CA1182676A - Photographic product including a spacer layer containing light reflecting pigment and inert polymer particles - Google Patents
Photographic product including a spacer layer containing light reflecting pigment and inert polymer particlesInfo
- Publication number
- CA1182676A CA1182676A CA000403748A CA403748A CA1182676A CA 1182676 A CA1182676 A CA 1182676A CA 000403748 A CA000403748 A CA 000403748A CA 403748 A CA403748 A CA 403748A CA 1182676 A CA1182676 A CA 1182676A
- Authority
- CA
- Canada
- Prior art keywords
- layer
- silver halide
- halide emulsion
- image
- dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/42—Structural details
- G03C8/52—Bases or auxiliary layers; Substances therefor
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Thin Film Transistor (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Liquid Crystal (AREA)
Abstract
Abstract or Technical Disclosure Photosensitive elements are disclosed which employ a spacer layer between a silver halide emulsion layer and the adjacent layer of image-providing material, the spacer layer comprising a light-reflecting pigment in a dispersion of inert polymeric particles. The photosensitive elements are particularly useful in photographic films for forming multicolor diffusion transfer images.
Description
;~ ` 3 ~ 6~
`I
This invcnt:ion rclato3 ~o uho~o~Jraphy ~nd, mo~c particularly, ~o di~fusiorl trans~er phot:ography.
U . S . P~ter~t ~lo . 2, 9~3, 6Q6, issucd M~y 9, 1961 to 11oward G. P~ogers, a pho~osensi.t;ive elcmen~ containiny ~ clye S d~:veloper and a silvcr hAli~e cmulsion is p~,otoexposct;l and a proccssing compositiosl ~pli~d thereo~ or ex~mple, l~y ,l imtnersion~ coatin~/ ~ipxaying, ~lowin~, cl:c., in l;ht- d~rk.
,¦ The exposed photosensi~ive elemen~ superposctl priQr t;o, 'l during~ or ~ cr th~ processil ~ composition is applied, on ,l 10 a ~;heet-:Liko suppor~ element which may be ul~ilized ~s ~n .!1 ima~ rec~ivir~ ~lcmeni;. In 3 pre~rr~wd embodimenkl l;he E)roc~ss~ng composition is applied l:o the exposed pho~osensi~ ivc ~lemen~ in a substan~ially uni~orm layer as ~hc photosensi~ive ! element is ~rou~ht ir~to superposed relationship with thc image~r~ceiving layer~ 'rhe proc~ssing composition, posi~ioncd ! intermediate the photosensi~ive element and the ima~e-rec iving , layer~ p~xme~tes ~he emulsion to initiate developm~nt o the ii latent image contained ther~ . The dye developcr is i~TuTIobilized ¦ or precipitated in exposed a~eas as a cons~uence of ~he ! 20 develo~men~. In unexposed and partially exposed areas o~
the emulsion, the dye developer is unxeacted and dif~usible and thus provides an imagewi~ distribution of unoxidized ¦ dye dev~loper, diffusible in the proccssing composition, as a ~unction o~ the point--to-point decJree of exposure o~
the silve~ halide emulsion. At lcast part of this imacJe~Ji~c dis~ribu~i.on of unoxidized dye deYeloper is ~ra~sf~rred, by in~ibitiorl, to a superposed image receiving la~er or ~lemen~, said ~rans~Gr substantially excludinc3 oxidi~cd dye d~-veloper.
The i~age-receiving layer receives a depthwise dif~usion, ; -1~
.
826 ~6 .~om thf dev~loped ernulsiQn, o~ unoxidl~,ecl dy~ dcvclopcr without appreciably dis~urbin~ the imagewis~ dis~ribu~ion .¦ ~hereof to provide a xeversed or posi~ive color im~c o~ c !~ developed image. The image-receivin~ elernent may contain agents adap~ed to mordant or o~herwise ~ix ~he di~u~ed, unoxidized d~e developer. In a prefexred embodimc~t ~ said ¦ U~ S. Pa~ent ~o. 2,983,606 and ln cer~ain commcrcial .1 applications thereo~, ~he desired posi~ivc imagc is reve~lcdby saparatinc the image-receiving lay~r ~rom ~he pho~osQnsi~iv~
.1 10 element at the end o~ a suitable i~ibition period. Al~er~a-,~ tlv~ly, as also disclosed ln said U. S. Paten~ No. ~,9~3,G06.1¦ ,and as embodied in certain other co~mercial applications 'I thereo~, the image-receiving layer need not be separ~ted from its superposed ccntact with the photosensitive element, subse~u~nk to trans~er image ~oxmation, if ~he suppor1 for . the image-receiving layer, as well as any other layers l in~ermediate said support and imag~-receiYincJ layer, is ;~ transparent and a proces~i~g composltion containing a ~, substa~ce, e.g., a white pigment, e~ectiv~ to m~sk ~he developed silver halide emulsion or emulsions is applied be~ween the image-receiviI-g layer and said silver halide ' emulsion or ~mulsions.
Dye developers, as noted in ~aid U. S. Patent ~o.
`I
This invcnt:ion rclato3 ~o uho~o~Jraphy ~nd, mo~c particularly, ~o di~fusiorl trans~er phot:ography.
U . S . P~ter~t ~lo . 2, 9~3, 6Q6, issucd M~y 9, 1961 to 11oward G. P~ogers, a pho~osensi.t;ive elcmen~ containiny ~ clye S d~:veloper and a silvcr hAli~e cmulsion is p~,otoexposct;l and a proccssing compositiosl ~pli~d thereo~ or ex~mple, l~y ,l imtnersion~ coatin~/ ~ipxaying, ~lowin~, cl:c., in l;ht- d~rk.
,¦ The exposed photosensi~ive elemen~ superposctl priQr t;o, 'l during~ or ~ cr th~ processil ~ composition is applied, on ,l 10 a ~;heet-:Liko suppor~ element which may be ul~ilized ~s ~n .!1 ima~ rec~ivir~ ~lcmeni;. In 3 pre~rr~wd embodimenkl l;he E)roc~ss~ng composition is applied l:o the exposed pho~osensi~ ivc ~lemen~ in a substan~ially uni~orm layer as ~hc photosensi~ive ! element is ~rou~ht ir~to superposed relationship with thc image~r~ceiving layer~ 'rhe proc~ssing composition, posi~ioncd ! intermediate the photosensi~ive element and the ima~e-rec iving , layer~ p~xme~tes ~he emulsion to initiate developm~nt o the ii latent image contained ther~ . The dye developcr is i~TuTIobilized ¦ or precipitated in exposed a~eas as a cons~uence of ~he ! 20 develo~men~. In unexposed and partially exposed areas o~
the emulsion, the dye developer is unxeacted and dif~usible and thus provides an imagewi~ distribution of unoxidized ¦ dye dev~loper, diffusible in the proccssing composition, as a ~unction o~ the point--to-point decJree of exposure o~
the silve~ halide emulsion. At lcast part of this imacJe~Ji~c dis~ribu~i.on of unoxidized dye deYeloper is ~ra~sf~rred, by in~ibitiorl, to a superposed image receiving la~er or ~lemen~, said ~rans~Gr substantially excludinc3 oxidi~cd dye d~-veloper.
The i~age-receiving layer receives a depthwise dif~usion, ; -1~
.
826 ~6 .~om thf dev~loped ernulsiQn, o~ unoxidl~,ecl dy~ dcvclopcr without appreciably dis~urbin~ the imagewis~ dis~ribu~ion .¦ ~hereof to provide a xeversed or posi~ive color im~c o~ c !~ developed image. The image-receivin~ elernent may contain agents adap~ed to mordant or o~herwise ~ix ~he di~u~ed, unoxidized d~e developer. In a prefexred embodimc~t ~ said ¦ U~ S. Pa~ent ~o. 2,983,606 and ln cer~ain commcrcial .1 applications thereo~, ~he desired posi~ivc imagc is reve~lcdby saparatinc the image-receiving lay~r ~rom ~he pho~osQnsi~iv~
.1 10 element at the end o~ a suitable i~ibition period. Al~er~a-,~ tlv~ly, as also disclosed ln said U. S. Paten~ No. ~,9~3,G06.1¦ ,and as embodied in certain other co~mercial applications 'I thereo~, the image-receiving layer need not be separ~ted from its superposed ccntact with the photosensitive element, subse~u~nk to trans~er image ~oxmation, if ~he suppor1 for . the image-receiving layer, as well as any other layers l in~ermediate said support and imag~-receiYincJ layer, is ;~ transparent and a proces~i~g composltion containing a ~, substa~ce, e.g., a white pigment, e~ectiv~ to m~sk ~he developed silver halide emulsion or emulsions is applied be~ween the image-receiviI-g layer and said silver halide ' emulsion or ~mulsions.
Dye developers, as noted in ~aid U. S. Patent ~o.
2,983,606, are compounds which contain, in ~he same mol~cule, both ~h~ cbromophoric sy~te~ o~ a dye and also ~ silvex halide developing ~unc~-ion. By "a silver halide developin~ ~unctLon"
~ -2-6 ~ ~
~, is meank a cJroupincJ acla~t~d ko clevelop exposccl ~ilvcl halidc.
~ A pre~erred silvex halid~ development ~uno~ioll i5 a ., hydroquinonyl yroup~ Xn cJen~r~l, the developmen~ ~unction includes a benz~.noid developing ~unction, th~t is, an ~rom~tlc ,~ 5 developing group which ~o:L~ms ~uinonold or qulJlone subs~ancc~
i when oxidized.
~ul~icolor imacJes may be o~in~d usinc~ cl~c ~ d~vclopers in di~usion trans~er prooesses by several "
t~chni~ues. One such ~echniqu~ co~empl~tes obtaini~lcJ
~ 10 mul~icolor transfer imag~s utilizing dye dev~lopers by ,i~ ~mployment o~ an i~gral mul~i.layer photosensitiv~ element, ;I such ~s is disclosed in ~he a~oremen~ioned U. S. ~atent ~o.
i 2,983,606 ancl in U. S. Pate~t No. 3,345,163 lssued Ockober 3, 1967 to Eclwin ~ Land and l~owaxd G. Rogers, wher~in a~ le~s~
two sel~c~ively sensi~izecl photosensitiv~ skra~a, superposed . on a single su~poxt, are pxocessed~ simultaneously and wi hout , sep~ration, with a single common image receiving layer. A
suitable ar;:a~geme~t o~ this type comprises a sup~ort carryincJ
a red-se~sil:iv~ silver hali~e emulc!ion str~um, a yreen-2a sensi~ive silv~r halide emulsion stra~um and a blue sensi~ivc silvex halide e~ulsion s~ratum, said omulsions h~ving ~ssociated th~rewith, resp~ctively, for example, a cyan d~e developer, a magenta dye developer and a yellow dye developer~ The dye develQper ~y be utili~ed in ~he silver halide emulsion stxatum, ~or ex~mple in ~he forn~ G~ particl~s, or it may be dis~osed in a stratum behind the appropriate silver halidc ~mulsio~ strata. Each sat o~ silve~ halide ~mulsion and ¦ associat~d dye develop r s~rat~ may be separated ~rom o~her s~ts by suitable in~erlay~rs, for ex~mpl~, by ~ l~yer ox s~r~tum of yelatin or polyvinyl alcohol. In ccr~in ~3~
1.
