CA1193129A - Photographic elements containing scavengers for oxidized developing agents - Google Patents

Abstract

ABSTRACT
Useful scavengers for oxidized developing agents in photographic elements are 2,4-disulfon-amidophenols, or alkali labile precursors of such phenols.

Description

~33~

PHOTOG~APHIC ELE~ENTS CONTAINING SCAVENGERS
~{~ .
Thi6 inYention rel~tes to pho~o~r~phic elements, And in partiGular to color photo~r~phic 5 elemen~s containing novel 6c~vengers for oxidized developing ~gent.
It ls known in the ~rt to ~dd ~c~veDgers for oxidized developing ~gen~ to pbotogr~phic ele-ments in order for the scsvenger to iDteraCt ~ith 10 the oxidized developing agent and prevent lt from reacting ~t ~n unde~ired location or at ~n unde~ired poi~t in time. Included ~mong the ~cavenger~ for oxidized developing ~gent knowo io the ~rt ~re the ball~sted 2,5-d;~ulfon~midopheools ~hown in Erik60n 15 et al, U.S. P~tent 4,205,987 i~sued June 3, 1980 snd the 2-, or 4-~ulfon~midophenols Ghown in Rerearch Disclosure, February, 1979, Item No. 17842~
Research Disclo6ure i~ publi6hed by Indu6trial ~ __ __ Opport~nIties Ltd., Homewell, H~vant, Hamp~hire, PO9 20 lEF, United Kin~dom, It is known in the art th~t cert~in phenol~
~re dye-forming coupler6 ~nd tba~ they will react with oxidized color developiog ~gen~ ~o vrm cysn dye . 4-Sulfonamidophenols ~re specif icslly di~
25 closed in Salminen et ~1, U . S ~ P~tent 3, 737, 316 is~ued June 5, 1973 ~ being dy -forming coupler~
In view of the knowled~e which tho~e skilled .n the art po~efi~ ~eg~rding the ability of phenols to couple with oxldized color developing 30 ~gent~, it would be expectgd that the sc~venger~
de~cribed ~n Erik~on et al, snd Re~e~rch I~6clo~ure, referred to ~bove, would couple wi~h oxidi~ed color developing ~gent~ to orm dye ~tain and therefore would be of l~mited utility in photograpll~c element~
35 intended to be proces~ed wilth oxidized color developing agent~ where ~uclh ~ltain would be

2 -objection~b1e. Thu~, the su1fonamidopheno1~ of Er ikæon et al ~nd Re~earch DiE3c10sure h~ve found their principa1 uti11ty in tho~e image ~r~nsfer ma~erial~ which do not emp10y co10r developing 5 8gent5 for proc2&~ g or in ~ho~e m~eria1~ where the scavenger i~ in ~ 1~yer where ~ i5 no~ vi~lble upon viewing of the f ina1 image ~
We have confirmed th~t ~,5-di~u1fon~mido-pheno1s of Erilcson et a1 ~nd 4-su1fonamidopheno1~ of 10 Re~earch Di~o10~ure do in faet coup1e with ~xidized co10r deve10ping agen~s. However, ~e have une~spec-ted1y found that 2 ~4~di~u1fGn~mido2heYlo1~ do not couple. Thus, such compound~ would be u~eful not only in image tran~fer ~pplication~ but ~lso in 15 materi~1s înten~ed to be proce~æed with eo10r deYelopirlg a~,ents.
In accordance with the present invention, there i~ provis~ed ~ photogr~phic element compri61ng a support and at lea~t one 6i1ver h~1ide emul6ion 20 layer, the e1ement cont~ining ~æ ~ ~c~venger for oxidized deve10ping ~gent, a 2 ~4~di~u1fonaDIidopheno1 or ~n ~lkali labile prectJrsor o 6uch ~ pheno1.
Preferred ~uïfoD~midopheno1 ~c~vengers or oxidized developing agent of the pre~en~ invention 25 c~n be represented by the ~tructura1 formu1~:
G

