Note: Descriptions are shown in the official language in which they were submitted.
`~` 2~71~3
1109~45
PCr/~J5gO/074S4
~
1! ~1
~ h~ ~nven~on s~l~t~s to h~gh~ aet ~ hal~de~
photog~aph~ aterl~ or u~ in th~ ld af~ g~phi~ ~rtB and
~ ~ pro~ red~ci~ . bl~k ~po't8 (~pepp~") in exposed
ph~togr~phi~ ~ats~ o~ th~ f~goin~ typ~.
, ~0 ~
I~ th~ ~ield o~ ?h~ , a~ or~n~ sy~tem
p~o~i~ing ~ p~h~h oon~ao~ phot~gr~p~ic ch~r~l~tori~tl~,
~a8p~ y oa~ h~ing a ~nei~ t~ h) 0~ 10 0~ more, i6
x~g ir~ or ~a~pr~duction o~ oon~inuo~ torl~
; : ~S ~n~q~ or lln~ by dot ~g~ or ~hi~ pu~po~e, a
~p~ v~l~p~r ~ d ~ l~th-l:yp~ ele~p~ i8 ~en~rally
~a4~ h~ h dq~ on~in6~ ~ a c~ p~ nt~
hy~gui~on~ a~d, 1!~8 ` el p~Bl~ul:E$t~ u~lIy in th~
f~ o~ ~n ~u~t witl~ mald~hyd~ ~ a 04r~ t~at~o~ ~f no~
. 3~ ~n~r~ O .,1 ~vl/l ~ the~by pr~v~ ng ~t~ r~tl~n of the
in~ ti~ d~v~lopm~t ~ lity 0~ ~h~ d~V~10Pit~g ~gent~ ~he
1i~h eil~V~ r h~ iOUB ~ d~an~ ha~ ery
~U~EItib1e tO a~ OX~d~t1S~n ~nd ~4nnOt ~ h~t~A-q U~e ~r
P~iOd ~ Xa~d~ h~r8. InC~r~ g ~he ~U1~it~
35 ~nt~nt o~ th~ deV~1dP~ 1mPrQ~ U~U~ e bUt
., ~k~ri4~t~s it~ hi~h~ tr~s~ devQlopm~n~; ~ha~C~ tiC~.
X~QWrl WAY,e ~0 ~ t~n ~i3uiv~1erlt ~r ~ub~t~rltially
~uivalezlt hi~ n~r~s~ photograp~ic cha~c~eri~ with ~
~ta~ lop~r ~ncl~de th~ Sl~a of hy~r~ln~ Dr hydx~ide
., :.~ . ,, :
.: . ~ .':' .
.~
" ` , 2071499
~YO ~ 93~
P~/US90/07
derivat~Y~s as d~$cr~.b~d ~or ex4mpl~ in U~S. PAt~nt No~.
4,~q,4~1, 4~1~8~77~ ~,16~,,742, 4,311,7~1, 4~72,~06,
4,211,~57 And 4,2~13,7~9 all ~n~rpor~d by ra~r~nc~ ~n thelr
~nt~ ~ety. U8~ hyd~ n~9 or h~z~e c~mpounds ~Ln ~age
5 f or~at~on ~yet~b prc~vld~ ~upe:r-hi~h ~on~r~t an~ high ~en~
. al~t~ity, ~nd ~l~o ~h~ures gr~atly ~prov~d ~hll~t~ ~ the
~velo~r a~in~t ~r oX~stion ~3 co~npa~d tQ ~he ~n~ n~1
l~th ds~lopsr l~ u~e h~drazln~ d/or derivAt~v~ ~ pr~e~co
in th~ ~lan or in ~he d~vel~p~r p~ ul~e of ~ h~gher aulflte
10 ion ~onoant:ratlon ln t:h~ developer ~
B~weYer, lt ~ b~n ~our~d that u~e k~ hydraz~n~ or
hydr~zide co~paund~ high-s~ontr~t lsn~e fa~nati~ y~teme
~ds to c~u~ bl~k ~ver ~ot~ tal~o ~all~ "bl~ck p~ppar~
o~ P1Y "pepp~rn ~ on no~ a ar~ . 1n area~ o~ no ex
.1~ po~u~e ~ r ~xample betwe~ dotB r Th~ ~ ph~o~ n ~oohl~s
particularly ~un~pl~:u4us wh~n ~he ~ul~i~e ~on con~en~ ln Q
d~v~op~r is d~ ed or th~ p~ o~ ~ ~elle~op~r l~cr~as~,
ue to ~at~gu~ o~ th~ d~v Et~OpQX ~ 4Ad ~U~ n~ an'c
impainn~nt ~f photogr~phio qu~ y~
~0 ~a~ou~ ~t~emp~ h~v~ hlthe~o b~n m~ D ~liminate
~h~ p~ob:Lem o~ ck ~po~, bu~ whatev~r ~d ho~ ~p~ova~qnt w~
aolii~ved was ~e~u~nSly ~aompanied b~ redu~ion 1~ ~nslt~ity
~s~ or ~x~pl~, u~e o~ ~veral hy~ra~id~ disalo~ed in
IJ.~ en~ No. 4,~B6,167 ~in~o~porh~d b~ r~f~ren~e in ~t;8
2$ ~n~l~qty~ ~oser~$ ~ov~r~l h~r~ hioh, b,~llen u~d in
pho~ographi~ ~ul~iosl~ ~ p~u~ ~ goPd ~e~ul1~ ludir~g
~v~ pe.ppa:r ~t~g~ w~y~j n~ g~n~ ppl~cab~ lity
m~ans~ h~ 'De~n propo~ E4~ ~lving th~ problem ~ k ~pot~
wl~h4ut *uh~n1:~ally hind~r~n~ ~h~ ~blli~y o~ the above-
~0 ~e30r~d hy~z~ r hyd~zid~ ~o~pound~ to in~r~s~ ~en-
~ y And con~r~ot, ~opo~ally ~ red ~y dot gu~lityO
: Mor~o~o~, althou~h l:hla h~d~a~i~a~ f V.8. ~t~n~ No. 4,~6,167
produ~e l~w papper whe:n p~o~ ed in r~h developes, th~
p~pp~ or~A~e~ up~ pro~ n~ in exhnust~d oxid1zed or
lnh~ v~14~ h~r~ bl~
p~oYld~ a metho~ ~c:r ~nh2lnclng ~h~ perf Or~ Q of~ pho~o~ ph~c
~nat~ by xub~ lly x~du~in~ or ~limin~ting p~pper ov~3r
. .
` ` ` 2 0 ~ 9
WO 9l/~9~4S
PCr/l~S~0/07~
a w~d~ proces~ng latitud~ ( i d e~ d proee~ing ~ol~l:ior~ qu41ity
- an~ ~g~ ) es~enti~lly w~tho~lk ~eotlng th~ ~ntra~t And
8en~ y prvp~ eæ o~ th~ pro~ s~d phot~gr~phl~ at~r~
U . S . Pat~nt ~30 . 4, ~ 51, 3 ~ u~d 7 J2 5 J a a 9 to Tskhg~
dl~ o i~yd~zid~ Lin~ qt low~en~itivlty, h~gh~o~r~t
photo~x~ph~ o m~k~r~a~ Ln wh~:h ~sn~ ivi~y ( ~rd p~pp~r ~ h~
~erl low~d by ~d}~e 0~ lopm~l~nt: ~os~r~in~r. Su~h
re~trhin~r~ a~ L~ ~o ordins,~lly ~ low~r oontra~t.
A~ ding ~o ~h~ a~n~, oon~A6t i~ not lowEa~ed l~o~uss the
10 photograph~c~ ma~ so s20n~in~ ~ ~on~ t~-~nhnnclr~g ~om~
pouY~d~ ~he hydr~z~es ~pee~' ~ioally c~onts~plat~ are ~o~myl
phenyl hydra2~d~s ~h va;r;~ous ;~ub~titu~nt~ ~nd c~th~ ~unctlon~
~lit1Q apper~ded ~o the phenyl ring . ~he x~tra~n~r6 cc: n-
templat:~d ( "~rg~nic~ de~e~a~itiz~r~N ~ ar~ e~mpound~ hæ~vin~ a
pos~tivQ p~l~rog:~ph~c hal~w~ve pc~ntlal tCol~ 24:57-b5) an~
~re ropr~n~ by f c~rmulas dia~l4~ed at C~ 6 . ~ec
~estralnar ~x~mpl~ a~e ~ ed at C~ 7~31 and ir~ d~
XI~1 2~ l ~, 6 di~itrophensJlthio~th~r~ b~nz~n~ ~ar~oxy~ic
~daz~le,
X~-3 2-14,6 d~n~ ph~nyl~b~Dethsr~3-~b~n~n~ o~
id ~ -b~nz~a201~,
XII- 1 5~ ~ p hlkrob~nzeli~ine ~ - 3 - l aarbo~th~ hb~n~n~,
sn~
XIII-~ 3~ nit~o~n3~1~d~n~ rho~nin~ .
25~h~ ~ount~ of x~ r~nge b~w~e 10~ d10-4 m~l~m2
(u~in~ 3.~ /m2) ~ColO 31~S~-6~J~
-; Al~ o~ the ~k~gi pboto~raphi~ mate~ mu~t ~anta~n
oont~a~ nh~lnc:ihg ~o~p~u~d ~nd ~re intqnded ~o h~ 14w sen~
t~ity . ~rh~ at~i d4e~ ~IOt provide c. ~olut~n to the
3D peppar pre~ 2n o~ ~ h~ ~h~n~ rlty, high-oontt~a~t
phot-og~aphi~ ~at~riRl4
u.s. P~ar;t ~a~. 4,737~442 issued 4/l~JB8 to Yogih~rA
di~clo~ pho~gr~phic m~er~ on~a~ ng a ~onnyl phenyl
hydrzL~id~ r ~er a~n deri~ra~ivo~ t ~ w~ e ~ r~rainer ~
3~ th~ type ~ B wh~rQ~n. k~ :L~ a ~lo~)cir~g ~roup ~pa~le o~
~læ~ ~ ng ~ n~ ~h~ velopm~nt pro~¢~ ~ d~velopm~nt
reets~aln~r or ~ preaur~4~ ther~o~ rl3~arc~1e~s 4:~ tha . degrqe O~
. .
` ~0714~9
W~ g34~
PCr/V!SDO/074~i4
. Qxp~ure o~ She photog~ph1~ m~t;e~ial/ and D i~ a ~e~x~lne~ or
a pre~ur~or of A ~e~tr~ r . Ex~mpl~s o~ ~o~t~lne~ includ~;
1- t ~ ~ 4~Aihy~r~ph~nyl ~ ~ 5-~reap~o~e~r~ole,
4-ph~rlyl-~-m~t ~yl~3-~esc:~p~ot~r~ole,
. ~ ~-n~rc~ ra~ptoben~d~zol~,
~mgrn~ptobenzox~a:o~
b~nz~ld~zole ~ ~nd
~-nit~Qind~ol~ ~
~h~ purpo~ o~ ~ddis~g th~ ~est~n~n~r ~ roid
- ~q p~pp~r. The ~unt o~ ine~ ~n~es bqtw~sn ~bout 5.4~c10~4
~' ~c~ lxlO~ le/~nol~ ~g . ~he ~e~rain~r~ cls:l~a~l ~n ~h~ ' 442
, p ~ent ~ra of ~he ~o-call~d ~Ist~b~ e~ 'cype whl~h ~u~n $trong
, ~ilv~ B ~d I~t ~ ~ch~ if og~antH typ~ I ~tAbili%e~-
. ~ype ~ r~in~r~ WDUld de!Æ3~ e 8p~!Jd ~arkedly more than -
.. 1 15 ~rlti~ogg~nt ~yp~ ~ompound~ wh~n u~d wi~h hy~razid~, not~ly
. th~ hydra2i~ o~ the ~ormul~ ~, bel~w~
U,.~ enk Ns. 4~3~,~5~ uad 6/l~lB9 ~o Sas~oka
' d~h~lo8~s hy~raYid~e ~ oont~ ln~ photog~ph~c ~ak~x~al~ th~t a~Q
! ` r3e~ 1co have æimultah~ously hi~h 6en3itiYity 1~U~B) 2l~nd are
~, ~q ~r~e lo~: ~ub~t~n~ally ~x~ o~ bl~ck Bpt;~t~ or peppe~. ~he
i: ~ p~pper~ree gu~l~ty a~ording ~o the pAt~9~it iB lmp~rt~d by ~he
u~ oi~ d~l d~trelopii~ a~ln~s i,n oo~ln~l:Aon wi~h ~ ~ul~ite
pr~s~r~a~l~o ~d a pH ~n the r~nge o~ 10~$~12~.3. Option~l
~ngred~nt~ includ~ ~n~t~in~ ~y~bb So i~npro~ Ul~Q~
2~ ~n~it~vity ~ or Y~rl~u~ conv~s~t~osl~l ant1~og~ant~tt~bil~z~r~
: ~h ss b~slzothia20~ n~.~xob~nzo~hl~oles ~ ~anæot~i~zol~ .
c. ~ol. 10:26-4~ hb ~ntl~o~gant~ oarJ ~ ded ~o ~h~
I d~relope~ .
U~S. P~l;on~ No. 4,7~9,61~ u~d :l2/~6/88 ~ In~u~ ~t
a l d ~ l o s ~ 8 M b l ~ k ~ ~ p ~ ~ " P ~ h~ G ont ~ ~n ~
, photogr~phic ~t~ al~ in wh~h bl~s~k ~p~t~ ar~3 ~Aid ~o IDe
r~du~d c~r prev~n~d by in~o~por~ on o~ arl oxldl~i~g ~gen~ (~t
lO-5 ~ le/mol~ A~ ) ~uoh ~ N~bromosuecin~mlde ~ hydrogen
, ~ peroxide ~nd ~t~ ~dtl~n px~du~t~ ~ p~ aicl ~alts, pe~oxy
35 G~mp~x~o, o o~e, ~t~ onvent1on~1 ~ntifogg~t stAb~li20ra
. ~uch ~ 8, m~x~lpt~enæothl~ol~D ~ nitrol~en~xi~ol~,
o.. ~r~ d a~ ~ptl~n~l in~r~len~ ~Col. ~1:4-~4 ) ~c~r
.J ..
"i"'.':.",~ '` ;.' ` .
