CA2111723A1 - Water-resistant ink formulation - Google Patents
Water-resistant ink formulationInfo
- Publication number
- CA2111723A1 CA2111723A1 CA002111723A CA2111723A CA2111723A1 CA 2111723 A1 CA2111723 A1 CA 2111723A1 CA 002111723 A CA002111723 A CA 002111723A CA 2111723 A CA2111723 A CA 2111723A CA 2111723 A1 CA2111723 A1 CA 2111723A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- water
- ink formulation
- fatty alcohol
- ink
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Abstract
ABSTRACT:
Water-resistant ink formulation Ink formulations consisting essentially of a) at least one water-soluble dye, b) at least one fatty alcohol polyglycol ether, oxo fatty alcohol polyglycol ether, alkyl polyglycol ether or ethylene oxide-propylene oxide block polymer or a mixture thereof, and c) water, with or without d) further, customary additives, are suitable for dyeing or printing paper with water-soluble dyes, including reactive dyes, using the ink-jet process or some other minimal add-on spraying technique, producing brilliant and water-resistant prints.
Water-resistant ink formulation Ink formulations consisting essentially of a) at least one water-soluble dye, b) at least one fatty alcohol polyglycol ether, oxo fatty alcohol polyglycol ether, alkyl polyglycol ether or ethylene oxide-propylene oxide block polymer or a mixture thereof, and c) water, with or without d) further, customary additives, are suitable for dyeing or printing paper with water-soluble dyes, including reactive dyes, using the ink-jet process or some other minimal add-on spraying technique, producing brilliant and water-resistant prints.
Description
'J~ ' .Q f ~
HOECHST ARTIENGESE~SCHAFT ~OE 92/F 417 Dr.~U
DESCRIPTION
Water-resi~tant ink formulation The ink;et printing process i8 the only one of the non-contact printing proceeees which makee it possible to produce colored imagos rapidly, guietly and in high re~olution. The procoss is usually carried out with aqueou~ lnk~, which are sprayed as small droplets directly on to the substrate. Thore is a continuous form of the proces~, in which the ~nk i~ pressed at a unlform rate through a nozzle and the ~et is directed on to the paper, or into an ink collector, by an eloctrlc fisld depending on the pattorn to be printod, and there is an interrupted ink~et or drop-on-demand process, in which the ink iB expulsed only where a colored dot le to appoar, the latter form of the proce~s employlng a piezoelectric cryetal or a heated hollow needle (bubble or thermal ~et procese) to exert pressure on the ~nk eyetem and 80 e~ect an ink droplot. Thoee techniques are described in Text. Chem. Color 19(8), 23-29 and 21 (6), 27-32.
It iB aleo known that by adding thickeners, for examplo glycerole, or other organ$c aide it ie poeeible to influence the pr~nting specification of wat-r-~olublo anionic dyes on paper (cf. tho Japano~e patent application publicatione sho-62-39665, he~-1-103482 and hei-2-36278 and aleous-~-5,196,0s7. Furthermore, sho-63-260477 discloeee coatings of special papere which are ~aid to enhance the print guality of moet aqueous inke.
Non- of the cited referencee, however, provides a eolutlon to the problem of the water faetness of paper printed with water-eoluble dyee. Colored ink~et prints in particular have hitherto had the disadvantage of a remarkably poor water faetness.
7~ i It i8 an object of the pre~ent invent~on to ~ake available a formulation of wator-~olublo, preforably anionic, dye~ which produces print~ of high water fastnes~ and water droplot fa~tne~s on paper by the ink~et proco~ or ~omo othor minimal add-on spray~ng technique. `~
It has been found that this ob~ect i8 surprlsingly achieved by adding a commercially availablo wallpaper stripper to the water-solublo dye.
Commercially available wallpaper strippers are mixturo0 which essentially contain one or more compounds from the group of the fatty alcohol polyglycol ethors, oxo fatty alcohol polyglycol ether~, alkyl polyglycol ethers and ethyleno oxide-propylene oxido block polymors and, a~ a diluent, a C1-C~-alcohol, u~ually i~opropanol.
