Note: Descriptions are shown in the official language in which they were submitted.
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FLUORINATED l-H~DROXY-2-NAPHTHAMIDE COUPI,ER COUPLER
_ . .. .. . ... .
COMPOSITIONS AND PHOTOGRAPHIC ELEMENTS SUITED_TO FORMING
INTEGRAL SOUND TRACKS
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FIELD OF THE INVENTION
This invention relates to photographic elements
and compositions adapted to form infrared absorbing dyes,
particularly those useful in forming integral dye sound
track motion picture films, and to coupIers particularly
suited for forming microcrystalline infrared absorbing
dyes when dispersed in selected coupler solvents.
BACKGROUND OF THE IN~ENTION
In black-and-white motion picture pro~ection
films it is frequently desirable to provide an integral
sound track. Both the photographic image and sound track
images in the film are silver. The sound track, which can
be of variable density or variable area, is read optically
by a photocell which detects infrared radiation passing
therethrough. The peak sensitivity of these photocells,
generally referred to as S-l photocells~ is typically at
about 800 nm plus or minus 50 nm. The wide variance in
peak absorption is of little importance, since silver has
a substantially uniform absorption in the infrared region
of the spectrum.
In color photography, instead of employing silver
images, as in black-and-white photography, the oxidized
developing agent which is generated in imagewise developing
silver halide to silver is used to form a dye image. The
formation of color photographic images by imagewise
reaction (coupling) of oxidized aromatic primary amine
developing agents with incorporated color forming couplers
to form dyes is well known. In these processes, the
subtractive process of color formation is ordinarily used,
and the image dyes customarily formed are cyan, magenta
and yellow, the colors that are complementary to the
primary colors, red, green and blue~ respectively. The
silver image which is formed by development is an unwanted
by-product which is removed by bleaching.
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In color motion picture proJection films it is
conventional to employ a silver sound track. The require-
- ment that silver be retained in the optical sound trackof the motion picture film is distinctly disadvantageous
because the developed silver must be removed from the
picture area without disturblng the silver in the optical
sound track. This has given rise to processing techniques
which require the separate treatment of a portion of the
film at least once during processing in order to obtain
a silver sound track.
The desirability of employing dye sound tracks
in color motion picture projection films, particularly
dye sound tracks compatible with pro~ection equipment now
in use designed for films having silver sound tracks,
has been long recognized. Un~ortunately, the subtractive
dyes which form the picture image have their regions of
maximum absorption in the range of from about 400 to 730 nm
and are relatively transparent in the infrared region where
; the S-l photocells are most sensitive. In looking for
dyes suitable for use in forming infrared absorbing sound
tracks for color motion picture proJection films two
principal obstacles have been encountered. First, the
dyes have for the most part lacked sufficient peak
absorption in the required region of the spectrum. Second,
the absorption peaks of the dyes have not been broad
enough to accomodate the plus or minus 50 nm variation in
peak sensitivity of S-l photocells. Infrared absorbing
dyes which have been disclosed ~or use in forming integral
dye sound tracks are illustrated by Vittum et al U.S.
3 Patent 2,266,452, issued December 16, 1941, and Frohlich
et al U.S. Patent 2,373,821, issued April 17, 1945. More
recent disclosures which address maximum absorption peak
densities, but which do not address the breadth of the ;~
absorption peak, are illustrated by Japanese Publication
59838, laid open Au~ust 22, 1973, based on patent
application 94266, filed November 24, 1971, and United
Kingdom Patent 1,424,454.
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Cyan dye-~orming couplers containing fluorine
substituents are known in the art. Beavers et al U.S.
Patent 3,758,308, issued September 11, 1973, discloses
~ ~fluoro substituted phenolic couplers which can con-
tain a perfluorinated phenyl substituent. Lau et al U.S.Patent 3,998,642, issued December 21, 1976, discloses a
difluoro substituted phenolic coupler. N-Biphenylyl-l-
hydroxy-2-naphthamide couplers use~ul in forming infrared
absorbing sound tracks are disclosed by Ciurca, Research
Disclosure, Vol. 134, June 1975, Item 13460.
BRIEF DESCRIPTION OF THE INVENTIOI~ .
In one aspect this invention is directed to a
photographic element comprising a support and, coated
thereon, at least one layer unit which comprises a photo-
graphic silver halide emulsion layer and coupler solventparticles dispersed in a photographically useful amount in
said emulsion layer or in an ad~acent hydrophilic colloid
layer. The photographic element is characterized by the
improvement wherein the coupler solvent particles are
comprised of a combination, capable of permitting the
formation of a microcrystalline dye, of a coupler of the
formula
F-~ -N~-(C~ ) -O-~ -
F R
wherein R is a coupling-off group, Rl is an alkyl group
of from 1 to 6 carbon atoms and a coupler solvent which is a
lower alkyl ester of phthalic acid, wherein lower alkyl
is from 1 to 6 carbon atoms, the coupler and the coupler
solvent being present in a weight ratio of from 5:1 to
1:2.
In another aspect, this invention is directed to
a composition, which can be coated to form a layer of a
photographic element, comprising a hydrophilic colloid and
coupler solvent particles dispersed therein in a photo-
graphically useful amount comprised of a combination,
,
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capable of permitting the formation of a microcrystalline
dye, of a coupler of the formula :~
1 ~ O
F ~ ~ C- N H- ( C H 2 ) 4 - O~ R
F R
wherein R is a coupling-off group, Rl is an alkyl group of
from 1 to 6 carbon atoms and a coupler solvent which is a
lower alkyl ester of phthalic acid, wherein lower alkyl is
from 1 to 6 carbon atoms;-the coupler and the coupler
solvent being present in a weight ratio of from 5:1 to 1: 2,
In still another aspect, this invention is ;~
directed to a photographically useful dye-forming coupler
capable of forming a dye having an absorption peak in the
infrared portion of the spectrum of the formula:
F OH O
F-I ; 0 I H (CH2) 4 0 ~ -R
F R 1
: wherein R is a coupling-off group, R is an alkyl group of
from 1 to 6 carbon atoms.
It is a surprising feature Or this invention
1 25 that the microcrystalline dyes which can be formed with ~.
coupler-coupler solvent combinations identified above have
absorption peaks in the infrared portion of the spectrum
and, when incorporated in a photographic element, are
capable of producing densities at 800 nm well above 1. It
. 30 is still more surprising that broad absorption peaks can
be produced in the 800 nm region of the spectrum. ~articu- :
larly, it is surprising that these coupler-coupler solvent
combinations can produce infrared absorbing dye images
having suf~icient peak densities and spectral peak breadth
to be useful in modulating the response of an S-l photocell
when coated in a photographic element to form a sound
track. The present invention offers the speciric
advantage of permittin.g color motion picture projection
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films to be formed with integral infrared absorbing dye
sound tracks, thereby eliminating the disadvantages in
processing of selectively retaining silver in sound track
areas and offering the distinct advantage of allowing such
integral infrared absorbing dye sound track color motion
picture films to be employed in proJection equipment
having S-l and similar photocells intended for modulation
with a silver sound track.
BRIEF DESCRIPTION O~ TH~ DRAWINGS
Figure l shows dye absorption curves produced by
plotting density on an ordinate versus wavelength as an
abscissa.
DESCRIPTION OF TXE PREFERRED EMBODIMENTS
The couplers capable of reacting in a coupler
solvent particle with an oxidized color developing agent to
form a microcrystalline infrared absorbing dye can be chosen
from among N-(2,4-dialkylphenoxybutyl)-5,6,7,8~tetrafluoro-
l-hydroxy-2-naphthamides of the following formula:
'i~ I C-NH-(CH ) - o~ -R1
F R
wherein R is a coupling-off group, Rl is an alkyl group of
from l to 6 carbon atoms.
Coupling-off groups, represented by R, are well
known to those skilled in the art. Such groups are dis-
placed when the coupler reacts with oxidized color develop-
ing agent. Thus, the coupling-off group is not included
3 in the dye formed by this reaction. The coupling-off
group can perform useful photographic functions, such as
determining the equivalency of the coupler (e.g., deter-
mining if the coupler is a two-equivalent or a four-
equivalent coupler)~ modifying the reactivity of the
coupler or releasing a photographically useful fragment
which can modulate other characteristics~ such as inhibit-
ing or accelerating bleaching, inhibiting development,
color correction and the like. Representative of useful
.
, ~ .' ` '
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.
conventional coupling-off groups are hydrogen, alkoxy,
aryloxy, arylazo, thioether and heterocyclic groups, such
as oxazoyl, diazolyl, triazolyl and tetrazolyl groups.
Hydrogen is a preferred coupling-off group.
Rl can be a lower alkyl group--i.e., any alkyl
group having from 1 to 6 carbon atoms, such as methyl,
ethyl, or any one of` the various isomeric forms of propyl,
butyl, amyl and hexyl groups. Rl can in each occurrence
be independently selected, but in a prererred form Rl is
the same alkyl group in each occurrence.
The couplers can be chemically synthesized by
techniques well known to those skilled in the art. For
example, the synthesis of N-~2,4-di-t-amylphenoxybutyl)-
5,6,7,8-tetrafluoro-1-hydroxy-2-naphthamide set forth
below can be adapted to the synthesis of other of the novel
couplers according to this invention by employing varia-
tions, such as the substituents in the starting materials
which provide the coupling-off and/or ballast groups.
The preferred coupler solvents contemplated for
use in combination with the above couplers can be lower
alkyl esters of phthalic acid. The lower alkyl group can
contain from l to 6 carbon atoms and can be methyl,
ethyl, or any of the various isomeric forms of propyl,
butyl, amyl or hexyl groups. The alkyl ester of phthalic
acid can be the half ester of phthalic acid or, preferably,
the diester.
The following are exemplary of preferred coupler
solvents contemplated for use:
dimethyl phthalate
3 diethyl phthalate
~` di-n-butyl phthalate
di-i-amyl phthalate
-amyl phthalate
Okher conventional coupler solvents which are
capable of permitting associated couplers, described above,
to form microcrystalline dyes can be employed. Coupler to
coupler solvent weight ratios of from 5:1 to 1:2 can be
selected. A preferred range of weight ratios is from 4:1
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`` ~ 4~ :
- 7 - :
to 1:1, with the optimum being from about 2.5:1 to 1.5:1
for the preferred coupler solvents.
. Coupler solvents of the type descri~ed above and
techniques for dissolving couplers therein are known to
those skilled in the art. ~echniques are also well known
for dispersing coupler-containing coupler solvents in
hydrophilic colloid-containing coating`compositions useful
. 25
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742
in forming photographic elements. The coupler-contalning
coupler solvent is typically dispersed in the hydrophllic
colloid-containing coatin~ composition in the rorm of
partlcles o~ relatively small slze, typlcally rrom about
0.3 to about 3.0 microns ln mean diameter, usually by
-colloid milling. The coupler solvents herein employed,
the dispersion of couplers therein, the introduction o~
the coupler-containing coupler solvents into hydrophilic
colloid-containing coating compositions and the coating of
the composition to form layers in photographic elements 9
are illus~rated by Mannes et al U.S. Patent 2,304,940,
issued December 15, 1942; Jelley et al U.S. Patent
2,322,027, issued June 15, 1943; Vittum et al U.S. Patent
2,801,170, issued July 30, 1957; Fierke et al U.S. Patent
2,801,171, issued July 30, 1957; Thirtle et al U.S. Patent
2,835,579, issued May 20, 1958; and Julian U.S. Patent
2,949,360, issued August 16, 1960, as well as the Japanese
Publication 59838 and U.K. Patent 1,424,454, both clted
above.
In a simple form the photographic elements o~
this invention are comprised of a photographlc support
~ having coated thereon a single layer unit which comprlses
; a photographic silver halide emulsion containing therein
in a photographically useful amount partlcles which are
comprised of the coupler and coupler solvent comblned in
the weight ratio descrlbed above. In a variant form5 well
known in the art, instead of incorporatlng the coupler-
containing coupler solvent particles directly in the
silver halide emulsion layer, the particles can be dis-
3 persed ln a hydrophilic colloid layer lmmedlately ad~acent
to the sllver halide emulsio~ layer. In this form the
hydropnillc colloid layer containlng the particles and the
silver halide emulsion layer together form the layer unit.
Such a slngle layer unit element can be empl3yed
for the sole pur~ose of forming a sound track or, prefer
ably, the element can be employed to form both a photo-
graphic image and a sound track. It ls posslble wlth such
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an element to form an infrared absor~ing dye sound track
and a silver photographic image or~ alternati~ely, a sll-
ver sound track and an infrared absorblng phatographlc
dye image. In a speci~ically prererred use an integral
dye sound track is formed. As employed herein, the term
"integral sound track" lndicates that a sound track and a
i photographic image are formed in separate portlons of the
same element and that following exposure the separate areas
are concurrently and ldentlcally processed (l.e., re~ulring
no process steps other than those required for processing
the photographic image portion) to ~orm sound track and
photographic records, respectively. Slnce the novel
couplers employed in the pract~ce of thls invention produce
dyes whlch absorb not only in the lnfrared~ but also in the
visible portion o~ the spectrum, both a sound track and a
photographlc image can be formed solely by the dye. For
~ example~ an integral sound track and photographic image
I can be formed by the dye, the sound track portion being
read by an S-l or slmilar infrared responslve photocell
~ and the photographic image being read by the eye as a r
I pro~ected dye image. Other variant uses will readily
occur to those skilled in the art.
~ In a form capable of recording multicolor images
i 25 the photographic element contains in addl~ion to the
3 support and the single layer unit described above at least
two additional layer units, and the photographic element
is capable of producing multlcolor photographlc images.
The slngle layer unit described above can contain a red-
sensitized silver hallde emulsion and be employed to ~orm
a cyan dye image as well as an infrared absorbing dye
image. The same dye can ~orm both the cyan and the lnfra~
red absorbing dye lm ge, but lt is preferred in ~hat
instance that ~he single layer unl~ described above be
modiried to include in addition a conventional cyan dye-
forming coupler. The cyan dye-~orming coupler is prefer-
ably dispersed in separate coupler solvent particles from
those containing the in~rared absorbin~ dye-~orming coupler
or coated without employlng a coupler solvent. A second
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39~742
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layer unit is present containing a blue-sensit~ve silver
halide emulsion and a yellow dye forming coupler, and a
third layer unit is present containing a green-sensitlzed
sllver halide emulsion and a m~genta dye ~orming coupler~
The construction of the second and third layer unlts and.
their relationship to the first layer unit is conventional
and requires no detai}ed description.