NHS02R' U
R ~ ~R
NHSO~R
wher e in:
G i~ hydroxy or ~n ~ all 1~bile precur~or thereof~
E~ch Rl l~ individlJally alkyï of ~ to 30 s~rbon ~tom~r aryl of 6 to 30 c~rbon ~toms or heterocyelyl of 5 to 30 ~tOlD~ Con'L~inin& one ~r more ring hekero~tom6 ~elected from nltrogen D
osygen, sulfur ~nd selen~um; ~nd R2, R' aod Rb are eacl ~nd~vidually hydrogen, halogen, ~lky~ of 1 to 30 c~rboD
a~oms, alkoxy of 1 ~o 3û carbon ~oms, ~ryl OI 6 ~o 30 carbon a~om~ or ~rylogy of 6 ko 30 c~rboD
~toms ~
the scavenger being of ~uf f icien~ bulk ~o }16 lt:O be 10 non-diffu~ible in the ~lkali permeable l~yer~ s~f the e lement ~
Especi~lly preferred ~ulonamidophenol ~cavenger~ have the ~tructur~l formula:
OH
R\ ~ NHS02R
1!
R 3 '~ ~ o ~ ~'R a NHSC)2 R
wherein:
Each Rl i~ individu~lly ~lkyl uf 1 to 30 carbon atoms, or ~EY1 Of 6 to 30 c~rboD ~tOm6;
and Ra, R~ ~nd R~ ~re each iindividuslly hydrogen, ~lkyl of 1 to 30 carbon ~tom~ or 811COXY Of 1 eo 30 carbon ~toms~
In particular:ly preferred scavengera R9 is ~lkyl of 1 to 4 c~rbon ~tom~ or ~llcoxy of 1 to 4 c~rlbon ~toms and R2 ~nd Rlt are hydrogen.
A~ indic~ted ~bove, the moiety G c~n be a hydroxy group or ~n ~lk~ bi:le precur~or o:f a hydroxy group~ ID the ~lkali l~bile precur~ors, the hydrogen ~tom o the lhydroxy g~oup is repl~ced with ~ blocking group which 1~ removed upon cont~c~ h 30 ba6e. Typic~l b10c!~ing group~ ~re removabl e by hydroly~is or by in~r~molecullr nucleoph:llio dis , !

3~3 pl~cemcnt. Typic~l groups remoY~ble by Ihydroly~i~
~re ~cyl group~ ~uch ~ ~liph~tic ~nd ~romati carbonyl and ~ulfonyl group~. Typic~l group~
removable by lotr~molecular nucleophilio displ~ce-5 ment ~re described in klooberry et al, 11.S. P~ten~4,310,612 is~lJed J~nuary 3L2r 1982.
The ~lkyï, ~lkoxy, ~ryl ~ ~nd aryloxy sub-~tituent6 de~crib~d above c~n be ulether ~ub~tl-tu~ed. Repre~entative ~uch ~ubsti~:uentæ include 10 halogen, DitrO, ~llkyl, ~ryl, ~lkenyl, ~lko~:y, ~syloxy, ~lkenyloxy 9 he~erocyclyl, ~llcylc~rbonyl, ~rylc~rbonyl, ~lkenylc~rb~nyl, ~l~ylsulfonyl, arylsulfonyl, alkenyl~ulfonyl, ~m~no, ~minoc~rbonyl 7 smino~ulfonyl ~ o~rboxy ~ ~lkoa~yc~rbonyl, 15 aryloxycarbonyl~ alkenyloxyc~rbonyl, and the l~ke.
Thus, alkyl is inclu6ive of, e.g., ~ryl~lkyl ~nd aryloxy~l~yl9 ~ryl i~ inclusive of, e.g., ~lk~ryl and alkoxyaryl, ~nd alkenyl i~ inclusive of, e.g ar~lkenyl. The ~mine portion~ of ehe~e fuTther 20 ~ubstituent~ include primary, ~econdary, ~nd terti~ry ~mine~ ~ well ~B acyl~ted ~mine~.
Repre~entative sc~vengers of the present invention are shown below, pH
, 25 (1)~ ~ ~MHSO2~ OC,~ n ~=~
I~J 5 0 / ~ OC H - n NHSO
~-3/~=o~
~NHCOCH20--~ ~ C5 1 1 t i~lH50--~3/ ~1~C H ~t 2 ~ / 5 1 1 3~

OH o=~
~3) ~ NHSO2~ 4tl2~
~ /~
/~
NHS0~ 0C H -n OH

~H50 R R 0~ C5~l ~NHCCCH2--~ ~0 C5H11 ~5) R = ~
~CON (Cl aH37 n) 2 (~3 CH (CH3) 5 " R ~ --9~ ~--CH ( CH
Cl~(Ch3) 2 pH /~=o CH o/I~7/ /~=~
3 i~lHSC -O~ ~-t)C H - n pH
NHS2c1 6H33-n ~/
~IHSO2CH3 CH /~ C~ T
HS0 \~ 50 NH a~
R =~~ C ~I n ~3 .~.3~, (10) I~ `E'N 2 ~ _o~ 12 25 I~IHSO ~ ~
~o3~