,-, .' "'',~;,' ' ' `
''~' ~ ' i .'.'.'. ; '
` . ` ` ~7~ ~9
WQ 91/D934~
PCr/US90/D74~4
th~3ix QCIl~VllntiOnAl antifOygl~nt/~abi~ er pUEpO8~3~ el8 ~n
~a~a~k2~ .
t~ at~nt N4. 4,7135,5~7 i~u~d to Xuw~b~ra
11~2~/~8 di~lo~ hydr~ t~te.ln~ng phots~s1r~phlo ~'se~ial8
of h~lgh ~a~ lt.rlty~ ~d ~v0r~ high'l ocr~ra~t in ~hich pepp0r
a ~ld .t~ b~ redu~ed by u~ing two dl~aræn~ ~ilver hal~de
~ul~on~ wh~h di~3~ m~n ~r~ 0~2e ~ithin speclf l~d
: ~ ll~ h~a~les ~nd ~hodanl~ r~ qloo~d ~ ~opk~onal )
~n~ z~ o~ #/~b~l~2~rB ~u~h ~ ~h~201~
1 O a~ al~o d~cl~ed a~ OP~QJ]~1 in~rsl~dient~ (CO1D 13s37-60).
Europ~an Appll~atlQn ~o. A~ 3~6,83~ oi~ P`u ji ~hoto Film
pub~ish~d or~ 3/1$~8~ ~isolos~R photoyraphl~ mAte~ of high
. ~ntra~t *.nd ~n~ y g~on~air~ hydrazin~ dsriya~i~e ~nd
two additior~ o~pound~ ~ ~
1 5 ~ ph~o~raphl~ ~x~ra~n~r ~r~s~g ~ l~to~ or~n~
~roup P~ ~i~e~t ~ L~[l) and ~ te~r~æol~ der~4ti~. As~tlf~g~
nt~/~ta~ B A~ c~ ~d~d. ~pp~ d~ Jl ~iB æt--
txibu~ahl~ t~ ~ho el~t~on-wi~hd~wsl proportloa o~ ~he n~ro
group.
~2 OBurop~n ~ppl~ati~n Ncl. Al 2~6,840 ~ lo~ g~dly
r~ d~ ed pePPe;r photo~raphl ~ ma t~r~ ~l s ~ o~n p~ ng a hyr~ ra z in
aompour.~ ~ th~ g
02-~H-~-N--
. whoreln ~ iB ~ ul~onyl, flu~o~c~r, pho~phory:l or ~ b~ki~u~
or un~ub~tits~t:~d ~ thylelle~ ~ha p~pper-~edu~ pr4por-
tio~ ~ro ~ttributabl~ t,o th~ hy~r~id~
~3 NoT~ o~ th~ ~b~ Lt~d dw~n~ h~ d~cl~su~ o~
whi~h ~ ~noo~po~a~d ~r r~r~n¢o ) d~ a ~ mali
slt Oæ ant~ nt/~ ~blliz~r o~ l?ormul~ to reclu~a
papp~r, ~or ~ ~on~ tion o~ ~h~ hy~r~ oiE U ~ S . Patent No .
-i . 4,686,167 w~h ~ p~pp~r-~du~l~g a~e~tiv~ ~uTount o~ a
. ~t~iliz~rfarltifc~g~nt ~1 hlgh-~ontr~t, hiqh~enoi~ivlty
. photogr~phio m~e~l0. .
~IQ~
rd~n~, an b~ thi~ inv~ on i~ ~ p~ rid~
. . .
.
,... ~ . .
71~9
WO 9~ 45
P~/lJS~ 7~
a ~ighly ~ensi~ hi~h-o~tr~t silv~r h~lide photog~aphic
~ter~l whlch ¢~ bo daY~l op~à wlth ~ ~t~bl ~ d~ per in the
pr~erl~e ( itl ~ho pho~o~phl~ ter~ r ~ n the developer ) of
a hyd~lne o~ hyd~n~r~ nha~olrlg oompo~ to obt~in
a ~up~-h~gh ~on~r~wi~ch ~ub~ntlal ~eàu~t~o~ or
~llmi~a ~on o~ bl~c~ ~pot~,
~ h~r o~ t o~ ~h~ Y~n~ to pr~ d~ ~ ~e~h~
for reduol ng a~ in~ bla~k ~pot~ upon d~v~opm0~t of
sLl~e~ h~lide ph~o~aphlc ma~ri~ lah oon~a~n~, nr l,7hich 1
; ~ d~lrelc~ped an ~ d~elope~ ~:or~æ.lnlng, a hydr~ ne or hydr21zid~
c~o~pou~nd ~nd whi~h y~ a ~up~r-high ~orlt:r~ 'civ~ ~g~.
~ rh~ ~bove a}~ t~ n be ~ocompl~hed by ~he lncorp~ra~
t~on in ~ phok~graphio ~n~t~ r ln i~ ~ devel~p~r ~f
oP~pouncl ~ithin Fo~nula I~ ~lo~ in ~n ~ount ~e~t~ve ~o
S r~u~e or el~na~ bl~ck 9pot ~or~a~i~n bu~ not ~apable o~
~bal;~n~glly ~fag~in~ ~n~lt~vity ~s 00~ 6~ (~.e. not
rBdUI~ n~ ty mo;c~ th~n about 10~ c)r ~peed ~o~ th~n nbout
a quArl:~r~top or ~a~ç~e the ~:lu~ b~low 10 ) .
Pr~f~r~b~y~ ul3~ o~ thi~ c~ompolaa~ e in ~ nag~2.v~-wor~c~ n~
2 ~ur~aoe~ ent i~g~ ~t~ ~bu~ ~he pr~nt in~ tic~n ~ t
l~t~d to ~u~h ~y5~8rm~ he Formule~ ompou~d i~ pr~f~r~
ly t ~ p~x~d ~n ~ ph~qr~E~h~ torilll, ln a~ 10~6~ ~ne
of ~h~ ~mu~lon lh~er or itl ~no~h~r ~ e ~ ~ . a hy~rophill~
~ ~ ~ ~Qllold ~ l Ay~r ~o~t~d on ~be phatogr~phl~ ~a~er~ Uppoxt
:~ ~ ~o~t pre:~e2~ly, ~h~ photog~ph~o m~$~rial C~ mpril~38 th~
~ollow~.n~ uppor~ h~vin~ pr4~i~ed th~ n ~ on~
~i~vox h~lide e~uls~c:n lel~r, ~h~r~n ~ld ~uls~n l~ye~ or
~rlother l~y~ f ~he ~ er hal ~ de ~ho~o~raphi~ m~e~
prot.r~d~d on th~ qupport ~ont~ln~ ~t ~ ne compound
3 ~ ~3pxe~ d by ths F~ul~ ~ ~nd ~118t~ lt~l~n8 Al; ~oA~t ona
n~0ua~d o~ t;h~ ~oa~ul~ a ~g~ mph~i2~d, howover~
that th~ proo~hnt ~nv~n~:~on i~ nok l~i~ed ~o hydr~zld~ ~riva-
~iv~a o ~oramlla I ~t to hydx~ s ~r hyd~ld~ pre~n~ ~n
~h~ F~a:my~ ph~nyl' hy~ ould, ~ox ~x~pl~ ed
3~ , ~n ~he d~veloper with a ~o~p~urld ~E Fc~smuln II lr~ the ~1lsn ~in
c~ w~th ~he p~ n~ ~n~
A ~upe3:-h~h l:~Oht;r~ t rleg~t~ve l~na~e 1~ ~onned by
,.,, .,
,
.
`` ` 2071~9
.,
WO 91/093~ PCI/U~90107~4
prooe~s ao~p~ n~ l~lZlgelWil3Q expo~ g ~ h~dr~ne- or
hydra~lde- ~nt~in~hg photogr~phic m~orl~l lpre~e~bly a
~exi~l ~ontC~n~ng ~ ~or~ul~ I ~ompoun~) ~o light 4nd devel4p~
~ n~ the ~xpo~ed ~ ri~l w~th ~ deY~loper ~nt~ ing
5 d~hydr~xyb~nz~n~ der~rati~e ~lB 1~ t3@veloping ~g~lit) ~ Zl b~ln~
20~ ~Yol~ ~nt~gg~nt, a su~fite pre~ tive an~ ~n ~f~ctive
~n~u~t o~ hn ~min~ cc~pDund.
~ompound~ o~ F~rntula I ~n~luda:
. ~ y DO
Rl ~N~ )nCN~ N~N~CCX ~P~onnula I )
R3
5 whe~e~n:
X=-N~5~6 ~ ~r ~4R7 ~
Rl and ~2 ara lnd~penæ~ntly hydroger~ ar~d sub~t~ d ~r
unsu~stitu~l3d 1 i ) ~ yl, havi~ ~p ~o 18 ~r~or~
~ycloalk~ ph~nyl ~r ~phthyl ~r (~ ulfonyl.
O ~3 l~ hydrogæn, phany~ or ~onzyl, ~h~ te~ 1G
aub~t~ttltb~ sr un~b~t~ut~d, ~ut 1~ neith~r ~1 nor R2 18
hydro~n th~n ~R3 i~ hyd~og-an.
. R4 ~ a 11~;U}:IB'i~ U ed o~ ~n~ tltutet diva~ent ~o~at~
~ro~p.
S . R~, R6, ~nd ~7 ~re ~ n~ep~r~d~n~ ly hydrog~n, ~ub~titut~d
or un~u~t~t~d ~ lkyl baq~n~ up ~o 12 ~arbon~; ~11 )
ay~lo~lkyl; t 111~ ph~nyl o~ ph~hyl
~1 ~nd ~3 o~ Rl ~d R~ o}~.r b~ linked to ~orm a
. . h~t~rocy~lic ~ y~t~ w~th th~ ri~ or;~nlng three to t~n. .; O ~t~.
and R6 c~ln be l ~ ~ked t~ ~orm a h~t~ro~y~l~c rir~g
~y~ ' wl~h h~ x~ oont~nln~ 3-lO ~tom~.
y ~ n c~xy~n or ~ul~ur a~m; n~O, 1, but lf Y i~.
,. ~ul~u~ th~n s~Sl~
. ~lt~31e sub~tiitu~n~ in~lu~ w~h~ ation
h~logen, hydro~, ~lkbxy, ~ o, ~llcylamlno, ~ryl, ~ryl~ino,
~yano, ~cylam~n4. ~rhe i~ul~itu~nt~ th~m~ may b~ ~ur~h~r
~ubst ~ tuted .
.~omp~un~ r~ :F'4~ el. 2I, in~lud~ ~ampound~ ~n~ain~ng
,' .
.,
.
.: ' ' -' ':'.
. ,',~ .
` ` ~ \ 2 ~ 7 ~
WO 91/~ 5
P~r/USgO/~745~
c3nP m~l~ty s21~a~d ~rom the group con~is~in~ of ken~
~o~h~zole~, quln~l~n~, ln~ol~l~ine benzotr~zo~es, ~nd
. ~hodanln~ h~ins3. on~ or mor~ r~itro ~roup~ ~ttn~h~ to ~
: ~ne n~cl~u~, wh~h iB either ~ pa~ o th~ h0'c~rocy~1i¢
~np~urld or ~ a~aohed ~ lt ~ , d~ubly~onded c~rbon-
to-o~rbon ohai~ . ~he qllatern~ry ~lt~ g ~u~h ~ nium,
. ~riethyl~n~ne, pip~r3d~n~ An~ ~lk&ll ~etAl ~t~, pro~er~ly
. ~ne hanol~olubl~ he ben~o~Gh~oleB ~ q~nol~n~ and in
dol~n~n~ a~ ~loo ~u~ leO ~ompoun~ o~ ~o~ula II ~Xe
O d~flnad ~ ollowo:
wh~rein m i~ an lnt~r ~tw~a O and 6 lnclu~iive; ~
~el~ted ~som the ~rc:up conGis~lng of ~n~o~hlllzo~e, ~uinoll~er
-2 indol~J~ine, nitrob~othlnxola, ~ zotr~zol~ ~nd rhodanine,
~ ~aob Oæ ~h~h m~y b~ ur~u~tituted or eu~st~tu~ed 3~y, . e~g~
ha~og~n, hydrox~, ~lk~xy~ aryl, ~ o, ~ryl~n~, sul~u~i~
a~id, ~2r~03rylic~ a~ld9 ph~nyl, e~c,., or ~u~ed t;9 th~ nitr~ber~-
. l zer~e nu~l~ufi.
: 1 2 Pxe~ ly, ~ u~ itu~ed l~y hy~xog~n or CaE~OX
~r~d an 1B 1. ~ur~h~ox~, th~ ~u~sti~uents i~ Rl ~Ee p~o~e~bly
. ~n lt he 3~p~.ition 1~ th~ rin~ S ~ nd n~ring i~ sl~ok-
, wiJe,
,~ ~
$0~Y~2~l o~ th~ oompound~ r~pr~ t~d by Fo~
~ ord~ n~ to tho pr~ t inY~ntion w~r~ pr~lou~ly known ~n~
u~0d ~ pho~raph~o ~t~ r~ oggan~B . ~in am~unt~
. q~n~lail~r r~n~ln~ betws~ bout lO-~ ar~d ~l~out 1 ~ole~/mol~ P.g
. ~ ~o i~pro~ th~ ~p~ on~r.cy o~ phot~g~aphi~ u~ n8~
~ i Url~xp~o~edly~ ln oxp~rl~ent~ t~tin~ the ~ y o~ ~u~h
~ ~ qompbunù to ~pro~ pe~d ~tahll~ ty o~ or h~lide e~ul~ion~
. oonta1 ~lng h~dr~ld~ d~riv~tive~ p~ lly hydr~lcl0 d~rlv~ ~
`ti~ 8 cs;f ~he Formula I ~ype, ~t w~ disa~v~ed th~'c auc~h
oo~po~nds ell30 ~duo~ ~n~/03;~ ~llmin~ed "pepper" ih ~1!1 aOrl-
~ntrat~ or~dep~nd~t mannar but ~t ver~ ~m~l~ cun¢~ntr~t:i~n~ .
' ;1
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'
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WO 91/~93~5 P~T/W~90107q5~
M~t unexp~c2tly, ~t ~uch s~all oç~ncentr~ion, ~uc~h c:c~mp~u~d~
~em~rk~bly r~du~e or el~lrlat~ blAok ~po~ wlthouk ~nh~ bi~ing
~I:he abil~ty ~ ~hg oompound ~ep~e~ont~d by khe ~o~uln I t~
ino~a~ ~en~itl~ y nd. ~:ont2~ t~ ~h~ r~n~ o~ 4nki~1
p~pper r~du~kion ~ Ye~ u~h ooxnpour~ en~x~Llly
b~t.w~en ~ou~ 5X10~8 ~nd ~bou~ ~xlO-~ ~ole~/~nol~ Ay ~n~
pr~ bl~ ~bo~k :~O~~' ~o ~bc~ 4 ~ol~/~ole ~g. ~h~
pr~ t ~ul~on io p~ rably u~ a~ 3.6 g P.g/m2~
: ! ~h~ oo~pound of the ~o~ul~ I or ~oth~r c~n~a~t-
10 ~nh~t ~ hydraz1de ~nd th~ ~ompoua~d o~ th~ ~o~mul~ II A~
E~ rably inco:rpora~ed in~o the ~ame l~y~r, but m~y e~ o be
i~o~ rat~d ink~ dl~eren~ r8 or ~he compo~ c~ Fos~
c~n be u~ed ~n ~h~ v~lDplng solu~ion~ ,
~ he g~n~ o~ula I dsff~r~ ed abov~, ~1 pr~fer~bly
15 r~px~ t~ ~ hyd~o~n A~ ln u~3~u~ti~ut~ or ~ub~tltuts~
. alkyl ~roup ( ~;u~ta~le pr~rr~d ~u~ nt~ in~lu~ without
l ~mi~a~ yl , ~yan4 , hAlo , or ~lkoxy ), a ~u~ uted ar
un~1lb~tut~d ~ loal3cyl g:e oup or a ~ub~t~t~;ed or u~u~-
~t~ut~d ~yls~l~onyl ~xoup~ ~he t~t~l nu~r s~ ~arbon ~toms
2p in Rl ~:!A~ b6~ up ~o lB but prefer2~1y, ~houl~ be 1~tB~S than l i!o
~So~ p~6~~bly, Rl is ~nsubs~i~u~d ~lkyl o~ cy~oalkyl
eo~tainlr,g 1-~ oa~n ~tom~.
R~ 1B ~ pes~ently ~ho~n ~rom th~ up sepr~g~rlt~ng
p~f ~rably, howev~r, th~ to~l DUmb~ 0~ ~arhon ato~n~
2B batw~n R~, ~nà ~ ~hould ~ot ~x~e~d 12.
R~ pr~ ahly ~epr~ t~ ~ hydr~ggn at~ n u~b-
. ~lt~ d or ~u~t$~ut~d ~nz~ OUp ~ u~t~bl~3 presrr~d ~ub-
-~ I Bt~tUeal't~ ncl~ w~th~ut l~ ation ~lk~xy, ~lo or ~lkyl)
~ r Rl n~r ~ hydr~gen~ ~h~n R3 ~UO~G b~ hydroq~n~
: 3.0 Mo~'e prei~bly, ~ hydro~s~.
': ~n th~ pr~rred ~ , Y i~ ~ ~ul~ur at;4~ Y ~ a
~ulfu~ at:om th~n n~l, In th~ ~o~t p~~rr~ c~ae n~1.
~;
. . . ~,~ pref~r~ly repr~on~ s~thox ~n ~ uJastltuted or
. ~u~titl~t~d d~ nt ~romat~ group. ~uitahl~ ~u~titu~n~
35 inclu~ W~t~lOU~ nit~t~ on alkyl t ' s.lkoxy ~ halo, os a~yl~mino
.. ~ ~P~ O In ~he m~t pr~ 4 i~ ph~n~
w~h th~ th~ or ~id~ up ln ~h~ o:r~ho~ ~ p~a-p~
' ' '
' :'`1 ~ , . . .
.
2071 i99
~'0 91/Og345
P(~IU~9~/0~4~4
tian r21at~e ~b th~ hyd~azi~o ~oup~ ~urkh~or~, it i~
pr~e~ed th~ ~ny ~ult~ble ~ub6~$~u~nt as de~axlbed h~reiFI be
~ttA~hed ~t a r~Lainintg, unwt:up~ ~ a~tho- o~ pAra-po~tlon
X~ Y~ h~ hyd~ up~
~ pre~r~1y ~epr~Ler~t.~ ~th~r a hytrog~h ~tom, an
un~u~titut~d or sul~ ted a:Lkyl gxoup ~ ~ul~ p~f~rred
~u~tlt~n~s ~n~lude hydr~ry~ h.~ lkoxy, ~lkyla~no,
~cyl~nino, ~ino and aryl ~u~h a~ phenyl ), a ~y~l~hlkyl g~up,
~n ur~ubatl~ed o~ ~ub~k~ d a~yl ~oup ~ ~uitz~bl~ pre~er~ed
1 ) sub~t~uænts in~lud~ alk~ y~n~, hal~ ~r ~lk4xy 3 or ~n unteub-
st~ tu'cqd or sub~tltutad ~mihe . ~h~ ~ot~l n~ arbon
~tom~ in F~5 ~hould be ~p to 12. Pr~fer~hly, F~5 i~ ~l)cyl,
~y~lo~lk~lI di~lkyl~ o~lkyl ~r ~ min~slkyl e~h ~o~t~in~ng
1-~ ~arbon ~om~. ~
l! P.~ ~n~ R7 ~e in~ep@ndeintly choi~n ~m the gro~p
repxe~nting P~; prefe~bly, h~w~v~r, ~he to~Al Jlum~r o~
cashon ato~ ~e~w~n R5 ~nd R~; ~hould not excecid 1~. ~n
: addi~ior~, RE~ ~d ~;` pr~;~era~l~ d4 not cont~in amino
~' funckibnalitl~ th~t ~r~ dlre~ly ~ inked ~ ~he nitrogen a~om
a~ X.
~u~th~mo~g r P~5 ~nd ~6 ~n be link~d to f ox~7i a
h~t~ ycll~ rin~ ~y ~ wlth thQ rlng c~nt~inin~ 3~10 ~toms~
~ ~.ddition~lly, elther ~1 an~ R3 ~ Rl ~nd Ft~ ~hn b~
linked t~ fo~ a ~e~o~y~l~ c rir~g ~y~m ~th ~h~ rin~
~r oontais~lng 3-10 ~toms~
~ ~ The pr~ferrod qomp~unds r~p~e~n~d 1~ tb~ g~nera~
, - Po~ul~ I ~r~ ~h~s~ repre~ented b~ ~he ~a~nl ~o~uila ~A).
n ~ Ql n ~ Formul~l I A )
~NEICNB ~ NE~N~CC;!~
~.'
Irl th~ ~ormul~, Y ~ S or O; z ~ o o~ ~N; P~8 and R~
;~ hhve the 6ame ~eanin~ ~ R~ and ~5 r~i~p~ ly ~or the A~o~re
33i ~eiscr~d ~eneral Fo~u~a I. Moet pr~er~bly ~ e~hyl,
. n-butyl or ayol~h~xy1, ~9 i~ hydro~n, methyl, ethyl,
dlm~l;hy~a~ino~thyl or ~etyl~mlno~thyl t Z h; HN, and Y ~ S .
~p~ ex~np~B o~ th~ compoun~ repre~n~ed by the
:: .................
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WO 9110~345 2 ~ 7 ~
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~1
ener~ r~ula ~ ~r~ elow in q`abl~ ~, but the pre~nt
~ nvantior, i8` ~ot l~Li~d ~o th~e ex~npl~ f~t, the
px~sent ~n~ tlon bro~dly i.n~ol~q~ th~,u)3e or ir~o~pox~tion ~3~
~ul~ ompound, ~n ~n ~unt ~u~ t to ~educe or
~h t0 PPR~ y hi~h~o~ t ~g~
~pho~o~ra~ al ~d/~r ~ ng ~ n~r~t-
g ~u~t ~ ~ b~ r hysk~2~ d~
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~ h~ s~oun~ o~ th~ ~ompou~d ~ ~or~ula ~ ~dd~d ~ the
sllver hn~id~ ~aul~ca~ l~y~ o~ to on~ o~ mor~ hydxophili~
~ollo~ uoh ~h~'c the ~:~o~ ld enhano~ ~ontr~t
~U1: dl~lB not ~p~r~ai~bly ~un~tlos~ ~ a d~v~lop~x~ ~p~lly
~our~ o~ ~bout 10 ~ ~co ~bou~- ~xlO 3 ~ol~ol~ A~
p~ef~r~ly ~r~m ~bouk 10 ~ to ~bout 5a~10 4 mal~/mole ~g ar~ u~do
In the ab~e d~s~r~ b~ Eox~ula II the el~ctro~ ept-
in~ c:~mpou~ld~ ~Ire ~mpour~d~ h~vln~ or ~luo~e 3~tro grs~ups
~tt~hed ~o ~ benzez~e a UC~ h~c~ 1B ~lth~ ~ p~lr'c ~ th~
.,10 h~t~r~¢~c: ~o~p~und l~r~ ~ t~s:h~d to ~t ~hr~u~h ~ cioub~
~onded ;:a~on~to-carbon ~hal~ 38 d~c~b~d in ~S Pa ~ erJt ~41,47
. .~ inc~rporated ~y ~fer~Jlc~ P~C~ ~1Q ~ut non~ in~ ~xampl~
o~ ~or~nul~ I~ ac~:ordin~ ~o ou~ pr~er~k invent~on ~re ~hown ~low.
. ~n~rall~ sui~ble ~mounts ~f ~he Fo~ula II co~pound ~re within
, ~ l the ran~e o~ ~Ik1C~Ut: 10-~ t~ abou'c lD-3 m~le~tmole A~, with about
I . lxlO-5 to abou 4x10~4 be~ng pre~r~d~ Thi~ i~ dif~rent ~;c
,1 t~e ~t~bili2er ~e~v~' ~mount~, whl~h a8 ~t~ted ~bovQl a~ Inu~h
,',~
~. 8UB~3Tl~lA1T. 3;HlE,~
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WO 91/~9345
,, PCrtUS~o/~74S4
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high~r in th~ ~y~;~em emp~ oylng Fo~ul~ I hydr~id~s, In o'cher
- I~;y~:Q~nB ~2~g. u~,ny d~e;~en~ hydrazid~ or ~i~fer~nt 8ilver
h~llde ~u1~ , e~ he oonv~nti~rla1 ~ta~i1izi~g/antif~ggant
~unt~ be d~ r~nl: bU~ th~ anti-pepp~r ~ e~. ive ~mount~
~ 4 ~t~ ~pat~d ~;4 ~6~ szu~h ~ r . frh~ anti- p~pp~r ~act
w~ll p~s~1~t ~t hi0he~ amoun~ bu~ al8 the ~moun~ o~ ~o~au1~ II
~o~pounds ~ppro~ahc~ ~r ~eache~ th~ sntloslg~ tllbili~ar
~foctlve ~ g~ n~ ity w~ beyin t:D) b~ ~ffe~d. which
~ ~ ~nd~ ~ ra~ n ~he pr~s~n~ invent1On . ~ I b~low list~
lt celmpound~ w~thi~ ~ormu 1 a ~I as ~rl illu~tr~t~ O~ ho~ld ~e
~nd~rstc~d ~ha~ ~ny ~::ou~in~r)n ~ th~ le ~ group~ ~ ~nd 1~
:~ ~nd r~gh~ ~oiet~ ~u~itu~nt~ a~e fully within the æcope ~:E
F~rmulR ~I ~nd th~ pr~n~ ~ nY~n~ion, not only individ~ally b~t
ai~o ~n~:ally 1 e ~ g . "~thyl " ~hall b@ ~n 111~stx~t~n nf alkyl,
15 ~t~
. NO~
2~ C~ o
, ~ S
. ~ NO~ ~ `
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As ~at~t a~ove, . ~h~ p~pp~-r~du~ng ~n~un~ D~ th~
'4~1Ul~ ~'I compount~ ~hould not ~e high~ ~h~n ~bout 10-3
~nole~/~ole Ag lrl o~dar ~ vo~d deæ~n~iSlzAtion ~nd ~ of
~nt~t, ~he la~er due ~o lh~e r~rence wl~h the ~n~r~'c~
3nh~n~ing flln~tion o~ th~ o~ula X l ~ydr~zid~ ~
Th~ ~ompo~nd~i o~ ~ormula I ~nd II ~an ko ln~orpor~ed
15 . Ln th~ photo~r~phi~ m~n~ ~y well kat)wn 1:a~hn~que~ u~d 4r ~h~
. ~c~rpora~lRn o~ ~ddit~res ~o photo0raphic ~mul#lon~ or ~ ner.~6.
. 'h~ co~p~unds a~o ~ypic~lly di~;~olved ~z~ a solven~ ~le~te~ ~rom
~rganlc ~olverlts co~atibl~ wi~h w~ter, ~sch a~ hol~,
~lycol~, ke~na~, e~ t ~d~&, and th~ like whl~h ~x~ no-
~0 dv~ ln~luenc~ on photo~raph~c eh~ rl~ies, ~r~d th~
ollltaon 1~ ~dd~d to ~h~ photographi~ men~. P~e~:csed
olYent~ ln~lude ~ thy~orm~1~ , d~th~l~ul~ox~de
~MS0) ~nd N~me~hyl-~ -pyr~lidinolle (~
~lterna~iv~y, th~ ~ompoun~ ~ Fonnuls I ~nd I~ be
25 d~d ko ~ mul~n ~ a di~p~rgL;?Il by 3snow~ ho~s u~ed wh~n
htgr-~n~olul~ o-aalled `'o~ l so1uble" ~ upler~ ~re ~d~l~d to
ula~ ons. ~r~fer:cgd o~1~ ln~:lud~ N~butyl ~et~T~ilid~ thyl
~ ~an~1id~ ~hd ~l,N-d1~thyl~m-tsluamid~. ~h~ oi~ e ~om~r
o Ally ~Y~ ble~ Vltra~ound ;~an b~ employed ~o à~ol~t~ tmore
~0 P r~ sely ~nQly di~p~e) ~ln~lly ~lu~l~ ethan~ oio a~id
h yd~Aa~s~ ~h~ solut~orl~ or dlxp~r~ion~ n b~ ~dd~d to th~
P ~oto~x~ph~o ~mul~i~on ~At ~ny ls~ac3e ~u~s~que~t to ~h~ lsion
P re~pi~tion an~ w~h~ng ~t~p~ ~ P~ bly th~e ~gents ~hould
du~ g ~hem~Al r~peni~g ~ jU8t prio~ t~ ~oAt~n~.
i: ~gl~tin ~ ~d~nt,~aou~ly u~ed ~ a binder or p~ot~
., . t. l~tæ t~oll~1d in ~ie 3;~hotog~phio ~9~ulllion~ l~ut ~her hydrophlll~
q tlloid3 ~ e ~d . ~ xample, gelat~n ~oriv~ to~,
~ . ,~t p~lymar~ o:~ ~el~t1~ w~th other high mctlo~ul~s weight
., ~ ~rials, ~ct~ uch a~ n o~ ca~in; ~o~llu1~t~e der~v~-
t' .YkJil ~u~h a~ h~r~x~xye~h~ llu~a8e, Ç~ t~ o~llulo~e or
~ .
.~ , .
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2 0
W(:~ 91/OP34
PCr/USgO/07~5~
~lluloAe ~ul~t~ h~ride Ct~;~iYat:iV~ uoh ae 30cl~m ~l~in~te
c~;r ot~h de~ t,~v~s, poly~lyoo~ld~ dextr~n~ ~nd ~ u~
,~yA~het~ hydxophill~ h~h ~ol~cular we~ght ~terl~ uch A8
ho~oPo~ or ~:OpOl~!lr8 c)f ~ pol3rv~nyl Al~ohol, po~ nyl
41~ohol (p~:et~l a~:~tal) 7 pc~ly~N~vlnyl py~rolidDne, p~ly~oryllb
d, polym~th~cryli~ , p~lyc~cs~lE~.de, pol~ nyl ~z~le,
nyl pyr~L~ol~ , ~to ~, c~n ~ o be u~l-d ~ ~eldtln is
~ d~ ~11 th~t~ we~ ~4W~1 ~nd ~0r~11y
va~lable .