The present invention accordingly provldos an lnk formulation consisting essentlally of a) at least one water-soluble dye, b) at least one fatty alcohol polyglyool ether, oxo fatty alcohol polyglycol ether, al~yl polyglycol ether or ethylene oxlde-propylene oxlde block polymer or a mixture thereof, and c) water, with or wlthout d) further, customary additlves.
a) Suitable for the in~ formulation of the iuventlon i~
any wator-soluble, preferably anionic, dye, which preferably contain~ one or more sulfo and/or carboxyl groups and may oontain fiber-reactive groups. The dyes in questlon can belong not only to the class of the flber-reactlve dyes but also to the class of the azolc dyes,the class of the dlrect dye~, the class of the vat dyes or the class of the acld dyes, which can be for example azo dyee, copper complex, cobalt complex or chromium complex azo dyes, copper phthalocyanine or nic~el ~-` -phthalocyanine dye~, anthraguinone, copper formazan or 2 ~ h ~, r~ 2 3 triphendioxazine dyee. These dyes have boen de0crlbed in the literature in large numbere and are ln evory reepect conversant to the pereon ekilled in the art.
of the abovementioned dyee usable for the ink formulation of the invention, the fiber-reactive dyoe are u~ed with preference. Fiber-reactive dyee aro organic dyee which contain 1, 2, 3 or 4 fiber-reactive radicals of the aliphatic, aromatic or heterocyclic eerioe. Thee~ dyoe are doscribed in the litoraturo ln large nu~bsre. They can belong to a wide range of dye claeese, for exampl~
the claee of the monoazo, dieazo, polyazo and metal complex azo dyee, such ae 1:1 copper, 1:2 chromium and 1:2 cobalt complex monoazo and dieazo dyee, and alao the eerise of the anthraguinons dyse, copper and cobalt phthalocyanine dyse, coppor formazan dyee, azomsthino, n$troaryl, dioxazine, triph ndioxazine, phenazine and etilbene dyee. Fibsr-roactive dyee are dy-e with a "fiber-reactive" group, i.e. a group capabls of reacting with the hydroxyl groupe of tho cslluloeo to form a covalent chsmical bond. The fiber-roactivo radical can be bondod to the dyo radical diroctly or via a bridgs msmbor; it is preferably bondod to the dyo radical diroctly or via a poeeibly monoalkylated amino group, for exa~plo a group of the formula -NH-, -N(CH3)-, -N(C,H5)-or -N(C3H7)-, or via an aliphatic radical, euch ae methylono, othylono, propylono or an alkylone radical of 2 to 8 carbon atome which ie intorrupted by one or two oxy and/or amino groupe, or via an amino-containing bridge msmber, for example v$a a phsnylamino group.