'~ ins~anc~es, it may ~e des:Lrable ~o incorporate a yellow `~ fil~.er in ~ron~ of the ~rcen-sensi~ive emulsion ~nd su~h ,~ yellow fil~er may he incorporated in an int~rlay~L. ~lo~ever, ~¦ where d~ir~ble, a yellow dye dovclopcr o~ the appropria~
~,1 5 spe~ral cherac~eristics and preserl~ in a s~3te capa~lc~ OL
~u~ctioning as ~ yellow ~ilter may bc so employcd a~ a ¦ separat~ yellow ~ r omit~d.
;~ P~rticularly use~ul products ~or ob~aining multicolor dye develop~:r imases are clisclos~d in ~. S. Patent No. 3,ql5,64 . 10 issued December 10, 1968 to ~win ~1. Land. This pa~ent . disclQses photog~aphic products and processes wherein a
~ -2-6 ~ ~
~, is meank a cJroupincJ acla~t~d ko clevelop exposccl ~ilvcl halidc.
~ A pre~erred silvex halid~ development ~uno~ioll i5 a ., hydroquinonyl yroup~ Xn cJen~r~l, the developmen~ ~unction includes a benz~.noid developing ~unction, th~t is, an ~rom~tlc ,~ 5 developing group which ~o:L~ms ~uinonold or qulJlone subs~ancc~
i when oxidized.
~ul~icolor imacJes may be o~in~d usinc~ cl~c ~ d~vclopers in di~usion trans~er prooesses by several "
t~chni~ues. One such ~echniqu~ co~empl~tes obtaini~lcJ
~ 10 mul~icolor transfer imag~s utilizing dye dev~lopers by ,i~ ~mployment o~ an i~gral mul~i.layer photosensitiv~ element, ;I such ~s is disclosed in ~he a~oremen~ioned U. S. ~atent ~o.
i 2,983,606 ancl in U. S. Pate~t No. 3,345,163 lssued Ockober 3, 1967 to Eclwin ~ Land and l~owaxd G. Rogers, wher~in a~ le~s~
two sel~c~ively sensi~izecl photosensitiv~ skra~a, superposed . on a single su~poxt, are pxocessed~ simultaneously and wi hout , sep~ration, with a single common image receiving layer. A
suitable ar;:a~geme~t o~ this type comprises a sup~ort carryincJ
a red-se~sil:iv~ silver hali~e emulc!ion str~um, a yreen-2a sensi~ive silv~r halide emulsion stra~um and a blue sensi~ivc silvex halide e~ulsion s~ratum, said omulsions h~ving ~ssociated th~rewith, resp~ctively, for example, a cyan d~e developer, a magenta dye developer and a yellow dye developer~ The dye develQper ~y be utili~ed in ~he silver halide emulsion stxatum, ~or ex~mple in ~he forn~ G~ particl~s, or it may be dis~osed in a stratum behind the appropriate silver halidc ~mulsio~ strata. Each sat o~ silve~ halide ~mulsion and ¦ associat~d dye develop r s~rat~ may be separated ~rom o~her s~ts by suitable in~erlay~rs, for ex~mpl~, by ~ l~yer ox s~r~tum of yelatin or polyvinyl alcohol. In ccr~in ~3~
1.
'~ ins~anc~es, it may ~e des:Lrable ~o incorporate a yellow `~ fil~.er in ~ron~ of the ~rcen-sensi~ive emulsion ~nd su~h ,~ yellow fil~er may he incorporated in an int~rlay~L. ~lo~ever, ~¦ where d~ir~ble, a yellow dye dovclopcr o~ the appropria~
~,1 5 spe~ral cherac~eristics and preserl~ in a s~3te capa~lc~ OL
~u~ctioning as ~ yellow ~ilter may bc so employcd a~ a ¦ separat~ yellow ~ r omit~d.
;~ P~rticularly use~ul products ~or ob~aining multicolor dye develop~:r imases are clisclos~d in ~. S. Patent No. 3,ql5,64 . 10 issued December 10, 1968 to ~win ~1. Land. This pa~ent . disclQses photog~aphic products and processes wherein a
3 phokos~nsi~ive elemen~ and an image-receiving element are ,~ mai~tain~d in ~ixed relationship prior to exposu~e, and ~his ,~ relationship is main~ained as ~ lamina~e after processi~.~
~n~ image formation D In khese produc~s, the final imag~ is viewed thxough a transpareII~ (support) element ac3~ins~ a ~, light-x~lccti~g, i.e.~ white bacXground~ Photoexpos~e is i made ~hrough said txansparen~ element and applica~ion o~ ~he ~ processing composition provides a layer o~ light-re~lecting .¦ 20 m~erial to provide a whit~ b~ckgxoundO The light-re~l~cting ma~erial (re~erx~d ~o in said patent as ~n "opaci~yinc~ ~gent") ~ is pref~ably titanium dioxide, and it also performs an ¦ opaci~ylng ~unction, iDe., it is e~ec~ive to mask the ! i developed silver halide emulsio~s so that the transfer image mAy be ~iewed without l~ter~erellce there~rom, and i~ also ac~s to protect th~ photoexpose~ silvex halide emulsions rom post-exposure fogging by light passing thxough said transparent layex if the photo~xposed ~ilm unit is removed ~om ~he cam~r~
~efor~ image-~ormation is comp'eted.
,¦ ~. 5. Patent No. 3~6~.~7,437, issucd M~r~h 7, 1972 ~o ~¦ ~d~Jin H. L~nd, is concexrled wii~h improvemen~s in products and ;¦ proc~sses ~isclos~d in said U, S. P~t~nt No. 3,415,6'i4, and disclos~s the pr~vision o~ light-a~sorbincJ ma~erj.als to i; S permit such processes to bc p~1ormed, outside c~ ~he camora in which pho~oexposurc is c~ctQd, und~r much mo.rc in~ensc ient licJI~ conditio~ lic~h~-~bso~blng m~c~ial or eagent~ preferably a p~l~sensi~.ive phthal~in dye, is provided so positioned andJor constituted as no~ to intcr~re witn .' 10 photoexposur~ bu~ SQ posi~-ioned be~we~n the pho~oexpo~ed sil~er halide emulsions and the transpareI~t support during , p~ocessing after photoexposure as to abso~b light which other~ise might ~og the photoexpos~d emulsions. Fur~hermore, th~ light-~bsorbinc3 material is so positioned and/or '~ lS co~stitute~ af~er proc~ssiny as ~o~ to intcrere wi~h viewing the desir~d image shortly a~tex said image has been formed.
InO th~ pre~erred em~odiments, the lic3ht-absorbing ma~erial, also sometimes referred ~o a~ an optical ~ilter ayen~, I is initiall;y con~ined in the processing composition togeth~r ; 2Q with a light-reflec~ing ma~rial~ e.~., titanium dio~idc.
The conce~tration o~ the light-absorbing dye is selected to ~rovid~ the lic3ht tr~nsmission opacity rec3uired to pcrfo~m the ~ar~ic~lar process under the selec ed licJht conditions.
Jn ~ par~iculaxly us~Pul embodiment, the ligh~-absorbinc3 dye is hi~3hly colored at the p~l of the p~ocessing composition, eOgO~ 13-14, but is ~ubs~an~ially non~abso~bincJ
o~ visible light at a lower p~1, e.g., less than 10-12. This pH reduc~io~ may ~e ef~ected by an ~cid-~eac~inc3 reac3cn~
ap}~opria~ly positio~ed in the ~ilm unit, e.g., in a layer ~etwec~ ~he tr~nsparent suppor~ and the image-recelving la~er.
.
_5_ ¦ U. S. Patent No. 3,5~ 5 i~sued Jul~ 20, 19~/1 to }loward C~ Rogers discloses photographic produc~s and process~s whereln ~he image~receivincJ layer is part o~ ~he ~hotosensi~ive elemen~, and this element is main~ained in ~ixed rcl~tionshi~
S wi~l~ a t;;ans~ arer~t cov~r sheet prior ~o ~xposure, ~nd l;his ;; relatlonship is maintained as a laminate a:~er processing and image forma~ion~ In these products, ~he ~inal ima~J~ is . viewed throllc~-h the transparent support Eor ~he pho~osensl~lvc ;~ element, photoexposure beirlc3 e~ec~ed ~hrough the ~r~nspare ~1 lo cover sheet. The photosensitive elemen1- includes ~n o~aclue , layer b~tween the im~ge~receiving layer (positioned adj~cent the tra~sparent support) and the photosensitive layers, and the processi..g composition includes an opacifyinc3 material, ', pre~erably car~on black, so that the exposed ~ilm unit may ", 15 be processed in ambien~ ligh~.
'' As disclGsed in said patents and ln other publications, the image;~orming material may be ini~ially ,I di~usible or i~i~ially non-di~usible and i~ may be an image dye or an image dye intermedlate~
Ganadian Patent No~ 668,592 issued August 13, 1963 discloses the incorporation o~ a lic~ht-re~lecting laycr ~tit~nium dioxide in ~elatin) be~ween a silver halide emulsion layer and the associated layer o~ image dye-providing material, e.g~, a dye developer, to ef~ectively increase the speed o~ the silver halide lay~r. Such li~h~-re~lecting layers are indced use~ul to incr~ase ~he eff~ctivc ~ilm speed as a result o~ ~he reflection of light back to the silver halid~. ~owever, such liyht-re~lec~ing layers have been ~ou~ld tc~ undesirably slow dow~ ~he di~usion o~ ~he underl~ing ir,~age dye-provicling material and, in at leas~
:
some i-~stances, reduce l:he maicimum ~rans~er densil;y a~ a result o;e retention o;E the irnac3e dye i.n tne licJht;-rc:~lec ~ing : layer .
., ln accoxdance wit:h ~;he pxeserlt inven~:ion a spac~:r '~ 5 layer i5 proYided between a silver halid~ emul~;lor~ lay~
and LtS associclted, und~rlying layer oi~ imacJe dyc pxovidinc;
~ matexial~ the spacex layer comprisiny a l~cJh~ lcctlncJ
., pi~ment dispersed in inerl: polymcric :~art;icle~; whlch ar:~substar~tially non-swelling in alkali and substantlall~
la x~on-~ilm-~orming. Th~se sp~cer layers have been ~ound ~o re~quixe lowex coverages o~ the lic3ht-~e~lect;ing pigmen~
to ac:hieve a given light reflectanoe, and l:o pr~sen~
rela~ively little inhibition to ~he dif~uslon o~ th~ imac3e dy~-p~ovidirlg mate~ial to the silver halide cand to tne imag~3-xeceiving layer~
q~he light-le;~lecting pigment may be any picjment ¦ which is phot.ographically i~ert in ~he par~icul~r photogr~phic ~ proc~ss and ~Ihich exhi~its ~he desired reflec~i~ity ~or the ;~ silv~ halid~ emulsion with which it is to be associatedO
The pre~errecl liyht-re~lectillg pigment is titanium dioxide.
