Modified Dye for Water-Fast Ink-Jet Printing

Journal of Dong Hua University (Eng. Ed.) Vol. 18 No.4(2001) 49Modified Dye for Water-Fast Ink.Jet PrintingZheng Qingkang (郑庆康) , Zhu Puxin (朱谱新) , Wu Dacheng (吴大诚)Tearlle Cllege, Sicdeun Cnchersity, Chorgiu 60065, GuinaLewis DM.Dpartment of Color Chendstry, The Unhenaily of Leed, L829JT. UKA quatenuary ammnonium compound containing aninoIn this pper moditied dyes were prepred to impove theacid residue was ynthesized by Converting 3-chloro-2water fasmes of prinings. The resuls showed that the moifiedbyoroxr-ropallyldietntylasaimoniuonn chlorides into isdyes档a BDovel walrfas dye for inkjet pinting gave piningnsepaxide derivatives, then attaching an amino acid to theexcelleat water fastness.epode derivatives synthesized a quatenary amoniumcompound containing ammino acid residue. Modificed dyesExperimentalwere prepared by the ionotropy of anionic dyes with thequaternary armonium compound containing amino acidCenicalsresidue. It was discovered that the modlified dyes3-bcho-o-y-ryp.-vpllylmetylammoriuimn chloridecxhibited四excellent pH contollable solubility. These40% ( Dgussa). sodum hydroxide ( Aldrich)，sodiumndified dyes have good water solubility at pH> 8.0, butdicartonxide (Aldrich), cyseine 98% (Adrich), lysine 98%they were water insoluble at pH < 6.5. On the printing(Aldrich)。serine 98% ( Aldrich) was lbooatory reagents.paper, modified dyes in water-based ink-jet print inkConmercial dyes Onnge I , Carbolan Violet B, Acid Black 172,could convert to water insoluble form and give printsProcion Ble MX-R, Procion Orange MX-2R, Procion Red MX.excellent water fastness.5B were used wibout any furtber purification.Keyuords: Mficaton, Dye, PriningDyesuff prepralionAqecous solutio of sodium hydroxide was slowly sdd toapueous solutin of 3-chloro-2 hyrowpplakylineIntroductionthylarmonim chlorides under siring aul oom temperature. Ahersixty mieules, the pH value of the mixture was adjusted to pH6.5Mainly for technique but also for sufety and environmentand the sal produced was flered off to get he epoxtide deivativeeasonas, it is urully口choose thal he commerciul inks for ixkjtof3- chloro - 2 - hydruxyl - popalylietdylarniuonprinlers ane water-based and the colorants used ane water- solublechloride.dyes. These high waiter- souble and chrom dyes could produceThe counpound cosaining anino acid residhts was dsaivu instong vibant pintings and display he good pebity.isilled water and the pH of the solution was djusted to pH8.5.However, their madn deficlency versus oher main ffice inagingThe soluion of he comupound Was dripped into the suring aqueoustechniques such蹈pholocopier and lser printer is is poor watersoludion of the epoxide derdvalive produced above. The reactionfastness.took about4 hours under the pH 8.5 a room lempenture. At theWater fastuess is one of the most important properies forend of reation, the p斑of the product was djusted to pH 6.0.printings genenated by uwsing any kind of prining technique. TheThen th product Was coneentraled on a rotary eyaporalor 减50Cdevelopment of wer-fast dyes for inkjt prining has beento get a solid mixtune. The solid mixture was disolved iatnicting a lot of utention from many researchers for a long time.methanol and the nethnol soluion of the solid mixure WaFor erunple, a range of dyes for iakxjet pinting based on 