Fiber-reactive radicale are for oxampls: vinyleulfonyl, ~-chloroothyleulfonyl, p-eulfato~thylsulfonyl, ~-acotoxyothyleulfonyl, ~-phosphatoothyleulfonyl, p-thioeulfatoothyleulfonyl, N-mothyl-N-(p-eulfatoothyl-eulfonyl)amino, acryloyl, -CO-CCl.CH2, -CO-CH.CH-Cl, -CO-CCl.CHCl, -CO-CCl.CH-CH3, -CO-CBr.CH2, -CO-CH.CH-Br, -CO-CBr.CH-CH3, -CO-CCl.CH-COOH, -CO-CH.CCl-COOH, -CO-CBr-CH-COOH, -CO-CH.CBr-COOH, -CO-CCl.CCl-COO~, -C0-CBr=CBr-C00~, ~-ehloro- or ~-bromo-proplonyl, 3-phenyl~ulfonylpropionyl, 3-mothyl~ulfonylpropionyl, 3-chloro-3-phenyl 8ul fonylpropionyl, 2,3-diehloro-propionyl, a, 3-dibromopropionyl, 2-fluoro-2-ehloro-3,3-difluorocyclobutane-2-carbonyl, 2,2,3,3-tetrafluoro-cyclobutane-1-carbonyl or -l-~ulfonyl, ~-(2,2,3,3-tetr~-fluorocyclobut-l-yl)acryloyl, a- or ~-mothyleulfonyl-acryloyl, propiolyl, ohloroacotyl, bromo~eotyl, 4-(~-chloroethyl~ulfonyl)butyryl, 4-vinyl~ulfonylbutyryl, 5-(~-chloroethyl~ulfonyl)valeryl, 5-vinylnulfonylvaleryl, 6-(~-ehloroethyl~ulfonyl)caproyl, 6-vinyl~ulfonylc~pro~l, 4-fluoro-3-nitrobenzoyl, 4-fluoro-3-nitrophenyl~ulfonyl, 4-fluoro-3-mothyl~ulfonylbenzoyl, 4-fluoro-3-cyano-benzoyl, 2-fluoro-5-methylsulfonylbenzoyl, 2,4-dichloro-triazin-6-yl, 2,4-dichloropyrimidin-6-yl, 2,4,5-tri-chloropyrimidin-6-yl, 2,4-dichloro-5-nitro- or -5-methyl-or -5-carboxymethyl- or -5-earboxy- or -5-cy~no- or -5-vinyl- or -5-~ulfo- or -5-mono-, -di- or -triehloro-mothyl- or -5-methyl~ulfonyl-pyrimidin-6-yl, 2,5-di-chloro-4-methyl0ulfonylpyrimidin-6-yl, 2-fluoro-4-pyri-midinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimi-dinyl,2,6-difluoro-5-methyl-4-pyrimidinyl,2,5-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-m-thyl-6-ehloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-ehloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-eyano-4-pyri-mldinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-tri-fluoro-4-pyrimidinyl, 5-ehloro-6-ehloromethyl-2-fluoro-4-pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimldlnyl, 2-fluoro-5-bromo-6-ehloromethyl-4-pyrimidinyl, 2,6-d$-fluoro-5-ehloromothyl-4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-ehloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-ehloro-4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromothyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-n$tro-4-pyrimidinyl, 2-fluoro-5-trifluoromothyl-4-pyrimidinyl, 2-fluoro-5-ph-nyl- or -5-methyl~ulfonyl-4-pyrimidinyl, 2-~luoro-5-c~rbox~mido-4-pyriDldinyl, ? ~i'?
2 ~
2-fluoro-5-carbom~tho~ 4-pyrimidlnyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl, 2-fluoro-6-carboxamido-4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl, 2-fluoro-6-cyano-5 4-pyrimidinyl, 2, 6-difluoro-5-msthylsulfonyl-4-pyrimidinyl, 2-fluoro-5-~ulfonamido-4-pyrimidlnyl, 2-fluoro-5-chloro-6-carbomothoxy-4-pyrimldinyl, 2,6-difluoro-5-trifluoromothyl-4-pyrlmidlnyl, 2,4-bi~-(methylEIulfonyl)pyrimidln-4-yl, 2,5-bis(mothylaulfonyl)-10 5-chloropyrimidin-4-yl, 2-methyl~ulfonylpyrimidin-4-yl, 2-phenyl~ulfonylpyrimidin-4-yl, 2-methylculfonyl-5-chloro-6-mothylpyrimidin-4-yl, 2-methyl~ulfonyl-5-bromo-6-mothylpyrimidin-4-yl, 2-methyl~ulfonyl-5-chloro-6-ethylpyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-methylpyrimidin-4-yl, 2-mothyl~ulfonyl-5-nitro-6-methylpyri mi din-4-yl, 2,5,6-tri~mothyl~ulfonyl-pyrimidin-4-yl, 2-mothyl~ulfonyl-5,6-dimethylpyrlmldin-4-yl, 2-ethyl~ulfonyl-5-chloro-6-methylpyrimidin-4-yl, 