiation-sensitive silver halide emulsions can
be employed in the practice of this invention. Such emulsions are
illustrated by Research Disclosure, Item 38755, September 1996, I.
Emulsion grains and their preparation.
[0030] 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. If desired "Redox Amplification" as described in
Research Disclosure XVIIIB(5) may be used.
[0031] A "color negative element" utilizes negative-working silver
halide and provides a negative image upon processing. A first type
of such element is a capture element, which is a color negative
film that is designed for capturing an image in negative form
rather than for viewing an image. A second type of such an element
is a direct-view element that is designed, at least in part, for
providing a positive image viewable by humans.
[0032] In the capture element, speed (the sensitivity of the
element to low light conditions) is usually critical to obtaining
sufficient image in such elements. Such elements are typically
silver bromoiodide emulsions coated on a transparent support and
are sold packaged with instructions to process in known color
negative processes such as the Kodak C-41 process as described in
The British Journal of Photography Annual of 1988, pages 191-198.
If a color negative film element is to be subsequently employed to
generate a viewable projection print as for a motion picture, a
process such as the Kodak ECN-2 process described in the H-24
Manual available from Eastman Kodak Co. may be employed to provide
the color negative image on a transparent support. Color negative
development times are typically 3' 15" or less and desirably 90 or
even 60 seconds or less.
[0033] A direct-view photographic element is one which yields a
color image that is designed for human viewing (1) by reflected
light, such as a photographic paper print, (2) by transmitted
light, such as a display transparency, or (3) by projection, such
as a color slide or a motion picture print. These direct-view
elements may be exposed and processed in a variety of ways. For
example, paper prints, display transparencies, and motion picture
prints are typically produced by digitally printing or by optically
printing an image from a color negative onto the direct-viewing
element and processing though an appropriate negative-working
photographic process to give a positive color image. The element
may be sold packaged with instructions for digital printing or for
processing using a color negative optical printing process, for
example the Kodak RA-4 process, as generally described in PCT WO
87/04534 or U.S. Pat. No. 4,975,357, to form a positive image.
Color projection prints may be processed, for example, in
accordance with the Kodak ECP-2 process as described in the H-24
Manual. Color print development times are typically 90 seconds or
less and desirably 45 or even 30 seconds or less. Color slides may
be produced in a similar manner but are more typically produced by
exposing the film directly in a camera and processing through a
reversal color process or a direct positive process to give a
positive color image. The foregoing images may also be produced by
alternative processes such as digital printing.
[0034] Each of these types of photographic elements has its own
particular requirements for dye hue, but in general they all
require cyan dyes whose absorption bands are less deeply absorbing
(that is, shifted away from the red end of the spectrum) than color
negative films. This is because dyes in direct-view elements are
selected to have the best appearance when viewed by human eyes,
whereas the dyes in image capture materials are designed to best
match the needs of the printing process.
[0035] A reversal element is capable of forming a positive image
without optical printing. To provide a positive (or reversal)
image, the color development step is 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 elements
are typically sold packaged with instructions to process using a
color reversal process such as the Kodak E-6 process as described
in The British Journal of Photography Annual of 1988, page 194.
Alternatively, a direct positive emulsion can be employed to obtain
a positive image.
[0036] The above elements are typically sold with instructions to
process using the appropriate method such as the mentioned color
negative (Kodak C-41), color print (Kodak RA-4), or reversal (Kodak
E-6) process.
[0037] The photographic element of the invention can be
incorporated into exposure structures intended for repeated use or
exposure structures intended for limited use, variously referred to
by names such as "single use cameras", "lens with film", or
"photosensitive material package units".
[0038] Preferred color developing agents are p-phenylenediamines
such as:
[0039] 4-amino-N,N-diethylaniline hydrochloride,
[0040] 4-amino-3-methyl-N,N-diethylaniline hydrochloride,
[0041]
4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl)aniline
sesquisulfate hydrate,
[0042] 4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline
sulfate,
[0043] 4-amino-3-(2-methanesulfonamidoethyl)-N,N-diethylaniline
hydrochloride, and
[0044] 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene
sulfonic acid.
[0045] Development is usually followed by the conventional steps of
bleaching, fixing, or bleach-fixing, to remove silver or silver
halide, washing, and drying.
[0046] The entire contents of the patents and other publications
referred to in this specification are incorporated herein by
reference.
[0047] Synthesis of Couplers of the Invention
[0048] Compounds of the invention can be synthesized by methods
known in the art. Intermediate i can be synthesized by the method
found in JP 2002318446 and JP 2001242606. 4
[0049] The ballasts are attached using the appropriate sulfonyl
chloride in the presence of pyridine to yield ii by any of the
methods common in the art. The final coupler is obtained by
chlorination by methods common in the art. The synthesis of M-1 is
shown below. 5
[0050] 2.0 g of 1 (0.00783 mol) and 0.65 ml pyridine (0.00800 mol)
were dissolved in 10 ml THF and 1.9 g (0.00783 mol) dodecylsulfonyl
chloride added and the reaction stirred room temperature overnight.
The reaction mixture was added to dilute HCl and ethyl acetate
added. The organic layer was separated and washed with water three
times, dried over magnesium sulfate and concentrated to an oil
which when stirred with acetonitrile yielded 2 as a salmon colored
solid. This solid was dissolved in 10 ml THF and 0.54 g (0.00403
mol) N-chlorosuccinimide added and stirred 30 minutes at room
temperature. 1.0 g hypo was dissolved in 1 ml water and added to
the reaction mixture and the reaction stirred vigorously for 15
minutes. The reaction added to water and ethyl acetate added. After
shaking the organic layer was separated and washed with water three
times, dried over magnesium sulfate and concentrated to an oil
which was then stirred with acetonitrile to yield, after filtering,
0.9g of M-1 as a white solid, mp 116-118.degree. C., nmr and ms
consistent with desired product.
[0051] Crystallization Properties of Compounds of the Invention
[0052] The tendency of various couplers to crystallize in coupler
solvent and consequently in film was measured. Dispersions of
couplers useful in the invention as well as comparative couplers
were prepared as follows. 0.020 g of the couplers were dissolved in
0.080g of a 1:1 mixture of coupler solvents S-1 and S-2 with gentle
heating (60.degree. C.) and the solutions were allowed to stand at
room temperature. After 48 hours and one week the presence of
crystals was determined by visual inspection. The results are shown
in the following table. The melting points, which roughly correlate
with the solubility of the couplers in photographic dispersions are
also shown.
1 MPt.sup.1 Crystals?.sup.2 M-1 6 116 NO M-4 7 124 NO M-5 8 124 NO
M-7 9 136 NO M-8 10 glass NO C-1 11 207 YES C-2 12 140 YES C-3 13
226 YES C-4 14 240 YES C-5 15 188 YES C-6 16 271 YES C-7 17 178 YES
C-8 18 171 YES C-9 19 177 YES .sup.1Melting point in .degree. C.
.sup.2These observations were the same after 48 hrs and 1 week.
[0053] The solvents used were as follows: 20
[0054] It can be seen that, for the couplers useful in the
invention, no crystals were observed even after one week while for
comparative couplers crystals were observed after 48 hours. Sample
C-1 bears only a C-8 R group. Samples C-2 through C-6 bear aromatic
R groups. Samples C-7 and C-8 bear aliphatic R groups with
unpermitted amide or sulfonamide groups. Thus it is apparent that
the solubility of the couplers useful in the invention is greatly
improved over similarly substituted couplers as well as those
presently used in the art such as C-9.
[0055] The invention has been described in detail with particular
reference to certain preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *