CA2071499A1 - Super-high contrast silver halide material - Google Patents

Abstract

A silver halide photographic material and a method for processing the photographic material to form a super high contrast negative image are disclosed. The photographic material comprises a radiation-sensitive silver halide grains capable of forming a surface latent image, a binder, a dot quality-promoting amount of a hydrazine or hydrazide compound and a pepper-reducing effective amount of a compound of formula (II), wherein R'1 is selected from the group consisting of benzothiazole, quinoline, indolenine, nitrobenzothiazole, benzotriazole and rhodanine, each of which may be substituted or unsubstituted, and m is an integer between 0 and 6 inclusive.

Description

`~` 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 ) 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 ~, .
' . : . .
.~ . . .

2 ~ 9 ~
~ i 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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~/US901~74~4 ~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,~
__ . .. . ..... .... . .... ............ ... ....
~; , ,. ' ' ., ! . ~ ..................... .
' :- . i ~ 2 ~ 9 , WO 91/~9345 ,, PCrtUS~o/~74S4 1~
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~

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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 ~ .

.~ , .
.` ~ : ' .

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 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 . , .

r . . . ~ . , .

; . ~ 2071~

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 ~,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

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

Claims (22)

What is claimed is:

1. A silver halide photographic material comprising radiation-sensitive silver halide grains capable of forming a surface-latent image, a binder, a dot quality-promoting amount of at least one compound of the Formula I, and a pepper-reducing effective amount of at least one compound of the Formula II:

(I) wherein:

X =-NR5R6, or -OR7 R1 and R2 are independently selected from the group consisting of hydrogen, substituted and unsubstituted alkyl having up to 18 carbon atoms; substituted and unsubstituted cycloalkyl, phenyl and naphthyl;
R3 is selected from the group consisting of hydrogen, substituted and unsubstituted benzyl provided that R3 is hydrogen when neither R1 and R2 are hydrogen; wherein R1 and R2 and R1 and R3 can be linked together for form a heterocyclic ring system with the ring having 3-10 carbon atoms;
R4 is a divalent aromatic group with the two valences being ortho- or para- to each other said group being substituted or unsubstituted;
R5, R6 and R7 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl having up to 12 carbon atoms; substituted or unsubstituted cycloalkyl, phenyl and naphthyl; wherein R5 and R6 can be linked to form a hetercyclic ring system with the ring containing 3-10 atoms;
Y is selected from the group consisting of sulfur and oxygen atoms;
n is zero or one; provided that n = 1 when Y is sulfur;

(II) R'1 is selected from the group consisting of ben-zothiazole, quinoline, indolenine, nitrobenzothiazole, ban-zotriazole and rhodanine nuclei, each of which may be substituted or unsubstituted, and m is an integer between 0 and 6 inclusive;
and wherein said amount of said Formula II compound is insufficient to substantially decrease sensitivity of said emulsion.

2. A silver halide photographic material as in claim 1, wherein said at least one compound represented by the Formula I is present in an amount of 1X10-6 to 1X10-1 mol per mol of silver halide and said at least one compound represented by the Formula II is present in an amount of 5X10-6 to 1.0 mol per mol.
of silver halide.

3. A silver halide photographic material as in claim 1, wherein said at least one compound represented by the Formula I is present in an amount of 1X10-5 to 4X10-1 mol per mol of silver halide and said at least one compound represented by the Formula II is present in an amount of from 1X10-5 to 5X1-4 mol per mol of silver halide.

4. The material of claim 1 wherein both said com-pounds are incorporated in said emulsion.

5. The material of claim 1 wherein at least one of said compounds is incorporated in another hydrophilic layer of said material.

6. A silver halide photographic material as in claim 1, wherein said at least one compound represented by the Formula I and said at least one compound represented by the Formula II, are independently incorporated in at least one of a silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, and an antihalation layer.