2-methyl~ulfonyl-6-chloropyrim din-4-yl, 2,6-bl~(methyl-aulfonyl)-5-chloropyrimidin-4-yl, 2-methyleulfonyl-6-carboxypyrimidin-4-yl, 2-methyl~ulfonyl-5-sulfopyri-midin-4-yl, 2-methyl~ulfonyl-6-carbomethoxypyrimidln-4-yl, 2-methyl~ulfonyl-5-carboxypyrimidin-4-yl, 2-mothyl-~ulfonyl-5-cyano-6-methoxypyrimidin-4-yl, 2-methylcul-fonyl-5-chloropyrimidln-4-yl, 2-sulfoethylculfonyl-6-methylpyrimidin-4-yl, 2-methyl~ulfonyl-5-bro~opyriml-d$n-4-yl, 2-phenyl~ulfonyl-S-chloropyrimidln-4-yl, 2-carboxymethylculfonyl-5-chloro-6-methylpyrimidin-4-yl, 2,4-dichloropyrimidine-6-carbonyl or -6-culfonyl, 2,4-di-chloropyrimidine-5-carbonyl or -5-sulfonyl, 2-chloro-4-methylpyrimidino-5-carbonyl, 2-methyl-4-chloropyri-midine-5-carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine-5-carbonyl, 2,4,6-trichloropyrimidine-5-carbonyl, 2,4-dichloropyr~
dine-5-~ulfonyl, 2,4-dichloro-6-methylpyrimidine-5-car-bonyl or -5-~ulfonyl, 2-methyl~ulfonyl-6-chloropyrimldin-4-yland-5-carbonyl, 2,6-bi~(mothylsulfonyl)pyrimidin-4-or -5-carbonyl, 2-ethyl~ulforlyl-6-chloropyrimidine-5-carbonyl, 2,4-bis(mothyl~ulfonyl)pyrimidine-5-~ulfonyl, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-Eulfonyl or -5-carbonyl, 2-chloroqulnoxaline-3-carbonyl, 2- or 3-monochlorogu$noxaline-6-carbonyl, 2- or 3-monochloro-quinoxaline-6-oulfonyl, 2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloroquinoxaline-5- or -6-sulfonyl, 1,4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-~ulfonyl or -carbonyl, 2,4,6-trichloroqu$nazolins-7- or -8-sulfonyl, 2- or 3- or 4-(4',5'-dichloropyridaz-6~-on-1'-yl)phenylsulfonyl or -carbonyl, ~-(4',5'-dichloropyridaz-6'-on-1'-yl)pro-pionyl, 3,6-dichloropyrldazine-4-carbonyl or -4-sulfonyl, 2-chlorobenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-aryl~ulfonyl- or 2-alkylsulfonylbenzo-thiazole-5- or -6-carbonyl or -5- or -6- 8ul fonyl, such a8 2-methylsulfonyl or 2-ethylsulfonylbenzothiazole-5- or -6-sulfonyl or -carbonyl, 2-phenylsulfonylhenzo-thiazole-5- or -6-sulfonyl or -carbonyl and the corre~-ponding 2-sulfonylbenzothiazole-5- or -6-carbonyl- or -~ulfonyl derivatives with eulfo groups in the fused-on benzene ring, 2-chlorobenzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chlorobenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-l-methylbenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-4-mothylthiazole(1,3)-5-carbonyl or -4- or -5-~ulfonyl, a~monium-containing triazine rings, ~uch as 2-trimethyla~monium-4-phenyl-amino- and -4-(o, m- or p-~ulfophenyl)amino-6-triazinyl, 2-(1,1-dimethylhydrazinium)-4-phenyla~ino- and -4-(o-, m-or p-Rulfophenyl)amino-6-triazinyl, 2-(2-i~opropylidene-1,1-dimethyl)hydrazinium-4-phenylamino- and -4-(o-, m- or p-sulfophenyl)amino-6-triazinyl, 2-N-aminopyrrolidinium-, 2-N-aminopiperidinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)~mino-6-triazinyl, 4-phenylamino- or 4-(~ulfophenylamino)-6-triazinyl which contain~ 1,4-bie-azabicyclol2.2.2] octane or 1,2-bisazabicyclo[0.3.3]
~. . .