In another form, which is speclfically preferred,
the photographic element is provided with four separate
layer units. Three layer units are conventional cyan,
magenta and yellow dye-~orming layer units of the ~ype
~ound in conventional silver halide photographlc elements
intended to form multicolor dye images. The fourth layer
unit can be identical to the single layer unlt described
above. In a preferred form the silver hallde emulsion ln
the fourth layer unit is sensitized to a portlon of the
spectrum to which the remainlng layers are relatively
insensitive. For example, the fourth layer unit emulslon
can be spectrally sensitized to the infrared portion of
the spectrum or to portions of the visible spectrum which
lie a~ the ~ringes o~ the spectral regions the remaining
layer units are intended to record. The blue portion of
the spectrum ls nominally defined as from 400 to 500 nm,
2 the green portion o~ the spectrum from 500 to 600 nm and
the red portion of the spectrum ~rom 600 to 700 nm. The
- spectral regions in the viclnity of about 500 nm and 600
nm are frequently relatively insensitive to light as com-
pared to the mid-regions of the blue, green and red
0 portions of the spectrum. This is done intentionally to
avoid recording in a layer unit llght exposure from one o~
the two remaining thirds of the visible spectrum. By
; spectrally sensitlzing the emulsion of the fourth layer
-~ uni~ to a peak sensitivity ~n a region of the spectrum
~; 35 where the sliver hallde emulsions of the other three layer
units are relatlvely insensitive~ ~or instance at about 470
to 500 nm, the fourth layer unit can be exposed by light ~n
this region o~ the spectrum to form a sound track. In one
preferred form the fourth layer unlt is spectrally sen-
- . . :...................... .
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sitlzed to the infrared portion of the spectrum. The
fourth layer un~t can be coated ln any convenient order
with respect to the remaining layer units~ but it is
preferable to coat the fourth layer uni~ nearer the expo-
sure light source than the remainin~ layer unlts, typleally to overcoat the other three layer units, so that the
bes~ possible definition of the sound track image will be
produced. Useful layer arrangements are disclosed in
Japanese Publicatlon 59838 and U.K. Patent 1,4249454
cited above.
Still other variant forms o~ the photographic
elements can be employed. For example, the emulsion of
the sound track layer unit can be employed with only lts
native spectral sensitivity. In this lnstance the re~
sponse of the sound track layer unit is confined to expo-
sure to ultraviolet and the ad~acent blue portion of thespectrum, the blue response varying to some extent with
the silver hallde chosen. In still another variant form
the speed rather than the spectral response of the sound
track recording layer unit can be di~erent from that of
another, image-forming layer unit~ The sound track record-
ing layer unit can be either faster or slower than an
image-forming layer unlt Or similar spectral response. A
combination of both differing spectral respon~e and speed
can also be employed to allow selective exposure of the
sound track and image-forming layer units.
While any photographically useful amount of
particles of the lnfrared absorbing dye-forming coupler
and coupler solvent can be present in the layer units
3 described above, for sound trac~ applications employing S-
l photocells it i5 preferred that these particles be
present ln a concentration suf~icient to provide a maxlmum
dye density of at least l.0 over the spectrai region of
fro~. 750 to 850 nm, ~referably at least 2~ Such dye
3 densities can be ob~alned readily with the preferred
coupler-coupler solYent combinations within the concentra-
tion ranges conventionally employed for coupler solvent
par~icles containing cyan, magenta and yellow dye-forming
,~
' : ~
3`~2
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couplers. Generally coupler concentrations ranglng from
about 0.40 to 1.30 grams per square meter are contemplated,
preferably from about 0.65 to 1.05 grams per square meter,
optimally from about 0.75 to 0.95 gram per square meter.
The photographic silver halide emulsion layers,
the adjacent hydrophilic colloid-containing layers ln
whlch the infrared absorbing dye-forming couplers can be
incorporated and other layers, including overcoat, subbing
and interlayer coatings of conventional character~ can
contain various colloids alone or in combination as
vehicles. Suitable hydrophilic vehicle materials include
both nakurally-occurring substances such as proteins, for
example, gelatin, gelatin derivatives, cellulose deriva-
tives, polysaccharides such as dextran, gum arabic and
the like; and synthetic polymeric substances such as
water soluble polyvinyl compounds like poly(vinyl-
pyrrolidone), acrylamide polymers and the like.
Photographic emulsion layers and other layers
of photographic elements such as overcoat layers, inter-
layers and subbing layers, as well as receiving layers in
image transfer elements can also contain alone or in com-
bination with hydrophilic, water~permeable colloids, other
synthekic polymeric vehicle compounds such as dispersed
vinyl compounds such as in latex form and particularly
those which increase the dimensional stabillty of the
photographic materials. Typically synthetic polymers
include those described ~n Nottorf U.S. Patent 3,1429568
issued July 28, 1964; White U.S. Patent 3,193,386 issued
July 6, 1965; Houck et al U.S. Patent 3,o62,674 issued
3 November 6~ 1962; Houck et al U.S. Patent 3,220,844 issued
November 303 1965; Ream et al U.S. Patent 3,287~289 issued
November 22, 1966; and Dykstra U.S. Patent 3,411~911
issued November 19, 1968. Other vehicle materials include
those water-insoluble polymers of alkyl acrylates and
methacrylates, acrylic acid, sulfoalkyl acrylates or meth-
acrylates, those which have cross-linking sites which
facilitate hardening or euring as described in Smith
U.S. Patent 3,488,708 issued January 6, 1970, and those
~ , ~: : : .,
1~99 ~912
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having recurring sulfobetaine units as described ln
Dykstra Canadian Patent 774,054.