The compolJrad~ ~f tbe pre~ent inveDtic)n ~re Icnown eompound~ or ~imil~r to known compound~ ~nd c3n be prepared by known re~rtionE. To prepare CDm-5 po.~nd~ ~n which th~ sulfc>na~Dldo ~rOtlp6 iln the 2- and

4~po~it~on are ldeDtic~l, a 2,4-dlaminophenol i~
reactcd with the ~ppropri~te 6ulfonyl h~lide. If dis~imilar eulfon~m~do group~ ~re de~ired, a 2~
~mino-4 nitropherlol or ~ 4-~mino-2~rlitrophenol 16 10 reacted w~th ~n ~ppropri~te sulfonyl hslid2 to ~t~acll one o 'che group~ to ~he ~mino 6ub~titueDt, the ni~ro group i~ then red~eed and ~ ~econd ~ul~
fonyl halide is ~ tached to ~he ~mino group formed lby reduction of the ni~ro group. If bloc~:ed 15 compounds ~re to be prepsred ~ the blocl~iog glr9Up c~n be attached ~o ~he hydroxy either before or ~fter ~ttachment o the sulfon~mido gr~up~.
Representative prepar~tion~ ~re BhOwn in the wor~
exsmples .
The ~c~vengers of thl~ invention c~n be u~ed in the way~; snd for the purpose6 th~ scDven-gers for ox:idized dev2loping ~gen~ are employed in the ~rt. They can be incorpor~tecl in ~ 6ilver h~-lide emul~ion l~yer of the photogr~phic eleDlent e:~r 25 in a separate l~yer o the element. ~en incor~
por~ted in a ~ep~r~te lsyer, that l~yer i~ prefer~
ably ~n in~erlayer between ~ilver halide emul~ion l~yer6 although it c~n be ~n underco~t l~yer co~ted b210w all of the ~ilver h~lide emul6ion layers or an 30 overco~t l~yer co~ted ~bove all of ~he Bilver lb~slide emul~ion layer~0 ~, 1 ~ he ~mount of ~cavenger compound employed will depend upon the particulflr purpo~e fo~ ~hich the ~cavenger is ~o be u~ed and the degree of ~e2-venging desired. Typically useful re~ul~s ~re ob-

5 t2ined when ~he ~c~venger i~ employed ln an ~mountof between about 5 snd 2~00 mg/~q. meter.
The ~cavenger c~n be incorpor~ted ln photo-graph;c element~ by technigue~ ~nown ln the ~rt. In certain preferred em~odimeDt6, the ~c~venger iE dl~-lO solved in a high boil~ng ~olvent~ ~uch ~s ~ w~te~in~oluble coupler 601vent ~nd then di~persed either in ~ silver h~lid~ emul~ion layer or In ~ 6eparste vehicle such ~s gelatin. Typic~l u~eful coupler solvent~ 8~e moderately pol~r svlvent6 such ~ tri-15 tolylphosphate~ di-N-butyl~hthalflte~ diethyllaura-mide, 2,4-dipentylphenol, ~nd the likeO Typical vehicle~ ~re gelatin, and other hydrophilic colloids co~monly employed iD ~ilver halide photographic ele-ments. The~e veh~cles ~re deseribed in ~esearch 20 Di6clo~ure, December 1978, Item No. 17643~ Se~tion IX. The cc~veng~r6 c~n be introduced into the element in a polymeric 13tex. Sult~ble techniques for di~per~ing the ~csvenger6 in a latex are descrbed in V.S. Patents 4,203,716 ~nd 4,214,047 25 and in Re~ealch Di~clo~ure, July 1977, Item 15930 and July 19~0, Item 19551.
The photogrsphic elements of the preRent Invention can be ~imple black-and-whlte or mono-chrome element~ compri~ing ~ ~upport bearIng a l~yer 3O of the ~llver halide emulsion, or they c~n be multi-l~yer ~nd/or multicolor element~. They can be de~lgned for processing with ~eparate 601ution8 or f~r in-camera proce6~ing. Multicolor elements COD-tain dye image forming unit6 eensl~ive to each of 35 the three prim~ry reglon~ o t`he ~pectrum. Each ~nit can be compri~ed of a ~ingle emulsion layer or ~ ~3~