octane bonded in quaternary fashion in the 2-position via a nitrog~n bond, 2-pyridinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl) amino-6-triazinyl and corresponding 2-onium-6-triazinyl radicals which aro substituted in the 4-poeit$on by alkylamino, 6uch as methylamino, ethyl~m~no :: : :: :~
2 ~ ~ ~ 7 ~ 3 or ~-hydroxyethylamino, or alkoxy, ~uch a~ methoxy or ethoxy, or aryloxy, auch as phenoxy or sulfophenoxy b) Useful fatty alcohol polyglycol ethor~ aro thoao whlch are derlved from a fatty alcohol unlt having 8 to 30, preferably 12 to 18, ln partlcular 14 to 16, carbon atoms, for example octyl, pslargonyl, capryl, undecyl, dodocyl, tridocyl, myristyl, pentadecyl, palmltyl, heptadecyl, atoaryl and oloyl alcohol, ln partlcular also those fatty alcohols derived from natural product~ ~uch as coconut oil fatty acid, tallow fatty acld, tall oil fatty acid, palm oil fatty acld, linseed oll fatty acid, castor oil fatty acid and rizinonic acid The polyglycol ether unlt~ are preparable for example by condensation of ethylene oxide with the fatty alcohols mentioned and advantagoously consist of 2 to 50, preferably 2 to 20, ln particular 5 to 15, ethylene oxide unitc ~ ;
Oxo fatty alcohol polyglycol others are fatty alcohol 20 polyglycol other~ ac mentionod abovo which carry a froe -hydroxyl group on a carbon atom of the fatty acid chain or contaln a carbonyl group Uceful polyal~yl glycol etherc are C,-C30-al~yl, proferably Cl~-Cl,-al~yl, ln partlcular Cl~-Cl,-al~yl, polyglycol othorc ha~ing 2 to 50, proforably 2 to 20, in particular 5 to 15, ethylone oxide unitc, for oxamplo the i~
reaction product of 1 1 of iaotridecyl alcohol wlth 7 to 9 mol of othyl-ne oxide Ucoful thylon oxido-propylono oxido bloc~ polymorc aro those ~ ich contain 10 to 80 % by mole, preferably 10 to 40 ~ by mole, ethylene oxide and 90 to 20 % by mole, preferably 90 to 60 %
by mole, proQylene oxide. The blodk polymers should advantagecusly gi~o cloar colutiona ln wator ln tho concentratlon range uced according to tho invontlon Tho HLB (hydrophilic-lipophilic balanco) value of the-e bloc~ polymerc ic ( 2 3 greater than 2, preferably greater t~an 4. Partlcular preference is given to block polymers having an HLB ~alue between 8 and 15.
Al~o of partieular intere~t are mixture~ of one or more of the aforementioned (oxo)Eatty alcohol polyglycol ethers, alkyl polyglycol ethers and/or ethylene oxide-propylene oxide bloc~ polymer~.
d) The dye ~olutions may con ~in aids which are customarily present in ink~ for ink~et printers, for example antiaggregants, ~uch as N-methylpyrrolldone, dimethylformamide and dimethylacotamide, wettlng agonts, such ae ionic or nonlonic ~urfactant~, triethanolamine as buffer, and glycols such as diethylene glycol as viscosity controllers. -When the commercially available wallpaper ctripper used contains one or more of the compound~ mentioned ln b), the ink formulation of the lnvention will contain the diluent, too. This diluent, u~ually isopropanol, has no advantageou~ effect within the meaning of the pr~sent -~
invention, but it does not have an adverse effect either, provided its level in tho ink formulation does not exceod 10% by weight.
. . . -. , Preference for the purpo~es of the pre~ent invention is given to an ink formulation containing 25 3 to 10% by weight, preferably 4 to 6% by weight, of component a), 1 to 10% by weight, preferably 2 to 5% by weight, of component b), 94 to 77% by weight, preferably 92 to 86% by weight, of component c), and 0 to 5% by weight, preferably 2 to 3% by weight, of component d) with the proviso that the percentages of tho components a) to d) add up to 100% by weight.
The present invention also provides a proces~ for dyeing ;
:
i 2 3 g or printing paper with water-~oluble, preferably anionic, dyoe, in particular reactive dyos~ ueing ~he in~et process or some other cus~y min~E~ add-on spraying tK~ique, which comprisee dyoing or prlnting with an ink formulation according to the invontion.
