CA1166631A - Bis aryl-azo derivatives of 2,3-naphthalenediol and electrographic liquid developer compositions containing them - Google Patents
Bis aryl-azo derivatives of 2,3-naphthalenediol and electrographic liquid developer compositions containing themInfo
- Publication number
- CA1166631A CA1166631A CA000391577A CA391577A CA1166631A CA 1166631 A CA1166631 A CA 1166631A CA 000391577 A CA000391577 A CA 000391577A CA 391577 A CA391577 A CA 391577A CA 1166631 A CA1166631 A CA 1166631A
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- Canada
- Prior art keywords
- compound
- naphthalenediol
- pigment
- developer
- compositions containing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/02—Disazo dyes
- C09B33/04—Disazo dyes in which the coupling component is a dihydroxy or polyhydroxy compound
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/122—Developers with toner particles in liquid developer mixtures characterised by the colouring agents
Abstract
ABSTRACT OF THE DISCLOSURE
Novel 1,4-bis aryl-azo derivatives of 2,3-naphthalenediol in which the aryl groups are substituted with alkoxy and with sulfonamide or fluorosulfonyl groups. These compounds are useful as neutral density pigments in electrophotographic developers and have good light stability.
Novel 1,4-bis aryl-azo derivatives of 2,3-naphthalenediol in which the aryl groups are substituted with alkoxy and with sulfonamide or fluorosulfonyl groups. These compounds are useful as neutral density pigments in electrophotographic developers and have good light stability.
Description
~166631 --I--BIS ARYL-~ZO DERIV~TIVES OF
2,3-NAPHTHALENEDIOL ~ND ELECTROPHOTOGRAPHIC
LIQUID DEVELOPER COMPOSITIONS CONTU NING THEM
Thi- lnventlon r-late- to nov-l cbemlcal compound~ and to liquit electtophotogr-phic dev-l-oper compo~itlon~ containing ~uch compound~ as colorant~
Electrophotographic developer~ r- used for teveloping electrostatic charge pattern~ or, in other words, for making l~tent electrostat~c image6 vi~ible For instance, in th- electrophotographic copying of document~ an electrostatic charge pattern i~ formcd on J photoconductivc ~urface and tben i~
made vi~ibl- with a develop-r compo-ition or the ch-rge p~ttern i~ tran~f-rred to a sheet of paper or oth-r ~urfac- where it l- then developed and made vi~ibl-Both dry and liquid developer compo~itions r- known Liquid d-v-lop-r- have cert-in ~tvan-tJg~ uch J~ ~mall particle ~ize, which permlts th-ir u~- ln sy~tem~ requiring fln- lin~ resolu-tion. Llquid d-v-lop-r~ norm-lly r- compo~ed of -fin-ly divid-d pigment di~p-r~ed in an insulating 2S c-rri-r liquid ~uch - vol-tll- hydrocarbon mlxtur- To blnd th- pigment to an imaging surf-ce a bind-r r-~ln c-n l-o b- lncluded ln th- di~per-~lon. Oth-r po~lbl- compon-nt~ include charge control g-nt~ whlch ~t-blllze th- collold-l di~per-~lon by r-t~rdlng the ~ettllng of the plgment from th- c-r~l-r llquld.
Of th- m~ny color-d ~ub~t-nce~ that h-v-b--n ur-d ~ plgment~ for llquld d-veloper-, c-rbon bl-c~ h-~ b-en ~pecl-lly popular. Varlou~ bl-c~ and color-d orgJnic compound~ h-v~ o becn u~ed ,' ~.
Thc p-tcnt to Ford t Jl U.S. 4,14S,299 dl~clo~c~ ~ cl-~r of organlc compound~ thJt ~r-u-eful ~ plgment~ ln llquld l-ctrophotogr-phic d~v~lop~r~ Th~ compound~ ~rc bl~ ryl--zo d~rlvatl~ of 2,3-naphth~len~dlol When disper~d, thelr opeic-l d~n~lty 1- ~ub~t~nt~lly n-utr-l; th~t 1~, thcy rc bl-c~ or nc~rly blac~ in huc Th~y ~l~o form rea~on-bly ~tablc dl~per~lon~ ln hydro-c~rbon c~rrler llquld~ ruch ~ the commonly u--d l~op~r~fflnlc llqu$d c-rrl-r-. Ll~ m~ny organlc dycr, ho~cver, member~ of thl- cl-~ h~vc poorer light ~t-blllty th-n would bc de~lr-d. Con---qu-ntly, th- lmage~ devclopet wlth them tend to f~dc whcn cxpo~cd to llght or ultr~vlol-t r-dl-tion ov~r cxtcndcd pcrlod~ of tlm .
~ -n--d thcr for- cxlrt~ for pigmcnt~ h-vlng ncutr-l dcn~lty nd goot dl~pcr~lon ~t~blllty but ~l~o h-vlng good llght ~t-blllty. Th- compound- of th- prc~cnt lnvcntlon ~upply thl~ nccd. Th-y form ct~bl- di~p-r~lon~ ln c-rrl-t llquld-; th- lm~g~
d-v-lopcd ~lth thcm r- of ~ub~t-ntl-lly neutral d-n~lty; nd th-~- compound~ o h-v- good llght ~t-billty.
Th- compound~ of th- lnventlon ~rc of thc formul-,o~
N . N
~o ~w 1'2 . N ~
bal
LIQUID DEVELOPER COMPOSITIONS CONTU NING THEM
Thi- lnventlon r-late- to nov-l cbemlcal compound~ and to liquit electtophotogr-phic dev-l-oper compo~itlon~ containing ~uch compound~ as colorant~
Electrophotographic developer~ r- used for teveloping electrostatic charge pattern~ or, in other words, for making l~tent electrostat~c image6 vi~ible For instance, in th- electrophotographic copying of document~ an electrostatic charge pattern i~ formcd on J photoconductivc ~urface and tben i~
made vi~ibl- with a develop-r compo-ition or the ch-rge p~ttern i~ tran~f-rred to a sheet of paper or oth-r ~urfac- where it l- then developed and made vi~ibl-Both dry and liquid developer compo~itions r- known Liquid d-v-lop-r- have cert-in ~tvan-tJg~ uch J~ ~mall particle ~ize, which permlts th-ir u~- ln sy~tem~ requiring fln- lin~ resolu-tion. Llquid d-v-lop-r~ norm-lly r- compo~ed of -fin-ly divid-d pigment di~p-r~ed in an insulating 2S c-rri-r liquid ~uch - vol-tll- hydrocarbon mlxtur- To blnd th- pigment to an imaging surf-ce a bind-r r-~ln c-n l-o b- lncluded ln th- di~per-~lon. Oth-r po~lbl- compon-nt~ include charge control g-nt~ whlch ~t-blllze th- collold-l di~per-~lon by r-t~rdlng the ~ettllng of the plgment from th- c-r~l-r llquld.