of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element;
including ~he layers of the image-orming units, cAn be arra~ged in variou~ orders as known in the art.
In an alternative format, the emulslon or emulsions can be disposed as one or more segmented layers, e.g., as by the use of microvessel6 or microcells.
A preferred photographic element according to this invention comprises a support bearing at least one blue-s~nsitive silver halide emulsion layer having associated therewith a yellow image dye-providing material, at least one green-sensitive silver halide e~ulsion layer having associated therewith a magenta ima8e dye-providing materlal and l; at least one red-sensitlve silver halide emulsion layer having associated ~herewith a cyan image dye-providing material, the elemeDt containlng a scavenger of this invention. Preferably the scavenger is in an in~erlayer be~ween silver hallde emulsion layers sensltive to different regions of the visible spectrum although lt can be in a silver halide emulsion layer or in an interlayer ~etween silver halide emulsion layers sensitive to the same region of the visible spectrum.
The elements of the pre~ent invention c~n contain ~dd~tlsnal l~yers conventional in photo-graphic elements, ~uch as overcoat layers, spacer layers, filter layers, antihalation layers, pH
lowering layers (sometimes referred to as acid layers and neutralizing layers), timing layers, opaque reflecting layer~ opaque light-ab60rbi~g layers and fhe like. The support can be any sultable support used with photographic elements.
Typi~al supports include polymeric films, p~per ~ 3~
I (includirlg polymer-co~ted paper), g1~B~ and ~he like~ Detail6 regarding ~upport~ and other l~yer~
of the photographic elen:ent~ of thi~ vention ~re contained in Resesrch Dit:clogur2, December 1978, . 5 Item 17643, ref erred to ~bove .
The light-~n~itive ~ilver h~31ide emulsion6 employed in the photo~3r~ph~c elemenlts of ~hi~ inven-ticn c~n include co~r6e, regulsr or fine gr~in ~ilver halide cryRt~ls or misi~ure~ thereof ~nd can 10 b~ compri6ed of ~7uch ~lver hsiLide~ ~a6 ~ilver chlo-ride, ~ er bromide, ~ilver bromoiodide, ~ilver chlorobromide, ~ilver chloroiodide, 611ver ehloro-bromoiodide 7 and mixture~ tbereof . The emul6ion~
c~n be neg~tive working or d1rect po~itive emul-15 sions. They can form latent ~mage~ predominantly onthe 6urface of the ~ilver hallde grain~ or iLn the interior of the ~ilver halide grains. They csn be chemic~lly and ~pectr~lly 6en~itized in ~ccordance with u~ual practices. The emul~ion~ typirally wîl~
20 be gelatin emul~is7ns althou~,h other bydrophilic colloid~ can be u~ed in aecordance with U6U~l prac-ticeO Detail~ regarding the ~ilver bal~de emul~ion~
are contained in Re!:e~lrch Di~elo~ure, Item 17643, December, 1978 ~nd the reference~ ted therein.
The photographic ~ilver halide emul~ioll~
can contain other addenda conventional in the pboto-graphic ~rt. U~eful addenda ale de~cribed, for example, in _search isclo6urc, December 1978, Ieem 17643, Useful ~dder~d~ include spectral ~en~itizing 30 dyes and desen~itizer6, ~ntlfogg~nt~, m8~1cir~g COUp-ler~, DIR couplers ~ DIR compound6, ~nti-~ain ~gent~, lm~ge dye ~t~bllizers, ~b~orbing msterî~l~
~uch a~ filter dye~ ~nd UY ab~orber~ ight ~catter ing materi~l~, coating ~id~, pl~ticizers ~nd lubri-35 cant~ ~ ~nd the like .