2-[7-filered. The fltered methanol soluion was ewapocaited on a roary(2-ulpbo pheny 800 )-hydroxy-3, 6-disulpho nphtyl amino]-evaporator 其30七1 obuain a quatcmary anmoiun derivaivetriazine unis are descnibedDl. Recenly, relaively water-fat dyescontaining amino acid residue.have been proposed, wWecrein a di-sulpkouscid groups was dsss'd in dsiledphthalocyanine hromophore is sustiuted with中国煤化工- solulia of the qualcmary annoniunpipenizinyl group via an lkylene slfomunid! ncid esidoe was slowly dripped iatnHowever, no existing dyes for wailer-based ina.jet iMHC N M H Gg The Hotl mitre solinwifast to an adequste degree. Therefore, many new ppoucnes D8qjuslbd 10 ube pount at wuch the dye precipitaued ou. The productimpove the water fasiness of pinting ingges are repotied everyof modied dye was ollected by flrntion and washed thoroughlyyear.(3-8]with disiled water to remove any excess quatemary anmoniunSppotod ly the Nationl Inomtin Fund 00C 2021512031locivnd Ag. 23.200050Jounal of Dong Hua University (Eng. Ed.) Vol. 18 No .4 (2001)derivative containing anino add resldue.quatemary momonbum derivative containing amino scid residue.AnalysThe quatemary ammonium derivadive containing anino aucid residue3alr2-gryryolplalayeltyoim thloridewitha lauger mes/charge mtio showed a longer migyation tineand这derivatives were analysis by capllay elccropboresis wsing(13.5 minues) as indcaned s the peak 2 in Figurt 4.he Dionex Systen 1. The cpillary ecrptporesiss coditiosos wereh is shown in Fig.5 that the spetrum of 3-chlo-2- hydraxy-鹤fllows:papyllaylie/thy omorium chlonide exhibits 4 strongBuffer sytem: 10 mo Clidine pH 4.2 (being justed viabsarpin peak at 691 em-', which confms he presence of C-the aditian of sufurie acid) Constan vlage: 15 kVCI bond within the molecule. Adition of sodium hydroxide to theAvenage cunent: 20以3-chloro-2-bdroxy- pulylui thylanmonium chlonde solut.Injection method: Gnvity 40 mm for 8 secondsion results in the foumatioa of epoxy group within the molecule andIndircet Uv dicator; Indirel dication at 254 mthe rnove of the c-a bond. The spectrum in Fg.6 shows anCapillary; 60 cm fused slica capilay with intemal diamneterabsopdon peak at 1 267 cm" I which indicates the presence of theof75所epoxy groop.Samples of the oniginal dye, inemeeatrs and the fimalqualemary ammonium derivatives wene characterized using the0.03Perkin-Elmer system 2000 NR FT-Raman and Peurkin-BImer0.02syste1700 FIR spcrometers.Evaluation of water Fastness0.01Ink Fomuluion0.00Dye 2% - 3%，Teithanolaunine 1%， polyviny alcbol(M= 0000)) 2%-00--1------- 207 r一tineminnDietylengyol 5%De inisei water 90%Firs，it is tD make sevetal dops of he tested inis on omalFgue2 Eectrophorogpaom for the eporxide drivaive of 3.choro- 2-hydroxy- prolaylylnelpalalmmoniuomnmoficeA4 paper. Then, he spots of air-dried drops were nubedcoidewitha wet finger to evaluate the rubbing resistance and washedwith dilld water to evalute the washing resistance.0.001Results and Discussion0.0030.002The peak 1 and2 in Figure 1 represeat the mignation peaks of山00sdiumn aud 3-lor-ydroxr-rpalkylioethylahmooiomn-.001chloride sparately. As showed as peak2 in Figure 1 and Figure-00022, the epoxidie derivative of the quatemary ammociuom compoundtime/min)obtained by epixidizing reaction exhibis a shorter mignation timne(9. 