Of th- m~ny color-d ~ub~t-nce~ that h-v-b--n ur-d ~ plgment~ for llquld d-veloper-, c-rbon bl-c~ h-~ b-en ~pecl-lly popular. Varlou~ bl-c~ and color-d orgJnic compound~ h-v~ o becn u~ed ,' ~.
Thc p-tcnt to Ford t Jl U.S. 4,14S,299 dl~clo~c~ ~ cl-~r of organlc compound~ thJt ~r-u-eful ~ plgment~ ln llquld l-ctrophotogr-phic d~v~lop~r~ Th~ compound~ ~rc bl~ ryl--zo d~rlvatl~ of 2,3-naphth~len~dlol When disper~d, thelr opeic-l d~n~lty 1- ~ub~t~nt~lly n-utr-l; th~t 1~, thcy rc bl-c~ or nc~rly blac~ in huc Th~y ~l~o form rea~on-bly ~tablc dl~per~lon~ ln hydro-c~rbon c~rrler llquld~ ruch ~ the commonly u--d l~op~r~fflnlc llqu$d c-rrl-r-. Ll~ m~ny organlc dycr, ho~cver, member~ of thl- cl-~ h~vc poorer light ~t-blllty th-n would bc de~lr-d. Con---qu-ntly, th- lmage~ devclopet wlth them tend to f~dc whcn cxpo~cd to llght or ultr~vlol-t r-dl-tion ov~r cxtcndcd pcrlod~ of tlm .
~ -n--d thcr for- cxlrt~ for pigmcnt~ h-vlng ncutr-l dcn~lty nd goot dl~pcr~lon ~t~blllty but ~l~o h-vlng good llght ~t-blllty. Th- compound- of th- prc~cnt lnvcntlon ~upply thl~ nccd. Th-y form ct~bl- di~p-r~lon~ ln c-rrl-t llquld-; th- lm~g~
d-v-lopcd ~lth thcm r- of ~ub~t-ntl-lly neutral d-n~lty; nd th-~- compound~ o h-v- good llght ~t-billty.
Th- compound~ of th- lnventlon ~rc of thc formul-,o~
N . N
~o ~w 1'2 . N ~
bal
3~
`
~166631 wherein al iB low~r al~yl snd, R2 1- -F or -N ~
~ R4 , wherein R3 and R4 are hydrogen, lower al~yl, phenyl, nspbthyl, or lower al~yl-substituted phenyl or napbtbyl nd can be the ~ame or different Although the compound~ in which Rl i~
methyl and R2 i8 fluorine or amino ~re preferred, the compound~ of the invention al~o include tho~e ln which Rl ~nd R2 ~re other ~lmilar groups The~e includo, in the case of Rl, other lower al~yls such a8 thyl, n-propyl and t-butyl In ehe ca~e of R they include mono- and disubstituted amino groups ~uch ~ methylamino, dimethylamino, methylethylamino, dl-t-butylsmino, diphenylamino, d$tolylamino and nsphthylamino The invention Jl~o includes an electro-photographic liquid dev-loper comprising a dispet-~ion of ~ pigment compound o~ defined above in an~l~ctric-lly in~ulat1ng c-rrier llquld The compound~ of the inv-ntion can be pr-p~r-d by the known method~ for pr-paring aromatic t~-zo compound~ A pref-rred method i~ to form a diazonium ~alt of an Jl~oxybenzene-~ulfonamite which ha~ ao cetamido ~ub~tituent and then to couple two mol-~ of the diazonium ~alt with one mole of 2,3-naphthalenediol Th- example~ which follow illurtr-t- prepar-tion~ of interm-diate~ and of tho de-ir-d fin-l compound~
ExamPle 1 ~) Preparation of o-Acetanisidide 3S ~ ~ ~
`
~166631 wherein al iB low~r al~yl snd, R2 1- -F or -N ~
~ R4 , wherein R3 and R4 are hydrogen, lower al~yl, phenyl, nspbthyl, or lower al~yl-substituted phenyl or napbtbyl nd can be the ~ame or different Although the compound~ in which Rl i~
methyl and R2 i8 fluorine or amino ~re preferred, the compound~ of the invention al~o include tho~e ln which Rl ~nd R2 ~re other ~lmilar groups The~e includo, in the case of Rl, other lower al~yls such a8 thyl, n-propyl and t-butyl In ehe ca~e of R they include mono- and disubstituted amino groups ~uch ~ methylamino, dimethylamino, methylethylamino, dl-t-butylsmino, diphenylamino, d$tolylamino and nsphthylamino The invention Jl~o includes an electro-photographic liquid dev-loper comprising a dispet-~ion of ~ pigment compound o~ defined above in an~l~ctric-lly in~ulat1ng c-rrier llquld The compound~ of the inv-ntion can be pr-p~r-d by the known method~ for pr-paring aromatic t~-zo compound~ A pref-rred method i~ to form a diazonium ~alt of an Jl~oxybenzene-~ulfonamite which ha~ ao cetamido ~ub~tituent and then to couple two mol-~ of the diazonium ~alt with one mole of 2,3-naphthalenediol Th- example~ which follow illurtr-t- prepar-tion~ of interm-diate~ and of tho de-ir-d fin-l compound~
ExamPle 1 ~) Preparation of o-Acetanisidide 3S ~ ~ ~
-4-To 100 ~1 of c-tic nhydrlda w - add-d dropwl~ with rtirring 100 g (0 813 mol~) of o--ni-idin~, th~ t~mp~r~tur- ri-in8 to bout 60-C
during additlon. Tna r~actlon ~ixeura w-- h--tad on S t~-m b-th for 15 minut~-, llow~d to cool to 45-C
and w-~ pourcd onto 500 g of cru-had ic-. The whlt-~olld that pt-cipltatcd war coll-ct-d, wa~h~d fr--of cid wlth w-tcr and ir dricd to giva 100 ~, m p 84-86-C, of product.
(b) Pr~p-r-tion of 3-~cetamido-4-methoxybenzene-ulfonamid~
~ ~ Cl ~ 3 lS ~ ~ ~ ~
o-~cat-nl-ldidc (100 g, 0 605 ~ol~) wa-dd-d in portlon- to 200 1 of chloro~ulfonic cid t bout 50-C ~coollng i~ n-c-~--ry). ~ft-r th~
ddltlon, th- ~olutlon w-~ h--tcd t 50-60-C for four hourr, cool-d to roo~ tc~p~r-tur- and c-r~fully dd-d to n lc--w-t-r mixtur- ~l.S ~g). Th- whit-pr-clplt-t- w-~ coll-ct-d, w-~h-d with n ddltion-l ount of w t-r ~1 llt-r) nd pr-rr-d dry with a 2S rubb r d~ for ~-v-r-l hourr. Th- d-mp ~ulfonyl cblorld- w-r dlr~olv-d ln S00 ~1 of t-trahydrofuran, cool-d to O-C nd tr--t-d wlth ~tr--m of ~mmoni-g-c ~th- t-~p-r-tur- rl~lng xoth~r ic-lly to bout 2S-C) for 10 ~lnut~. Th- whlt- cryrt-llln- rolid th-t r-p-r-t-d w-- coll-ct-d, w-rh-d wltb 100 1 of w-t-r nd drl-d to glv- 114 g ~80~ p.
227-230-C, of rulfon-~idc.
SS
~6631- -~ c) PreParation of 1,4-Bi~(2-methoxy-5-sulfamoylphenylazo)-2,3-naphtb--lenediol ~ 8Cl ~ ~ ;
N~202~BCOC ~ ~NO~ rl4 CJ~30 ~ , ~ ~
~ .
3-~cetamido-4-methoxybenzenesulfonamide (72 4 g, 0 297 mol-) w-~ ~u~pent-t in 180 ml of 6N
hydrochloric acid and heat-d on a ~t-~m bath for 60 minut-~ Th- mber ~olution wa~ cool-t to 0C, the r-~ultlng ~lurry w-~ treat-d with ~olution of 21 g ~0 30 mol~) of ~odium nltrite in 40 ml of wat~r 2S ~ft-r th- addition, the rolution wa~ ~tirred for 15 minut-z t O-C nd th-n filtered to remove any in~ol-ubl- m-t-ri-l Th~ di-zonlum ~alt zolution wa~ th~n ddod dropwi~c at 0-lO-C to ~tirrcd ~olution of 22 0 8 (0 142 ~ole) of 2,3-naphth-len-tiol in 900 ml of pyridin-. Th- mixtur- waz ~tirred for one hour t 0-5-C ~ft-r ddition w-- compl-t-, then ov~rnight wlthout further cooling Th- dark ~olid wa~
coll-cted, wa-h-d with 100 ml of pyridin-, th-n 500 ml of meth-nol and fln-lly w-rm w-t-r to give 71.8 g of crud- product, ~ p Jbout 34S-C ~shrln~
ft-r drying Thl~ product wa~ ~lurried ia 500 ml 116663~
of refluxlng dimethylform-mld~ ~olv~nt for 30 minut~-. Th~ d~r~ mixture w-- cool~d to roo~
temp~rature, th~ ~olld w~a eollected, w--h~d wlth methanol until tb~ filtrat- w-- eolorle~- nd dri~d to giv- 62 8g (76S) of produet m p ~400-C.
Ex-mPle 2 (~) PreD-ration of 3-~c~tamldo-4-methoxvb~nzen~ulfon~l fluoride To ~olution of 33 8 (0.35 mol~) of 10 pota~iu~ fluorid~ 2H20 in 500 ml of diox-ne/H20 (1 1) w-~ ~dd~d ~ equimol-r mount of 3-ac-tumldo-4-methoxybenz~n~ulfonyl chloride prap-red a in Ex-mpl- l(b). Th~ r~action mixture wa~ refluxed for 90 minut-~, th~n chill-d in an ic~-b~th Th~ r~ulting whit- ~olid w~ collected nd w--h~d wlth w-ter to giv~ 61 8 (72 5~) of th-d--ir-d fluorid- m p 162-164-C.
(b)PraP-r-tion o 1,4-Bi~(2-methoxy-S-fluoro~ulfonylphenylazo)2,3-naph-20 th~l-n-diol Thi~ eompound w-- prep-r-d in the manner d-aerib-d ln ExJmpl- l(e), but ub-tituting 8 9 g (0.036 mol-) 3--e-t-~ido-4-m-thoxyb-nz-n-~ulfooyl fluorid- for th- e-t-mido~ulfon-mid- of l~b) and 2S u~ing eotr-~ponding mount- of th- oth-r m-t-ri-l-~ft-r w ~hing nd dtying th- mount of th- de~ir-d eompound ~-~ 4.3 ~ ~35S), d-eompo~ing t 330 C
wlthout -ltln8 Th- leetrie-llg in~ul-ting e-rrl-r liquid 30 for th- d-v-lop-t eompoaltion~ of th- inv-ntion i- -llquld of typ- ~oown in th- rt. ~ nown, e-ttl-t llquld- fot l-ettophotogr-phle d~v-lop-ra ebould h-v- lo~ dl-l-ettie eon~t-nt and v-r~
hlgh l-etrie-l r-~i-t-ne-. Suit-bl- llquid~ h-v- -3S dl-l-etrie eon~t-nt 1--~ th-n 3 ~nd volum~
re~i~tlvit~ gre-ter th-n bout 101 ohm-em.
They should also be st~ble under conditions of u~e.
Examples of carrler liqulds lnclude hydrocarbon liqulds such a~ the lsopsraffinlc hydrocarbon~
having a boiling range from 145 to 185C whlch are sold under the trademark "Isopar G." Others lnclude halogenated hydrocarbon llquids boillng from 2C to 55C, for example, fluorinated hydrocarbon6, such as trlchloromonofluoromethane and trichlorotri-fluoroethane. Still other useful carrLer liquid~
include polysiloxane~, odorless mineral spirits, octane and cyclohexane.
Although the developer can consl~t ~imply of a dlspersion of a novel pigment of the invention in the carrier llquid, it i~ u~ually des$rable to include a binder polymer to fix the pigment psrticles to the paper or film or other ~urface to be developed. Especially u~eful a8 binder polymer~
are the acryllc copoly~er~ disclo~ed in Stahly et al U.S. 3,849,165 and the polyesterionomers disclosed in Merrill et al U.S. 4,202,785.
The liquld developer of the invention can also contain a charge control agent to provlde un$form charge polarlty on the developer particles and to aid in stabilizing the disper~lon of pigment and binder resin. The chsrge control agent is also referred to as a stabilizer. The amount of charge control ~gent i~ preferably in the range from 0.1 to 2 weight percent of the developer composition.
Examples of uoeful charge control agents or stabilizers are disclosed in Stahly et al, U.S.
3,849,165, Ford et al, U.S. 4,145,299, Merrill t 1, U.S. 4,170,563 and Merrlll et al, U.S.
4,229,513. Preferred polymeric charge control gents ~nclude poly(styrene-co-lauryl methacrylate-co-sulfo~thyl methacrylate), poly(vlnyltolu ne-co-l-uryl -thacrylate-co-lithiu~
~eth-crylate-co--eth-crylic cld), poly(p-tert-butyl tyrene-co-llthiu~ ~eth cryl-te) nd poly(vlnyl-tolueno-co-lauryl ~ethacryl-te-co-~ thacryloyloxy-ethyltrim thyl-~ oniu~-p-tolu ne ulfon-t-) They are either ~olubl- or re-dily di~per~ible in the usual hydroc-rbon carrier liquid- nd do not settle out Non-poly~eric charge control agent- re ~180 useful such ~ the oap- of 4gnesium aod heavler ~etals disclo~ed ln the patent to Beyer, U S
3,417,019 The developer can bo prepared ~8 described in Ford et 1 U S 4,145,299 by 8rindini or ball ~illing the pig -nt with a ~olutlon of the blnder poly~er ln n ro~atlc hydrocarbon llquid to obtaln a dev loper concentr-t- Thls 1- then dlluted wlth th- ln-ul-tlng c-rrler llquid, uch 8 sn i~opar-ffinlc hydrocarbon llquld, to obt-ln a di~per~ion of th- pig~ nt nd binder poly~or The charg- ag-nt, lf u~ed, c-n b- incorporat-d at the a-~- ti~- or l-ter The dovelopor will contaln from 0 01 to 1 0 8r-~ of pig~-nt p-r liter of developer Wh n bind-r poly r i~ u~-d th plgment to bind-r welght r-tio c-n v-ry, 8 , fro- 1 20 to 2 1 2S Th following x-~pl- illu~trate~ the pr-p-r-tioo of d-velop-r of the inventioo X--Pl- 3 To 22 5 g of a 7 w lght p-rcent solution of th ~t-billz~r poly~or, poly(vinyltolu-n--co-lauryl -th eryl-t--eo-lithiu -th-cryl-te-co-~eth crylic eit), ln "Solv ~o 100" ro~-tlc hydroearbon ~olv nt w-~ dd-d 2 8 Of th- plg~ont of Exa~pl- 1 ("801v --o 100" i~ th- tr-do--rk for n lkyl-ted ro-~tle hydroe-rbon ~ixtur- boillng fro 150 to 18SC) Th xixtur w ~ b-ll--ill-d for 15 d-ys to .. . .
obtaln a disperslon conc-ntrat- To th~
concentr-te w-s added 9 3 g of 14 w ight p-rc-nt solut~on of blnder polymer in "Solvesso 100"
- aromatic hydrocarbon The blnder poly~er w~s S poly(ethyl acrylate-co-ethyl ethacrylate-co-l-uryl methacrylato-co-lithlu~ sulfoethyl ~ethacryl-te) quantlty of the ~ixture (4 2 8) was then dlsper~ed in 500 ~1 of "I-opar G" isoparafflnlc carrler llquld by ultrasonic ~eano Example 4 In ~ub~tantlally the ~a~e manner a8 ln Exs~ple 3 another developer of the inventlon was prepared but u~ing dlfferent plg~ent, nsmely, the pig~ent of Example 2 Thr-- other developers were prep~red ~ ln Example 3 but u~lng instead of a pigment of the lnventlon one of the followlng pigments Control Exa~Dle S
~ N ~ 3 ~-3 Control EXa~P1e 6 ~1~
OC~3 ~-03 T~
OC~3 11~6631 Control Exumple 7 ~N
~ OC~3 N~N
In esch of the e~umples of the invention, Ex~mples 3 and 4, and ~n the Control Examples 5-7 the p~gment~ formed stable d-veloper dispersions Each developer wa8 usod to develop charge patterns formed by unlformly charglng a polyethylene terephthalate film In each instsnce the electro-statlcally charged film surface wss ~ucc-ssfully doveloped to substantlally black or noutral density Each devoloped fll~ sample was then sub~octqd to a llght f-dlng test The tost con-l~ted of xpo~ur- to hlgh lntensity, simulated north rn okyllght ov r a poriod of day~ The re~ult~ of th- t-~t~ r- roport-d ln terms of Nigh Intonolty D-yllght, whlch 18 a ot-ndard ~easure of llght ~t-bllity t-~ting of lmages This is abbr-viat-d ~ HID nd 1~ qual to 50,000 lux Thus an HID xposure for perlod of one week (168 hours) 18 qual to 8 4 x 106 lux-hours ~ssu~ing that th lnten~ity of av~rage northern skyllght is 2500 lux, lt c-n bc c-lculat-d that on- woek of HID
xposur- 18 equlv lont to 3,360 hour~ of northern daylight xposur- ~8 4 x 106 lux-hour~/2500 lux ~ 3,360 hours) ~t 12 hour~ of dayllght per day, 280 d-y~ of ver-go northern dayllght Jre oquivalont to on w-ek of HID expooure In tdltion to theoe a~umptlono, certain othor assu~ptlons re relovant to the re6ults li6ted below for the light stability tests. The other assumption6 are ~hat there i8 no photographic reciprocity effect, ~here i8 no inter-mittency, the p~gments tested have equivalent spectral energy distributions and in the test~ there was no significant sensitivity to temperature or humidity changes.
The test results were as follows:
Pi&ment Percent Fading 10Example 1 (Invention) 7 at 7 days HID
" 2 " 6.5 at 7 " "
3 (Control) 31 at 4 " 4 " 40 at 4 " "
~ 5 " 46 At 4 The test re6ults show that although all five pigments formed satisfactory dispersions and neutral density images, the pigments of the inven-tion tExamples 1 and 2) were markedly superior to the pigments of the control examples ln llght 20 stability or, in other words, in resistance to fading when exposed to simulated northern 6kylight.