10~e-prw~d gel~ nd ~c~id~ proc~3sed ~ol~ n can
.ltern~ively ~o ~the ~elat~h. Rydroly2ed or er~zymtt-
q~ompox~3à g~latin c:~n ~ O b~ ed . ~u~ t~bl~ g~l~kis~ d~
v~ p~ep~red ~ oti~g ç~ tin w~th ~rAriDU CNIPOUhdE~
uch ~ d halide~ id ~nhy~xld~, 1BO~Y~na~ omoac~k4c
~5 ~id, allcstla~u~ne~ viny~lJlfPn~l~o~ lalr~ ompound~,
p~ly~lXyl~ne 0X~ 419 or ~poxy co~pourld~ d, pre~er~bly, ~lth
- p~th~lio anhyd~de c: ~ euo~iN~ anhytrlde ~ ~p~ x~pl~ o~
t ~e~ la~ de~lv~ iv~ d~rL~ed ~n ~Ø, U,S. P~t~nt ~o~.
2 , ~ 2 ~, 3 ~ 132, ~ 4 5, 3, l ~ ~, a~ d l, a o~ ~ 7 ~ nb~p~ d
20 ~ y r6~f~renoe.
. Ea~ o ~ultAbl~ ysl~n dr~t poly~o~ in~lud~
t o~ prepa~d ~y ç~sa~ti~q a homopoly~r ~r ~ ~op~ r of
~nylic ~on~m~r su~h a~ ~rylla ~d, ~n~tha~ryl~c ~ld, ~h~
~ , ~si~tlv~ tho~o~ ~ ~u~h ~ th~ b~t~r~ or the ~dos there6~ J,
~5 a rylorli~ri~e or s~y~ne to g~l~t~ In pA~t~cul~r, yr~t
P lyme~ p~r~d ;~um pol~ r~ ~hi~h ~r~ o~patlble with g~l~tin
~om~ de~ u~h ~ ~ho~o ~ 4c~ Lc: a~id, m~h~ id~ o~
a hy~roxy~lkyl ~th~rylate t~?h~ch e4~ p~ rr~d~ Exa~pl~
tl ~ e p~lym~r~ ~e ~ c~b~d 1~ g 1~ atsnt No~
~0 ;~ 763,~$, 2,~3~7~7 ~nd 2~9565~ yp~c~l ~ynthet~
h~ dx~phlll~ high mol~ul~r ~ei~lit ~at~ri~ e d~ribed 1~,
~,~. ~ ~an P~tent ~?pl~tion (O~S) ~,31~70B, ~v~ Pntont Nos~
fi~D,751 ~nd ~,~73,~05~ n~orp~t~A by ~e:feren~
~ h~ pho~og~phic e~ul~io~ d ~n ~hll; ln~ant~on can be
35 ~r ep~red u~ln~ th~ w~ kn~wn m~th~d8 ~o~ari~d ~n, 8-g- t P~
fXLda0, ~h~ie ot Phys~gue ~hot~gr~ph~gu~, Paul Mont~l, Pari~
~1~67), B~ ~. Du~fin, Pho~o~phia ~mul ion Chemi~try, ~h~ ~oaal
11
2~71~99
W~ g345
PC~U~gOt~7454
PE~ ondon ( 19S6 ), V. ~. Zel~km~n et al ., Naking and C~atin~
h4tO~P~O ~mU~ n~, the FOO~1 Pr~, I.OnàoTt (1~64 ~
~ao~pos~t~d by ~of~r~nc:e. ~h~e m~thod6 ~nclude the ~cid
~th~d~ ~h~ n~u1;2e~ tho~, the ~un4nia ~e~hod ~nd o~h~rs.
5 oreoYar, ~ ~oluble 8l l~er 8~ n b~ 2e~tod w~th ~ ~lubl~
~logon salt u~ing ~ny o~ tD~ me~hoel, ~he d~u~ e~
~thod and a ~o~bin~on th~e~ he w~ snown ~ hoà of
~n~ h~ pre~en~e of ~n e~e~ of ~lv~r ~on~ 1 kh~
lled "r~r~e n~xing m~Z:hod" 3 ~a~ o ~e u~ed. The
10 'l~os~trolled double ~ hod" (al80 oall~d ~controll~d di~u~ion
D!lethc~d" ) i~ pr~rr~d. ~cc~xda.ng ~o . hi~ me~hod, the pAg o~ th~
lliquld ph~se ( ln whi~h the 8ilv~r hal~d2 i B to b~ pro~luoe~ ) ie.
k~p~ ~on~stant. ~hi~ ~nethod c:an pa:ov~d~ ha~e e~ul~lons
h~v~ng ~ ~g~ ~st~l ~o~ ~n~ ~n ~l~as~ LlnL~orm ~r~ln zize.
1~ ` Th~ ~lv~r halide gr~ln~ in the ph~tsgraphlc e~ul6ion
u ~ in th~ g inYent~on ~n h~Ye a ~lAtlvely w~ grain ~size
d i~t~bu~ioll, but ~ n~ow sra~ n 8i~ d~r~ b~ i æ pre~rred .
~ art~ul~r, ~h~ ~liZP o~ ~h~ l3ilvor h~lld~ g;l:Ai~l~ ~o~ntlng to
~ o~ t:h~ 1, b~6~d on the w~yht or nu~er o~ the grains, lg
20 p. re~er~ly wlthlr~ ~ ~ 0~ of ~he averAg~ ~r~ln l3ize ( ~uoh ~n
~1 nul~l:or, ~ ually ~ d A ~onodi~pe~ emul~lon). ~ln ~e
Ci ~n b~ c~ntroll~d ~y known ~chn~q~ u~h ~ ~re d1sclo~d 1~,
eLg. u.s~ P~t~nt~ No. 3,~71,1S7; N~. ~,704,130; No~ 3,~74,~28;
?~ ~ ~ 276, 374 ~;ld No~ 4 ,297, ~39 and in ~ aroh Di~alosu~8 R~
2S ~l ~. 17543, P~e~ nd 1871~Nov~ r l~g~ or-
` ~ P~ ~r~d ~y r~fq~
q'he ~dicridu~1 re~k~ts c~ dded ~o the r2~'cion
' ~ ~88~1 ~h~ugh ~u~ E~e ~r ~u~ ac~ del~very ~tlb~ ~y ~ravlty
~ ~ or hy d~ y ~pp~:r~u~ ~or ~lntAinin~ ~on~r~l o~ ~h~ p~
30 ll~d!0~ pAg ~ ~h~ r~aotlon.~e~ on~ent~t ~ Ilu~'cr~Lted by
,lh~n~ ~ al U~. Pa~ent No. 3,a21,0t)2, Oliver U.S~ ~a~en~ ~P.
3, 031,~0~ orporatç~ ~y ~o~er~no~. In ord~r ~o o~aln
; ~ p~d di~t~ibut~on of th~ . rei~ct~nts with~n th~ t1On v~s~el
. . E ~cl,~lly ~nstr~rk~d ~s~in~ d~ hr~ ~pl~yod,
~: 35 Lt: 4tr~t~d ~y P.~dran U.8. ~ton~ No. ~,~96,~87, Mc~s~6~en et A
. J~ ~. P~t~nk No. 3,342,~05~ F~ A1 IJ~, P~t~nt NP~ 3,41~,650
. ~olrt;~ ~t al U~S. P~t~n~ l~o~ 3,785,777, ~lto ~t al G;es~natl o~
r
. __._ .. _ .___.. .................
: .
~' ; " . , ,. ' .
: . ,: . ,
2~714~.
W~3 ~110~45
PC~r/V~g~/074
~o~ 2,556/~B~ ~Ind ~to et al Ge~ra 0~5 No. 2,S~S,~4 ~ cor~
p~xat~d by ~ en~e. An ~rlolo~ed ~aa~on ve~sel a~n b~
ompl~y~d to r~ei~ asld ~lx reaut~nt~ upstr2~ o~ the main
æ~action ~s~el t ~ llustr~t~d by ~or~er qlt ~1 ~ . S ~ P~ent No .
3,397,935 æ~d Po~ t ~1 U"~. Pat~nt ~o. 3,790,3~ 11 lncor-
por~t~d ~y ~e~ronc~,
~h@ grain 5i~ze: d~rL~ut~ora ~ the ~ilYe~ halide
~ul~ions o~ os~t~lle~ ~y ~lv~r h~l~d~ gra~ epa~ion
te~:hr~ u~d 8 ~r b~ bl~dlng ~i~v~r hhl~d~ ~Ynul~lon~ o~ d~4ering
n 81~Q~ ~ ~h~ ~ul~ion~ can in~l~de ~mmonia~al ~mulsions ~ a~
~11U8~S~I od by ~lafkidss, Ph~to~raphi~ Ch~m~, Vol. 1,
Fpuntaln P~ , Losldo~ 1958, pp . ~5-368 ~nd pp . ~Ol~Og;
lo~yanate rip~r~ed ~mul~ns, h~ 11u~tgated b~ ~lling~worth
P~ent Nv. 3, ~20, 06g; thio~th~sr x~pen~d ~nu~lon~, a~
15 1 ~8t2~ak~d by McB~lde U.S. ~P~tes~t ~. 3/27l,l57~ Jon~ U.SO Patent
N ~- 3/~4~&~8 asld ~e~nt~ o~ al U.~ n~ N~. 3,~37,313 or
nul~on~ c~nt~ in~ weAk ~ r h~ olv~nt~, Isu~h ns
n~On~ a~U~at~d ~Y P~ig~On U.S" P~ten~ NQ.
3 7~4,3Bl and ~ r~h I)i~ loJs~ f Vol. l~4, ;rune l~5, It~3m
201 452 ~ o~po~At~d by ~ enG~9 ~h~ me~h~d uaing ~monium
8 ~ p~f ~rr~d O
Th~ cry~ r~ oi~ th~ s~lv0r halide gra~n~ ih th~
~3 otographl~ *hiul~lon ~y be a:~gt~ uch A8 ~U}:~C or cla-
: ~ ~ h~dr~l ) ox irr~gulhr ( ~uch ~ sphor~ ~1 oa~ plat~-like ~ or lt
~5 ~y ~e ~ c:~mpD~t~ o~ t:h~ o~ Th~! ~rains ~y ~mp:rise ~xed
al~ h~ing ~ OUB ~ ta1 ~O~.
~he ~nt~rlo~ and ~ 3ua~ y~r C):E ~h~ a~lv~: h~l~d~
7rsi~ ~y be ~ er~rlt ox th~ gr~Ln~ may b~ unlf~xn thr~ughout~
~! ~ ~in~ th~ pro~ of ~h~ æo~atl~n o~ phy~ 1 r~p~nlng ~ the
3û , 7~ ~8, c~dm;~m 8~lt9, ~ lt~ a~ 81A~ / thallium ~Al~8r
; ;h o~lum ~alt~ Dr oomplex ~al~ th~r~o~ an 6alts or iron
mpl~x ~alt~, and ~he l~k~ aan ~ p~s~nt, R~6 ca" mix~ures
, .~o~. Prefe~d a~ ~u~h d~pelnt~ e rho~lu~ or i~dium ~alt~
~ ~r Dl~x~ur~ th~r~
3~ ~ ~ ~wo or m~o ~ ~ilY~r h~l id~ emul~iosl~ whlch ~xe
E e ~ t~y pr~par~d c~n ~Q mix~d ~nd ~h~ sed, ~f de~l:ced.
A~ r th~ ~s~mation D~ ~h~ p~ciplt:~te~ or af~
:' . .
~,
. ,
.
2 ~
WO 911Og~4~
PC~/~JS90/07~54
2~
phy~lcal ~p~nin~, ~he 601ubl~ alts ~re u5u~11y ~moved from the
~ul~ . For th~ purpo~ th~ well h~own n~odl4 wA~hln~ methocl
ay be u~ed. ~t~r~ ly, ~ Lo~ul~t~orl m~thod ~y ~e UBl:!d.
~ hi~ hod ~pl~ys ~n ~nD~ganic ~ h~vln~ a pol3~1~rt ~n~on
5 Lu~ 118 oodiu~ oul~ake, 4n ~nlonl~ ~ur~ tiv~ a~nt ~ ~n
~t~ion~ polymer ( ~uch ~5 poly~t~sen~ ~ul~onl~ d ) ~r ~ g~lat~
~x~ative I ~u~h ~s ~ aliphatl~ ~cyl~ed g~l~tin, ~n a~om~tl~
~ylated g~l~tin o~ ~ sro~tig ~rb-lmoyl~t~d g~l~t~n ~ . The
,~mov~l o~ th~ ~olu~ ~y 3a~ om~t~d, ~ d~oeirQd~
Al~hough ~he ~ e~ hAl~d~ ~mul~ios~s u~ h~
r~se~t ln~ention do nO~ n~d t~ be ~h~ lly senoeitiz~d,
hsnL~oally ~ns~t~d ~lver h~lid~ ~mul~iono ~r~ pr~rx~d.
r~ ch*micAl ~n~i~12~tion of ~h~ sll~er h~l~de
mu~sion~ wh~h ~arl b~ d ~nalud~ knowra ~ul~ur ~ns~ti~at~on,
15 edu~ti~n ~en~itlz~tion ~fll~ e m0t~1 a~ngitizat~an proces~
~jn ~ddi~ion ~ sulfur ~ h~lon, ~el~n~u~n, t~lluri~, rh~n~m
~r phosphor~ ~ensit~ze~r~ ~r ~o~in~t~ons ~ th~a ~0n~it~ze~
C¦~!ID be ua~d q ~h~mic~Al rlperlin~ can be per~o~sd at pAg ~v~l of
~rom ~ to ~ 0 t pH level~ Qf ~r~m 5 to ~ ~nd a~ te~p~r~ure~ ~om
c
~ h~ p~ s~cs ~e de3~ ed in r~f~r~n~ u~h ~8 P~
la:Ekid~/ Ch~o ~t ~hy3i~aue ~hotogr~phl~ue, Paul ~o~tel, P~
( 1~67 ) Q~ 2elikm~3n, Makin~ q~nd ~o~tin~ Photo~raphic Emulsione,
~ ~e ~ocnl ~ o~, L~n~on ~1964 ) Q~ ~. Frl~3qe~ utldl~g~n d~
2$ ~otPgr~ph~sche~ ~o~ t ~ilberhal~g~ n, ~kademl~;che
vlarlag~ge~gll~ch~ lg~ . The di~losure o~ th~e r~f~ren~e~
- ~ ~ ln~orp~r~tod by ro~ rao~. In the n~ble met~ n~ ation
p. -o~ o~n~ti~ on p~oc~a~ ~R ~ ~;ypiC~ pro~
w ~e 0O1d ~mpour~6 o~ ~old 40m~ x~ are ~d.