The pigment E~article si~e most sui~able ~or an~ partic~lar application may be determined by routine experimentation.
. In the preferred embodiments o~ this inventivn the titanium - dioxide has a particle si~e o~ about 0.2 micron~
The inert, non-swelliny polymeric particles are provaded as a non-coalescing latex to provide minimum inhibition o~ di~using reagents4 The polymer may have an index o~ re~raction which is higher, lower or a~out the same as that o~ gelatin but the index shou}d be le5s than that o~ thP light-re~l~ct:Lng pigment~ hereby increasing ~L
-the reflectivi-ty of a given coverage o:E the pigmen-t. Suitable polymers inclucle polyme-thylmethacrylate, polystyrene and polytetrafluoroethylene.
The spacer layer may include a minor portion of another polymer, such as gelatin or polyacrylamide, to provide a blnder for the pigment and inert polymeric particles, and to provide additional flexibility to the spacer layer.
Thus in a first embodiment -this invention provides a photosensitive element comprising a suppor-t carrying a layer of a silver halide emulsion, a spacer layer, and a layer of an image dye providing material, said spacer layer comprising a light-reflecting pigment and organic photographically inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming, said spacer layer being positioned between said silver halide emulsion layer and said layer of image dye providing material.
In a second embodiment this invention provides a multicolor photosensitive element comprising a support carrying, in sequence, a layer of a cyan image dye-providing material, a layer of a red sensitive silver halide emulsion, an interlayer, a layer of a magenta image dye-providing material~ a layer of a green-sensitive silver halide emulsion, an interlayer, a layer of a yellow image dye-providing material and a layer of a blue-sensitive silver halide emulsion, at least one of said silver halide emulsion layers and its associated layer of image dye-providing material being separated by a spacer layer com-prising a light-reflecting pigment dispersed in organic photo-graphically inert polymeric par-ticles which are subs-tan-tially non-swelling in alkali and substantially non-film forming.
In a third embodimen-t this invention provides a photoyraphic process comprising providlng a layer of a viscous aqueous alkaline processing composition between a first sheet-like element and a second sheet-like element; said Eirs-t sAeet-like element comprising a support carrying an exposed silver llalide emulsion having an imaye dye-providing material in a layer behind said silver halide emu:Lsion; said second shee-t-like element comprising a transparent suppor-t; an image-receiv-ing layer in one of said sheet-like elements, said applica-tion of said processing composi-tion being effec-tive to develop said exposed silver halide emulsi.on and to form a visible image in said image-receiving layer; said silver halide emulsion layer being separated from said layer of image dye-providing material by a spacer layer comprising a ligh-t-reflecting pigment dis-persed in organic photographically inert polymeric particles which are substantially non~swelling in alkali and substanti-ally non-film forming.
In a fourth embodiment this invention provides a diffusion transfer process film unit includiny a first sheet-like element and a second sheet-like element, said fi.rst sheet-like element comprising a support carrying a silver halide emulsion layer; said second sheet-like element compris-ing at least a support; an image-receiving layer carried on one of said sheet-like elements; a viscous aqueous alkaline pro-cessing composition releasably contained in a rupturable container positioned to release said composition for distri-bution between said first and second sheet-like elements with said supports outermost; said first sheet like element includ-ing a spacer layer between said silver halide emulsion layer and a layer of an image dye-providing material associated with said silver halide, said spacer layer comprising a light--8a-re~lec-tlng pigment dispersed in organic photographically inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming.
For convenience r fur-ther description of -this inven-tion will be in the context of -the use of dye developers and positive transfer images.
The Figure illustrates in diagrammatic cross-sec-tion a film unit embodying the present invention, and adapted for use as an integral film lmit of the type described in the above-mentioned United States Patent No. 3,415,644. ~s shown in the Figure, a photosensitive element 60 is positioned in superposed relationship with a transparent image-receiving element 70 through which photoexposure of the photosensitive element is to be effected. Positioned between the photosensi-tive and image-receiving elements 60 and 70 is a rupturable pod 50 releasably holding a processing composition 52. The photosensitive element 60 comprises an opague support 10, a neutralizing layer 12 of a polymeric acid, a layer 14 adapted to "time" the availability of the polymeric acid by preventing diffusion of the processin~ composition thereto for a pre-determined time, a cyan dye developer layer 16, a spacer layer 18 in accordance with this invention, a red-sensitive silver halide emulsion layer 20, an interlayer 22, a magenta dye developer layer 24, a green-sensitive silver halide emulsion layer 26, an --8b-interlayer 28, a yeLlow dye cleveloper layer 30, a blue-sensitive silver halide emulsion layer 32, and a top coat 36. ~'I}le top coat serves as an anti-abrasion layer and also may carry a component of the photographic system9 e.g., an auxiliary cleveloping agent, an ultraviolet light absorber, etc., as is well known in the art). The image-receiving layer 70 compriscs a transparent support ~0 and an image-receiving layer ~2. Photoexposure of the silver halide emulsion layer is efEected throLIgh the transparent support ~0 and the layers carried thereon also are tr~msparent, the film Ullit be:ing so positioned withill the camera that ligh-t admitted through the camera expo-sure or lens system is incident upon the outer or exposure surface o:E thetransparen-t support 40. After exposure the Eilm unit is advanced between suitable pressure-applying members (not shown), rupturing the container or pod 50, thereby releasing and distributing a layer of the opaque processing composition 52 and forming a laminake of the photosensitive element 60 and the image-receiving element 70 with their respective support members provid-ing the outer layers of the laminate. The opaque processing composition con-tains a film-forming polymer, a white pigment and has an initial p~l at which the optical filter agents contained therein are colored; the optical filter agents are selected to exhibit the appropriate ligh~ absorptionJ i.e., optical density, over the wavelength range o:f light actinic to the particular silver halide emulsions. As a result, ambient or environmental light within that wavelength range incident upon the surface of transparent support ~0 and transmitted transversely through said transparent support and the trans-parent layers carried thereon in the direction of the exposed silver halide emulsions is absorbed, thereby avoiding further exposure of the photoexposed and developing silver halide emulsions. In exposed and developed areas, the dye developer is oxidized as a function of the silver halide development and immobilized. Unoxidized dye developer associated with undeveloped and part-ially developed areas remains mobile and is transferred imagewise X
2~
to the image-receiving layer 42 to provide the desired positive :image thereill Permeation of the alkaline processing composition through the timing layer 14 to the neutrali~ing (polymeric acid) layer 12 is so controlled that the process pH is maintcL:ined at a high enough level to effect the requisite development and image transfer and to retain -the optical :E:i.lter agents in colored form withill the processing compos-ition layer and on thc silver halide emulsion side o:E sa-id layer, a:Eter which pH reduction ef:Eected as a result oE alkali permeation :into the polymeric acid layer 12 i.s effective to reduce the pH to a level which changes the optical fi.lter agents to a colorless form. Absorption of the water from the applied layer of the processing composition results in a solidified film composed of the film-forming polymer and the white pigment dispersed therein, thus providing a light-reflecting layer which also serves to laminate together the photosensitive component 60 and the image-receiving component 70 to provide the final integral image. The positive transfer image in dye developer present in the image-receiving layer 42 is viewed through the transparent support 40 against the light-reflecting layer which provides an essentially white back-ground for the dye image and also effectively masks from view the developed photosensitive element 60.
The spacer layer 18 in accordance with this invention com-prises a light-reflecting pigment, e.g., titanium dioxide, dispersed in inert, substantially non-swelling and non-fi.lm forming, polymeric particles, e.g., an uncoalesced polymethylmethacrylate latex. Light passing through the red-sensitive emulsion layer 18 is reflected by the spacer layer 20 to the red-sensitive silver hali.de emulsion, thus effectivel.y increasing the efficiency (speed) of the red-sensitive silver halicle layer. The amount of l:ight reflected by the spacer layer 18 may be adjusted in accordance wi.th the needs of the parti-~cular photographic film by :i.ncreasi.ng or decreasing the coverage of the light-re:flecting pigment.
In the f:ilm Imit i.llustrated in the Figure the l.;gilt-:reflect-ing pigment-conta:in;.llg spacer layer is shown between the cyan clye developer layer and the red-sens:it:ive silver ha].ide emulsion layer. [t w:i.ll be unclerstood that such spacer ].ayers 20 also may be pos:itioned between the magenta dye developer layer 2~ and the green-sensitive silver halide emul.si.on layer 26~ between the yellow dye developer layer 32 and the blue-sensitive silver halide emulsion layer 36, or in any combination of these three locations. Where the light-reflecting pigment-containing spacer layer is so positioned that there is another silver halide emulsion behind it, as in the two positions not illustrated but noted above, it will be understood that the coverage of the light-reflecting pigment may be reduced and the speed of the underlying silver halide emulsion(s) may be increased to adjust for any light loss and thus obtain proper exposure of the underlying silver halide emulsion(s).
The optical filter agent is retained within the final film unit laminate and is preferably colorless in its final form, i.e., e~libiting no visible absorption to degrade the transfer image or the white background therefor provided by the reflecting layer. The optical filter agent may be retained in the reflecting layer under these con-ditions, and it may contain a suitable "anchor" or "ballast" group to prevent its diffusion into adjacent layers. Some of the optical filter agent may diffuse into the photosensitive component and be mordanted by the gelatin or other material present on the si.lver halide ~mulsion side of ~he reflectillg layer; optical filter mordanted in the photosensitive compollent 60 may be colorless or colored in its final state so long as any color exhibited by it is efectively masked by the reflecting layer. In the preferred embodiment, the optical filter agents are pH-sensitive phthalein dyes.
The concell-tratioll oE optical fll-ter agent (indicator dye) is selected to provide the op-tical transm:issioll density required, in combination with other layers intermedia-te the silver halide emuls:ion layers and the inciden-t radiat-ion, to prevent nonimagewise exposure, i.e., fogging, by incident actinic light during -the performallce of the particular photographic process. The transmission density and the optical filter agent concentration necessary to provide the requisite protection from incident light may be readily determined for any photo-graphic process by routine experimentation, as a function of film speed or sensitivity, processing time, anticipated incident light intensity, etc., as described in said United States Patent No. 3,647,437. It will be recognized that a particular transmission density may not be required for all portions of the spectrum, lesser density being suffi-cient in waveleng-th regions corresponding to lesser sensitivities of the particular photosensitive material.
In a particularly useful embodiment, the optical filter agent is a light absorbing dye which is highly colored at the pH of the pro-cessing composition, e.g., 13-14, but is substantially non-absorbing of visible light at a lower pH, e.g., less than 10-12. Particularly suitable are phthalein dyes having a pKa of about 13 to 13.5; many such dyes are descrlbed in the aforementioned United States Patent No.
3,647,437. This pH reduction may be effected by an acid-reacting reagent $
appropiately pos:itioned in the film unit, e.g., in a layer of the photo-sensitive element as shown in the Fi.gure or in a layer between the transparent support and the image-rece:iving layer or in other positions as knQwn in the art.