The vehicles and binders are typically coated
from aqueous dispersions. The preferred hydrophilic
colloids for coating purposes are gelatin and related
derivatives. Gelatin and gelatin der:lvatives are typically
coated in a concentration of from about 0.1 to 10 percent,
preferably 2 to 6 percent, by weight, dry, based on total
weight. The other hydrophillc colloids can be coated in
similar concentration levels.
: The silver halide photographic emulsions employed
can be Or any conventional, convenient ~orm. For example,
the silver halide emulsion types set forth in Paragraph I,
Product Licensing Index, Vol. 92, December 1971, Item 9232,
15 can be employed. The emulsions can be washed as described -~
in Paragraph II, chemically sensitized, as desc:ribed in
Paragraph III and/or spectrally sensitized, as described
in Paragraph XV. The emulsion and other hydrophilic
colloid-containing layers of the photographic elements
can contain development modifiers, as described in
Paragraph IV, antifoggants and stabillzers, as described
in Paragraph V, developing agents, as described in
Paragraph VI, hardeners, as described in Paragraph VII,
plasticizers and lubricants, as described ln Para~raph XI,
:~ ~5 coating aids, as described in Paragraph XII, matting
agents, as described in Paragraph XIII, brighteners, as
described in Paragraph XI~, and absorbing and ~llter dyes,
as described in Paragraph XVI. The various addenda can be
incorporated by known methods of addition, as descrlbed
3 in Paragraph XVII. The photographic elements can contain
antistatic layers, as set forth in Paragraph IX. The
color-forming materials, particularly the dye forming
couplers, can be chosen from those illustrated by
Paragraph XXII. The dye-forming couplers which form the
dye image to be vlewed need not be coated in a coupler
solventg but can be coated ln any conventional manner
lllustrated by the patents in Paragraph XVIII. As these
patents further illustrate, interlayers can be provided
.
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~95~'7~2
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between adjacent layer units containing compounds such as
ballasted hydroquinones to prevent migration out o~ the
layer unit of oxidized developing agent. Coating of the
various materials can be undertaken employing procedures
such as those described in Paragraph XVIII. Product
Licensing Index is published by Industrial Opportunitles
Ltd., Homewell, Havant Hampshire, P09 lEF, UK.
The silver halide emulsion and remaining layers
of the photographic elements can be coated on any con-
ventional photographic support. For proJection film
applications including an integral sound track the support
; i~ specularly transmissive--eOg., transparent For such
applications conventional photographic film supports can
be employed, such as cellulose nitrate film, cellulose
acetate film, poly(vinyl acetal) film, polystyrene film,
poly(ethylene terephthalate) film, polycarbonate film and
similar resinous film supports.
In one preferred mode of exposure the photo-
graphic element is panchromatically exposed and an edge
portion of the film is exposed to infrared radiatlon to
form the sound track. When this mode of exposure is
undertaken, the silver halide grains in the sound track
recording layer unit are spectrally sensitized with lnfra-
~ed absorbing spectral sensitizing dyes. Typical useful
25 infrared spectral sensitizing dyes are described, ~or
example, in Trivelli et al U.S. Patent 2,245,236, lssued
June 10, 1941; Brooker U.S. Patents 2,095,854 and 2,095,856
issued October 12, 1937; Dieterle U.S. Patent 2,G84,436,
issued June 22, 1937; Zeh U.S. Patent 2,104,064, issued
3D January 4, 1938; Konig U.S. Patent 2,199,542, issued May
7, 1940; Brooker et al U.S. Patent 2,213~238, issued
September 3, 1940; Heseltine U.S. Patents 2,734,900 and
3,582,344, issued February 14, 1956 and June lg 1971,
respecti~elyS Barth et al U.S. Patent 2,134,546, issued
October 25, 1938; Brooker U.S. Patent 2,186,624~ issued
January 9, 1940; Schneider U.S. Patent 2,073,759, issued
March 16, 1937; Thompson U.S. Patent 2,611a695, issued
September 23, 1952; Brooker et al U.S. Patent 2,955,939,
.. . . . .
- 15 -
issued October 11, 1960, Jenkins et al U.S. Patent 3,573,921,
issued April 6, 1971; Jeffreys U.S. Patent 3g552~974
issued January 5, 1971; and Fumia et al U.S. Paten~s.
3,482,978, 3,623,881 and 3,652,288, i.ssued December 9,
1969, November 30, 1971 and March 28, 1972, respectlvely.