Complex~o o~ noble grDup ~ netals othnr ~h~n g~ld,
:, ~ 3t7h 118 t;h~ o:E p;lal;~ p~ dl~ o~ rho~ or i~idium,
. . :~. c~ o b~ u~d ~o ~h~mie~l ~ens~2~rs. A r~duc~ion
~, ~ne ~t~zat~on pro~:e~ ~ay ~ u~d i~ th~ proo~ oe~ n~t
~1 ~ at~ ~I!o~ ~o ~A d~ W~iab ~aus~ pr~ti~al di~i~ul~ieY
3~ ~ 1~th o~ ch~a~c S;ho ~e3 o~ k~own anti~og~er~t~ pAr~ul~y
p~ ,o~orr~d oh~m~oal ~ ation p~oo~ ~ ~or ~hfl pras~nt inven-
ti .on '18 th~ u~ o~ a ~ulfur 4~ tion pro~s.
`, : ' ' ' ' .
2 ~1 7 1 ~ r9 9
Yi ~O91/0~
P~T/VS~tl)7~54
~xample~ o~ ux ~n~ .21ng ~gent~ whlc:h c~n 1:~ u~ed
.ncludo not ~nly ~ul~ur ~ompound~ p~ n~ ~n tho ~elatin p~r ~e,
l ~lt ~l~o ~a~iou~s ~ul~r ~ompouT~ 8u,c:h ~ thio~ul~t~,
~lhl~ur~ h~a~oles or ~hodan~ns~, te~. ~xample~ of ~ui~ble
5 l ,ul~u~ ~o~p~urld~ deA~:clbed ;in ~ . P~nt ~o~ l 1, 574, ~94,
: ,410,~9~, i,27~,947,, ~ 8,~6B ~ncl 3,~5~,~S5, all irlcorporat~d
y r~r~nc~ ~yp~ x~mpl~o o~ uo~i~n-s~!n~t~21ng ~g~nts
n~ude ~t~ ou~ ~alt~, amin~ orm~idine ~ulf~rlic a~d and
~l~ne ~pound~ thyld~ hl0rct;~1~nR, hy~zlAe d~iv~tiv~,
10 o~an~ ~ueh a~ ~min~x~rle~, ~hioureEI Biox~de, hyclr~gen, and
ther ~oror~ hyd~id~ h as ~ b~oh~dr~ cl~ . R~ductl~h
~h~ti~at.~ on ~n ~l~o be ob~aln~ y low pA~ th~r~ 5 J or
~gh pH fqr~a~er 'ch~n ~) ~ri~tm~ntJ ~ wal~ nown ~n ~h~ ~rt~
9p~ci~ically ~4nt~mplat~d ~ ~h~ oom}~n~d ~e o~
15 ~ ~veral o~ ~h~ ~;Eorem~nti~ned chemle~l rlp~ ng t~chn~q~ s; ln
., P a~ ul~r ~old~ u~ 8en8itiz~ ,on ~o~lnation~ a~e hi~hly
P ~æf e~red ~
photographl~ ~at~rl~l u~d ~ hl~ lnv~rlt I on ~ay
~ o~ ln ~n ~nt~:Eo~an~ Ex~mpl~ n~l~ogg~nS;~ ~?hi~h ~n be
20 a ~tant~30u~y u~d for the pho~cl~r~phl~ a~a~rlal u~ in thi~
1 nY~ntiC>n Ar~ , 4-tri~ole oo~pound~ ~u~t~ tut~d w~th a
3~ ~ pto ~roup a~ th~ . 3-p~ition~ ~erlzotri~zol~ oo~pourld~,
2 ~me~aapt~hQnz~ z~l~ co~pour.ds ~whic:h ~to r~t a~rJtain ~A nit~;4
ro~p) O ~-~ner~pt~pyr~iflols, 2~m~x~ptot;hi~z~1e~ me:rcAp-
t ~enzoth~ &~ol~, benz~ ol~ o~poundo ~ ~uch a~ lk~rlb~n-
~! ~ z ~thL~zoli~ h~ trobe~z~n~azol~, oub~itut~d tri~zain-
~1~2~ (t~tr~a~ d~n~ r N~ rlb~0~ 2~1~ h~ ) 9
~a ld ~ x~apt~-1,3,4~hi~z41~. An~foggan~ whl~h ~ not
~ Ef~ot~v~ wh~n usod lc~ u~h ~ 6~n~tx~benzi~idazolg~ however,
30: & ~n be u~d i.D l:~C~ OYI w~th Advan~g~ou~ ~ntlf~g~nt~0
~t h~ a~n ol: ~e~t th~t ~oth ~9 ~du~tlon and ~n
i l~r2a~ ~n can~et ~s~ ob~ais~bl~ by ~mpl~ying ben~o~r~ ~zole
a ~t~g~nt~. Wh~n th~ b~nzotrl~ole 1~ at13d in thæ
P ~togr~phlc ~l~ment ~n~e~t~tion~ o~ 10 4 ~o 10 1, p~e~bl~
.: 35 ~ ~~3 :'co 3xlO ~, mole p~r ~ol~ o~ ~ilver ~re ~5aploy~d~
Us~ul l:~r.z~trl~ol~:~ can ~e oho~n ~r~ ~3 on~ oonv~n-
; ~ tton~ h~tri~ o ~nti~o~g~ntA, ~u~h ~8 those di~lo~e~ ~y
., I . , .
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; . ~ 2071~
WO 91/0
PCI~US90/0745
~6
L~nd U.~. P~t~nt No. 2,7~4,721 ~nd Rog~r~ a~ ~1 U.~3. P~ken~ ~lo.
3, 2~5,498, both ~ncorpora~ed by refexen~e. The pre~r~ed
. ben~otriA~ol~ ~o~ use in tbi~ inlverltion ~r~ b*n~otri~zole (~hat
1~ , tha uh~ub~tituted benzotria~ol~ ~o~pound ~, h~lo -~ub~ti~llted
5 ! ~næ~triazole~ le.g" S~cblorok@n20t~azolfa, 4-b~o~nob~n~otri~zole
~nd 4~c~10ro~enzotr~azol~) and a,l1cyl-~ubs~i~ut~ ~erl~Qtr~azs)le~
!~ her~ the alk~l mnie~ contAln~ ~r~m ~bout 1 to 12 c~r~on ~tom~
. ~ e.g. ~ 5-m~thylbRnzot:ri~2ble) . 5~methylb~n20tri~ole i~ mo~t
IP ~ef~red. ~h~ us~ o~ 5-m~hylb~nzotri~zol~ ~8 an an~i~ogg~nt i~
~ l~u~trat~d ~y ~ld~ari et al V~. P~t~nt No. 3,9~,08~, lnoor-
!P or~ted ~y refere~e,
: ; ~he e~fec~ a~ ~hi~ in~n~lo~ i~ enha~bd ~n more by
a ~ding a s~all amoun~ o an iodide ~alt (eu~h a~ po~ um
Ii dide) t~ ~h~ ~mu~sion a~t~r the ~o~mation of the g~n~, ~e~ore
,~ ~mical rip~nlng, a~ar ch~mi~al ripening ~r be f o~e co~ting . A
;5 itable am4un~ o~ iod~d~ added ran~e~ ~rom about 10 4 to about
1 ~ mol~ol A~ ~a~50r amount~ ~re not harm~ul ~ut a~e ~n~c~
. ~ry~ S~all~r ~unt~ may ~till b~ effective in ~olaked ~
t ~ a ~aneral ~ule a~ou~nt~ within th~ a~o~e~tl~n~d ~sn~e
, ~0 ~ .ould b~ used.
-~ The ~hotogr~phi~ em~ 0~8 u~ed in t~i~ inY~ntic~ c~
. , ~ UB~d ~OX ~amera ~Xpbaux~. To in~u~e ~oQ~ ~a~el~ght pro~ection
~bsoxbing ~omp~unds are u~ed, ~h a~ ~ho~ ln U.B~ P~t~n~s
~ c ~0 ~33,794~ 3~ ,7~4 and ~,3S2,681, ~ bo~po~atod by
: 25 ~e~@nae. ~ ght dye~ such ~ o~onol~, hemioxo~ol~, ~ty~yl
y ~, me~oçy~ine dy~ ~nd ~30 ~1$~ an al~n be u~d~ A~J long ~LS
: u h ~e~ ~re ~ily r~mo~d ~r deo~lori~d du~l~g proc~sing
us PMtents No~ ~,27~,71325 X,956,879~ 3,42~,207~ 3,976,661
n 3,384,487, ~11 in~orpor~ted ~y r~:~er~nc~ e~n~lti~lng
3D cy ~ ~0~ . U~S, P~tes~t ~ t501,307, lnc:o~porat~d by
I ~1 ~ar*~ an al~o be u~d.
~he present ~mulB~on o~n be ~p~ lly ~nsltized (~.g.
long blue ~ ~reen ~ r~d or in~r~red) with At lea~ one methina~
t r e ~nd/or ~t~er sp~trall~-s~nsitlz,ing dye~ 5uitabl~ sen~ltiz-
~-, 35 i, ~ dye~ in~lude ~yanlne d~,,merocy~n1n~ dy~ omplex ~y~n~ne
d Yt~ ~o~pl~x m~ro~y~1ne dy~i~, hoL~pol~r cy~nine dy~,
h ~ y~n~n~ ~y~ t~x~ 6 ~nd h~miD~onbl d~e~ Par~ularly
. ' I
, ,
"` 2~7~9
WO 9~ 34~
P~r/u~so/~74sq
~7
ful dye~ ~o ~y~n~ne dy~, Dl~rocyanin~ d~ hhd comp~ ex
~R~o~yanlne dy~. These dy~ n cor~t~in, a8 ~ ~ ba~lc
h~to~ocycl~ ~uc:Leu~, ~ny ~f the hu~lel whi~h ~ uRuslly
~ploy~d lrJ ~yanin~ d~e~: ~ pyx~line nucl~u~, ~n oxa~olin~
nu~l ~u~, ~ thl~zolln~ ~ucl~u~, ~ pyr~4lb nu~l~u~, ~n oxa2ble
huc? eu~ ~ ~ tbl~z~ u~l~u~ ol~n~xol~ anucl~u~, ~n ~nid~zol~
~; nu~ B ~ 13 t~tr~!L20J.e ~1Ut:~lU3 r a py~ d~ nu~l~u4 ~n~ the llk~;
~n~ o~ th~ ab3ve-d~scr~h~d nu~ ond~n6~d w~th 4(~ All~yQlic
: hydroo~bon a~ln~; ~nd osla o~E ~h~ ov~d~xibed r~uc~i oon~n~Q~
rith ~n ~o~ic hyd~o~arbon ~Lng, such ~ An lndol~n~n~ nuoleu~, - 4 ~o~zlr~dol~nln~ ~ucleu~, ~n i~dole nlJel~u~, ~ b~n20xa2~1e
u~ naphth~xAzol~ nu~su~, A b~nz~hl~zole nu~l e~
~aphthothiazole nuc:lou~ ~ fi b~n~oç~lena~o~e r~ucl~ , A b~n-
~id~z~ nu~lo~ ~nd A qulnollne nucl~b~ ~rhe c~xbon ~to~ o~
lS he Jlbov~-d~so~i~ed nuolel ~ay b~ mor~ dl- or poly-sub~ tu~ed
it~ ~u~h d.~Yer~e ~ub~t~ tu~ y~ c~xb~xy/ ~ulfo~
h~nyl~ ~lkPxy ~rld h~lo, wlth~ut llmltati~n, and~ ~ptlonaîly
. h~m~elv~ :u~ther su~tltut~d~
~h~ m~ocy~ dyQ~ ~r ~p3 ox sne~Dcy~ n~ dys~
;i!l~ or~ain, as ~ U13 ha~r~ng ~ ketom2thyl~n~ ~tru~tur~ to
. 6 -~mbe~à h~erocyolia n~lcl~ u~h a~ A pyr~olin~5-one
S~ C 101~8 ~ A ~h~ohyd~rlt~in nucl~u~, ~ 2~h~o~xazo~1dit~ ~, 4~dione
n ~1~U~ a tb~A~ dll~-2,4-dlon~ ~u~l~u~, a rh~d~n~ne nucl~u~ or
a thiob~rb~tu~lG ~id nucl~u~ .
25 . U~ul ~n~itizlng dy~s include tho~e de4cribed in,
~Y 5., Ge~an Pa~slt No. 9~,080, U.~ nk Nog. 2,~ ;58,
.` 2 ~g3~593~77~ 51~,001, ~12,~29~ ~,656,~59, 3,672,6~7
d 3~4~;!17r ~ d Brill~ 1h ~ en~ No. 1,24~,5~ ll ln~orpor~t~d
~ ~ncq~ ~r~ ed ~n~lt~æi~y ~y~ lud~ o~y~ n~
31~ ~ ~Yat~ve~ and t~i~a~booy~ln~ ~e~lv~tl~ lB~: p~fcrably
0, r~et~ ensit;lzing withln ~he r~n~ o~ ~ou~ 6R0 to ~bPut B50
: P ~ .
': ¦ ~h~o t~h~itiz~ dy~ y b~ u~d indlvldually or n~ ~
c ~binatl~n,, A ~om~n~t~n o~ n~itl~ing dy~ n ~ploy~d
35 ~ rtl~ul~rly g~o~ ~he pu~p~ uper~nel~12ation, ~yp~o~l
~mples o~ D~ah co~l~ ns ~o ~s~r~ed ln, e.g., UOS;~ Pat~
8. 2l6aBls4s~ Z~77~22~ 3~7~fi~, 3,5~2,~52, ~,5~ 41/
..............................
~ 2~71~9
~110~34S
Pcr/US90~07454
2R
~,617,~3, 3,~2~,g64, 3,~6~,480, 3,679,428, 3,7D3,37~, 3,76~,301,
~, 81q, 609 ~rd ~, 837, 862, ~n~ Brltl~h Pa~ent ~o~ 1~ 344, ~B1, ~11
9~nc~poratet by r~@~snce~ Pr~ ,ed ~n~t~zll~g dye ~ n~-
~lon~ ~ra ~lxtu~o~ o;E c:y~r~n~ and ~r~cyanin6~ ~yt~s that o~-
tho~hromAt~ally ~ itive at w~v~lell~th~ b~tw~n 400 ~nd ~BO n~n.