It will be understood that a mixture o:E light-absorbing materials may be used so as to obtain absorption in all cr:itical areas of the visiblc and near-visible by which the silver halide emulsion being used are exposable. Many dyes which change :~rom colored to colorless AS a ~urlctiQn of pll reduction, e.g., phthalein dyes, are known (see, for example, the aforementioned United States Patent No. 3,6~7,~37) a.nd appropriate selection may be made by one skilled in the art to meet the particular conditions of a given process and film unit.
In those embodiments of this invention involving a ~ilm unit of the type shown in United States Patents No. 3,415,64~ and 3,6~7,~37 and in the Figure and having an optical filter agent in the processing compositi.on, it is advantageous to ,~
~z~
utilize an image-receiving elernent having cl su-rface layer adapted to decolorize the optical filter agent adjacent the interrace.
Suitable decolorizing layers are described in Edwin ~. Land, Leon D. Cerankowski and Neil C. Mattucci, United States Patent No. 4,298,67LI; Irena Bronstein-Bonte, Edward P. Lindholm and Lloyd D. Taylor, United States Patent No. 4,29LI,907 and Charles K. Chiklis and Neil C. Mattucci~ United States Patent No. 4, 367,277 filed concurrently herewith. Of the several "clearing coats" described in said copending applications, the unhardened gelatin clearing coat described and claimed in said application of Chiklis and Mattucci is presently preferred.
Inert, non-swelling polymeric particles of the type herein contemplated for use in spacer layer 20 are described in Peter 0. Kliem, United States Patent No. 4,3Ll7,301 and Canadian Patent No. 1,148,008. The following illustrative example of the preparation of a polymethylmethacrylate latex suitable for use in the practice of this invention is reproduced from said copending applications:
Example A
Water 118 1.
Methylmethacrylate 51 kg.
Potassium persulfate 0.15 kg.
Ascorbic Acid 0.01 kg.
Dowfax* 2A1 20% solution 1.275 kg.
(dodecyldiphenyl oxide disulfonate sodium salt, sold by Dow Chemical Co., Midland, Michigan) ~Trade Mark 63~
A reactor was charged with 102.1 of demineralized water and the Dowfax 2Al and heated under nitrogen to 83C whereupon 7.65 kg. of methylmethacrylate was added and mixed until the temperature returned to 83C. After 5 min~ at 83~, 4.93 kg. of initiator solution (O.lS
kg. of potassium persulfate and 14.79 kg. water) was added. After tl-le exotherm the temperature was reduced to ~5C and the remaining methyl-methacrylate was added at a rate of about 361 g/min. and the remaining initiator solution at a rate of about 111 g/min. At the end of the monomer and initiator solution, the temperature was maintained at 85C for 10 min. and then the ascorbic acid was added. The resulting latex had a 30% solids and about a 0.125 ~ average particle size.
As noted above, the use of the inert polymeric particles permits the use of lower coverag0s of the light-reflecting pigment to achieve a given reflection of light incident on the pigment-containing layer. Thus it has been found that a white light reflection density of about 1.0 may be obtained from a titanium dioxide coverage of about 1000 mg/m2 by the use of a coating comprising, by weight, 8 parts titanium dioxide, 1 part gelatin and 3 parts polymethylmethacrylate.
About 40Q0 mg/m2 of titanium dioxide was found to be needed to give 2Q the same white reflection density when coated using an 8:1 by weight ratio of titanium dioxide and gelatin. ~The white reflection density was measured of the described titanium dioxide layers coated on opaque polyethylene terephthalate having a neutral density of 1.o2.) It will be readily apparent that the present invention provides the ability to use less silver halide to obtain a given film speed.
This in turn may reduce the concentrations needed of other components of the system.
The following example of a film wherein the photosensitive element includes a spacer layer in accordance with this invention is intended to be illustrative and not limiting.
Example l A photosensitive element was prepared by coatingJ on a poly-ethylene glycol tereph~halate baseJ the following layers:
(1~ A neutralizing layer of a partial butyl es~er of poly-ethylene/maleic anhydride copolymer at a coverage o:E about 23,700 mg/m2 and polyvinylbutyral at a coverage of about 2,600 mg/m2.
~2) A timing layer of a 60.6/2~9/6.3/3.7/0.4 pentapolymer of butylacrylate, diacetone acrylamide, styrene, methacrylic acid and acrylic acid at a coverage of about 3,500 mg/m2 and about 524 mg/m2 of gelatin.
(3) A layer of a gelatin dispersion of a cyan dye developer, 6-dodecylaminopurine, and ~'-methylphenylhydroquinone coated at a coverage of about 600 mg/m2 of dye, 225 mg/m2 of 6-dodecylaminopurineg 120 mg/m2 of 4'-methylphenylhydroquinone, and 300 mg/m2 of gelatin.
~n~ image formation D In khese produc~s, the final imag~ is viewed thxough a transpareII~ (support) element ac3~ins~ a ~, light-x~lccti~g, i.e.~ white bacXground~ Photoexpos~e is i made ~hrough said txansparen~ element and applica~ion o~ ~he ~ processing composition provides a layer o~ light-re~lecting .¦ 20 m~erial to provide a whit~ b~ckgxoundO The light-re~l~cting ma~erial (re~erx~d ~o in said patent as ~n "opaci~yinc~ ~gent") ~ is pref~ably titanium dioxide, and it also performs an ¦ opaci~ylng ~unction, iDe., it is e~ec~ive to mask the ! i developed silver halide emulsio~s so that the transfer image mAy be ~iewed without l~ter~erellce there~rom, and i~ also ac~s to protect th~ photoexpose~ silvex halide emulsions rom post-exposure fogging by light passing thxough said transparent layex if the photo~xposed ~ilm unit is removed ~om ~he cam~r~
~efor~ image-~ormation is comp'eted.
,¦ ~. 5. Patent No. 3~6~.~7,437, issucd M~r~h 7, 1972 ~o ~¦ ~d~Jin H. L~nd, is concexrled wii~h improvemen~s in products and ;¦ proc~sses ~isclos~d in said U, S. P~t~nt No. 3,415,6'i4, and disclos~s the pr~vision o~ light-a~sorbincJ ma~erj.als to i; S permit such processes to bc p~1ormed, outside c~ ~he camora in which pho~oexposurc is c~ctQd, und~r much mo.rc in~ensc ient licJI~ conditio~ lic~h~-~bso~blng m~c~ial or eagent~ preferably a p~l~sensi~.ive phthal~in dye, is provided so positioned andJor constituted as no~ to intcr~re witn .' 10 photoexposur~ bu~ SQ posi~-ioned be~we~n the pho~oexpo~ed sil~er halide emulsions and the transpareI~t support during , p~ocessing after photoexposure as to abso~b light which other~ise might ~og the photoexpos~d emulsions. Fur~hermore, th~ light-~bsorbinc3 material is so positioned and/or '~ lS co~stitute~ af~er proc~ssiny as ~o~ to intcrere wi~h viewing the desir~d image shortly a~tex said image has been formed.
InO th~ pre~erred em~odiments, the lic3ht-absorbing ma~erial, also sometimes referred ~o a~ an optical ~ilter ayen~, I is initiall;y con~ined in the processing composition togeth~r ; 2Q with a light-reflec~ing ma~rial~ e.~., titanium dio~idc.
The conce~tration o~ the light-absorbing dye is selected to ~rovid~ the lic3ht tr~nsmission opacity rec3uired to pcrfo~m the ~ar~ic~lar process under the selec ed licJht conditions.
Jn ~ par~iculaxly us~Pul embodiment, the ligh~-absorbinc3 dye is hi~3hly colored at the p~l of the p~ocessing composition, eOgO~ 13-14, but is ~ubs~an~ially non~abso~bincJ
o~ visible light at a lower p~1, e.g., less than 10-12. This pH reduc~io~ may ~e ef~ected by an ~cid-~eac~inc3 reac3cn~
ap}~opria~ly positio~ed in the ~ilm unit, e.g., in a layer ~etwec~ ~he tr~nsparent suppor~ and the image-recelving la~er.
.
_5_ ¦ U. S. Patent No. 3,5~ 5 i~sued Jul~ 20, 19~/1 to }loward C~ Rogers discloses photographic produc~s and process~s whereln ~he image~receivincJ layer is part o~ ~he ~hotosensi~ive elemen~, and this element is main~ained in ~ixed rcl~tionshi~
S wi~l~ a t;;ans~ arer~t cov~r sheet prior ~o ~xposure, ~nd l;his ;; relatlonship is maintained as a laminate a:~er processing and image forma~ion~ In these products, ~he ~inal ima~J~ is . viewed throllc~-h the transparent support Eor ~he pho~osensl~lvc ;~ element, photoexposure beirlc3 e~ec~ed ~hrough the ~r~nspare ~1 lo cover sheet. The photosensitive elemen1- includes ~n o~aclue , layer b~tween the im~ge~receiving layer (positioned adj~cent the tra~sparent support) and the photosensitive layers, and the processi..g composition includes an opacifyinc3 material, ', pre~erably car~on black, so that the exposed ~ilm unit may ", 15 be processed in ambien~ ligh~.
'' As disclGsed in said patents and ln other publications, the image;~orming material may be ini~ially ,I di~usible or i~i~ially non-di~usible and i~ may be an image dye or an image dye intermedlate~
Ganadian Patent No~ 668,592 issued August 13, 1963 discloses the incorporation o~ a lic~ht-re~lecting laycr ~tit~nium dioxide in ~elatin) be~ween a silver halide emulsion layer and the associated layer o~ image dye-providing material, e.g~, a dye developer, to ef~ectively increase the speed o~ the silver halide lay~r. Such li~h~-re~lecting layers are indced use~ul to incr~ase ~he eff~ctivc ~ilm speed as a result o~ ~he reflection of light back to the silver halid~. ~owever, such liyht-re~lec~ing layers have been ~ou~ld tc~ undesirably slow dow~ ~he di~usion o~ ~he underl~ing ir,~age dye-provicling material and, in at leas~
:
some i-~stances, reduce l:he maicimum ~rans~er densil;y a~ a result o;e retention o;E the irnac3e dye i.n tne licJht;-rc:~lec ~ing : layer .
., ln accoxdance wit:h ~;he pxeserlt inven~:ion a spac~:r '~ 5 layer i5 proYided between a silver halid~ emul~;lor~ lay~
and LtS associclted, und~rlying layer oi~ imacJe dyc pxovidinc;
~ matexial~ the spacex layer comprisiny a l~cJh~ lcctlncJ
., pi~ment dispersed in inerl: polymcric :~art;icle~; whlch ar:~substar~tially non-swelling in alkali and substantlall~
la x~on-~ilm-~orming. Th~se sp~cer layers have been ~ound ~o re~quixe lowex coverages o~ the lic3ht-~e~lect;ing pigmen~
to ac:hieve a given light reflectanoe, and l:o pr~sen~
rela~ively little inhibition to ~he dif~uslon o~ th~ imac3e dy~-p~ovidirlg mate~ial to the silver halide cand to tne imag~3-xeceiving layer~
q~he light-le;~lecting pigment may be any picjment ¦ which is phot.ographically i~ert in ~he par~icul~r photogr~phic ~ proc~ss and ~Ihich exhi~its ~he desired reflec~i~ity ~or the ;~ silv~ halid~ emulsion with which it is to be associatedO
The pre~errecl liyht-re~lectillg pigment is titanium dioxide.