~ The photographic elements can be processed to
form dye images which correspond to or are reversals Or
the silver halide rendered selectively developable by
imagewise exposure by con~entional techniques. Multlcolor
reversal dye images can be formed in photographic elements
having differentially spectrally sensitlzed silver halide
layers by black-and-white development followed by a single
color development step, as illustrated by the Kodak Ekta-
chrome~ E4 and E6 and Agfa processes descrlbed in 3rltish
Journal of ~ Annual, 1977, pp. 194-197, and
British Journal of Photography, pp. 6~8-669. The photo-
graphic elements can be adapted for direct color reversal
processing (i.e., production of reversal color images
without prior black-and-whlte development), as illustrated
by Barr U.S. Patent 3,243,294, Hendess et al U~S. Patent
3,647,452; Puschel et al U.S. Patents 3,457,077 and
3,467,520 and German OLS 1,257,570, Accary-Venet U.X.
Patent 1,132,736; Schranz et al German OLS 1,2~9,7003 Marx
et al German OLS 1,259,701; Muller-Bore German OLS
2,005,091 and U.K. Patent 1,0751385.
Multicolor dye images which correspond to the
silver halide rendered selectlvely developable by image-
wise exposure, typically negative dye images, can be
produced by processing, as illustrated by the Kodacolor C-
22, the Kodak Flexlcolor C-41 and the Agfa color processes
described in British Journal o~ Photo~raphy Annual, 1977,
pp. 201-205. The photographic elements can also be pro-
cessed by the Kodak Ektaprint-3 and -300 processes as
described in Kodak Color Dataguide, 5th Ed., 1975, pp. 18-
19, and the Agfa color process as described in British
Journal of Photo~raph~ Annual, 1977, pp. 205-206.
The photographic elements can be processed in
the presence of reducible species, such as transltion
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metal ion complexes (e.g. cobalt(III) and ruthenium(III)
complexes containing amine and/or ammine ligands) and
peroxy compounds (e.g. hydrogen peroxide and alkali metal
perborates and percarbonates~.
Dye images can be formed or amplified by pro-
~esses which employ in combination with a dye image-
generating reducing agent an inert transition metal ion
complex oxidizing agent, as illustrated by Bissonette U.S.
Patents 3,748,138, 3,826,652, 3,862,842 and 3,989,526 and
Travis U.S. Patent 3,765,891, and/or a peroxide oxidizing
agent, as illustrated by Mate~ec U.S. Patent 3,674,490,
; Research Disclosure, Vol. 116, December 1973, Item 11660,
and Bissonette, Research Disclosure, Vol. 148, August
1976, Items 14836, 14846 and 14847. The photographic
elements can be particularly adapted to form dye lmages by
such processes, as illustrated by Dunn et al U.S. Patent
3~822,129; Bissonette U.S. Patents 3,834,907, 3,847,619
and 3,902,905 and Mowrey U.S. Patent 3,904,413.
In a specific preferred application the photo
graphic elements of this invention are employed to form a
motion picture film for pro~ection containing an integral
sound track useful in a pro~ector having an S-l photocell.
The photographic element is comprised of a transparent
film support on which are coated, ln the order recited, a
25 red-sensitized cyan dye-forming coupler contalning first
layer unit, a green-sensitized magenta dye-forming coupler
containing a second layer unit, a blue-sensitive yellow
dye-forming coupler containing third layer unit and an
infrared-sensitized fourth layer unit containing coupler
solvent particles according to this invention, as has been
described above. The picture recording portion o~ the
; element is flashed to infrared and is then exposed to the
blue, green and red portions of the spectrum through a
master image film. The master image film has a transparent
support and has been processed so that lt carries a posi-
tive mlllticolor dye image. The edge of the photographic
element on which the integral sound track is to be formed
is panchromatically exposed through a positive sound track
1~9~
17 - ;
master by a light source to which at least the rourth layer
unit is sensiti~e. In a preferred form this ls a whlte
light source which exposes the red-sensltized~ green-sensi-
tized and blue-sensitive layer unlts. The fourth layer
unit by reason of its natlve sensitlvity to blue llgh~ ~s
a-lso exposed ~y the white light source. The white ~ight
source can also emit infrared to expose the fourth layer
unit. The photographic element after exposure of bot~ the
picture and sound track areas is reversal processed. In
reversal processing of negatlve-working silver halide
emulsions, positive dye images are formed in unexposed
areas. Since the picture area was uniformly ~lashed to
~ infrared~ no density attributable to the fourth layer unit
; is present in the picture area. In the sound track area
the ma~or portion of the infrared density is attributable
to the fourth layer unit, but the other layer uni~s can
also add to the total infrared denslty.
In another speclfic application whlch further
illustrates the diversity o~ uses contemplated, a motion
picture pro~ection film containing an lntegral sound trac~
- can also be obtained using a fourth layer unit which ls
spectrally sensitized to the region of 470 to 500 nm. The
element can be exposed in picture recording areas through a
multicolor negative master lmage film with red, green and
blue (420 to 470 nm) light. The film sound track area can
be exposed through a negative master sound track using a
light source emitting ln at least the 470 to 500 nm region
of the spectrum. Using negative-working silver hallde
emulsion in the layer units~ development produces in pic~
3 ture and sound track areas of the element positive dye
images. The sound track image ls formed prlmarily by the
fourth layer unit.