Depending upon ~he dye-~mage-provid~n~s materia1 employed in the photog~ph1c ele~Dent, it c~n be ~ncorporated in the ~ilver h~llde emul~ioD
layer or iri a ~ep~r~te l~yer ~ociaDced ~ith ehe emulsion layer. The dye~ ge providing sn~teria1 5 can be any of a numbçr known in the ~rt, ~uch dye-forming coupler~, bleachabl2 tyes ~ dye deve1op~
ers ~nd redox dye-releasere, Qnd the p~rticlll3r one employed will depend on the nature of the element ~nd tl-e type of image de~i~ed.
Dye-image-providing ma~er~a1s employed with converlt;ona1 color m~terial6 de~igned for proce~ing with separa~e solution~ re prefeTa'Dly dye formin~
coupler~; i.e., compounds whiLch couple with oxidized developing agen~ ~o form ~ dye~ Pr~ferred coupler~
15 which form cyan dye ~m~ge~ ~re phenol6 and n~p-thols. Preferred couplers which orm magents dye images are pyra~olone~ ~nd pyr~zol~tri~æoles, Preferred couplers whieh form yellow dye im~ge~ are benzoyl~cet~nilides ~nd pivslyl~cet~nilide~.
Dye-im~g,e providis~g materi~l6 u~eful in diffusion tran~fer fiîm unit~ contain a dye moiety snd a monitoring moiety. The monitorin~ moiety, in the presence of an alkaline proces~ing ~olution ~nd as ~ function of silver h~lide development, ~ ~
25 re~pon~ible for a ch~nge in mobi 1 ity ~f the dye moiety. These dye-image-providing msteri~l~ c~n be initi~lly mobile ~nd rendered ~obile a~ A func-tion of ~ilver h~lide development D aB de~cribed in U.S. P~tent 2~983,606. Altern&tiYely, they C~Fl be 3 initially immobile and rendered mobile, in the pre~ence of sn ~lkaline proce~6ing ~ollltion~ ~ a unction of ~llver h~llde development O Thi ~ l~tter cl~ o mater ia~ clude redox dye-relea~ g com-pounds. In ~UGh compound~, ~he morlitorlng group 1~
35 ~ carrier from ~hich the dye i~ released a~ ~ dlrect ~ i ~3~¢~1 `

1~ ~
unction of ~ilver halide developmeDt or ~ ~n ln verse iEunction of silYer h~lide development~
Compound~ whieh rele~se dye ~8 a direc~ furlc~ion of ~ilver halide development ~re re:Eerred to aB
5 neg,ative~workin~s rele~e compounde, ~I ile compound~
which release dye ~ ~n inveræe func~cion of 6ilYer halide developmer!t are referred to ~s pusi~iYe~
working release compounds.
A preferred c1~8s of negatlYe-working 10 release eompound6 ~re tl:le ortlbo or para 6ulfon~mido-phenol~ ~nd raphthol~ de~cribed in U. S . Patent6 4,0549312, 4,055,~28 and ~,076,529, In the~e com-pounds the dye moiety i8 at~ched to a ~ulfon~mido group which is ortho or psra tt~ the phenolic hydroxy 15 group and i5 released by hydrolyfi16 s$ter oa~idation of the sulfon~mido compound during development.
A preerred cl~ss o po6iti~7e-wor!king rele~e compounds ~re the nitrobenzene and quinone compounds de~cribed in V.S. P~tent 4,139,379. In 20 these compound~ the dye moiety i 6 attached to ~n electrophili cleavffge g~oup, ~uch ~s ~ c~rb~mate group, ortho to the nitro group or tlhe quinone oxy-gen, and iB released upon reduction of the cDmpound by an eleetrvn donor compourld contalned in the ele-25 ment or the proces~ g c3mposition, unle~ the elec-tron donor i 8 oxidized during development .
The developing ~gents whieh can be u~ed to develop the photographie elements of thiæ inveDti~n, 'che oxidized form of which can be reduced by the 30 ~cavenger~ of thi6 invent:ion, inclulde hydroquinorle~
~minophenol~, 3~pyr2zolidone~ and phenylene di~-mines. 50me of the~e develop1n& agents, wh2n u~ed for eertain 9pp~ atiOn8, are referred to in the art ~ e1ectron tr~n~fer agen~, The partlcll1ar devel-35 oplng ~gent emp10yed wi11 depelld on tlhe psrticu1~rtype of photographic e1emen~ to lbe proces~ed. For ~; ~