88minues) han tht of 3-chloro 2-yroxyopayFigue3 Elactrophonoguam for the amino aidmlylamooiom choride, because the expoxide derivative has amv;smaller mass/change racion thon 3-chlo-2-hydroxy palylmetylumonium chlonde.2lSince there is not ary cationic goup in the amio acidmnoleule under the test condition, n0 arlio acid migration peako1|can be dictated in Figure 3 except a sodium mignation peak.mwyD15 20~ imcminl.02|子phorogran for qustenary amnoium中国煤化工ecoalsnarst00DYHCNMHGetino acid with the epoxide derivative of thezuted in the formetion of the quatemary5202mmooion derivafive containing anino acid residue. The strongFguro 1 Flactuopbonogpum t J-doo-2-lydoxy)peak a2 554 cm° 'of absorpion band in Fg.7 stows the presenceprllineteylummonium chioideof- -SH group wihin amino acid molecule. After reacion, theThe reaction of the anino acid with th epoxide derivaive ofpeakst2554 cmn-1 in Figure 8 dispearsp und a new uborptiohe quitemuary ammonlun compound reults in the outcome of apeak appears al 500 cm~ "，which confimms the renove of-一-SH,group and the formution of S- C bond within the molecule. TheJounal of Dong Hua Universiy(Eng. Ed.) Vol. 18 No.4200) 51CHNTIcr RN+ CH,CHCIHCI + NaOH20-30CCH OH200.5Mar RN CILCHCH +NaCo16002000 1400800200 an"R: CHy- ,CgHg- - .CaHo- - .CgHr-Fgae 5 FT-Buma spungun for 3-dlao2.Scteme 1. Conrvension of quatemary amnociom to islydauaylpaybylduetylarencniumeparide derivadive.hlcidear RN aHQt ;% +Hx∈CH子L-20-0,622ChHu8Cr RN+ CH,CHCH2X(CH+山800 200cn"*助:1-4X:-0-，1m ,-8-Fgure6 FT.Ranan secuogan for 咖qouidlederivaive of 3 cho-2-lydoxpepyalkyCOOHMimethylummoaium choideL: -CHNH,O 。abarptio peaks 2923 m-1 and 149cm"' in Fg.8 mCoossignod to te quatemary anoniun grop.CH -C009T%u80Sthene 2. Reacio of te epoides derivaive wilh凹snino50addOnce the soluobon of quatemary urmoriom derivotive40contairing umnino scid resiue was stowly dippod ino a dyeoluion and the pH of the mixture soluticn was ajusted 4 pH<7.0, the dye peipiuied out since咖qutcmary arnoium sah20001400800 400cm'bloclad or "io-pined" the aulpbonle acid goups of he dge adFgn7 FTR spocuagrenfx t unino soidthe umiso scid residue in the quacmary derivadive modecule pickeduprouon to change into a nournl fomor团iner sal apH<7.0.Corpred wih the spectrum of orfginal aeid dye Onnge IFgue9, he specinm o the modifel scid dbe Onng. I in80-Figure 10 editst atotbunce pabs a2923 cm-' ad I 499 an-'70-. atemary sonoriurn group. while he中国煤化工1391 n iniate tie peme_he "ion-pired' 'dye molecule .4000”MHCNMHGieddeissowed血sherxe3Fgur 8 FTR spectagam for the quatemarysmmorium dertvatve couining sninoD- SO.Na + cr RN* CH.CHCHX(CH),CH盟28.audd residueH OHNIEThe eatbon mechaniors we sggsted in b flowinshenes.52Journal of Dong Hua University (Eng. Ed.) Vol. 18 No.4 (2001)Table1 pH Churecterisics of Modihed Dyes灯T，70pH of Modfied Dye Sobuple pH明fModtifed DyesPrcipitating OuModid Dyes60 "50-OnageI6.548.050-Cartbclun Videt B6.768.030.Acid Bhack 1726.733.5125Podion Blae MXR400020001400800 400cm"Pocion Onnge MX-2R6.757.05Figut9 FTR spctrogamn foer adid p orange IProcion Rad MOX-SB6.77.0Table2 Waer Fastntes of Moifed Dyes und he Originl Dyesom paper7URutbingWating reitance"60-Moditiod DysRestunce' snde40Oege 132.5-+-Carbolant Violet B2000 I 400800 400cm"'Acid Blick 172Fgue I0 FTR spatogzam for the modiad seldPhocon Blue MOX-R妮Onaye IPocon Orange MX-2RPocion Rad MX-SB3D-SOJN+ (CH)2CHCHCH2X(CH).CH2.0