Note: Descriptions are shown in the official language in which they were submitted.
~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
NHS0 R
~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
N H S 0
CH o/I~7/ /~=~
3 i~lHSC -O~ ~-t)C H - n
1 2 25
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 .
-10-
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.
-13 -
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
-16
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~
17 -
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
-18-
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.