I ~h~ ~n~ ælng dy~s mel~r b~ pr~ t in t~e 69mlll810n
t .o~eth~ wl~h dye~ wh~ ch ~h~ e~ do not h~ ny ~p~ctral
en~itizing ~ ec~ ~ut exh~bit ~ ~upqsr~en~ hg ~ t when
1,: f3ed ~n 60~iz~ Qn w~t:h ~en~ zirly dy~, or wi~h other
10 ~t~ whi~h do rlo~ su~ nti~lly ~b~rb ~ light ~DU~
hiblt ~ super~e~iti~ ng e~ t wbe~l u~ed in com~in~ lon with
~ en~ g dyas - ~x,~ ple~ o~ ~u~h ~ 3riA L~ e ~y~3e ~
h ~tero~ycl~q m~rcapt~ns, ~y~ 8f~3 ~ alt~ . gu~ rnh~y
~ n2norlium ~lt~ ) and h:~gh-~ol~cul~ w~i~h~ ~ul~oni~ a~id~ ~u~h ~
15 ~ ~ilben~ or~ spæci~ically, ~xampl~ inelude ~til~es~o ~uoh as
a ~inostilbet,~ cYmp~und~ p~er~bly ~ul~itu~et sr~t~ ~s
t~g~ o~ lnlng he~ero~y~lic rl~ ~s4up (~.g., ~ho~
~e:rik~d ~ U , ~ ~ Pat~t No~ ~ 2 , ~ ~ 3 1 ~ ~ 0 ~Ind 3 , 6 3 S , ~ ~ l ), aron~ti~
~ ~R~a ~d fonn~lt~hyd~ oonden~at~ ~e~ h~s~ ds~ bed 1~
20 U g. Pat~t No. 3,74~,510~ aind~n2 co~pound~9 ~ th~ llke,
. ~ ,n ~ p~e~gnt, ~he ~o~inatl~llg d~crl~d ln U. g O Pat~nt No~ -
61~,613~ 3~15~6~, 3,617,2g5 ~d 3,635,721 ~r~ p~tlaularly
lOE qfl~ he d~sclosu~ of ~11 p~t~n~s ~fl~ion~ in th~
~r~g~ph i~ corpvr~t~d by :~of~ron~
~ ¦ ~ A w~t~r~-~olul;~le dy~ ~y ~e px~ t ~n ~ny o~ th~
~jdsophi~ O11Q~ hsa ph~to~r~ph~ h~-~en~lki~e
- ~ ~ ~a~rial~ U~ ln thll~ inv~ntion, ~o~ ex~npl~, n~ A ~ dye cr
o ~ p~entl~n o~ l~ght ~tterin~, ~r ~r antih~ ion.
x ~npl~ o~ ~ho~ dye~ lude oxcnol dy~, ho~iPxon~l dy~e,
3~ t ~ y~ rooy~n~rle dy~ ya~ln~ dy~a8 ~nd A20 dy~
t h 3~ yel8~ OXOJa~ h~n~iox~nol dy~ and mero~y~nine dye~ are
~cul~ly ~e~ul. ~pe~ exampl~ of dy~ wh~h o~n ~e u~d
l;Ao~ d~sc~ d ~n ~ $~h ~ter~t Noe. 5~4,60~ ~nd 1,177,4~,
U.~ tOllt No3~. ~,274 j7B2, 2,5~3,47Z, 2,9~,879, ~,14B,187,
3~ 31, 77,07B, 3~47,~7, 3,~0,~87, 3,~75,7~4, ~,6$3,gQ5 ~nd
3 f 18,472, a~ o~p~rAted ~y ~er~nc~,
.... . ~ ~ in~r~anl~ o~ orqani~ hqr~en~r ~a~f he ~re~ent i~ ~ny
__.. , . . I , .. _,, .~_ .. ~ , .. ..... _ .. _.. , ,., ,, ..... , ... _
.~ ' .
2071 i9!~
~o ~/o~
I . P~JV~90/~74~4
I
29
~:~ the hy~opbil~ llo~d lay~r ln ~he ll~ht-~e~itlve ~n~t~sl
psed in th~ ln~t~s:n~ ~h~a hl~xd~nQr~ lud~, ~o~ ex~ple,
:hro~ u~h ~1 ohro~e ~lum or ~:hrom~ e~Bte )
~ l~ehy~ u~h All~ ~o~ald~hy~æ , ~lyox~l or ~lu -ar~ld~hyd~ ),
5 . J-~thylcl ~ompound~ ~ucsh ~ dim~.h~l~lur~a or ~ethyl~ld~thyl-
~y~ahtolr~ x&~n~ ~er~.va~ uch 4 ~ 2 , 3~d~ hy~oxyd~oxnne ),y l ~ p ~ d ~ ~ ~ u ~ h ~ ~ 1, 3, ~
,~ryls~yl-hex~yd~ z~gle o~ bl~ .nyl~ul~onyl~ hyl ethb;c),
~ ,cti~r~ h~logen co~npouz~ds ~ ~uch ~ 2, 4-d~hloro-
14 1 -hydroxy-~tri~z~e), ~u~he~lio ~Pide ~uch a~ Dlua~hlo~c a~ià
~r ~ucophenox~hlor~ id) ~ i~ooxAzole~, ~iald~hyd~ ~t~r~h,
2;-cbloro ~ hyd~oxytrln~inylaked ~ ln ~Ind th~ Q ~a~a b~ u~d
i~dividu~lly or ~ n ~e~mbinl3.t~.0n, Speci~ ex~s~pla~ of ths~a
Ic ~poun~l~ axe sl~gcrl~edl e.~ J~ nt No~ 870~ 354,
~1 oao, ~,16~, 3, ~70, ~13~ ~, 5183, 611, 2 ~ ,10~,
3 ~47,3~ 3,057,72~, 3,10~,43~, 3,~21"313, 3,325,~7, 3,362,B27,
3 539,~4 ~n~ 43,~, Britl~h P~tent ~o~. ~7~,~2~, ~25t54~ ~d
1 270,578~ Ge~a2l ~zl1~ont ~o~. B72,1S3 ~nd 1,090l427, ~ acox
)r~ted b~ f~8~. A pr~rr~ h2r:1en~ o~e t]l~t will ~ok
~u~ uct~on-~en~t~ ion (fo~ld~hyde, ~or ax~ple, ~holald
: ~ ~avoid~d ) ~ ~n ~x~plo of ~ p~f~r~d haL~ e~ iEs
i~hlo~hydro~rla~ine .
~h~ ht-~o~slt~v~ ~t~rl~ khis invenl;lon ~Ay
C ~a~t~in Y~r~u~ ~owr~ r~e a~t~v~ Atla ~Eo;l~ riou~ phrp~eB~
25 O. g. ~ B~; a c:oatinc1 ~d, or p:r~ent~n~ ~h~ g~x~t:~on o~ R`1:2lti~
~h ~ a I lmp~ n~ p c~ tl~8f ~IP~I)Vi~ n
i ~p~ QIl~ pr~e~ti,~g adh~ n, ~mpEo~ing phot~gr~phi~ ~hara~
ri~e~g., ~ orat~n~ . de~ p~n~ in~r~a~in~ ~o~tra~,
~ n~ tion) I etc.
;~0 ~3X~lpl~8 t:~ ~u~ta~ ur~a~an ~ n~nlon~a ~u~fa~
~ $ivte ~ge~t~ ~ch l~h ~p~nln ( ~t~rold8 3 ~ alk~l2~ ox~d~ :leriva~
i ~ ut:h ~l~ pol~eth~l~ne ~ ol ~ poly~thyl~n~
. ~¦1 ~o~p~ypsopy~esle slyool cosldensa~e~ PO1YQthY~ne gls~c~l
a yl o~ ~lkyl~a:yl ~ , polyethyl~n~ ~lyc~ t~r~,
3~ p yekh~ n~ol ~or~t~n ~to~s ~ poly~lkylen~ gly~l
a y~a~in~ o~s or ~ilic~n~oly~thyl~ne ox~de adduot~ J,
~ ~idol de~ ti~u~h ~ ~lk~ylgu~ini~ Aoi~l poly~ly~::oa:ide~
;' .~ .
.
- ~ ~
` 1 ~71~99
`I ` --
;;wn 9110~34~
P~/U~90/074S4
' ~0
o~ ~lk~lph~nol polyglyae~ld~6 ), Alipha~ er~ of p41yhydr~
$, ~lkyl e~ of 8UCt`/:16~, u~ath~n~ ~r othe~ ~ An~onic
. i ~ur~ o~lve agen~ ~on~A~nirl~ an ~d~ c group ~u~h ~s
~rb~xy group, a ~ul~o ~oup~ ~ 1pho0ph~ ~roup, ~ ~ul~u:~lc ~c~d
~ter ~oup or ~ phos~horis: ~c~d ~ r g:~oup, ~u~h ~ t:rlt~r~
~n~d ~yp~ sap~nlh, al~yloarb~ t ~llcyl~ul~n~te~ I alkyl-
~o~zQn~ul:E4n~e~, ~lkylslap~ n~u~on~ , al~eyl ~ul~uxia
~id ~t~ , alkyl pho~phor~ oid ~er~, N-~cyl~N-~13cyl-
~au~ lf~uo~in~tg~, ~ul~&l~ olyo~y~thyl~ lkylph~nyl
10 ~ ~th~rE or poly~xy~thyl~ kylpho~phat~s ~ amph~torl¢ ~r~o~
~tl~e ~nt* ~ h ~ no 3.01d~, s~rlo~lkyl~ul~c~nio ~ids,
~nino~kyl~ul~ur~ ac~d e~ter~ oalkylE~ho~phori~ a~id e~t~rh~
4 lkylb~a~ s, aminQlm~d~o ~r ~ine oxid~ S ~nd ~ ia ~ aoe
~ C~ti~B ~ JltB ~u~h ~ ~lkylamLine 8~ 11, al~ph~tic or ~ro~at~
1~ ~ u~te~na~y a~lllllQn~ U~ ~al~ u~h a~ py~ldi~1~ or i~d~æoli~m
alt~ o~ pho~phonium ~r ~ul~oni~ ~ D ~o~ ning ~n ~llphati~
hetça~o~y~
Speci:Elc ~x~pl~ o~ t:h~e ~u~ae~ ~atlve ~LgaA~s ~re
~ ho~q d2~c~bed in~ ~t9.~ U~5. ~aton~ ~o~. 2~40~472, 2,~31,766t
2~ ~ 1~8,484, 3~10,191, 312g4,540 arld 3,50~6D~ ~r~i$h Pat~nt
N ~. 1,01~4~S; 1,022,~7R, 1,~7~,290 a~d 1~ ,4~0, U,~ Paten~
N ~ ,739,~1, 2,3~ 3, 3,û~,101, ~,415,~4~, 3,66~,47B An~
3 756~28~ ~1ti~h P~tent N~ 1,3g7,~8, U.S~ P~llt~ B.
3 133~16, 3,441t413~ 3,475,17~, 3,~4~,~74, 3,7~6,~3 ~n~
3 ~43,3~ium P~ont No. 731~L26, ~rl~ioh ~t2n~ No~.
:: ~ 138,514,ltl59,1~$ ar~d 1,374,7Y~, U~8. P~3n~ No~. 2,271,6~3t
2~ 4~0~t 3~5~ ! 3,671~2~t 3,77~ ,5~tg~6
~¦d 3 ~ ~$4, 9~4 1 all lncorpo~t~d b~ ref~no~ . Spec~ lly
~ ~eferre~ ~ a n~xt~ ap~n~n, nonionla ~ur:~aotants ~uch ~lB
30 l~phatl~ ~t~r~ ~f po:Lyh~drl~ Al~oh~ nd ~n ~hi~nic ~urfac-
1 ,~ lalt oont ~nlr~ a ~u~ur~a ~id ~ r ~oup.
~he phot~g~pl ~ ~mul~ion u~ed ~n thi~ inventiorl e~h
nt~in A di~par~lon o ~ synth~tl~ poly~er tRh~ch i~ ln~Q~ubl~ or11~ht~y solubl~ in wa~or ~ tha pur3?o~ o~ lmpro~i~q ths
~S 6 litn~n~onal ~t~bil~y~ the dev~l~pm~nt ~ the ~ixing ~nd drying
3 ~1~9~. ~x~nple8 0:~ ~oly~e~o wh~ch ~n b~ l~8~d ln~ do polymer~
e o~poe~ o~ on~ or ~re alkyl ~t~xyl8~ r meth~c~ te~,
- -- L
~ .. .. .
.. .. . . .. . . . .. .
, / ,, .~. .,, ;.,'. .
.... ,. .... .. , . .. .... .. . ;
! ( 2 0 7 ~ ~ 9 9
., WO 91/0~ P~r/lJS90/07~4
:~llcoxy~lkyl ~late~ or ~eth~ t~ lyc~idyl ~crylate~ or
~thaeryl~te~, a~yl or ~oth~c:rylamide, ~iny~ B (for ~xampl~,
~rlnyl ~o~t~ ), a~ trll~ , vi~f in~ and ~tyr~ne , et~ nd
~ e~s ~ompr~ g A ~ombl~a~lon a~ th~ ~ov~ f~e~c~b~d ~onomer~
5 ~n~ ac~ cld, ~a~h~ Lo~d, un~4tu~ato~ di~xboxyl~
¦ ~id~, hydro~e~.lkyl ~ryla~e~ or m~the~ t~ ~r ~yr~ne~ulfonic
~it~ ~t~.. Fo~ ex~mpl~, tho~e ~ao~np~und~ d~sc:rl~e :l ln ~ ater~
~o~,. 20376tO05, 2,7~9,~37, 2,B53,457, 3,062,674, 3,4il/gll,
~4~,70~, 3,525,620" 3,607~X9~ 35,715 ~n~ 3,645,740, ~nd
10 1 ~r~tL~3h ~ nk No6. 1~1~6,~ nd l1307,373, *.11 ~n~o~p~ d ~y
a lofe~n~e, ~ uoa~ able a~ourlt o~ ~he p~ r~n~
i rom ~bout ~0 ~;~ 80?6 ~y wei~ht h~eà ~n th~ total w~i~hk o~ th~
~ ndgrs. Sln~e high-~o~ a~ ul~ion8 ~uch a~ l;h~ u~d ir~ thi~
~ ~v~tion eLr~ ~ult~ble ~or ~he ~ep~oduc~ion ~ n~ d~awlr~gs and
- 15 the di~n~n~ abil~ o~ ~mpor~ aR ~o:~ ~uoh ~ ~u~poae, 1~
1¦3 p~ @~d to use th~ ~bQ~*-de~c~ d p~ per8i~n t~ be
e~pl~ed ~
In ~d~tioll to tho oompDrae~t~ o~ th~ photographic
e ~ul~lon~ ~nd o~h~r hycl~ophil~ oollo~d l~yere cl~c~ d Ab~
~Q i r ~ appr~ai~ed ~h~ her oonv~nt~ on~l ag~r~t~ ~omp~tibl0 wl~h
.. . ~ ni~g ~latl~ ely hi~h ~ont~ ~ge~ ~n b~ p~ nlt. For
. ~ple, tho pho~grsphi~ nt~ ~n ~o~t~ d~v~loplng ag~nts
~ o~b~d ~luw in c~n~ on with th~ pr~ao~;Lr~ ~t~p~ ~,
~ v~l~p~nt ~o~ , pl~ticizer~ qnâ lub~ie~nt~ ~oatin~ ait~,
25 ~ ~ tic ~at~ri~ at~n~ ~g~nt~ h$~n~rs And ~ol~r
. ~ ~2ial~ th~ ao~ve~ o2~ ri~l~ belng. illu~t~ d ir
; ~ '~ r~rapha V, t7IX~, XI, X~ nd XVI o~ ~o~e~rah Di~clo~ur~,
~; 3 ~ c~ o~ 197~ 17~3, ~ll lr,aoxpQr~t~d by r~feror~e.
r~ ~ly~ ~h~ ph~o~r~phi~ smu~ion ~118C~ ~ont~in~3 ~ntl~ in~
a Iq ~nl:~, u~ t~ p~o~or~ the ~h~ h~ o~ull~lon~
U ltable ~nt~ge~ e~t~ ~8pelll~ Ly or rhodlum d~ped
~: e m ~ Ln~l~d~ polyh~d~Qxysplro ~io~ d~ !IB di~lo~ in
U ~ . P er~t ~o. 4,348111;7 4f E- ImELto~li and pr~~r~bly ~h~ni~one
: i . ( t~ 2 ~kg o~ ~mul~ion~. ~5 di~o~ed in U~S. ~t~n~ ~o.
h 35 2 t~l~29~ o~ ood.