The pigment E~article si~e most sui~able ~or an~ partic~lar application may be determined by routine experimentation.
. In the preferred embodiments o~ this inventivn the titanium - dioxide has a particle si~e o~ about 0.2 micron~
The inert, non-swelliny polymeric particles are provaded as a non-coalescing latex to provide minimum inhibition o~ di~using reagents4 The polymer may have an index o~ re~raction which is higher, lower or a~out the same as that o~ gelatin but the index shou}d be le5s than that o~ thP light-re~l~ct:Lng pigment~ hereby increasing ~L
-the reflectivi-ty of a given coverage o:E the pigmen-t. Suitable polymers inclucle polyme-thylmethacrylate, polystyrene and polytetrafluoroethylene.
The spacer layer may include a minor portion of another polymer, such as gelatin or polyacrylamide, to provide a blnder for the pigment and inert polymeric particles, and to provide additional flexibility to the spacer layer.
Thus in a first embodiment -this invention provides a photosensitive element comprising a suppor-t carrying a layer of a silver halide emulsion, a spacer layer, and a layer of an image dye providing material, said spacer layer comprising a light-reflecting pigment and organic photographically inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming, said spacer layer being positioned between said silver halide emulsion layer and said layer of image dye providing material.
In a second embodiment this invention provides a multicolor photosensitive element comprising a support carrying, in sequence, a layer of a cyan image dye-providing material, a layer of a red sensitive silver halide emulsion, an interlayer, a layer of a magenta image dye-providing material~ a layer of a green-sensitive silver halide emulsion, an interlayer, a layer of a yellow image dye-providing material and a layer of a blue-sensitive silver halide emulsion, at least one of said silver halide emulsion layers and its associated layer of image dye-providing material being separated by a spacer layer com-prising a light-reflecting pigment dispersed in organic photo-graphically inert polymeric par-ticles which are subs-tan-tially non-swelling in alkali and substantially non-film forming.
In a third embodimen-t this invention provides a photoyraphic process comprising providlng a layer of a viscous aqueous alkaline processing composition between a first sheet-like element and a second sheet-like element; said Eirs-t sAeet-like element comprising a support carrying an exposed silver llalide emulsion having an imaye dye-providing material in a layer behind said silver halide emu:Lsion; said second shee-t-like element comprising a transparent suppor-t; an image-receiv-ing layer in one of said sheet-like elements, said applica-tion of said processing composi-tion being effec-tive to develop said exposed silver halide emulsi.on and to form a visible image in said image-receiving layer; said silver halide emulsion layer being separated from said layer of image dye-providing material by a spacer layer comprising a ligh-t-reflecting pigment dis-persed in organic photographically inert polymeric particles which are substantially non~swelling in alkali and substanti-ally non-film forming.
In a fourth embodiment this invention provides a diffusion transfer process film unit includiny a first sheet-like element and a second sheet-like element, said fi.rst sheet-like element comprising a support carrying a silver halide emulsion layer; said second sheet-like element compris-ing at least a support; an image-receiving layer carried on one of said sheet-like elements; a viscous aqueous alkaline pro-cessing composition releasably contained in a rupturable container positioned to release said composition for distri-bution between said first and second sheet-like elements with said supports outermost; said first sheet like element includ-ing a spacer layer between said silver halide emulsion layer and a layer of an image dye-providing material associated with said silver halide, said spacer layer comprising a light--8a-re~lec-tlng pigment dispersed in organic photographically inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming.
For convenience r fur-ther description of -this inven-tion will be in the context of -the use of dye developers and positive transfer images.
The Figure illustrates in diagrammatic cross-sec-tion a film unit embodying the present invention, and adapted for use as an integral film lmit of the type described in the above-mentioned United States Patent No. 3,415,644. ~s shown in the Figure, a photosensitive element 60 is positioned in superposed relationship with a transparent image-receiving element 70 through which photoexposure of the photosensitive element is to be effected. Positioned between the photosensi-tive and image-receiving elements 60 and 70 is a rupturable pod 50 releasably holding a processing composition 52. The photosensitive element 60 comprises an opague support 10, a neutralizing layer 12 of a polymeric acid, a layer 14 adapted to "time" the availability of the polymeric acid by preventing diffusion of the processin~ composition thereto for a pre-determined time, a cyan dye developer layer 16, a spacer layer 18 in accordance with this invention, a red-sensitive silver halide emulsion layer 20, an interlayer 22, a magenta dye developer layer 24, a green-sensitive silver halide emulsion layer 26, an --8b-interlayer 28, a yeLlow dye cleveloper layer 30, a blue-sensitive silver halide emulsion layer 32, and a top coat 36. ~'I}le top coat serves as an anti-abrasion layer and also may carry a component of the photographic system9 e.g., an auxiliary cleveloping agent, an ultraviolet light absorber, etc., as is well known in the art). The image-receiving layer 70 compriscs a transparent support ~0 and an image-receiving layer ~2. Photoexposure of the silver halide emulsion layer is efEected throLIgh the transparent support ~0 and the layers carried thereon also are tr~msparent, the film Ullit be:ing so positioned withill the camera that ligh-t admitted through the camera expo-sure or lens system is incident upon the outer or exposure surface o:E thetransparen-t support 40. After exposure the Eilm unit is advanced between suitable pressure-applying members (not shown), rupturing the container or pod 50, thereby releasing and distributing a layer of the opaque processing composition 52 and forming a laminake of the photosensitive element 60 and the image-receiving element 70 with their respective support members provid-ing the outer layers of the laminate. The opaque processing composition con-tains a film-forming polymer, a white pigment and has an initial p~l at which the optical filter agents contained therein are colored; the optical filter agents are selected to exhibit the appropriate ligh~ absorptionJ i.e., optical density, over the wavelength range o:f light actinic to the particular silver halide emulsions. As a result, ambient or environmental light within that wavelength range incident upon the surface of transparent support ~0 and transmitted transversely through said transparent support and the trans-parent layers carried thereon in the direction of the exposed silver halide emulsions is absorbed, thereby avoiding further exposure of the photoexposed and developing silver halide emulsions. In exposed and developed areas, the dye developer is oxidized as a function of the silver halide development and immobilized. Unoxidized dye developer associated with undeveloped and part-ially developed areas remains mobile and is transferred imagewise X
2~
to the image-receiving layer 42 to provide the desired positive :image thereill Permeation of the alkaline processing composition through the timing layer 14 to the neutrali~ing (polymeric acid) layer 12 is so controlled that the process pH is maintcL:ined at a high enough level to effect the requisite development and image transfer and to retain -the optical :E:i.lter agents in colored form withill the processing compos-ition layer and on thc silver halide emulsion side o:E sa-id layer, a:Eter which pH reduction ef:Eected as a result oE alkali permeation :into the polymeric acid layer 12 i.s effective to reduce the pH to a level which changes the optical fi.lter agents to a colorless form. Absorption of the water from the applied layer of the processing composition results in a solidified film composed of the film-forming polymer and the white pigment dispersed therein, thus providing a light-reflecting layer which also serves to laminate together the photosensitive component 60 and the image-receiving component 70 to provide the final integral image. The positive transfer image in dye developer present in the image-receiving layer 42 is viewed through the transparent support 40 against the light-reflecting layer which provides an essentially white back-ground for the dye image and also effectively masks from view the developed photosensitive element 60.
The spacer layer 18 in accordance with this invention com-prises a light-reflecting pigment, e.g., titanium dioxide, dispersed in inert, substantially non-swelling and non-fi.lm forming, polymeric particles, e.g., an uncoalesced polymethylmethacrylate latex. Light passing through the red-sensitive emulsion layer 18 is reflected by the spacer layer 20 to the red-sensitive silver hali.de emulsion, thus effectivel.y increasing the efficiency (speed) of the red-sensitive silver halicle layer. The amount of l:ight reflected by the spacer layer 18 may be adjusted in accordance wi.th the needs of the parti-~cular photographic film by :i.ncreasi.ng or decreasing the coverage of the light-re:flecting pigment.
In the f:ilm Imit i.llustrated in the Figure the l.;gilt-:reflect-ing pigment-conta:in;.llg spacer layer is shown between the cyan clye developer layer and the red-sens:it:ive silver ha].ide emulsion layer. [t w:i.ll be unclerstood that such spacer ].ayers 20 also may be pos:itioned between the magenta dye developer layer 2~ and the green-sensitive silver halide emul.si.on layer 26~ between the yellow dye developer layer 32 and the blue-sensitive silver halide emulsion layer 36, or in any combination of these three locations. Where the light-reflecting pigment-containing spacer layer is so positioned that there is another silver halide emulsion behind it, as in the two positions not illustrated but noted above, it will be understood that the coverage of the light-reflecting pigment may be reduced and the speed of the underlying silver halide emulsion(s) may be increased to adjust for any light loss and thus obtain proper exposure of the underlying silver halide emulsion(s).
The optical filter agent is retained within the final film unit laminate and is preferably colorless in its final form, i.e., e~libiting no visible absorption to degrade the transfer image or the white background therefor provided by the reflecting layer. The optical filter agent may be retained in the reflecting layer under these con-ditions, and it may contain a suitable "anchor" or "ballast" group to prevent its diffusion into adjacent layers. Some of the optical filter agent may diffuse into the photosensitive component and be mordanted by the gelatin or other material present on the si.lver halide ~mulsion side of ~he reflectillg layer; optical filter mordanted in the photosensitive compollent 60 may be colorless or colored in its final state so long as any color exhibited by it is efectively masked by the reflecting layer. In the preferred embodiment, the optical filter agents are pH-sensitive phthalein dyes.
The concell-tratioll oE optical fll-ter agent (indicator dye) is selected to provide the op-tical transm:issioll density required, in combination with other layers intermedia-te the silver halide emuls:ion layers and the inciden-t radiat-ion, to prevent nonimagewise exposure, i.e., fogging, by incident actinic light during -the performallce of the particular photographic process. The transmission density and the optical filter agent concentration necessary to provide the requisite protection from incident light may be readily determined for any photo-graphic process by routine experimentation, as a function of film speed or sensitivity, processing time, anticipated incident light intensity, etc., as described in said United States Patent No. 3,647,437. It will be recognized that a particular transmission density may not be required for all portions of the spectrum, lesser density being suffi-cient in waveleng-th regions corresponding to lesser sensitivities of the particular photosensitive material.
In a particularly useful embodiment, the optical filter agent is a light absorbing dye which is highly colored at the pH of the pro-cessing composition, e.g., 13-14, but is substantially non-absorbing of visible light at a lower pH, e.g., less than 10-12. Particularly suitable are phthalein dyes having a pKa of about 13 to 13.5; many such dyes are descrlbed in the aforementioned United States Patent No.
3,647,437. This pH reduction may be effected by an acid-reacting reagent $
appropiately pos:itioned in the film unit, e.g., in a layer of the photo-sensitive element as shown in the Fi.gure or in a layer between the transparent support and the image-rece:iving layer or in other positions as knQwn in the art.