~ 1~
ex~mple, phenylene diamine~ ~re ~he developer6 of choice for u~e with color photogr~ph~c element6 con-taining dye-forming couplers, while 3-pyrszolidone~
~re prefer~bly u~ed with lmage tran~fer ~e~i~ls : 5 con~aining redox dye rele~6er~.
Repre~ent~t.ive developing ægent6 include:
hydroquinone, N-methyl~minophenol, l-phenyl-3-pyrazolidone, l-phenyl~4,4-dime~hyl-3-pyr~zol~done, : l-phenyl-4-methyl 4-hydroxymethyl-3-pyrazolldone, 10 N,N-diethyl~p-phenylenedi~mine3 3-methyl-N,N-di-e~hyl-p-phenylenediamine, 3~methoxy-N,N-d~ethyl-p~phenylenediamine, N,N,N~, N'~tetr~metbyl p phenylenedi~mine.
The term "non-diffusible'~ used here;n h~
15 the meaning com~only applied to tbe term ln photo-: gr~phy and deno~e~ ma~erial~ tha~ for all practical purpo~e~ do not migr~te or w~nder through organic colloid l~yer~ ~uch a~ gel~tin in an ~lkaline ~edi-um9 in photographic element6 ~nd prefer~bly when 20 proceæ~ed in a medium having a pH of 10 or greatern The term ~'diffusible~' has the COnVerBe meaning ~nd denote6 the materisls having the property of diffus-ing effectively through the colloid layers of photo-graphic element~ in an ~lkaline medium.
The term ~ soeiated there~ith" ~6 u~ed herein 1~ lntend2d to mean th~t the msterl~l~ e~n be in either the æame or differen~ layer~ ~o long ~
the material~ ~re acce~ible to one ~nother during proces6ing.
The following example~ further illu~trate thi~ invention.

Ex~mple l~ P~par~tion of~

S~ 3H2 ~ 2~rS0 C ~ S~2~r ~ Pd/C ~q/ NaHC0 ~
1~0 Nh ~ISO Ar ~la) (lb) Ar = ~ ~~ 2t~25 A mixtlJre ~f 4~5 g (0.03 mole~ 2 amino 4~ rQphenol and p~lladium OD charcosl cataly~t is~ 60 ml di-5 methylformamide w~ reduced in a Parr bottle with 40 p~i hydrogeD until the theoretic~l amount ~ taken up~ Immedi~tely ~fter remov~l of the cat~ly~ by filtration~ 6.3 g (0.075 mole3 60dium blc rbonate and 21.7 g (0.06 mole3 4-dodecyloxybenæene~ulfonyl 10 chloride ~ere ~dded ~ith ~tirrin~ ~nd the mixture was heated ~o drive off earbon dioxide. The product isolated by poLtring the re~sction mixture l;sto ice w~ter was recryst~llized in t~rn fra~D oneth~rlol, etbanol/hexane, and acetonîtrile to yield 7~5 g 15 nearly colorle6~ cry~tal~, ~.p. 137-139C ~ith the c~rrect elementsl arlalysi~ or Compound 1~

~H ~H pH
N05 ~ ~ ~N 2 3 H2 ~ ~ ~N 2 ,E ~ C I S05CH3 ~ Pd/C ~ ~ ~
~H ~llS0 CH ~HS0 CH
2 2 ~s 2 3 ~2a) ~2b~ S2c~
C150 C H n IHS0 C H -n s2 18 ;~3 ~6 :~3 pyr./THF

bHS()2CH~

To a ^10C solution of 46.2 g ~0.~ ~ole3 4~mlno-2-nitrophenol in 500 ml ~etr~hydrour~n and 240 ml pyridine wa~ added dropwise over 10 minute~ wi~h s~irring 34.4 8 ~3.3 mole) meth~ne~ulfonyl chlo-5 ride. After ~tirring overnigh~ ~he liquld reaetionmix~ure W8S poured into ~ vigorously $~irred solu-tion of ~40 ml concen~r~ted hydrochloric ~cid ln 800 ml water ~nd the re~ultlng precipi~ate W~B collec~-ed, wa~hed, dried, deeolorized9 and recry~alllzed 10 from acetonitrile ~o yield 32.5 g yellow cry6t~1e of (2b~, m~p. 164-6nC; with the rorreet infr~red ~nd NMR ~pectrum ~nd ~ good element~l ~n~lys~.
A ~olu~ion of 15 g tO.065 mole) (2b) in 80 ml tetrahydrofuran ~nd 80 ml meth~Dol wa~ hydroge-15 nated overnight over palladium on charcosl in ~ P~rr~pparatu~. Then the c~t lyet wa~ removed by filtra-tion and ~he solvent by evapor~ion. The resultsnt ~ray solid (2c) W8~ dissolved in 200 ml tetr~hydro~
furan ~nd 50 ml pyridine and ~ ~olution of 21 g 20 (0.065 mole) l-hex~decanesulfonyl chloride in 100 ml tetrshydrofur~n wa~ added dropwi~e w~th 6tirring.
After 4 hour~ the re~ction mixture w~s poured onto 600 ml ice water contsining 50 ml concentr~ted hydrGchloric ~cid and the precipi~ate collected.
25 Recryst~llizat~on from ace~oni~rile afforded 15.7 g ~hite cryst~l6, m,p. 14~ 9~C~ wlth the rorrect analysis and ~peotra fo~ Compound 87 To evaluate the compounds of thi~ i~ventiQD
30 with respect to their ef fectivene~fi a~ interlsyer ~cavengerE fol oxidized color developing ~gents ~
oolor negative tes~ forma~ w~ employed repre~ented by the following ~chematic tructure:

1~ -Overco~t: Gel~in a.86 ES/m2~ H~rdener :1.75 %
Causing Layer: Silver Halide 1.61 g/D12 Yellow Coupler 0, 34 ~/m2 Gelatin ~.42 g/m2 Interl~yer: Te~t Compouod 00123 ~ol/m2 Receiving Layer: Cyan CoLIpler 1.12 g~m~
Gelatln 2.42 g/m2 In thiz element tlhe hardener iB bi6 (vinyl6ulfonyl~
10 methyl~ether and the coupler~ h~ve the followlng structur s (C~3) 3C@~@N~;~ ~
Yellow Coupler: y \N 52 ~6 33 ~ ~2~ 2 '~ _~
Cyan Coupler ~

~ ~ C~Ht 1 ;
i Coupler~ and te6t compound~ were co~ted a~ disper-15 sion in dibutylphthalate or eomp~rable coupler sol-vent. In thi~ 6y~tem, oxidlzed color developer, originating in the cau6ing layer ~ the eXpOfied silYer h~lide develop~ can re~ct with the yellow coupler to form a yellow dye. Xt c~n ~l~o migr~te 20 through the interl2yer to the receiving lflyer to react with coupler there to orm ~ cy~n dye. Reac-tive te~t compound~ in the interl~yer c~n ~l~o reac~
~ith oxidized developer, thu~ llmit~ng cy~n dye or~
m~tion in the rec~iver l~yer. For color neg~tive 25 materiJls it i~ usu~lly more de~ir~le th~t the te t 3~L2 comp~und reduce oxidized developer r~tber ~h~n coupling wi~h it, BinCe ~he l~tter re~c~ioo t:8D re sult6 in unwsn~ed dye ~t~in.
Scflvenging ef f iciency of e~ch teBt compound 5 can be de~erloined by me~urlng the developed den~i~y ratio of cyan dye ~ 665 nm) eO yell~w dye (~t 450 nm). The more aetive ~eB~: colapounds reduce ~hi~
red/bllJe den~i~y r~io to ~bout 0.2 from ~ control value (no sc~venger in the int~rlayer~ of ~out 10 0.4O The mo~t u~efu:L cavengeræ will continue to give a low den~ity r~io after Qn ~cceler~ed ~eepr ing te~t of the unexpo~ed elemen~ ~hile other6 will 106e their effectiveness by being oxidized snd higher ~ed/blue den6ity ratio will re~ult.
The rate of ~c~venger oxid~tic)n ob~erved durlng normal film keeping, condition e~n be 8c-celeratcd, for example, by incre~islg the temper~-ture, h~lmidity, or p~rtial pre~sure of oxygen ~n the test sy~tem. One ~uch ~ccelerated l~eeping te6t I s 20 de~cribed in Example 3 of U~S. Patent 4,205~987.
One ~ample of each of the photo~en~ltive element~, prepared a~ de~crlbed ~bove ~o cont~in a different desired test comp~und, was expo~ed through a gr~duated den~ity te~t object and then proce~sed 25 as de~cr ibed in the ~
July 12, 1974, pp. 597~8. A second ~mple of each element WA5 incuba~ed ln an accelerhted keeping ~es~
~nd t~en exposed ~nd processed in ~he ~me wsy a~
the fre0h sample~. The cyan dye contamin~tion (red 30 den~ity) of the f in~l yellow dye image (blue den6-it:y) W8E; then messured for the sample~, both fre~h and incubated~ Goupling of the ~cavenger w~ de-~ermined by visual in~peckion of a crosfi-~ect lion of the sample. If cy~n dye deDsity w~ ob~rved io tbe 3~

interlayer, the ~c~venger wa~ coa~sldered to h~ve ~oupled with oxidized developing ~gent. The result~
~re presented in t~e ollowlng table.