-r . In ~orDu~n~ phot~gr~phio ~men~, t}~o l~yer~ ~An be
E l1~3tl on ph~togr~phic ~u~po~ by ~r~r1ou~ pro~adu~Q~, includlng
; :,'i,,~:.
,, ;,,~, ..
., .
WO 9~/~9~S
Pcr/~)S91)/074~q
32
~e~3ion ~ d~p c~ting, rollar ~ting, rev~e roll c~8ting~
alr krll~e c:~atlr~, doct~r blad~ ~oa~in~, grsvur~ nq, ~p~y
c:o~tin~, ~xt~u3ion ~::oatln~ a~ co~tlrlg, str~t~h~ w ~u~tlny
~nd ~u2~ain ~oat~rlg. ~i~h ~p~æd 04~t:ing u~g ~ pr~ re
5 d~f~sx~ntial ~ lllu~tra~d by }~o~uln ~. I?atent No. 2,6B1~94~
~on~oll~ ri~ n ln ~he pr~pur~ d~ ~ar~s~ti~l to ~lllt~ce
~oating ~l:art~ llu~rated ~y ~7Ohn~on U ~ S . PBt~rlt NO ~
3,220,8~7 ~n~ tO m1~ pll~ln~ dis~up~io;R~ llu~t~at0d ~y
~ow~le U.~, Pa~t No. 3,~16,043, ~o&tln~ at ~duc~d p~e~uxes
; lD i:o a~c~lerat~a d~ g i~ illu~t~at@d b~r B~k U.~ t NoO
~,~15,307. Ve~y h~gh ~p~d cu~t~n aoat:irlg ~ illu~trated ~y
~uiller V"8. Pa~e~l: No. 3,S32,374. ~wo o~ or~ layer~ ~n b~
oo~ted ~i~ul1~an0ollsly, ~B i~lu~rated ~ ~u~0ell U.~ en~
~,7~1,7~ ynn U.S. P~ont No. ~,~41,8~8, ~i~ller ~ al ~.S~
15 ~at~r N4. 3,2a6,323, B~Qn at ~1 U.~. P~tent NO~ 25~7,
h~ U.SO Paten~ NO. 3~0~,947, ~3~rZho~ . P~nt NO~
~20~09~ ~;C~h~ et a1 U.5. P~t~3nt N~. 3r~4S,773 ~nd ~it~n
~ ~1 U~S. Patallt N}~ 001,~a4. In ~.mU1t~na~ mU1t11~Yer
I ~Oatin~ ~ri~d CO~hOPPeS~ G~n be ~ad, ~ U~t~te~ ~Y
~U~ V.~ te~ N~ 2~761,417, RU~ U~ t~nt NOB,
1,7~1,41~ and 31'474~75~ grCier ~ U.S~ P~t~t NO~ 2,761,419,
ht t.J~S. Patent ~i~. 2~75,7$4, Pa~ y U.S~ Pat~t NO~
,00$,440, Mex~ a~nt No. 3,S27~5~4, ~on ~.~. P~ent
b~, ~,74g,0~ as~d 3,~5~,~3~, J~c~kl~on U~,8~ PAt~nt No~ 3,93~,01g
: ~S nd ~ on ~t ~ aten~ ~o~ 3,g~6,8~5, ~llv~r hal~de
aye~ n ~ bo ~o~ko~ ~y ~auum ~v~por~tiQn, ~ ~llustr~ted
b f Lu Vall~ ~ al V~,S. ~A~en~ No~. 3~ 4~ a~d 3,~19,4$1.
~ h~ pho~ phi~ e~ul~ ~ ~ns ~o ~t~d on ~nv~nt~n~l
.' ~ ppo~k~, whl~h ~ t: und~rgo ~ ou~ ~men0~0n~1 ch~n~ dur1ng
30 p oc~d~in~ a~ ~111tAb~e E~Upport~ wh~ ch ~an b~ u~ r~
o ~llu~o a~et~e .il~, ~ poly~tyrs3n~ ~llm, ~ po~yethyl~n~
t 3r~phthala~e i~ poly~arb~n~te ~ l~in~te ther~of,
p,~p~r, b~ta pap~x, p~p~ Ro~t~d ~n l~n~t~d wlt~ ~ hydropho}~
p~lym~ ~u~h ~B polyeth~lene, ~olypropylen~, ~t~ r~
35 ~C~mQ~1Y u~ed ~ox ph~o~p~ ~ light-ses~s~tl~e m~ori~
T~ an~pas~slt ~uppor~s oaln ~e ~mpl~y~ ~or oer~airl ~nd u~ the
1~ ,ghk-~en~ltiv~ mate~ l. Al~, tr~n~p~ uppc)rt~ ~y be
r
~:
: .
~ 20~1~9~
WQ ~/09~4~
,,. PCr~S~0/~)7~54
33
colored by ~ddin~ ~ dy~ or a p~m4n~ ~h~r~to ~ ~esari~ed in J~
8MPTE, 67, 2~ ~195~ r Cl~r~ Pa~ No. ~,8~2,1~1
4 ~ po~t~ e~r~x30~. ~h~re the ~dh~ion ~t~tw~en
~he Al~ppO3~ d ths pho~o~rap~lic G~u~ on la~r ~ l8U~f ~
5 ~l~nt, A ~u~ g ~ye~ ~ an ~dh~ yer ~ ~h~t al~hex~ to both
$he ~upport ~nd the phn~ogr~p~ n l~y~r ( o ) ::AA be
~ ~mplo~ed~ A~o, in ~rd@r to ~pr~a ~h~ ~dh~on, B~ c:~l oi~ the
..~ ~ uppor~ ~ay ~ ~u~ oted ~o ~ pr~l ~ nA~y p;r~ln~ ~u~h ~
s !o~ona d~ c~Aryet lxxa~ia~on wl~h ul~r~ hS, ~lame
10 t r~atall~nl~ o ~ ui~ 3 o~At~g unour.~ o~ Y~X 18 ~bO~lt O.S
5~m2 to a~out 10 g/~ o~ ~ho 8UppO:rl:~
¦ Th~ phot4gr~phi~ ele~ents c~n ~ w~ xpo~d s~rith
qariou~ ~o~ of er~gy, wh~ch e~Qo~pas~ the u~tr~lriol~ an~
lisl~le (e.~ tlr~ nd in~ared r~l4n~ of tha ~le~trom~-
lS n ~ti¢ ~p~ct~um as well a~ ~le~t~on l~ nd bo~t rad~ion, gamma
~y, X~ray, alpha po~ ol~, n~utxon ~ad~$on and o~h*r :~o~m8 C~
~;. c ~pu~ul~r ~d wav~l~lce ~di~r~t en~r~ lrl e~th~r s~on~h~rent
( ~ndom p~Ase) ~4rm~ or c:ohe~ in pha~e) ~rm~, ~e produ~ by
1 ~r~ sh ~ x~o~u~ 2hn be ~n~no~h~oma~icI
o rthochro~atic or pan~hr~ O Im~g~wi~ CpO!l~U~8 at ~i~nt,
leYat~d or ~u~d temp~ra~ur~ ~2.d~0r p~s~lr~s, ln~luding high
o r ~ow l~t~ y ~xpo~res, a~n~Lnuou~ ~r l~e~it~eglt expo6ure~,e KpOllUr~ t~ e~ s~n~ln~ ~x~m :~oinute~ to r~l~t~ y ~hoxt ~u:c~tlQn~
i~i th~ econd t~ mlcr~e~ond r~nge and ~ol~r~æing expo~ur~,
c~ o~ploy~d w~thLr~ ~he ~ ul ~el~pOrl8Y! r~n5~etl d~ermined ~y
c ~nv~ntioD~l ~en~k~ trlc ~:eohnl~ue~, a~ lllustrAt~d by
~1 ~ rh~ ~h~c~ thg Photo~r~phl~ oe~ , 4th Bd~, ~h~
lL~ 77, Chapt~r~ 4, 6, 17 ~ 18 ~ 3, in~o~p~ted ~y
~3f ~a~e~
30 I ~h0 ph~t~s raphi~ ht-~n~i~iv~ r~al of thl6
i ~rorit1On ~n be phn~og~sphlca11y prooe~d u~ing kn~wn method~
:~ ~. Id ~ n pr~R~n~ ~olu~ he p~ emp0ra~ur~
i 1 u~lly r~n~ ~m .?3bout 1~ to a~out 50~ ut te~per~ure~
11 ~wer than ~l~t ~B~. 4~ hi~h~r than ~Lbou~ 50~C. ~ y be u~d.
3~; ~, ~ n~an~1~n iB part1auI~r1y 1is~fu1 ~r the ~o~m~t~on ~ ~n
~ 13g~ ~ do~1Opme~t in whi~h ~ r ~age i~ ~orm~
b' .a~k-and~whit4 phot~grapb~c pr~ g ~ .
" .....
` 1 2~7~99
~O 9110~4
PCr/US~U745
3q
~h~ d~v~lopo~ u~ed ~or 'bl~k-and-white photog~aphic
p~o~e~6ing p~ 27a~ly ~orlt~ &S ~ d~v~lop~n~ agent,
~lnophenol~ (~u~h ~ ~a methyl~p~a2~no~h~r~ol), 3-pyr~zol~done~
~u~h ~ ph~n~1~3-pyr~zc~idone), l-phenyl-3~pyr~1in~,
d~hy~ æ~ne~ ~ ~ueh ~ hyd~oq~ n~ I an~ c~the2~ o~ ~h~!:
~ore~nt~ d d~srelop~ s~ent~0 ~p~ c ox~mpl~ o~ tl~e
t~ ul à~volop~n~ a~t~ ~n~lud~ hydr~ n~ne alone, hydroq~ orle
I plu~ hyl-p-~ln~phenol, hydrogulnon~ plu~
! l-phe~yl-3-pyr~ol~olle, ~nd hyd~o~u~norl~ plu~
lC N~ hyl~p~ phollol plta~ l~ph~yl~-3~py~zo~1done. M~r~o~e~,
the ~eloper~ u~uA~ly oo~t~n a known ~ntioxidant t ~n z~'l k~li
I ~g~nt~ ~ P~ bU~f~r O~ the 1ikQ ~nd~ r~d~ B d~ Do~1ving A~ld~
I a ~1O~ ~Or~in~ Ag~n~ ~ d~ P~ C~1~rat~X~ ~ ~Ur~ tiVe
BJI ~nt~ qnt ~ e;~ f t,~ne~ ~ a hf~r~ a
1~ k~ aY ~e PJr~ t- ~ ~n~ O~g$n~ a~nt ~ h ~8
~n a1kA1i m~t~1 h~1~d~ OS ~n20t~a~201~ u5y ~e Pr~ 'C 1n
I de~re1OPer-
n~ h~ Ve~t~On, ~V~n Wh~n ~V~1OPmant
I qa~r1~d OUt UE~i~g ~I deVIe10Plllr O ain1n~ ~IOr~ han ~OU.
'~ol ~l/l o~ ~ul~t~ ions/ ~ g~ o~ m~ th~n B o~n b3 ~taLned~
~h* p~ of ~h~ d~væloper i8 pr~f~r~bly ~l~o~ o a~ t 1~.3. 1
~h~ p~ ~xo~eds ~bout l~ . 3, th~ d~lop~r 1~ un~sble ~n wh~n
~lgh ~ en~ e ~n~ ~ p~e~ n~ di~-
~ ~ ~ult ~o ~ntair~ ~t~b~ p~otog~aphl~ oh~raoter~tic~ ~or ~r~
- 25 ~h~z~ 3 d~y~ und~r UBU~l Ull~ ndlt~Gnl~
- ¦Flx~.~ ~olution~ ha~ing ~ 60mpe~1!3it~ n ~n~rally
¦ ~ployad ~n th~3 ~r~ ~n ~ u~d ~rl the p~int i~lv~Rt~Qn~ No~
¦ on~y thio~ul~k~a ~n~ thio~y~n~ bu~ ~18~ organl~ lfu~
mpound~ k~ ixis~ ~gento ~n ~e u~d ~ ~ixirl~ ~g~ t~ 'Ih
30 1 ~b~ pr~e~t lntl~ntiaxl. .
e~d eae~mpl~s o~ fixlt~ ents ~?hi~h c~n ~ u~ed
¦ ~n th~ x~ olut~n ~nclud~ wat~r-~olu~l~ thic~u~t~s ~u~l~ &IR
d~u~n thl~ul~ e, pQtaa~ th~o~ lf~t~i~ ~nmoni~ thio~ulfate,
~ "; wfl~ 1u~ie ~h-o¢yan~teo ~uoh a~ ~odium thiocyarla~ ,
35 I pota~um thio~yast~o~ ~mmonium thio~y~n~ t~., w~t~r; ~oluh1e
o~gar~lc dlol ~ixa.n~ Ant~ ~ont~ralng aan oxy~n ~tom ~r a IRU7 ur
t~ ~u~h ~8 3~t:hla~ p~rJ.t~nediC-1, 3~6~dith~o~ oct~n~d~
: . ..... .... .
~'
.. . . ...
`; ,`~91/~45 ~7~9~
. ~ P~/US90/07~54
3s
~_oxOr3,~ ,15-t~t~th~4~1,17-~hep~deca~edlol, ~tc~ t~
~oluble ~ulfur-cont~ining orS7~n~ d~e~ cid~ ~nd wA~R~-~41ub~e
~lts th~of ~ ou~h ~; etbyl~r~ebi~th~og~y~oll~o: ~old ~lld the
~o~ium ~alt t~ aidA~ 1d~ hi~s ~ h ~8
5 ~ne~hyli~ida.~ol~ thlone~ et~ Th~s~ ~g~ de~cr~d in L. P"
A.Na~o~ Ph~to~ph~ Prc~e~g Cb~s~3~, p~$7u~ 1~7 to lB8,
196~ ) .
A E~art:~cularly pre~ d de~lopln~ 8~ cco~-
d~J~o~ ~lth the p~laellt ~ve~ie;n ~:or~B ~. hy~u~oD~e d~el~p~
j 1~ eD~ a ~n~o~ o~1g~ g~t (dQ~velop~t
~e~t~ t~l~iac~-p~p~ d~l / 8~ ~ lt~ p~
er (p~f~sbly NA~ an~fo~ 09J ~o ~us~ th~ p~ ~ 11.6
t: 0.5O ~a~ a~o~t pr~Ser~d dev~lop~n~ ~y~tem ~ oxth ~n th~
~x~mple~ ~low.