In processing to form dye images in the manner
described above any conventional color developlng agent can
be employed which will permlt the formation of a micro-
crystaliine dye. Depending upon the speci~ic color develop-
ing agent selected9 the maxi~um dye densities, the wavelength
of the peak densitles and the increased breadth of batho-
~i~.`7~ ,
.. ' ";' ;. ' '' ' ': ' ~ . ` ' `
9'9'7~:
. .
- 18 -
chromic absorption will vary. The color developing agent
4-amino-3-methyl N-~-(methanesulfonamide)ethylanlllne sul-
fate hydrate has been observed to produce microcrystalline
infrared absorbing dye images having a maximum denslty in
excess of 1.0, often in excess ln of 2.0, not only at 800
nm~ but over the entire spectral region of from about 750
to 850 nm. Such microcrystalline infrared absorbing dye
images are ldeally suited to forming dye sound tracks for
use in motion picture pro~ection film equipment employing
S-l and similar photocells intended to respond to silver
sound tracks. In the photographic elements Or this inven~
tion can be produced infrared absorbing dye sound tracks
which are comparable in fidelity with the silver sound
tracks they are intended to replace, although a somewhat
higher gain may be required for comparable decibel output,
since the dye sound track is of somewhat lower maximum
density than are silver sound tracks.
As employed herein, the term "microcrystalline
dye" refers to a dye which is present in a crystalline
physical form, but the slze o~ the dye crystals are too
small to be visually detected with the unaided eye. Such
crystals can sometimes be seen upon microscopic examina-
tion, but in many instances the crystals are of submicro-
scopic sizes. Since each dye is a reaction product of a
coupler and an oxidized color developing agent in a coupler
solvent particle, it follows that the steric configuration
of the coupler, the developing agent and the coupler solvent
as well as thelr relative proportions all influence the
crystallinity of the dye produced. The choice of the
coupler is generally most important to forming photographic
elements which can form microcrystalline dyes. The forma-
tion of mixed phases of microcrystalline and noncrystalline
dyes is specifically contemplated and is in many instances
preferred to permit the formation of broadened absorption
peaks. It is believed that the broadening of the absorp-
tion peak is the product Or two unresolved or fused absorp-
tion peaks---one attributable to the microcrystalline dye
produced and the other attributable to the noncrystalline
7~2
- 19 -
dye produced. Although at least a portion of the dye pro-
duced is microcrystalline, it should be noted that the
couplers are not themselves crystalline, since crystallinity
in couplers produces si~nificant loss of dye density attri-
butable to lack of availability of the coupler as well as
severe problems in dispersing and coating the crystalline
coupler.
Crystallinity, particularly submicroscopic micro-
crystallinity, can be ascertained by a number of known
general analytical techniques as well as by some techniques
which are peculiar to the photographic arts. In photogra-
phy microcrystalline dyes are commonly associated with
shifts in hue as a function of concentration and by
asymmetrical absorption peaks. Both hyposchromic and
bathochromic shifts attributable to microcrystallinity
have been observed in varied conventional dye structures.
Microcrystalline dyes have, for example, found applica-
tions in photographic elements because of their sharp
transition between high peak and low toe densities, as
illustrated by S. J. Ciurca, Research Disclosure, Vol. 157,
May 1977, Item 15730. Analytical techniques, such as X-ray
diffraction and detection of birefringence, can also be
employed to identify crystalline structure. Such analyti-
cal techniques are described by A. Weissberger and B. W.
Rossiter, Techniques of Chemistry, Physical Methods of
__ _ _
Chemistry, Vol. 1, p. 3A-D, Wiley, 1972.
Examples
The practice of this invention can be better
appreciated by reference to the following examples:
_ample 1
A. A sample of N-(2,4-di-_-amylphenoxybutyl)-
5,6,7,8-tetrafluoro-1-hydroxy-~-naphthamide, hereinafter
designated Coupler 1, was prepared in the following manner:
To 2.0 grams of phenyl 5,6,7,8-tetrafluoro-1-
hydroxy-2-naphthoate were added 2.0 grams 4-(di-2,4-t-
amylphenoxy)butylamine. ~he mixture was heated at 130C
for 1 hour with constant stirring. Following cooling to
1~9~
- 19a -
room temperature 100 ml of n-hexane were added~ The mix-
ture was heated to dissolve the gummy solid and then
cooled in an ice bath to give an off-white solid. Re-
crystallization from fresh n-hexane gave 1.2 grams of a
white product, m.p. 95 to 96C. Coupler 1 is of the
following structure:
.
:' 10
.