It will be understood that a mixture o:E light-absorbing materials may be used so as to obtain absorption in all cr:itical areas of the visiblc and near-visible by which the silver halide emulsion being used are exposable. Many dyes which change :~rom colored to colorless AS a ~urlctiQn of pll reduction, e.g., phthalein dyes, are known (see, for example, the aforementioned United States Patent No. 3,6~7,~37) a.nd appropriate selection may be made by one skilled in the art to meet the particular conditions of a given process and film unit.
In those embodiments of this invention involving a ~ilm unit of the type shown in United States Patents No. 3,415,64~ and 3,6~7,~37 and in the Figure and having an optical filter agent in the processing compositi.on, it is advantageous to ,~
~z~
utilize an image-receiving elernent having cl su-rface layer adapted to decolorize the optical filter agent adjacent the interrace.
Suitable decolorizing layers are described in Edwin ~. Land, Leon D. Cerankowski and Neil C. Mattucci, United States Patent No. 4,298,67LI; Irena Bronstein-Bonte, Edward P. Lindholm and Lloyd D. Taylor, United States Patent No. 4,29LI,907 and Charles K. Chiklis and Neil C. Mattucci~ United States Patent No. 4, 367,277 filed concurrently herewith. Of the several "clearing coats" described in said copending applications, the unhardened gelatin clearing coat described and claimed in said application of Chiklis and Mattucci is presently preferred.
Inert, non-swelling polymeric particles of the type herein contemplated for use in spacer layer 20 are described in Peter 0. Kliem, United States Patent No. 4,3Ll7,301 and Canadian Patent No. 1,148,008. The following illustrative example of the preparation of a polymethylmethacrylate latex suitable for use in the practice of this invention is reproduced from said copending applications:
Example A
Water 118 1.
Methylmethacrylate 51 kg.
Potassium persulfate 0.15 kg.
Ascorbic Acid 0.01 kg.
Dowfax* 2A1 20% solution 1.275 kg.
(dodecyldiphenyl oxide disulfonate sodium salt, sold by Dow Chemical Co., Midland, Michigan) ~Trade Mark 63~
A reactor was charged with 102.1 of demineralized water and the Dowfax 2Al and heated under nitrogen to 83C whereupon 7.65 kg. of methylmethacrylate was added and mixed until the temperature returned to 83C. After 5 min~ at 83~, 4.93 kg. of initiator solution (O.lS
kg. of potassium persulfate and 14.79 kg. water) was added. After tl-le exotherm the temperature was reduced to ~5C and the remaining methyl-methacrylate was added at a rate of about 361 g/min. and the remaining initiator solution at a rate of about 111 g/min. At the end of the monomer and initiator solution, the temperature was maintained at 85C for 10 min. and then the ascorbic acid was added. The resulting latex had a 30% solids and about a 0.125 ~ average particle size.
As noted above, the use of the inert polymeric particles permits the use of lower coverag0s of the light-reflecting pigment to achieve a given reflection of light incident on the pigment-containing layer. Thus it has been found that a white light reflection density of about 1.0 may be obtained from a titanium dioxide coverage of about 1000 mg/m2 by the use of a coating comprising, by weight, 8 parts titanium dioxide, 1 part gelatin and 3 parts polymethylmethacrylate.
About 40Q0 mg/m2 of titanium dioxide was found to be needed to give 2Q the same white reflection density when coated using an 8:1 by weight ratio of titanium dioxide and gelatin. ~The white reflection density was measured of the described titanium dioxide layers coated on opaque polyethylene terephthalate having a neutral density of 1.o2.) It will be readily apparent that the present invention provides the ability to use less silver halide to obtain a given film speed.
This in turn may reduce the concentrations needed of other components of the system.
The following example of a film wherein the photosensitive element includes a spacer layer in accordance with this invention is intended to be illustrative and not limiting.
Example l A photosensitive element was prepared by coatingJ on a poly-ethylene glycol tereph~halate baseJ the following layers:
(1~ A neutralizing layer of a partial butyl es~er of poly-ethylene/maleic anhydride copolymer at a coverage o:E about 23,700 mg/m2 and polyvinylbutyral at a coverage of about 2,600 mg/m2.
~2) A timing layer of a 60.6/2~9/6.3/3.7/0.4 pentapolymer of butylacrylate, diacetone acrylamide, styrene, methacrylic acid and acrylic acid at a coverage of about 3,500 mg/m2 and about 524 mg/m2 of gelatin.
(3) A layer of a gelatin dispersion of a cyan dye developer, 6-dodecylaminopurine, and ~'-methylphenylhydroquinone coated at a coverage of about 600 mg/m2 of dye, 225 mg/m2 of 6-dodecylaminopurineg 120 mg/m2 of 4'-methylphenylhydroquinone, and 300 mg/m2 of gelatin.
(4) A spacer layer of titanium dioxide, poly(methylmethacrylate), gelatin, the above pentapolymer, and polyacrylamide coated at a coverage 2Q of about 1,000 mg/m2 of titamium dioxide, 375 mg/m2 of poly(methyl-methacrylate), 125 mg/m2 of gelatin, 375 mg/m2 of said pentapolymer, and 270 mg/m2 of polyacrylamide.
~5) A red sensitive gelatino-silver iodobromide (1.8 micron) emulsion layer coated at a coverage of about 1,300 mg/m2 of silver and 1,014 mg/m2 of gelatin.
~6) ATI interlayer of the above pentapolymer coated at a coverage of about 3,000 mg/m2, about 158 mg/m2 of polyacrylamide and about 32 mg/m2 of succindialdehyde.
~7) A layer of gelatin dispersion of a magenta dye developer and 6-dodecylaminopurine coated at a coverage of about 575 mg/m2 of dye, 280 mg/m2 of gelatin and 23 mg/m2 of 6-dodecylaminopurine.
(8) A g-~een-sensitive gelatino-silver oidobromide emulsion layer comprising a blend of l.l micron grains coated at a coverage of about 373 mg/m2 of silver and 60 mg/m2 of gelatin and 1.8 micron grains coated at a coverage of about 1,027 mg/m2 of silver and 504 mg/m2 of gelatin.
(9) An interlayer of the above pentapolymer coated at a coverage of about 2,500 mg/m2, about 130 mg/m2 of polyacrylamide, about 31 mg/m2 of succindialdehyde and about 4 mg/m2 of formaldehyde.
(10) A layer of 2-phenylbenzimidazole and gelatin coated at a coverage of about 250 mg/m2 of 2-phenylbenzimidazole and 100 mg/m2 of gelatin.
~11) A layer of a gelatin dispersion of a yellow dye developer coated at a coverage of about 800 mg/m2 of dye and 320 mg/m2 of gelatin.
(12~ A spacer layer of titanium dioxide, poly(methylmethacrylate) and polyacrylamide coated at a coverage of about 200 mg/m2 of titanium dioxide, 150 mg/m2 of poly(methylmethacrylate) and ~0 mg/m2 of poly-acrylamide.
(13) A blue-sensitive gelatino-silver iodobromide emulsion layer comprising l.S micron grains coated at a coverage of about 950 mg/m2 of silver, 456 mg/m2 of gelatin, 250 mg/m2 of 4'-methylphenyl-hydroquinone, and about 3~0 mg/m2 of diethyldodecanamide.
(14) A top coat layer of gelatin coated at a coverage of about 484 mg/m2.
The thus-prepared photosensitive element was exposed and then processed by spreading a layer oE alkaline processing composition approx:i-mately 0.0030 inch thick between it and a superposed image-receiving element prepared by coating a transparent subcoated polyethylene tereph-thalate 4 mil (0.1 mm) support with the following layers:
1. an image-receiving layer coated at a coverage of about 300 mg/ft2 ~about 3,330 mg/m2) of a graft copolymer comprising 4-vinyl ~4VP) and viilyl benzyl trimethyl ammonium chloride (TMQ) grafted onto hydroxyethyl cellulose (~-IEC) at a ratio ~E:C/4VP/TMQ of 2.2/2.2/1, and about 4 mg/ft2 oE 1,4-butanediol diglycidyl ether cross-linking agent; and 2. a layer of unhardened inert bone gelatin coated at a coverage of about 100 mg/ft2 (about 1,076 mg/m2).
Water 41.0 g.
Potassium hydroxide (100%) 4.40 g.
Poly-diacetone acrylamide oxime 0.67 g.
Titanium dioxide 48.0 g.
Benzotriazole 0.456 g.
4-aminopyrazolo-(3,4d)-pyrimidine 0.21 g.
6-methyl uracil 0.25 g.
N-2-hydroxyethyl-N,N',N'-tris- 0.625 g.
carboxymethyl-ethylene diamine Polyethylene glycol 0.375 g.
(mol. wt. about 4000) Colloidal silica (30% dispersion) 0.77 g.
N-phenethyl-~-picolinium bromide 1.32 g.
2-methyl imidazole 0.70 g.
1-(4'-hydroxyphenyl)-5-mercaptotetrazole 0.04 g.
2,3-dimethyl pyrazo]e 0.167 g.
-1~-7~
o~l 01 1 COOI-I ~IOOC ~ '/ ~ 0 g.
C18H37--~'`~/'~ ~
HOOC HH NHS2C16~133-n 0.29 g.
J /~
~
After about 90 seconds a well-developed multicolor transfer image was visible through the transparent support ~40) of the laminate. Sensito-metric evaluation showed that the presence of the titanium dioxide-containing spacer layer behind the red-sensitive silver halide emulsion resulted in an :illcrease in red speed of about 0.5 stop as compared Wit]l a control wllich did not have this spa.cer layer. The -titanium di.oxide-containillg spacer layer behind tlle blue-sensitive silver halide emulsion layer gave a little increase :in blue speed w:ithout any s:igni-ficant loss in green and red light transmission to the unde-rlying layers.
The control of the yellow dye developer also was :improved.
The cyan, magenta and yellow dye developers used in the above examples were:
3 ._ ~ Nll- - O S~
cyan: Cl-12 2 ~ fH3 ~ ~ y- = C ~ C _ N SO - NH-- CH
fH~
llC - - NH - O2S N - C C - N l-IO
2 ~ ~ CIH 3 ~ OH ~ -SO2- NH -Cl-l HO ~ OH
HO
OC3il7 NO2 3 7 ~ o /
yel low ~ 2o C~2C112~
Oil ~11 magenta: ICH2 CH2 CH
CH3 CH ¦ 1 3 OH
N
6 3 ~ SO3- C3H
OH
OH
The polymethylmethacrylate latex employed in the spacer layers of the above example had an a~erage particle si~e of about 0.12 micron.
The titanium dioxide had a particle size of about 0.2 micron.
It is well Icnown in the art that for in camera processing the processing composition should include a viscosity-increasing polymer of the type wh;ch, when the composition :is spread and dried, forms a relatively firm and stable film. }ligh molecular weight polymers are preferred, and include cellulosic polyme:rs such as sodium carboxymethyl cellulose, hydroxyethyl cellulose and hydroxyethyl carboxymethyl cellulose. ~nother class of useful viscosity-incrensillg polymers comprises the oxime polymers disclosed and claimed in Unitecl States Patent No. 4,202,694 issued May 13, 1980 to Lloyd D. Taylor. Suitable oxime polymers include polydiacetone acrylamide oxime as well as copolymers, e.g., oximated poly diacetone acrylamide/acrylic acid, and oximated graft copolymers, e.g., grafts of diacetone acrylamide oxime onto hydroxyethyl cellulose. The pre:Eerred concentration of such oxime polymers is about 1% by weight or less, e.g., about 0.8% by weight as in the above example.