~5 ~h~ pr~rred ~h~r~edL~ic ac~ld ~y~z~des o~ th~
p~e~nt ir~ven'c~ axe ll~ed in T~h~ ~. Amo~ ~hem, tb~
ox~d*~ 3 ~d ~ 5 ~r~ p~ ula~ly pr~err~d~
~h~ ~p~ of ~ho pa~ e~ n, "I~, ~r~
~O~h~ ed ~ c~ 0d ~ P~ , 6~ 7 " The ~o~n-
2~ ~ound~ Foxnlul~ re ~nthe~lz d a~ *ollow~O
8 ~8 ~o
~rlefly, the ~e~otio~ c~rri~d out It 60~-9O-C in
~ pp~op~12~e ~ol~renk ~oh a~ d~i;hyl ~ r ~ridin~
with~u~ any cataly~t ~ein~ ne~s~ ll compound~ o~ ~o~ula
n ~ ~ynth~0i~d La~ing ~h~ ~oregoin~ ~ch~e. ~rtin~
t~tlal~ such as
2, 4-di3~it~ob~zaldehyde;
.' 2 ~15-t~ tx~ben~al~ehyde;
;, 2 ~ n;~ enz~l~ehy~e;
3-~itroben~ldehyde;
1~ ! 4-ni~r~h2~ld~hyde~
~: rhod~ine;
~ rhod~nine-3-acetic A~id; ~nd
,,
81lJ~37'1TVl''E 8HE~ET
_L-
;' ,.. ~ . ; ...... ~
. ': 2~7~3~
Wo ~i/093~s
P~r/U5~/074s4
36
S~n~t~o~uLnolin~
~r~ ~o~ c~1ly avall~b~e fr~m ~ n ~ocl~ ohaster, ~. Y~
at~d~4r Ald~ich C3~epi~ llw~l)cel~, Wi~c. and Go~poundo I~-3 and
II-25 ~ c~ms~c~ v~llabls ~ro~ tec, Elin~hamto~, ~ . Y .
~ h~ ~ollo~g ~xR~?la~ gl~r~n t~ u~kr~te the
pxo~t ln~rention in ~nor~ ~t~ e~r~r, th~ ~c~pe of the
p~esent ~nv~ t~o~ i6 not l~tod ~o ~hes~ ~xs~nple~
E 1 ¦ ~y:~h~
Co~pound ~-2~
l D ~o 'iD7~c of d~;ethyl ~o~,d~ (DM~) add 72 ~ ~P m-
n~txoben~aldehyde follg~w~d ~y ~he ~dd~ o~ ~0 ~ C1~ ~hoda~ln~
~m to di~s~olve ~601ld~ ~0 709~. ~àd s~lowly SO~c of py~idins.
c t~ 8~-70~C ~ith ~tl~lng ~r ~n~ h~ur~ ~ool ~4 2~'C, filte~
and ~ h ~i~h cool DM~. Dl~ e eake in 507~ D~I? (8D~9~C~,
1' i ~ilt~3~r. Cool to 20~C, ~ r ~oll~, w~h w~th D~ elt 4041~.
Sti~ 9 bo6~ e~h&nol ~ ~o~ ~.~p~t~r~
~ou~" Fllt~s, w~sh on ~nnel wlth an ~ddltLoAhl 450~ o~
meth~ol, dr~y~
., ~ ~ ~ ~
Th~ory ~IS.ll ~,27 1005~ 24.,06
2~ ~ound 45.39 2.3? 10.,21 ~3.7.'3
.:
Cv~pou~d II-3~ 5 m~t~-n~t~o~enzylld~e rh~d~nl~e~3-ao~
~ ~ ~o 1000 ~a o~pyrl~ln~ 166 ~ o~ ~-nLt~ob~n2~1dehyd~ ~r~ add~d follow~ by 1~ g o~ 3-~a~ox~thy:l rh~dsn~ne. ~t ~
3D ~pplied ~or S hou~ ~t 90-~S''C~ ~he ~xku~ th~n ¢ool~d and
4000 ~1 o~ ~th~ r~ ~dde~ th~n w~h~d with m~th~nol
~oll~wod. by AC~e!~;OSII" ;l~ld ~thy~ ~8tE~X l!~,Dd le;Et tC~ d;~. Th~ yi~ld
l180 g. ~.P~ ~ 3~0, ~xl~ nm.~tha~ol~,
~o~pou~ 4
~ 35 ~o 500 ~ d~m~thyl~ ~o~mlde (~M~?) 7~ ~ of p
~: ~lltr~b~nz~ld~hyde ~r~ ad~d ~llowed b~ ~ddltion of ~0 g o~
~hod~n~no. ~h~ mixtu~e 1~ w~r~o4 to di~ol~ ollds ~o ~0-7D~C.
~lo~ly 5D oq a~ py;~d~aae ~ add~d ~nd h~te~ t~ ~0~30~ ~or 1
hour ~hil~ r~g. I~ 1~ th~ ul~d to ~0-C, il~r~d and
:' 't
._ .
.
'' ~;" ',''' '`:' ' .' ' ",''. ' ' .',',; ' : ' ','
2071~9~
~0 ~1~0~4~
P~/US90/074~4
37
w~hed w~th oo~ F. Th~ ~ake 1~ di~lYod ~n 500 oa o~ solidE,
: ~nd wa~hsd w~th ~M~ at 40~ rhe ~c~d~ ~r~a ~tir~ed ~or 1 hour
ih ~00 ~ m~th~JIol ht ~ COm te~per~u~e, ~ilter~d ~nd w ~hed on
; ~unn~l ~ith th~ adà~tlon o 4gO ~ o$ ~ethanol and l~ft to dry.
x~m~ 371 ~ ~ m~h~nol2
cO~pound ~ 6~
TG 500 ~ ~f ~lm~tl~yl ~or~mide (~?) 72 g of m~ta-
~t~o~on~d~hyde a~ d~d ~ollowed b~ ad~ o~ 6 0 q of 3-
hy~ro;~h~d~nine ~Aldr~ch ~ ~ The mixture i~ warmqd to di~lv~
lQ, ~ d~ ~co 1;~- 70~ 510wly ~ e~ of py~ln~ ~re ~dd~d Jln~ hest~d
. to 80~0$C ~o~ 1 hour whl~ ~t~rr~n~ h~n ~ooled ~o ~D~,
filt~r~d ~sld w~h*~ th 0901 DME. ~he ~ak~ i~ d~solYed in 500
~ of DM}~ ~BO-90~ exed ho~, ~ool~ ~o 20~C. ~he ~olids
a~ ~ilte~od, w~hed wl~h D~ a~ 40~C a~d ~tlrr~d ~ h ~00 ca of
lS I methanol ~ox 1 hour ~ 300 c~o ~f meth~nol ~ room t~mp~r~ture.
Filter~d Qnd w~h~d c~n ~urln~1 wi~h ~h~ addi~iorl og 4~D s~
methænol ~ncl ~eft tP dry~ ~ax~mum 3~ nm in ~e~h~r~ol~
~o~p~ur~
~o 50D c:c of d$~e~hyl ~ ~de ~MF) 9G g of 7 nitro-
- 20 ' ~-naphthald~hyde (~ld~h) ~ra ~dded foll~wed ~ ~ition o~ 60
; ~f ~hPdanin~ ~h~ ~x~ur~ i8 w~d to ~ olvo ~olîdR ~o 60-
~O'C ~ S~ owly ~ cc of py~d~rle ~ d~d ~nd he~t~ 0-gO-C
. ~Dr 1 h81i~ whi~ ~t~ h~n ~018d ~0 ~O~C, ~ilte~ed
~nt wa~h~d w~h ~04~ h~ oak~ ol~d in 500 OF 4X DME
25 ~ ll( 80-90~ l ilt~r~ t, ~nd th~3n ,~001~d tc~ 20~E. ~ha ~o~ are
~h~d wlth DMF alt 404C, ~nd ~ ed ~r 1 hour Ind~r ~ddit~4n of
. ~00 ~ of ~th~nol ~k ~om ~lnp~r~kur~ ~iltexod ~nd w4a~h~d on
; ~unnel wl~h th~ sdd~ n of 450 ~ ~ m~tha~ol ~nd ~han ~t t~
I 1~ ~ximum 36~ ~ in D~a~hAnol.
, 3~ ~ ~
kin~sil~ro~ ~hlo~obxomolodide) e~ul~ion ~ntain-
.A~ Appro~ t~ly gO p~ro~nt ~hl~r~de, ~ pe~n~ brom1~ d 1
: , E ~rcs~nt 1od~,d¢ W~,8 p:r~par~d ~t 6~C ~Eor 10 mir~ute~ by B ~tandard
c lou~ addltio~ t~hn~u~ produc~ng ~i~ver hal~de ~rains
' 35 ~ ,~rin~ ~n ~ra~e ~5c~ ~ 0~,30 mior~ remov~1 ~f soluble
.` , 1~ ~1~,''3 .~y ~ oony~r~tl~A~ thod, ~he ~mul~i~n w~ ch~mic~lly
i ~ ~p~ned u~Ln~ labile ~ul~u~ ~ompound~a, ~t 61-C ~or 70 minu~
. . . ................
. i,
,
.. . .. . .
`; 2071~99.
91/~4~
PC~/~JS90/07454
38
~hl~ e~ul~ion c~ntaln~d g~lAtin ~ he ~nount of 71. 3 ~ per u1ole
~ilv~x hall~l
. EX~P~ :3
A g~ ino 1 silv~r ~Q~de ~ ~mul~o~ wa~ p~p~red a~
s ~S~ ~ox ~7 ~inut~ ~y ~ ~oatrolled double j~t additio;~ techhique
whlle ~h~ pAy w~ ~in~Ln~d ~n ~.30 ~h~ r~g~ n ~i213 0
th~ ~llver b~o~i~e a~yot~l~ w~ 0.,27 ~i~ron w1th a i~e dl~tr~u-
tiorl of 1~% 0 A$tor ~m~v~ th~ ~luble ~lt~ by ~aaventi~na~
~thod~, the ~m~ oD ~A~ ch~ liy r~pe~ed us~ng both labile
1 O ~ul~u~ ~n~ ~ol~ ~gon~ A 65 ~ C ~or ~S ~inut~ hi~ ourf a~
en~iti2~d ~muloion ~oTlt2~ ed ~ tirl in kh~ ~our~ ~f 81.~ g per
molæ 8iï~gr bro~ideq
In th~ ~x~nples ~hat ~ollow~ A eompa~ on ie ~ade
~twaen th~ pa~eferr~d ~o~pound ~rom G~oup ~ and ~ nli~carlt~
1 j p~ramet~r~ for ~o~p~ on 1nG1Ud~:
a ) ~ tl~ p~d
:. b J g~a
~) p~pper lsvel ~ r~ o~ om 1 (ba8t~ to 5
(W~ J (~y 1 BV~ low 4 i~ R~p~Rbl~
2 ~cr~a~ ln ~p~pp~ ~r~ any ~una~pt~ble 1aY~ 0 ~ny
~4~ b1~ ~V~1 ~e,.~. fr~tn 4 ~ J ~ 0~,5id~3r,~
sub~t~n~ialq
EXAMP~ 4
~h~ ~mul~ . d~rib~d in Exampl~ 3 w~ ~pli~ into ~0
pOX~lOll~. E~h p~rtio~ w~ ,idontic~lly p~p~red ~or ~ting ~y
ltbe ~ddit~02~ ~ an ~n~ra~d ~ z~n~ ~ye ~ ~u~ti'cu~ed d1~ar ~
bocycl~aln~ and ~u~a~ ~nk c:o~1:4~g ~id~ ~ekhoxyl~ pllonol).
:. Va~ou~ o~ co~poun~ o~ Fo3~ul~ d ~ w~ dd~d as ~n
~b~ low~ ~h~ d emul~n~ w~ o~ed ~t 3 . 7 g
30 ~ ubb~d p~lycstfllr ~ uppo~t ~lon~ w~h ~ g~lat~n
pr~te~tl~ lay~ wh~ch ~n~ ed ~ox~sld~hy~ thoxyl~t~d phenol
~ur~t~nt and ~ ~1lic~ ~ttin~ sn~.
~h~ ~xpoYs~d ~lsment wa~ pro~o~ d ~n atn "exh~usted"
~v~l~p~nt Q~l~m~ un ~hr~ h ~ t~ p pr~a~
i~. 35 hou~ 9Q~) h6l~ng th~ ~oll~win~ o~po~t~on (~TA
, ~thylen~-di~mln~ r~ao~tat~ )
:, .
,1
: .
` 2071~99
W~ 9l/~93~5
~9
H~O 850 ml
N~SO3 70 g
Hy~ro~uinone 3 3
$ NaBr 3 . 2
5-~nethylb~n~tria~ole 0.225
~DTA 1~ 0 g
eth~Tlemln~pr~paned~ 15 ml
SO% N~O~I 23 ml
2C~3 4S
~a~ to l.0 lit~r
pH ll~6 ;; 0.5
Devblop~n~n~ ~ndl~lon~ ~ ! 30 ~ . in a m~china
.
3 0~ 0 1~0 4~O
3 9xlQ II~2 ~ l~0 10.5 5
3 3 3x10~ 2 l.. ~OxlO~ 14D 10.3
4 3 9xlO 4Il~2 3.~5xlO~ 140 lO.D . 1
'J . 5 3 gxlO ~ 7.~ xlD 4 130 ~,5
.
:,
-~ ~ l 2 0 4 II 2 0 lD0 ~5
2 ~ ~xlO I~-2 V _ 20n lO.O 5
3 ~ 9xlO~ ~I-2 : l ~ gOX10 ~ 1~0 9 . ~ 2
4: ~ ~xlO 4 I~-2 3.g5~10 ~ 190 ~.4
2 ~xlû 4 II-2 7.~5xlO 1~0 ~.0
~ . .
.i . :
A~ illu~3tr~ted ~ n ~h~ ~bo~re ~t x~ul~ ompounds
t ar~ add~d ~ n~, g~na, ~oe~ up bu~ pepper ~l~o goe~ up. Pepp~r
u~ ntl~lly ~r~3a~d wlth in~orpo~ation o~ about lx10~4
mole ~ompouni~ ~X /~10l~ ~g . ~y ~ontsA3t, ~l~lkh~r sen~iti~7lty nor
~ma w~r~ ~ubEItsn~ially ~ a~d.
h~3 ~m~ ing q~pe I ~ompound~ n be ~ntic:ip~t,ed to
yielt ~mp~rab~e r~ul~ when t~t~d with ~h~ ~bove ~nd ~th~
Type I~ comp~und~
: Th~ amount o ~mpou~d II that ~ould be u~d in ~h~
:~ 10 cl~sl~plng ~o~u~lsn would ~e a}:out S00-lO00 t~me~ la~g~r (per
lit~x of ~olutiun) k~n in th~ pht~togr~phia mat~ri~lO
:
,j ,
''~ i'
SU~3TIT~ 8H~R~
.,
" ~ ~ . .. .
,. .
.,.; ,
i; ,,
.. ; . ,.. . ... . . .... . . . ' .