In addition to the uses described above, the compounds of the invention can be components of composite electrically photosensitive particles of 25 the type disclosed ln Merrill et al, U.S. Patent No. 4,322,487 for use in photoelectrophoretic migration imaging processes.
Although the invention has been described in considerable detail with particular reference to 30 certain preferred embodiments thereof, variations and modiflcations can be effected within the spirit and scope of the invention.
r~
during additlon. Tna r~actlon ~ixeura w-- h--tad on S t~-m b-th for 15 minut~-, llow~d to cool to 45-C
and w-~ pourcd onto 500 g of cru-had ic-. The whlt-~olld that pt-cipltatcd war coll-ct-d, wa~h~d fr--of cid wlth w-tcr and ir dricd to giva 100 ~, m p 84-86-C, of product.
(b) Pr~p-r-tion of 3-~cetamido-4-methoxybenzene-ulfonamid~
~ ~ Cl ~ 3 lS ~ ~ ~ ~
o-~cat-nl-ldidc (100 g, 0 605 ~ol~) wa-dd-d in portlon- to 200 1 of chloro~ulfonic cid t bout 50-C ~coollng i~ n-c-~--ry). ~ft-r th~
ddltlon, th- ~olutlon w-~ h--tcd t 50-60-C for four hourr, cool-d to roo~ tc~p~r-tur- and c-r~fully dd-d to n lc--w-t-r mixtur- ~l.S ~g). Th- whit-pr-clplt-t- w-~ coll-ct-d, w-~h-d with n ddltion-l ount of w t-r ~1 llt-r) nd pr-rr-d dry with a 2S rubb r d~ for ~-v-r-l hourr. Th- d-mp ~ulfonyl cblorld- w-r dlr~olv-d ln S00 ~1 of t-trahydrofuran, cool-d to O-C nd tr--t-d wlth ~tr--m of ~mmoni-g-c ~th- t-~p-r-tur- rl~lng xoth~r ic-lly to bout 2S-C) for 10 ~lnut~. Th- whlt- cryrt-llln- rolid th-t r-p-r-t-d w-- coll-ct-d, w-rh-d wltb 100 1 of w-t-r nd drl-d to glv- 114 g ~80~ p.
227-230-C, of rulfon-~idc.
SS
~6631- -~ c) PreParation of 1,4-Bi~(2-methoxy-5-sulfamoylphenylazo)-2,3-naphtb--lenediol ~ 8Cl ~ ~ ;
N~202~BCOC ~ ~NO~ rl4 CJ~30 ~ , ~ ~
~ .
3-~cetamido-4-methoxybenzenesulfonamide (72 4 g, 0 297 mol-) w-~ ~u~pent-t in 180 ml of 6N
hydrochloric acid and heat-d on a ~t-~m bath for 60 minut-~ Th- mber ~olution wa~ cool-t to 0C, the r-~ultlng ~lurry w-~ treat-d with ~olution of 21 g ~0 30 mol~) of ~odium nltrite in 40 ml of wat~r 2S ~ft-r th- addition, the rolution wa~ ~tirred for 15 minut-z t O-C nd th-n filtered to remove any in~ol-ubl- m-t-ri-l Th~ di-zonlum ~alt zolution wa~ th~n ddod dropwi~c at 0-lO-C to ~tirrcd ~olution of 22 0 8 (0 142 ~ole) of 2,3-naphth-len-tiol in 900 ml of pyridin-. Th- mixtur- waz ~tirred for one hour t 0-5-C ~ft-r ddition w-- compl-t-, then ov~rnight wlthout further cooling Th- dark ~olid wa~
coll-cted, wa-h-d with 100 ml of pyridin-, th-n 500 ml of meth-nol and fln-lly w-rm w-t-r to give 71.8 g of crud- product, ~ p Jbout 34S-C ~shrln~
ft-r drying Thl~ product wa~ ~lurried ia 500 ml 116663~
of refluxlng dimethylform-mld~ ~olv~nt for 30 minut~-. Th~ d~r~ mixture w-- cool~d to roo~
temp~rature, th~ ~olld w~a eollected, w--h~d wlth methanol until tb~ filtrat- w-- eolorle~- nd dri~d to giv- 62 8g (76S) of produet m p ~400-C.
Ex-mPle 2 (~) PreD-ration of 3-~c~tamldo-4-methoxvb~nzen~ulfon~l fluoride To ~olution of 33 8 (0.35 mol~) of 10 pota~iu~ fluorid~ 2H20 in 500 ml of diox-ne/H20 (1 1) w-~ ~dd~d ~ equimol-r mount of 3-ac-tumldo-4-methoxybenz~n~ulfonyl chloride prap-red a in Ex-mpl- l(b). Th~ r~action mixture wa~ refluxed for 90 minut-~, th~n chill-d in an ic~-b~th Th~ r~ulting whit- ~olid w~ collected nd w--h~d wlth w-ter to giv~ 61 8 (72 5~) of th-d--ir-d fluorid- m p 162-164-C.
(b)PraP-r-tion o 1,4-Bi~(2-methoxy-S-fluoro~ulfonylphenylazo)2,3-naph-20 th~l-n-diol Thi~ eompound w-- prep-r-d in the manner d-aerib-d ln ExJmpl- l(e), but ub-tituting 8 9 g (0.036 mol-) 3--e-t-~ido-4-m-thoxyb-nz-n-~ulfooyl fluorid- for th- e-t-mido~ulfon-mid- of l~b) and 2S u~ing eotr-~ponding mount- of th- oth-r m-t-ri-l-~ft-r w ~hing nd dtying th- mount of th- de~ir-d eompound ~-~ 4.3 ~ ~35S), d-eompo~ing t 330 C
wlthout -ltln8 Th- leetrie-llg in~ul-ting e-rrl-r liquid 30 for th- d-v-lop-t eompoaltion~ of th- inv-ntion i- -llquld of typ- ~oown in th- rt. ~ nown, e-ttl-t llquld- fot l-ettophotogr-phle d~v-lop-ra ebould h-v- lo~ dl-l-ettie eon~t-nt and v-r~
hlgh l-etrie-l r-~i-t-ne-. Suit-bl- llquid~ h-v- -3S dl-l-etrie eon~t-nt 1--~ th-n 3 ~nd volum~
re~i~tlvit~ gre-ter th-n bout 101 ohm-em.
They should also be st~ble under conditions of u~e.