It will be understood *hat the neutralizing layer 22 and timing layer 20 may be coated in the photosensitive element between the opaque support 10 and the cyan dye developer layer 16, as described in United States Patent No. 3,537,043 issued March 30, 1971 to Edwin ~-1. Land or between the transparent support 40 and -the image-receiving layer 42, as described in the above-mentioned United States Patent No.
3,415,044. Other techniques Eor controlling the p~l known in the art also may be usecl.
The positive component 60 and the negative component 70 shown in the Figure may be secured to each other along their marginal edges as described in United States Patent No. 3~415J644. They may be tem-porarily laminated to each other i~ -22-'7~
by a bond of such a nature that these e]ements may be readily separated by the distribution of the processing composition following rupture of the pod 50. A particularly useful method of providing such a temporary lamination is to apply an aqueous solution of a polyethylene glycol, e.g., a polyethylene glycol having a molecular weight of abo~ut 6000 such as that commercially available under the tradename "Carbowax 60oo"~ from Union Carbide Corporation. Such uses of` polyethylene glycols are disclosed in United States Patent No. 3,793~023 issued ~ebruary 19, 1974 to Edwin H. Land and to which reference may be made.
It will be recognized that this invention also may be practiced employing film units wherein the image-receiving element is adapted to be separated from the developed photo-sensitive element after the transfer image has been formed.
Neutralizing layers such as the polymeric acid layer are well known in the art and are described in detail, for example, in the above-noted United States Patent Nos. 3,415,644, 3,573,043 and 3,647,437 to which patents reference may be made.
This invention is applicable to a wide variety of photographic processes as will be readily apparent to one skilled in the art. Dye developers are preferred image-providing substances, as indicated above, and constitute an example of initially diffusible dye image-providing substances. Other useful dye image-providing substances include initially diffusible dyes useful as image dyes per se and which couple with the oxidation product of a silver halide developing agent to provide a non-diffusible product, initially diffusible ~Trade Mark color couplers which couple wi.th the oxidation produc-t of a silver halide developing ayent to provide image dyes, initially non-diffusible compounds which react with the oxidation product of a silver halide developing ayent, as by coupling or by cross oxida.tion, to release a diffusible dye useful as an image dye per se. The final image may be formed as a result of the diffusion transfer of a sol.uble complex o.f undeveloped silver halide, in which event the imaye may be i.n silver as is well known. In another dye release system a soluble silver complex formed from undeveloped silver halide may be used to effect a cleavage reaction and release a dye or dye intermediate for transfer. Since these imaye-forming processes are well known and form no part per se of the present invention, it is not necessary to describe them in detail herein.
It will be understood that the transfer image may be positive or negative, with respect to the photographed subject matter, as a function of the particular image-forming system employed. The silver halide emulsion may be negative-working or positive~working (e.g., internal latent image) as appropriate for the particular imaginy system.
Since certain changes may be made in the above product and process without departing from the scope of the invention herein involved, the invention is not intended to be limited thereto but to include variations and modifications obvious to those skilled in the art and which are within the spirit of the invention and the scope of the appended claims.
c . - 24 -`,,~? '
~5) A red sensitive gelatino-silver iodobromide (1.8 micron) emulsion layer coated at a coverage of about 1,300 mg/m2 of silver and 1,014 mg/m2 of gelatin.
~6) ATI interlayer of the above pentapolymer coated at a coverage of about 3,000 mg/m2, about 158 mg/m2 of polyacrylamide and about 32 mg/m2 of succindialdehyde.
~7) A layer of gelatin dispersion of a magenta dye developer and 6-dodecylaminopurine coated at a coverage of about 575 mg/m2 of dye, 280 mg/m2 of gelatin and 23 mg/m2 of 6-dodecylaminopurine.
(8) A g-~een-sensitive gelatino-silver oidobromide emulsion layer comprising a blend of l.l micron grains coated at a coverage of about 373 mg/m2 of silver and 60 mg/m2 of gelatin and 1.8 micron grains coated at a coverage of about 1,027 mg/m2 of silver and 504 mg/m2 of gelatin.
(9) An interlayer of the above pentapolymer coated at a coverage of about 2,500 mg/m2, about 130 mg/m2 of polyacrylamide, about 31 mg/m2 of succindialdehyde and about 4 mg/m2 of formaldehyde.
(10) A layer of 2-phenylbenzimidazole and gelatin coated at a coverage of about 250 mg/m2 of 2-phenylbenzimidazole and 100 mg/m2 of gelatin.
~11) A layer of a gelatin dispersion of a yellow dye developer coated at a coverage of about 800 mg/m2 of dye and 320 mg/m2 of gelatin.
(12~ A spacer layer of titanium dioxide, poly(methylmethacrylate) and polyacrylamide coated at a coverage of about 200 mg/m2 of titanium dioxide, 150 mg/m2 of poly(methylmethacrylate) and ~0 mg/m2 of poly-acrylamide.
(13) A blue-sensitive gelatino-silver iodobromide emulsion layer comprising l.S micron grains coated at a coverage of about 950 mg/m2 of silver, 456 mg/m2 of gelatin, 250 mg/m2 of 4'-methylphenyl-hydroquinone, and about 3~0 mg/m2 of diethyldodecanamide.
(14) A top coat layer of gelatin coated at a coverage of about 484 mg/m2.
The thus-prepared photosensitive element was exposed and then processed by spreading a layer oE alkaline processing composition approx:i-mately 0.0030 inch thick between it and a superposed image-receiving element prepared by coating a transparent subcoated polyethylene tereph-thalate 4 mil (0.1 mm) support with the following layers:
1. an image-receiving layer coated at a coverage of about 300 mg/ft2 ~about 3,330 mg/m2) of a graft copolymer comprising 4-vinyl ~4VP) and viilyl benzyl trimethyl ammonium chloride (TMQ) grafted onto hydroxyethyl cellulose (~-IEC) at a ratio ~E:C/4VP/TMQ of 2.2/2.2/1, and about 4 mg/ft2 oE 1,4-butanediol diglycidyl ether cross-linking agent; and 2. a layer of unhardened inert bone gelatin coated at a coverage of about 100 mg/ft2 (about 1,076 mg/m2).
Water 41.0 g.
Potassium hydroxide (100%) 4.40 g.
Poly-diacetone acrylamide oxime 0.67 g.
Titanium dioxide 48.0 g.
Benzotriazole 0.456 g.
4-aminopyrazolo-(3,4d)-pyrimidine 0.21 g.
6-methyl uracil 0.25 g.
N-2-hydroxyethyl-N,N',N'-tris- 0.625 g.
carboxymethyl-ethylene diamine Polyethylene glycol 0.375 g.
(mol. wt. about 4000) Colloidal silica (30% dispersion) 0.77 g.
N-phenethyl-~-picolinium bromide 1.32 g.
2-methyl imidazole 0.70 g.
1-(4'-hydroxyphenyl)-5-mercaptotetrazole 0.04 g.
2,3-dimethyl pyrazo]e 0.167 g.
-1~-7~
o~l 01 1 COOI-I ~IOOC ~ '/ ~ 0 g.
C18H37--~'`~/'~ ~
HOOC HH NHS2C16~133-n 0.29 g.
J /~
~
After about 90 seconds a well-developed multicolor transfer image was visible through the transparent support ~40) of the laminate. Sensito-metric evaluation showed that the presence of the titanium dioxide-containing spacer layer behind the red-sensitive silver halide emulsion resulted in an :illcrease in red speed of about 0.5 stop as compared Wit]l a control wllich did not have this spa.cer layer. The -titanium di.oxide-containillg spacer layer behind tlle blue-sensitive silver halide emulsion layer gave a little increase :in blue speed w:ithout any s:igni-ficant loss in green and red light transmission to the unde-rlying layers.
The control of the yellow dye developer also was :improved.
The cyan, magenta and yellow dye developers used in the above examples were:
3 ._ ~ Nll- - O S~
cyan: Cl-12 2 ~ fH3 ~ ~ y- = C ~ C _ N SO - NH-- CH
fH~
llC - - NH - O2S N - C C - N l-IO
2 ~ ~ CIH 3 ~ OH ~ -SO2- NH -Cl-l HO ~ OH
HO
OC3il7 NO2 3 7 ~ o /
yel low ~ 2o C~2C112~
Oil ~11 magenta: ICH2 CH2 CH
CH3 CH ¦ 1 3 OH
N
6 3 ~ SO3- C3H
OH
OH
The polymethylmethacrylate latex employed in the spacer layers of the above example had an a~erage particle si~e of about 0.12 micron.
The titanium dioxide had a particle size of about 0.2 micron.
It is well Icnown in the art that for in camera processing the processing composition should include a viscosity-increasing polymer of the type wh;ch, when the composition :is spread and dried, forms a relatively firm and stable film. }ligh molecular weight polymers are preferred, and include cellulosic polyme:rs such as sodium carboxymethyl cellulose, hydroxyethyl cellulose and hydroxyethyl carboxymethyl cellulose. ~nother class of useful viscosity-incrensillg polymers comprises the oxime polymers disclosed and claimed in Unitecl States Patent No. 4,202,694 issued May 13, 1980 to Lloyd D. Taylor. Suitable oxime polymers include polydiacetone acrylamide oxime as well as copolymers, e.g., oximated poly diacetone acrylamide/acrylic acid, and oximated graft copolymers, e.g., grafts of diacetone acrylamide oxime onto hydroxyethyl cellulose. The pre:Eerred concentration of such oxime polymers is about 1% by weight or less, e.g., about 0.8% by weight as in the above example.
It will be understood *hat the neutralizing layer 22 and timing layer 20 may be coated in the photosensitive element between the opaque support 10 and the cyan dye developer layer 16, as described in United States Patent No. 3,537,043 issued March 30, 1971 to Edwin ~-1. Land or between the transparent support 40 and -the image-receiving layer 42, as described in the above-mentioned United States Patent No.
3,415,044. Other techniques Eor controlling the p~l known in the art also may be usecl.
The positive component 60 and the negative component 70 shown in the Figure may be secured to each other along their marginal edges as described in United States Patent No. 3~415J644. They may be tem-porarily laminated to each other i~ -22-'7~
by a bond of such a nature that these e]ements may be readily separated by the distribution of the processing composition following rupture of the pod 50. A particularly useful method of providing such a temporary lamination is to apply an aqueous solution of a polyethylene glycol, e.g., a polyethylene glycol having a molecular weight of abo~ut 6000 such as that commercially available under the tradename "Carbowax 60oo"~ from Union Carbide Corporation. Such uses of` polyethylene glycols are disclosed in United States Patent No. 3,793~023 issued ~ebruary 19, 1974 to Edwin H. Land and to which reference may be made.
It will be recognized that this invention also may be practiced employing film units wherein the image-receiving element is adapted to be separated from the developed photo-sensitive element after the transfer image has been formed.