Proference i8 given to u~ing aqueoue reactivo dye solutions which may contain antiaggregante. For the inkjet procees ~t ~ ad~antagooue to uso domlnoralized roactive dye~ in order that tho lifotimos of the fine nozzlos may be prolongod, but by ink~ot it ie aleo po~siblo to apply dyo proparatione containing up to 50 by woight of electrolyto salt.
The a~ueoue dye solution is admixed with a mixture of the above-doscribod components b) and, if usod, d). Slnce many commorcially avallablo noutral to weakly ba~ic wallpaper strippors contain tho co~pounde mentioned undor component b) ln such a mixing ratio as is ~uitablo for the purposes of the present inventlon, lt le advantageous for roaeons of convenienco to add ~uch a wallpaper strlppor to the aqueous dye solutlon dlroctly. An amount of from 0.5 to 20% by weight, proferably from 3 to 10% by weight, of tho wallpapor strippor, basod on the total weight of tho in~ formulatlon, is advantngeous.
In many casos it le advantagoous for the a~uoous dyo solution first to bo hoatod togethor with componont b) or tho wallpapor stripper and thon to cool down with vigorous stirring in ordor that adoquato mixlng and dieassociation of possible dye conglomerates may be obtained.
~hen the ompty ink cartridgo is charged wlth the lnk formulatlon of the lnvontlon. It le also possiblo to ueo usod in~ cartrldgos aftor thoy have boen rinsod out with wator or somo othor suitable cloaning agont until tho runoff wae colorloss.
In tho caee of multicolor printing, a plurality of ink ~ r rl~ 2 3 cartridgeo can be connected ln eeriee, which are controllable by the preeent-day customary mean~ for the purpo~e of croating the print on the moving ehoet of material. It ie aleo pos~iblo to uee modern multichamber inkjet cartridges, whsreby a plurality of colore can bo applied at tho eame time in a eingle paes.
The preeent invention aleo providee for the U80 of an lnk formulation according to the invention for ink~et printing or for eome other non-contactlng printing proceee with water-soluble dyee on paper. It wae found that the brillianco of the dyoe ueod i8 not impa~red by the $nk formulation and that tho brilliant, etrong printe obtained have very good water faetneee and water droplet faetnese.
The Examplee which follow cerve to illuctrato tho invention. The parte mentioned thorein are parte by weight and the percentages too are by weight, unlees otherwiee etated. Parte by weight relato to parto by volume ae the kilogram relatee to the liter. The water roeistance wae toetod undor running wator.
Examplo 1 Tho com~orcial ink cartridge of a DOD (drop-on-demand~
inkjot printer of the piezoeloctric type i8 cleanod with wator and charged by moane of a eyringo with an ink formulation containing 6S by woight of a rod dye of tho formula ,~3--N O H N H - C 0 HO350H2CH2c025 N~`503H
.. , . . . ~, , . . " - . ~ . . ~ . . . .. . . . .
known from EP-A-158233 (USA-4 581 036 and -4 585 459), 3%
by weight of iootridecyl alcohol otherlfiod with 8 ethylens oxide unito, and 91% by welght of water. Ths mixture can be heated to speed up oolution. Th~o ink formulation brings about brilliant red printo of excellent water reoiotance.
Example 2 A commercial ink cartridge of a bubble ~nk~st pr~nter of the thermal jet type io cleaned wlth water and charged by means of a syrlnge with an ink formulation containing 6%
by weight of the dye C.I. Roactive Yellow 37 of the formula -S0~H
SO2CH2CH20SO~H
and 3~ by weight of coconut fat alcohol etherified with 8 ethylene oxide un$to, and 91% by weight of water. The mixture can be hoatod to apeod up oolution. This ink formulation bringo about brilliant yollow printo of excollent water reolotance.
Example 3 A commercial ink cartridge of a DOD (drop-on-domand) inkjet printer of the piezoolectric type io cleaned with wator and charged with an ink formulation containing 6%
by weight of a turguoioe dye of the formula ~ . , , . .. ~, . . . . . . . ... .. . . . . . .