Examples of carrler liqulds lnclude hydrocarbon liqulds such a~ the lsopsraffinlc hydrocarbon~
having a boiling range from 145 to 185C whlch are sold under the trademark "Isopar G." Others lnclude halogenated hydrocarbon llquids boillng from 2C to 55C, for example, fluorinated hydrocarbon6, such as trlchloromonofluoromethane and trichlorotri-fluoroethane. Still other useful carrLer liquid~
include polysiloxane~, odorless mineral spirits, octane and cyclohexane.
Although the developer can consl~t ~imply of a dlspersion of a novel pigment of the invention in the carrier llquid, it i~ u~ually des$rable to include a binder polymer to fix the pigment psrticles to the paper or film or other ~urface to be developed. Especially u~eful a8 binder polymer~
are the acryllc copoly~er~ disclo~ed in Stahly et al U.S. 3,849,165 and the polyesterionomers disclosed in Merrill et al U.S. 4,202,785.
The liquld developer of the invention can also contain a charge control agent to provlde un$form charge polarlty on the developer particles and to aid in stabilizing the disper~lon of pigment and binder resin. The chsrge control agent is also referred to as a stabilizer. The amount of charge control ~gent i~ preferably in the range from 0.1 to 2 weight percent of the developer composition.
Examples of uoeful charge control agents or stabilizers are disclosed in Stahly et al, U.S.
3,849,165, Ford et al, U.S. 4,145,299, Merrill t 1, U.S. 4,170,563 and Merrlll et al, U.S.
4,229,513. Preferred polymeric charge control gents ~nclude poly(styrene-co-lauryl methacrylate-co-sulfo~thyl methacrylate), poly(vlnyltolu ne-co-l-uryl -thacrylate-co-lithiu~
~eth-crylate-co--eth-crylic cld), poly(p-tert-butyl tyrene-co-llthiu~ ~eth cryl-te) nd poly(vlnyl-tolueno-co-lauryl ~ethacryl-te-co-~ thacryloyloxy-ethyltrim thyl-~ oniu~-p-tolu ne ulfon-t-) They are either ~olubl- or re-dily di~per~ible in the usual hydroc-rbon carrier liquid- nd do not settle out Non-poly~eric charge control agent- re ~180 useful such ~ the oap- of 4gnesium aod heavler ~etals disclo~ed ln the patent to Beyer, U S
3,417,019 The developer can bo prepared ~8 described in Ford et 1 U S 4,145,299 by 8rindini or ball ~illing the pig -nt with a ~olutlon of the blnder poly~er ln n ro~atlc hydrocarbon llquid to obtaln a dev loper concentr-t- Thls 1- then dlluted wlth th- ln-ul-tlng c-rrler llquid, uch 8 sn i~opar-ffinlc hydrocarbon llquld, to obt-ln a di~per~ion of th- pig~ nt nd binder poly~or The charg- ag-nt, lf u~ed, c-n b- incorporat-d at the a-~- ti~- or l-ter The dovelopor will contaln from 0 01 to 1 0 8r-~ of pig~-nt p-r liter of developer Wh n bind-r poly r i~ u~-d th plgment to bind-r welght r-tio c-n v-ry, 8 , fro- 1 20 to 2 1 2S Th following x-~pl- illu~trate~ the pr-p-r-tioo of d-velop-r of the inventioo X--Pl- 3 To 22 5 g of a 7 w lght p-rcent solution of th ~t-billz~r poly~or, poly(vinyltolu-n--co-lauryl -th eryl-t--eo-lithiu -th-cryl-te-co-~eth crylic eit), ln "Solv ~o 100" ro~-tlc hydroearbon ~olv nt w-~ dd-d 2 8 Of th- plg~ont of Exa~pl- 1 ("801v --o 100" i~ th- tr-do--rk for n lkyl-ted ro-~tle hydroe-rbon ~ixtur- boillng fro 150 to 18SC) Th xixtur w ~ b-ll--ill-d for 15 d-ys to .. . .
obtaln a disperslon conc-ntrat- To th~
concentr-te w-s added 9 3 g of 14 w ight p-rc-nt solut~on of blnder polymer in "Solvesso 100"
- aromatic hydrocarbon The blnder poly~er w~s S poly(ethyl acrylate-co-ethyl ethacrylate-co-l-uryl methacrylato-co-lithlu~ sulfoethyl ~ethacryl-te) quantlty of the ~ixture (4 2 8) was then dlsper~ed in 500 ~1 of "I-opar G" isoparafflnlc carrler llquld by ultrasonic ~eano Example 4 In ~ub~tantlally the ~a~e manner a8 ln Exs~ple 3 another developer of the inventlon was prepared but u~ing dlfferent plg~ent, nsmely, the pig~ent of Example 2 Thr-- other developers were prep~red ~ ln Example 3 but u~lng instead of a pigment of the lnventlon one of the followlng pigments Control Exa~Dle S
~ N ~ 3 ~-3 Control EXa~P1e 6 ~1~
OC~3 ~-03 T~
OC~3 11~6631 Control Exumple 7 ~N
~ OC~3 N~N
In esch of the e~umples of the invention, Ex~mples 3 and 4, and ~n the Control Examples 5-7 the p~gment~ formed stable d-veloper dispersions Each developer wa8 usod to develop charge patterns formed by unlformly charglng a polyethylene terephthalate film In each instsnce the electro-statlcally charged film surface wss ~ucc-ssfully doveloped to substantlally black or noutral density Each devoloped fll~ sample was then sub~octqd to a llght f-dlng test The tost con-l~ted of xpo~ur- to hlgh lntensity, simulated north rn okyllght ov r a poriod of day~ The re~ult~ of th- t-~t~ r- roport-d ln terms of Nigh Intonolty D-yllght, whlch 18 a ot-ndard ~easure of llght ~t-bllity t-~ting of lmages This is abbr-viat-d ~ HID nd 1~ qual to 50,000 lux Thus an HID xposure for perlod of one week (168 hours) 18 qual to 8 4 x 106 lux-hours ~ssu~ing that th lnten~ity of av~rage northern skyllght is 2500 lux, lt c-n bc c-lculat-d that on- woek of HID
xposur- 18 equlv lont to 3,360 hour~ of northern daylight xposur- ~8 4 x 106 lux-hour~/2500 lux ~ 3,360 hours) ~t 12 hour~ of dayllght per day, 280 d-y~ of ver-go northern dayllght Jre oquivalont to on w-ek of HID expooure In tdltion to theoe a~umptlono, certain othor assu~ptlons re relovant to the re6ults li6ted below for the light stability tests. The other assumption6 are ~hat there i8 no photographic reciprocity effect, ~here i8 no inter-mittency, the p~gments tested have equivalent spectral energy distributions and in the test~ there was no significant sensitivity to temperature or humidity changes.
