CA1099742A - Fluorinated 1-hydroxy-2-naphthamide coupler, coupler compositions and photographic elements suited to forming integral sound tracks - Google Patents

Abstract

Abstract of the Disclosure Fluorinated l-hydroxy-2-naphthamide couplers which are N-substituted with a lower alkylphenoxybutyl ballasting group are disclosed as well as compositions and photographic elements containing these couplers in coupler solvent particles. The coupler solvent particles are comprised of a combination of a coupler solvent and the coupler capable of permitting the formation of a micro-crystalline dye. Surprisingly these microcrystalline dyes exhibit a broadened absorption characteristic in the 750 to 850 nm region of the spectrum. Dye images having such absorption characteristics are particularly suited to forming integral infrared absorbing sound tracks in photo-graphic elements, such as motion picture projection films.

Description

FLUORINATED l-H~DROXY-2-NAPHTHAMIDE COUPI,ER COUPLER
_ . .. .. . ... .
COMPOSITIONS AND PHOTOGRAPHIC ELEMENTS SUITED_TO FORMING
INTEGRAL SOUND TRACKS
-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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~a~99~7~z 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

: 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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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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~'' : ~ 35 -. , , 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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g 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 ' '' 39~742 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 ,~

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3`~2 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 .

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 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, .. . . . .

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~ , .. ' ";' ;. ' '' ' ': ' ~ . ` ' `

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. .

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 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

, ~ . -: ~ . , . . , :, , ~C~9~ 2 ` - 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.

~.~. ...
~ ................ ... . . ... .. .
- ' ; , -,: ~ ~. :

." ~ . , ,: . :: . : .

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.

: . :, , : ~
. , .: . , , :

, 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 , ,: .. :
,. :,; , , ,,- :. . : ~
:-:, ,: :, : - -: : .

Claims (20)

What is claimed is

1. In a silver halide photographic element comprising a support and, coated thereon, at least one layer unit which comprises a photographic silver halide emulsion layer and coupler solvent particles dispersed in a photographically useful amount in said emulsion layer or in an adjacent hydrophilic colloid layer, the improvement wherein said coupler solvent particles are comprised of a combination, capable of permitting the formation of a microcrystalline dye, of a coupler solvent and a coupler of the formula wherein R is a coupling-off group and R1 is an alkyl group of from 1 to 6 carbon atoms.

2. In a silver halide photographic element comprising a support and, coated thereon, at least one layer unit which comprises a photographic silver halide emulsion layer and coupler solvent particles dispersed in a photographically useful amount in said emulsion layer or in an adjacent hydrophilic colloid layer, the improvement wherein said coupler solvent particles are comprised of a combination, capable of permitting the formation of a microcrystalline dye, of a coupler of the formula wherein R is a coupling-off group and R1 is an alkyl group of from 1 to 6 carbon - 24a -atoms, and a coupler solvent which is a lower alkyl ester of phthalic acid, wherein lower alkyl is from 1 to 6 carbon atoms, said coupler and said coupler solvent being present in a weight ratio of from 5:1 to 1:2.

3. An improved photographic element according to claim 2 wherein the coupling-off group is hydrogen.

4. An improved photographic element according to claim 2 wherein R1 is in each occurrence the same alkyl group.

5. An improved photographic element according to claim 2 wherein R1 is an amyl group.

6. An improved photographic element according to claim 2 wherein said coupler solvent is a lower alkyl diester of phthalic acid.

7. An improved photographic element according to claim 2 wherein said coupler solvent is dibutyl phthalate.

8. An improved photographic element according to claim 2 wherein said coupler and said coupler solvent are present in a weight ratio of from 4:1 to 1:1.

9. An improved photographic element according to claim 2 wherein said element includes at least three layer units, one spectrally responsive to the blue region of the spectrum and containing a yellow dye-forming coup-ler, one spectrally responsive to the green region of the spectrum and containing a magenta dye-forming coupler and one spectrally responsive to the red region of the spec-trum and containing a cyan dye-forming coupler.

10. An improved photographic element according to claim 2 wherein said coupler is present in a concentra-tion sufficient to yield a maximum dye density of at least 1 at the 800 nm region of the spectrum.

11. An improved photographic element according to claim 2 wherein said coupler is present in a concentra-tion of from 0.40 to 1.30 grams per square meter.

12. A photographic element adapted to form an integral infrared absorbing dye sound track capable of producing a maximum density in excess of 1 throughout the spectral region of from 750 to 850 nm comprising a transparent film support and a layer unit coated on said film support comprising a gelatino-silver halide emulsion layer containing coupler solvent particles comprised of N-(2,4-diamylphenoxybutyl)-5,6,7,8-tetrafluoro-1-hydroxy-2-naphthamide infrared absorbing dye-forming coupler and a dibutyl phthalate coupler solvent, said coupler and said coupler solvent being present in a weight ratio of from 4:1 to 1:1.

13. A photographic element according to claim 12 wherein said coupler and said coupler solvent are present in a weight ratio of from 2.5:1 to 1.5:1.

14. 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 photographically useful amount comprised of a combina-tion, capable of permitting the formation of a micro-crystalline dye, of a coupler solvent and a coupler of the formula wherein R is a coupling-off group and R1 is an alkyl group of from 1 to 6 carbon atoms.

15. A composition which can be coated to form a layer of a photographic element comprising a hydrophilic colloid and coupler solvent particles dispersed therein a photographically useful amount comprised of a combination, capable of permitting the formation of a microcrystalline dye, of a coupler of the formula wherein R is a coupling-off group and R1 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, said coupler and said coupler solvent being present in a weight ratio of from 5:1 to 1:2.

16. A gelatino-silver halide emulsion which can be coated to form a layer of a photographic element compris-ing coupler solvent particles dispersed therein in a photographically useful amount comprised of a combination, capable of permitting the formation of a microcrystalline dye, of a coupler of the formula wherein R1 is an alkyl group of from 1 to 6 carbon atoms and a coupler solvent which is a lower alkyl diester of phthalic acid, said coupler and said coupler solvent being present in a weight ratio of from 4:1 to 1:1.

17. A gelatino-silver halide emulsion which can be coated to form a layer of a photographic element compris-ing coupler solvent particles dispersed therein in a photographically useful amount comprised of N-(2,4-diamyl-phenoxybutyl)-5,6,7,8-tetrafluoro-1-hydroxy-2-naphthamide and dibutyl phthalate in a weight ratio of from 2.5:1 to 1.5:1.

18. 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 wherein R is a coupling-off group and R1 is an alkyl group of from 1 to 6 carbon atoms.

19. A coupler according to claim 18 wherein is amyl in each occurrence.

20. The coupler N-(2,4-di-t-amylphenoxybutyl)-5,6,7,8-tetrafluoro-1-hydroxy-2-naphthamide.