7. A process for forming a super-high contrast negative image, comprising imagewise exposing and developing a silver halide photographic material comprising a support having provide thereon at least one silver halide emulsion layer, said emulsion layer or another layer of the developer solution used to develop said image said material containing a dot-quality promot-ing amount of at least one compound represented by the Formula I
and a pepper-reducing effective amount of a compound of the Formula II:

(I) wherein:
X =-NR5R6, or -OR7 R1 and R2 are independently selected from the group consisting of hydrogen, substituted and unsubstituted alkyl having up to 18 carbon atoms; substituted and unsubstituted cycloalkyl, phenyl and naphthyl;
R3 is selected from the group consisting of hydrogen, substituted and unsubstituted benzyl provided that R3 is hydrogen when neither R1 and R2 are hydrogen; wherein R1 and R2 or R1 and R3 can be linked together for form a heterocyclic ring system with the ring having 3-10 carbon atoms;
R4 is a divalent aromatic group with the two valences being ortho- or para- to each other said group being substituted or unsubstituted;
R5, R6 and R7 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl having up to 12 carbon atoms; substituted or unsubstituted cycloalkyl, phenyl and naphthyl; wherein R5 and R6 can be linked to form a hetercyclic ring system with the ring containing 3-10 atoms;
Y is selected from the group consisting of sulfur and oxygen atoms;
n is zero or one; provided that n = 1 when Y is sulfur;

(II) wherein R'1 is selected from the group consisting of ben-zothiazole, quinoline indolenine, nitrobenzothiazole, ben-zotriazole and rhodanine, each of which may be substituted or unsubstituted, and m is an integer between 0 and 6 inclusive; and wherein said amount of said Formula II compound is insufficient to substantially decrease sensitivity of said emulsion.

8. A process for forming a super-high contrast negative image according to claim 7, wherein said developing is carried out with a developer containing a sulfite ion in an amount of from 0.4 mol/1 to 2.5 mol/1 and having a pH of 10.5 to 12.3.

9. The process of claim 7 wherein said Formula I
compound is present in the developing solution.

10. The process of claim 7 wherein said Formula II
compound is present in the developing solution.

11. The process of claim 7 wherein both said Formula I
and said Formula II compounds are both present in the photographic material.

12. A process for forming a super high-contrast image comprising imagewise exposing and developing a silver halide containing photographic material comprising a support having provided thereon at least one silver halide emulsion layer, at least one of said emulsion layer, another layer and the developer used to develop said image, said material containing a dot-quality promoting amount of a hydrazine or hydrazine compound and a pepper-reducing effective amount of a compound of the Formula II

(II) wherein R'1 is selected from the group consisting of ben-zothiazole, quinoline, indolenine, nitrobenzothiazole, ben-zotriazole and rhodanine, each of which may be substituted or unsubstituted, and m is an integer between 0 and 6 inclusive; and wherein said amount of said Formula II compound is insufficient to substantially decrease sensitivity of said emulsion.

13. The process of claim 12 wherein said image is a negative image.

14. The process of claim 13 wherein said emulsion is of the surface latent image negative-working type.

15. The process of claim 14 wherein said Formula II
compound is incorporated in the photographic material.

16. The process of claim 14 wherein said Formula II
compound is incorporated in the developer.

17. The process of claim 15 wherein said Formula II
compound is 5-metanitrobenzylidene rhodanine.

18. The process of claim 16 wherein said hydrazide compound is 1-[4,-(3"-ethylthioreido)-phenyl]-5-methyl-semioxamazide, and is also incorporated in the photographic material.

19. The process of claim 18 wherein the amount of said Formula II compound is withi the range of about 1X10-5 to about 5X10-4 mol per mol of silver halide.

20. The process of claim 19 wherein the amount of said semioxamazide is within the range of about 1X10-5 to about 4X10-1 mol per mol of silver halide.

21. The material of claim 1 wherein said Formula I
compound is Compound I-2 and said Formula II compound is 5-meta nitrobenzylidene rhodanine.

22. The material of claim 21 wherein said Formula I
and said Formula II compounds are incorporated in said emulsion in amounts within the range of 1X10-5 to 4X10-1 for the compound of Formula I and the range of 1X10-5 to 5X10-4 for the compound of Formula II.