3o
- . :-
~9~7~z
- 20 ~
F~I `5' I- -I`IH-(CH ) -0-~ -C H -t
S C H -t
F s 11 -
B. A sample of N-(2-tetradecylphenyl)-5,6,7,8-
tetrafluoro-l-hydroxy-2-naphthamide, hereinafter designated
Control Coupler l was prepared for purposes of comparison
with Coupler l. It is to be noted that Coupler l and
Control Coupler l have the same molecular weight and are
isomers. Control Coupler l is of the following structure:
F-~ -C-NH--~ \
F 14 2~ _
Example 2
A. A photographic element having a transparent
film support and a gelatino-silver halide emulsion layer
was prepared. The emulsion coatin~ contained the ingre-
dients set ~orth below in Table I. Unless otherwise
stated, all coating coverages in the examples are reported
parenthetically in terms of grams per square meter.
Silver halide coverages are reported in terms of silver.
Table I
Photographic Element 2-A
Gelatlno-Silver Halide Emulsion Layer: Silver
Bromoiodide (l.47), Gelatin (4.86); Coupler l
(0.93); Coupler Solvent Di-n-butyl phthalate
~o.46~
. .
Transparent Film Support
The coupler was dispersed in the coupler solvent which was
in turn dispersed in particulate form in the gelatin of
the silver halide emulsion.
B. A sample of the photographic element was
exposed for l/50 second at a color temperature of 3000K
, ~ . -
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` - 21 -
with an Eastman lB sensitometer through a graduated density
step ob~ectO The test object had 21 equal density steps
ranging from 0 density at Step 1 to a density of 3.0 at
Step 21.
C. The exposed sample of the photographic
element was then processed at 20C in the following manner:
The sample was developed for 10 minutes in the
color developer set forth in Table II.
Table II
Color Developer
800 ml Water
4.0 ml Benzyl alcohol
0.5 g Sodium hexametaphosphate ~:
2.0 g Sodium sulfite :
0.4 ml 40% Sodium hydroxide solution
5.0 g 4-Amino-3-methyl-N-ethyl-N-~-
(methanesulfonamido)ethylaniline
sulfate hydrate
50.0 g Sodium carbonate
1.72 ml 50% Sodium bromide solution :~
- Water to 1 liter~ pH 10.75
The sample was then immersed in a stop-fix bath
for 5 minutes. The composition of the stop-fix bath is
set forth in Table III.
: 25 Table III ~:
: Stop-Fix Bath
:
: 800 ml Water
240 g Sodium thiosulfate
g Sodium sulfite
304~ ml 28% Acetic acid solution
7.5 g Boric acid
15.0 g Potassium Alum
Water to 1 liter, pH 4.25
The sample was washed for 5 minutes in water
and then immersed for 5 minutes in a bleach bath of the
; composition set forth in Table IV.
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- 22 -
Table IV
Bleach Bath
800 ml Water
21.5 g Sodium bromide
100.0 g Potassium ferricyanide
7 g NaH2P04 H20
Water to 1 liter~ pH 7.0
The sample was again washed for 5 minutes in water,
again immersed for 5 minutes in the stop-fix bath of Table
III, again washed for 5 minutes in water and allowed to dry.
D. In Figure 1 a plot of density versus wave-
length is shown. The reference numerals applied to the
curves refer to the step number of the step tablet through
which that portion of the sample was exposed. It can be
seen where low maximum dye densities were produced the
absorption peak produced by the dye was in the vicinity of
about 700 to 725 nm. In Curve 15 and in the lower numbered
curves broadening of the absorption peak and shifting
the peak to well above 800 nm is in evidence. In Curves
13, 11 and 9 the absorption peak eY~tends over the entire
spectral region about 700 nm to above 850 nm. In Curve 9
the second absorption peak above 800 nm has clearly become
predominant.
E. When a procedure generally similar to that
described above was repeated substituting Control Coupler 1
for Coupler 1 a maximum dye density was obtained as illus-
trated by Curve Cl in Figure 1. It can be seen that the
dye had a maximum density in the range of about 700 nm.
There is no evidence of spreading of the absorption peak~
3 and the density of the dye in the region of 800 nm is
relatively low. The Curve Cl is the curve for the step
which produced the highest peak density. The other steps
produced progressively lower dye densities. In each
instance the peak dye density observed for a given step in
an element containing Control Coupler 1 was lower than
that for the corresponding step employing Coupler 1.
: . :, , : ~
. , .: . , , :
,
- 23 -
F. When another color developer was emplcyed
containing 4-amino-3-methyl-N,N-diethylaniline hydro-
chloride as the developing agent, a higher peak dye
density was obtained with Control Coupler l, but the
absorption peak remained at about 70Q nm and showed no
evidence of broadening. The absorption of the dye pro-
duced with Control Coupler l and this developing agent
was relatively low at 800 nm. With this developing agent
Coupler l produced a dye image, the peak absorption being
at about 720 nm. No broadening of the absorption curve
was in evidence, and the absorption was relatively low in
the region of from 800 to 860 nm.
The invention has been described with particular
reference to preferred embodiments thereof but it will be
understood that variations and modifications can be
effected within the spirit and scope of the invention.
; 35
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