The test results were as follows:
Pi&ment Percent Fading 10Example 1 (Invention) 7 at 7 days HID
" 2 " 6.5 at 7 " "
3 (Control) 31 at 4 " 4 " 40 at 4 " "
~ 5 " 46 At 4 The test re6ults show that although all five pigments formed satisfactory dispersions and neutral density images, the pigments of the inven-tion tExamples 1 and 2) were markedly superior to the pigments of the control examples ln llght 20 stability or, in other words, in resistance to fading when exposed to simulated northern 6kylight.
In addition to the uses described above, the compounds of the invention can be components of composite electrically photosensitive particles of 25 the type disclosed ln Merrill et al, U.S. Patent No. 4,322,487 for use in photoelectrophoretic migration imaging processes.
Although the invention has been described in considerable detail with particular reference to 30 certain preferred embodiments thereof, variations and modiflcations can be effected within the spirit and scope of the invention.
r~
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula wherein R1 is lower alkyl and, R2 is -F or , wherein R3 and R4 are hydrogen, lower alkyl, phenyl, naphtyl, or lower alkyl-substituted phenyl or naphthyl and can be the same or different.
2. A compound according to Claim 1 of the formula
3. A compound according to Claim 1 of the formula
4. In a liquid electrophotographic developer comprising a dispersion of a pigment and a binder resin in an electrically insulating liquid, the improvement wherein said pigment is a compound of Claim 1.
5. A developer according to Claim 4 wherein said pigment is a compound of Claim 2.
6. A developer according to Claim 4.
wherein said pigment is a compound of Claim 3.
wherein said pigment is a compound of Claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/264,312 US4414152A (en) | 1981-05-18 | 1981-05-18 | Bis aryl-azo derivatives of 2,3-naphthalenediol |
| US264,312 | 1981-05-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1166631A true CA1166631A (en) | 1984-05-01 |
Family
ID=23005485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000391577A Expired CA1166631A (en) | 1981-05-18 | 1981-12-04 | Bis aryl-azo derivatives of 2,3-naphthalenediol and electrographic liquid developer compositions containing them |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4414152A (en) |
| JP (1) | JPS57195157A (en) |
| CA (1) | CA1166631A (en) |
| DE (1) | DE3218758A1 (en) |
| GB (1) | GB2104910B (en) |
Families Citing this family (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654282A (en) * | 1986-05-01 | 1987-03-31 | Eastman Kodak Company | Plural electrophotographic toned image method |
| US5028507A (en) * | 1989-10-30 | 1991-07-02 | Minnesota Mining And Manufacturing Company | Infrared-transparent black liquid toner |
| US5541024A (en) * | 1990-02-07 | 1996-07-30 | Nair; Mridula | Toner particles produced by limited coalescence polymerization |
| US5411832A (en) * | 1993-09-24 | 1995-05-02 | Eastman Kodak Company | Method of modifying the charging propensity of carrier particles for electrostatographic developers and modified carrier particles |
| US5405727A (en) * | 1993-12-22 | 1995-04-11 | Eastman Kodak Company | N-(carbonyl, carbonimidoyl, carbonothioyl) sulfonamide charge control agents and toners and developers |
| US5385800A (en) * | 1993-12-22 | 1995-01-31 | Eastman Kodak Company | Bis and tris N-(carbonyl, carbonimidoyl, carbonothioyl)sulfonamide charge control agents, toners and developers |
| US5378269A (en) * | 1993-12-29 | 1995-01-03 | Scitex Digital Printing, Inc. | Recording liquids for ink-jet recording |
| GB9400972D0 (en) * | 1994-01-19 | 1994-03-16 | Zeneca Ltd | Process |
| US5480757A (en) * | 1994-06-08 | 1996-01-02 | Eastman Kodak Company | Two component electrophotographic developers and preparation method |
| EP0690355A1 (en) | 1994-06-08 | 1996-01-03 | Eastman Kodak Company | Humidity-stabilized toners and developers |
| US5516615A (en) * | 1995-01-31 | 1996-05-14 | Eastman Kodak Company | Stabilized carriers with β phase poly(vinylidenefluoride) |
| US5521268A (en) * | 1995-03-29 | 1996-05-28 | Eastman Kodak Company | Odor reduction in toner polymers |
| EP0757294A1 (en) * | 1995-07-28 | 1997-02-05 | Eastman Kodak Company | Toner compositions including crosslinked and N-alkylsarcosine soaps |
| US5783346A (en) * | 1996-03-06 | 1998-07-21 | Eastman Kodak Company | Toner compositions including polymer binders with adhesion promoting and charge control monomers |
| US6369136B2 (en) | 1998-12-31 | 2002-04-09 | Eastman Kodak Company | Electrophotographic toner binders containing polyester ionomers |
| US6696212B2 (en) | 2001-03-27 | 2004-02-24 | Heidelberger Druckmaschinen Ag | Single component toner for improved magnetic image character recognition |
| US6692880B2 (en) | 2001-05-14 | 2004-02-17 | Heidelberger Druckmaschinen Ag | Electrophotographic toner with stable triboelectric properties |
| US6797448B2 (en) | 2001-05-14 | 2004-09-28 | Eastman Kodak Company | Electrophotographic toner and development process with improved image and fusing quality |
| US7314696B2 (en) | 2001-06-13 | 2008-01-01 | Eastman Kodak Company | Electrophotographic toner and development process with improved charge to mass stability |
| ES2248460T3 (en) * | 2001-09-05 | 2006-03-16 | Eastman Kodak Company | ELECTROPHOTOGRAPHIC TONES CONTAINING HIGH CRYSTALLINE POLYCHYLENE WAXES. |
| US7087305B2 (en) * | 2002-05-30 | 2006-08-08 | Eastman Kodak Company | Fuser member with tunable gloss level and methods and apparatus for using the same to fuse toner images |