~ ~ ~ 1 7 2 3 N
~ (S~NH) ~ SO~CH2CH20SO~H)~
known from Example 2 of DE-A-l 179 317 (US-A-3 268 548), 3% by weight of an othylene oxlde propyleno oxld- block polymer havlng an ethylene oxlde con~ent of 20%, and 91%
by welght of water. The mixture can be hoated to ~peed up solution. This lnk formulatlon bring~ about brilli~nt turquoi~e print0 of excellent water roei~tance.
Examplo 4 A commercial lnk cartridge of a DOD (drop-on-demand) ink~et printer of the thermal type (bubble ~-t) is cleaned w~th water and chargod wlth an ink formulatlon whlch as well as water contalns 6% of a red dye of the formula C l HO3SOH2CH2CO~S ~ N OH N 1 N~1 N ~ SO H
HO~S ~ SO~H
known from EP-A O 094 055 (CA-A-l 221 360), 2% of a mixture of a coconut fat alcohol contalnlng predomlnantly Cl2-C,~ unlts and etherifled wlth 5 to 20 ethylene oxlde unlts, 1% of N-methylpyrrolldone (NMP) and 2% of lsopropyl alcohol. The mlxture can be heated to speed up solutlon. Thi~ ln~ formulatlon brlhgs about brllliant red prlnts of oxcollent wator resi~tance.
~xample 5 A commerclal lnk cartrldge of a DOD (drop-on-demand) 2 ~ ~
ink~et printer of the piozoelectric type Sbub~le ~et) i~
cleaned with water and charged with an ink formulatlon which a~ well a~ water contains 6% of a blue ~ye of formula O N H 2 . ' .
~,SO3H
O HN~ so2cH2cH2oso3H
known as ~ I Roactiv0 Blue 19, 2% of isotridecyl alcohol having an ethylene oxide number of 8, 1% of dimethyl-formamide and 1% of oleyl alcohol having an ethylene oxide number of 6 The mixture can be heated to speed up solution This ink formulation brings about brilliant blue prints of excollent water resistance Examples 6 to 3 6 To prepare further dyeings by the process of the lnvention, paper $~ printed with an ink~et printor, for oxampl- analogously to one of the mothods describod in the above ombodiment examplos, uslng 6% strongth agu~ous solutlons of ono or re of the ~nown dye~ lnd~cated below in the table examplos (the dyos are wrltten ln the form of free acidS howev-r, thoy ar- u~od ln the form of their alXali metal ~alt~) containing 3 to 5% of a commercial wallpaper stripper, for oxample T~3 from ARA-Chemie Clear, strong print~ are obtained in the hue indicated for the resp-ctive table example and with tho good fastn-ss proportle~ of the r-~p-ctlve dye, ln partlcular goodwater fa~tnoso propertl-s ':'~ ":
,,: ' ~;
.., . ~: ., ... ;.
',`'' .'.;'.'",' ~''' ,' '7 ~ 3 : :
_ -. --Ex. calt) Hue l ¦
I . I : -: "' 6 SO~H OH C I SO3H Scarlet II H~ H O, S~LN H--~N~N H ~
C H :s I ;
I '~ ~ ~
(known from C~ Patent 350,390) 1 : ~
. ._. I ::
. 7SO,H OH Scarlet l : :~
C H oJ~ H o3~L ~X~lrxc ~ ¦ : :
I
(known from DE-A-1 813 438, ~x. 1) 8SO~H HO NH-CO ~ X Red ¦
~N = N~ l : ~
h O 3 S~S O 3 H l : ~ - :
3 ~
I '' ' ~ ~' (known from DE-B-1 191 059) ¦
Red ' S O ~ H I I N~k I :
~N = N~ Cl ¦
H O 3 S~S O 3 H I
(k~own from ~olour Index a~ C.I. Reactive Red 11) .