Neutralizing layers such as the polymeric acid layer are well known in the art and are described in detail, for example, in the above-noted United States Patent Nos. 3,415,644, 3,573,043 and 3,647,437 to which patents reference may be made.
This invention is applicable to a wide variety of photographic processes as will be readily apparent to one skilled in the art. Dye developers are preferred image-providing substances, as indicated above, and constitute an example of initially diffusible dye image-providing substances. Other useful dye image-providing substances include initially diffusible dyes useful as image dyes per se and which couple with the oxidation product of a silver halide developing agent to provide a non-diffusible product, initially diffusible ~Trade Mark color couplers which couple wi.th the oxidation produc-t of a silver halide developing ayent to provide image dyes, initially non-diffusible compounds which react with the oxidation product of a silver halide developing ayent, as by coupling or by cross oxida.tion, to release a diffusible dye useful as an image dye per se. The final image may be formed as a result of the diffusion transfer of a sol.uble complex o.f undeveloped silver halide, in which event the imaye may be i.n silver as is well known. In another dye release system a soluble silver complex formed from undeveloped silver halide may be used to effect a cleavage reaction and release a dye or dye intermediate for transfer. Since these imaye-forming processes are well known and form no part per se of the present invention, it is not necessary to describe them in detail herein.
It will be understood that the transfer image may be positive or negative, with respect to the photographed subject matter, as a function of the particular image-forming system employed. The silver halide emulsion may be negative-working or positive~working (e.g., internal latent image) as appropriate for the particular imaginy system.
Since certain changes may be made in the above product and process without departing from the scope of the invention herein involved, the invention is not intended to be limited thereto but to include variations and modifications obvious to those skilled in the art and which are within the spirit of the invention and the scope of the appended claims.
c . - 24 -`,,~? '
Claims (38)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A photosensitive element comprising a support carrying a layer of a silver halide emulsion, a spacer layer, and a layer of an image dye providing material, said spacer layer comprising a light-reflecting pigment and organic photographically inert polymeric particles which are substantially non swelling in alkali and substantially non-film forming, said spacer layer being positioned between said silver halide emulsion layer and said layer of image dye providing material.
2. A photosensitive element as defined in claim 1 wherein said support is opaque and said layer of image dye providing material is nearest to said support.
3. A photosensitive element as defined in claim 1 wherein said support is transparent and said silver halide emulsion layer is nearest to said support.
4. A photosensitive element as defined in claim 1 wherein said image dye providing material is an image dye or an image dye intermediate.
5. A photosensitive element as defined in claim 4 wherein said image dye providing material is a dye developer.
6. A photosensitive element as defined in claim 4 wherein said image dye providing material is colored.
7. A photosensitive element as defined in claim 1 wherein said light-reflecting pigment is titanium dioxide.
8. A photosensitive element as defined in claim 1 wherein said inert polymeric particles are derived from a polymer latex.
9. A photosensitive element as defined in claim 8 wherein said polymer is polymethylmethacrylate.
10. A photosensitive element as defined in claim wherein said polymer is polystyrene.
11. A photosensitive element as defined in claim 8 wherein said latex particles have a diameter of about 0.1 micron.
12. A photosensitive element as defined in claim 1 wherein said spacer layer includes a minor proportion by weight of a film-forming polymer.
13. A photosensitive element as defined in claim 1 wherein said light-reflecting pigment in said spacer layer is present in a quantity by weight which is greater than said inert polymer particles.
14. A multicolor photosensitive element comprising a support carrying, in sequence, a layer of a cyan image dye-providing material, a layer of a red sensitive silver halide emulsion, an interlayer, a layer of a magenta image dye-providing material, a layer of a green-sensitive silver halide emulsion, an interlayer, a layer of a yellow image dye-providing material and a layer of a blue-sensitive silver halide emulsion, at least one of said silver halide emulsion layers and its associated layer of image dye providing material being separated by a spacer layer comprising a light-reflecting pigment dispersed in organic photographically inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming.
15. A multicolor photosensitive element as defined in claim 14 wherein said spacer layer is positioned between said layer of cyan image dye-providing material and said red-sensitive silver halide emulsion layer.
16. A multicolor photosensitive element as defined in claim 14 wherein said spacer layer is positioned between said layer of magenta image dye-providing material and said green-sensitive silver halide emulsion layer.
17. A multicolor photosensitive element as defined in claim 14 wherein said spacer layer is positioned between said layer of yellow image dye-providing material and said blue-sensitive silver halide emulsion layer.
18. A multicolor photosensitive element as defined in claim 14 wherein each said image dye-providing material is a dye developer.
19. A multicolor photosensitive element as defined in claim 14 wherein said light-reflecting pigment is titanium dioxide.
20. A photographic process comprising providing a layer of a viscous aqueous alkaline processing composition between a first sheet-like element and a second sheet-like element;
said first sheet-like element comprising a support carrying an exposed silver halide emulsion having an image dye providing material in a layer behind said silver halide emulsion; said second sheet-like element comprising a transparent support; an image-receiving layer in one of said sheet like elements, said application of said processing composition being effective to develop said exposed silver halide emulsion and to form a visible image in said image-receiving layer; said silver halide emulsion layer being separated from said layer of image dye providing material by a spacer layer comprising a light-reflecting pigment dispersed in organic photographically inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming.
said first sheet-like element comprising a support carrying an exposed silver halide emulsion having an image dye providing material in a layer behind said silver halide emulsion; said second sheet-like element comprising a transparent support; an image-receiving layer in one of said sheet like elements, said application of said processing composition being effective to develop said exposed silver halide emulsion and to form a visible image in said image-receiving layer; said silver halide emulsion layer being separated from said layer of image dye providing material by a spacer layer comprising a light-reflecting pigment dispersed in organic photographically inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming.
21. A photographic process as defined in claim 20 wherein said first sheet-like element is a multicolor photosensitive element comprising a support carrying, in sequence, a layer of a cyan image dye providing material, a layer of a red-sensitive silver halide emulsion, an interlayer, a layer of a magenta image dye-providing material, a layer of a green-sensitive silver halide emulsion, an interlayer, a layer of a yellow image dye-providing material and a layer of a blue-sensitive silver halide emulsion, at least one of said silver halide emulsion layers and its associated layer of image dye-providing material being separated by a spacer layer comprising a light-reflecting pigment dispersed in inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming.
22. A photographic process as defined in claim 20 wherein said light-reflecting pigment is titanium dioxide.
23. A photographic process as defined in claim 21 wherein said spacer layer is positioned between said layer of red-sensitive silver halide and said layer of cyan image dye-providing material.
24. A photographic process as defined in claim 20 wherein said image dye providing material is a dye developer.
25. A photographic process as defined in claim 20 wherein said polymer is polymethylmethacrylate.
26. A photographic process as defined in claim 20 wherein said first sheet-like element includes a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion, and a red-sensitive silver halide emulsion, said silver halide emulsions having associated therewith, respectively, a yellow dye developer, a magenta dye developer and a cyan dye developer.
27. A photographic process as defined in claim 20 wherein said image-receiving layer is positioned in said second sheet-like element.
28. A diffusion transfer process film unit including a first sheet-like element and a second sheet-like element, said first sheet-like element comprising a support carrying a silver halide emulsion layer; said second sheet-like element comprising at least a support; an image-receiving layer carried on one of said sheet-like elements; a viscous aqueous alkaline processing composition releasably contained in a rupturable container positioned to release said composition for distribution between said first and second sheet-like elements with said supports outermost; said first sheet-like element including a spacer layer between said silver halide emulsion layer and a layer of an image dye providing material associated with said silver halide, said spacer layer comprising a light-reflecting pigment dispersed in organic photographically inert polymeric particles which are substantially non-swelling in alkali and substantially non-film forming.
29. A film unit as defined in claim 28 wherein said second sheet-like element is transparent.
30. A film unit as defined in claim 28 wherein said image-receiving layer is positioned in said second sheet-like element.
31. A film unit as defined in claim 28 wherein said image-receiving layer is positioned in said first sheet-like element.
32. A film unit as defined in claim 28 wherein said light-reflecting pigment is titanium dioxide.
33. A film unit as defined in claim 28 wherein said first sheet-like element includes a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion, and a red-sensitive silver halide emulsion, said silver halide emulsions having associated therewith, respectively, a yellow dye developer, a magenta dye developer and a cyan dye developer.
34. A film unit as defined in claim 33 wherein said spacer layer is positioned between said red-sensitive silver halide emulsion and said cyan dye developer.
35. A film unit as defined in claim 33 wherein said spacer layer is positioned between said blue-sensitive silver halide and said yellow dye developer.
36. A film unit as defined in claim 28 wherein said image dye providing material is an initially diffusible image dye or image dye intermediate.
37. A film unit as defined in claim 28 wherein said image dye providing material is an initially non-diffusible image dye or image dye intermediate.
38. A film unit as defined in claim 32 wherein said polymer is polymethylmethacrylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26741781A | 1981-05-26 | 1981-05-26 | |
| US267,417 | 1981-05-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1182676A true CA1182676A (en) | 1985-02-19 |
Family
ID=23018683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000403748A Expired CA1182676A (en) | 1981-05-26 | 1982-05-26 | Photographic product including a spacer layer containing light reflecting pigment and inert polymer particles |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0066341B1 (en) |
| JP (1) | JPH0228137B2 (en) |
| AU (1) | AU549028B2 (en) |
| CA (1) | CA1182676A (en) |
| DE (1) | DE3273132D1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6091354A (en) * | 1983-10-26 | 1985-05-22 | Fuji Photo Film Co Ltd | Photographic element for color diffusion transfer method |
| US4542087A (en) * | 1984-09-04 | 1985-09-17 | Eastman Kodak Company | Use of reflecting agent in yellow dye image-providing material layer |
| US4728595A (en) * | 1984-12-26 | 1988-03-01 | Fuji Photo Film Co., Ltd. | Photographic element |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA668592A (en) * | 1963-08-13 | Polaroid Corporation | Photographic processes and products | |
| US3351470A (en) * | 1963-07-25 | 1967-11-07 | Polaroid Corp | Novel photographic products, processes and compositions |
| BE759459R (en) * | 1969-11-26 | 1971-05-26 | Polaroid Corp | NEW PRODUCTS AND PROCESSES |
-
1982
- 1982-05-25 JP JP8872782A patent/JPH0228137B2/en not_active Expired - Lifetime
- 1982-05-25 AU AU84136/82A patent/AU549028B2/en not_active Ceased
- 1982-05-25 DE DE8282200641T patent/DE3273132D1/en not_active Expired
- 1982-05-25 EP EP82200641A patent/EP0066341B1/en not_active Expired
- 1982-05-26 CA CA000403748A patent/CA1182676A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0066341A2 (en) | 1982-12-08 |
| EP0066341B1 (en) | 1986-09-10 |
| JPH0228137B2 (en) | 1990-06-21 |
| AU549028B2 (en) | 1986-01-09 |
| DE3273132D1 (en) | 1986-10-16 |
| EP0066341A3 (en) | 1983-06-22 |
| AU8413682A (en) | 1982-12-02 |
| JPS5811938A (en) | 1983-01-22 |
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