| JP2004163879A (en) * | 2002-06-13 | 2004-06-10 | Heidelberger Druckmas Ag | Electrophotographic toner in which wax is uniformly dispersed |
| JP2004252402A (en) * | 2002-06-24 | 2004-09-09 | Heidelberger Druckmas Ag | Electrophotographic toner and development process using chemically prepared toner |
| US20050220518A1 (en) * | 2004-03-31 | 2005-10-06 | Eastman Kodak Company | Treatment of preprinted media for improved toner adhesion |
| US8192909B2 (en) | 2005-12-21 | 2012-06-05 | Eastman Kodak Company | Chemically prepared porous toner |
| US7914963B2 (en) * | 2007-12-12 | 2011-03-29 | Eastman Kodak Company | Toner composition |
| US8435712B2 (en) | 2008-05-21 | 2013-05-07 | Eastman Kodak Company | Developer for selective printing of raised information by electrography |
| US7956118B2 (en) * | 2008-09-25 | 2011-06-07 | Eastman Kodak Company | Method and preparation of chemically prepared toners |
| US8221947B2 (en) | 2008-12-18 | 2012-07-17 | Eastman Kodak Company | Toner surface treatment |
| US8614039B2 (en) | 2010-04-26 | 2013-12-24 | Eastman Kodak Company | Toner containing metallic flakes and method of forming metallic image |
| US8722304B2 (en) | 2010-07-30 | 2014-05-13 | Eastman Kodak Company | Method for forming surface decorated particles |
| US8728692B2 (en) | 2010-07-30 | 2014-05-20 | Eastman Kodak Company | Surface decorated particles |
| US8626015B2 (en) | 2010-10-26 | 2014-01-07 | Eastman Kodak Company | Large particle toner printer |
| US8530126B2 (en) | 2010-10-26 | 2013-09-10 | Eastman Kodak Company | Large particle toner |
| US8147948B1 (en) | 2010-10-26 | 2012-04-03 | Eastman Kodak Company | Printed article |
| US8465899B2 (en) | 2010-10-26 | 2013-06-18 | Eastman Kodak Company | Large particle toner printing method |
| US8507089B2 (en) | 2011-01-04 | 2013-08-13 | Eastman Kodak Company | Articles with porous particles for security purposes |
| US8507088B2 (en) | 2011-01-04 | 2013-08-13 | Eastman Kodak Company | Porous particles with multiple markers |
| US8404424B2 (en) | 2011-02-08 | 2013-03-26 | Eastman Kodak Company | Security enhanced printed products and methods |
| US20120202022A1 (en) | 2011-02-08 | 2012-08-09 | Detlef Schulze-Hagenest | Printed product with authentication bi-fluorescence feature |
| US20120283337A1 (en) | 2011-05-05 | 2012-11-08 | Mary Christine Brick | Inorganic porous particles with stabilized micropores |
| CN103703063B (en) | 2011-07-28 | 2016-06-29 | 伊斯曼柯达公司 | The Porous-Organic granule of crosslinking |
| US20130071143A1 (en) | 2011-09-19 | 2013-03-21 | Thomas Nelson Blanton | Antibacterial and antifungal protection for toner image |
| US8744332B2 (en) | 2011-09-30 | 2014-06-03 | Eastman Kodak Company | Printer with wax management system |
| US8725052B2 (en) | 2011-09-30 | 2014-05-13 | Eastman Kodak Company | Wax management system |
| US8824948B2 (en) | 2011-09-30 | 2014-09-02 | Eastman Kodak Company | Method for managing wax on a print having a toner image therein |
| US9052624B2 (en) | 2012-05-02 | 2015-06-09 | Eastman Kodak Company | Use of fluorescing toners for imaging |
| US8755699B2 (en) | 2012-07-31 | 2014-06-17 | Eastman Kodak Company | Noise reduction in toner prints |
| US8760719B2 (en) | 2012-07-31 | 2014-06-24 | Eastman Kodak Company | Printing system with observable noise-reduction using fluorescent toner |
| US8749845B2 (en) | 2012-07-31 | 2014-06-10 | Eastman Kodak Company | System for determining efficient combinations of toner colors to form prints with enhanced gamut |
| US8805217B2 (en) | 2012-07-31 | 2014-08-12 | Eastman Kodak Company | Toner printing with increased gamut |
| US8916240B2 (en) | 2012-11-28 | 2014-12-23 | Eastman Kodak Company | Porous organic polymeric films and preparation |
| US9259953B2 (en) | 2013-09-27 | 2016-02-16 | Eastman Kodak Company | Tactile images having coefficient of friction differences |
| US9176405B2 (en) | 2013-10-18 | 2015-11-03 | Eastman Kodak Company | Polymeric composite materials, manufacture, and uses |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US603903A (en) * | 1898-05-10 | Shade-roller | ||
| DE82774C (en) * | ||||
| US2497246A (en) * | 1946-04-02 | 1950-02-14 | Gen Aniline & Film Corp | Azo dyes |
| US3077042A (en) * | 1961-08-16 | 1963-02-12 | William L Jasper | Trenching machine bucket cleaner |
| CA1096222A (en) * | 1976-06-01 | 1981-02-24 | Domenic Santilli | Electrographic liquid developers containing azo dye marking particles derived from 2,3-naphthalenediol or derivatives thereof |
| FR2353599A1 (en) * | 1976-06-01 | 1977-12-30 | Eastman Kodak Co | AZOIC DYES AND LIQUID ELECTROGRAPHIC DEVELOPER CONTAINING MARKING PARTICLES CONTAINING THEM |
| US4047944A (en) * | 1976-06-01 | 1977-09-13 | Eastman Kodak Company | Electrophoretic migration imaging process with neutral density bisazo pigments |
| US4247459A (en) * | 1979-07-10 | 1981-01-27 | Eastman Kodak Company | Azo dye derivatives of 2,3-naphthalenediols |
-
1981
- 1981-05-18 US US06/264,312 patent/US4414152A/en not_active Expired - Lifetime
- 1981-12-04 CA CA000391577A patent/CA1166631A/en not_active Expired
-
1982
- 1982-05-18 JP JP57082529A patent/JPS57195157A/en active Granted
- 1982-05-18 GB GB08214481A patent/GB2104910B/en not_active Expired
- 1982-05-18 DE DE3218758A patent/DE3218758A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3218758C2 (en) | 1990-03-29 |
| US4414152A (en) | 1983-11-08 |
| JPH0316391B2 (en) | 1991-03-05 |
| DE3218758A1 (en) | 1983-02-17 |
| GB2104910A (en) | 1983-03-16 |
| JPS57195157A (en) | 1982-11-30 |
| GB2104910B (en) | 1984-10-10 |
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