~ 3~3 K O U~ ~ O O o O
o z ~ ~ z: z z æ
a a~
~ In ~ . ~ ~
V N
O N
~ ~ C~ O ~
~0 ~ .
~ 0 ? ::1 o ~~ o O , U o~
~ C j~O~DO~ Z ~

ro ~ ~ ~ ~ ~ a /~\
P~ 1~ O O ~ c ~ e3 Zc 1~ ~.t) ,1 ~3 O O O
~J l.i COO O
a~
C :1 C ~ ~ r-æ ~ ~

3~

~ 19 -I~ can be ~een from the ~bove tDble ~h~t ~he ~ontrol compounds at equimolar levels ~how 1e~B ~C~Ven~,ing abili~y snd gre~t~r properleity for undesired coupl-ing to form dye lthan ds the compound~ of the 5 iDvention.
The inYentiOn ha~ beetl de~cribed in det~il with particul~r reference to preferred embodiment ~hereof, bu~ it will be under~tood ~h~ v~ri~iorl~
and modif ic~tion~ can be ef fected wi~lhin the ~pi2:i t o and ~cope of the inY~ntiOn.

Claims (14)

WHAT IS CLAIMED IS:

1. In a photographic element comprising a support and at least one silver halide emulsion layer, the element containing a scavenger for oxidized developing agent which does not form a dye or release a photographically useful group upon reaction with said oxidized developing agent, the improvement wherein the scavenger is a 2,4-disulfon-amidophenol or an alkali labile precursor of such a phenol.

2. A photographic element of Claim 1 wherein the scavenger has the structural formula:

wherein:
G is hydroxy or an alkali labile precursor thereof;
Each R1 is individually alkyl of 1 to 30 carbon atoms, or aryl of 6 to 30 carbon atoms or heterocyclyl of 5 to 30 atoms containing one or more ring hetero atoms selected from nitrogen, oxygen, sulfur and selenium; and R2, R3 and R4 are each individually hydrogen, halogen, alkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, aryl of 6 to 30 carbon atoms or aryloxy of 6 to 30 carbon atoms, the scavenger being of sufficient bulk so as to be non-diffusible in the alkali permeable layers of the element.

3. A photographic element of Claim 2 wherein the scavenger has the structural formula:

wherein:
Each R1 is individually alkyl of 1 to 30 carbon atoms, or aryl of 6 to 30 carbon atoms;
and R2, R3 and R4 are each individually hydrogen, alkyl or 1 to 30 carbon atoms or alkoxy of 1 to 30 carbon atoms.

4. A photographic element of Claim 3 wherein R3 is alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms and R2 and R4 are hydrogen.

5. A photographic element of Claim 1 wherein the scavenger is in an interlayer between two silver halide emulsion layers.

6. A photographic element of Claim 1 wherein the scavenger is in a silver halide emulsion layer.

7. A photographic element of Claim 1 wherein the silver halide emulsion layer has associ-ated therewith an image dye providing material.

8. A photographic element of Claim 7 wherein the image dye providing material is a dye forming coupler.

9. A photographic element of Claim 7 wherein the image dye providing material is a redox dye releaser.

10. In a photographic element comprising a support, at least two silver halide emulsion layers containing dye-forming couplers and a scavenger for oxidized developing agent which does not form a dye or release a photographically useful group upon reaction with said oxidized developing agent, the improvement wherein the scavenger is a 2,4-disul-fonamidophenol or an alkali labile precursor of such a phenol.

11. A photographic element of Claim 10 wherein the scavenger is in an interlayer between two silver halide emulsion layers.

12. A photographic element of Claim 10 wherein the scavenger is in a silver halide emulsion layer.

13. A photographic element of Claim 10 wherein the scavenger has the structural formula:

wherein:
G is hydroxy or an alkali labile precursor thereof;
Each R1 is Individually alkyl of 1 to 30 carbon atoms, or aryl of 6 to 30 carbon atoms or heterocyclyl of 5 to 30 atoms containing one or more ring hetero atoms selected from nitrogen 7 oxygen, sulfur and selenium; and R2, R3 and R4 are each individually hydrogen, halogen, alkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, aryl of 6 to 30 carbon atoms or aryloxy of 6 to 30 carbon atoms, the scavenger being of sufficient bulk so as to be non-diffusible in the alkali permeable layers of the element.

14. A photographic element of Claim 10 wherein the scavenger has the structural formula:

where in:
Each R1 is individually alkyl of 1 to 30 carbon atoms, or aryl of 6 to 30 carbon atoms;
and R2, R3 and R4 are each individually hydrogen, alkyl or 1 to 30 carbon atoms or alkoxy of 1 to 30 carbon atoms.