~;~ : . . : : : ~
7 ~ 3 -- I
Ex. salt) ~ue l . . I
O H Red I NH-CO-CH, l ¦ J ~N H C 0~ ~
CHz-OSO~H
(known from DE-B-1 126 647) 11 S 0 3 H N l Yellow ,~N =N ~ NH J~N~J--NH2 HO~jS SO~jH NH-CO-NH2 (known from Colour Index as C.I. Reactive Yellow 152) 12 H O N H 2 Navy ,~N-- N~N-- N ~3L
l C H 2 - O S O , H
CH2-OSO,H
(known from Colour Index a~ C.$. Reactivo ~lack 5) .
. ................... . .
salt) Pue :
13 HO NH~ ~C I Red S 2~ H 0 3~5 0 3 H
(known from JP-B-63-23287) 14 SO3H CH~ Yellow [~ ~N I
SOIH OH CH2-OSO,H :
I
(known from Colour Index a~ C.I. React~ve Yellow 37) ~ -I
SO~H Yellow ~ `
,0--N =N ~N H 2 C H 2 N H - C O - C H, ¦(bnown from ~P-3-0 073 ~B1) `~ t~ 3 _ .
Ex . ~alt) Hue ¦
16 SOsH (~) Blue ¦
H s S N ~ N ~ H
N~ N I H2 ~ 0 5 0 3 H
(known f rom EP-B- O 02 8 7 8 8 ) _ 17 ~ju ~ COOH Black N--N~ \I = N ~Il ~L S 0 3 H ¦
C H 2 - 5 s H ¦
' ~
Blaclc 3 I ) 18 5 o H l S O ~ H Reddi sh ,~ N = N ~ N =N ~N H ~`N~N H~ brown ~
5 0, H ~ -(known from DE-A-2 733 109, Ex. 2) . ~
., :. ::, 3 : ~
- 18 - :
13x. ~alt) ~ue N~ N ~
(known from EP-A- O 228 348) ~ `
2 0 Ni~ ( - ) Blu--¦ RC SJ~ 11~503U ( ~3 S O, - C H, - C H I - O S O
(1~nown from ISP-A-O 144 766) .
BlU~
N~ ~N 1 S O ~ H
` `~ ~ `
(Icnown from l~P-A- O 099 721) : ~
. . ._ .
Ex. Dye u~ed (in the form of an alkali motal Huo I .~ , 2 2 ~ H ~ ( - ) Blue N ~C u~ ~ 5 0 ~ N ~3 H ~ ~
~ C ~ I
~ I '.'.' (known from DE-A-2 342 197, Ex. 2) 23 SO~H Yellow N-N ~ NN-C0 ~ NX
(known from DE-B-l 191 059) ~:
.-24 Cl Yellow ~ N = N--Ç3N H~N~ H~ . ¦
H O 3 S O - C H 2 - c H 2 I ~' ' ' ''"' ~`''~ ' ~
(known from European Patont Appli~ation Publication No. 0 056 975) SO3H N~N S03H Yellow ~[~ N = N ~3N H~`N~N H~ ~ .
HO,S SO3H NH-CO-NH2 (known from Colour Index C.I. Rea~tive Orango 91) -:' ' _ . :
Ex. ~alt) Hue . . .
~0--N NN-CO-CN, I I HZ ) Z Y--llo (7H2)2 HO,SO-CH2-cH2-SOi (known from EP-A-0 457 715) 27 N~N Red S O ~ H H O N H--~`N~N H ~
$~ N= N ~ ~1~2 S O 3 H H O ~ S S O ~, H 7 H
~' '".'' ~ :,' ' ' _ (known from EP-A-0 022 575) 28 cl R~d H O N H l~N~ N H - ( Cl H 2 ) 2 ,~N=N~l~ o 1 2 H 0 ~ S S 0 ~ H ( C H I ) 2 CH2-OSO"H C I -CH2-CH2 ~' ,~', L (known from EP-A-0 144 766, Ex. 5) 7 ~ 3 ~alt) _ ~ ~ :
29 Cl Red I i :
~ J-- ¦ ., ¦ S ~ H0,5~5O~H
CH2-OSO,H ¦
L (known from EP-B-0 094 055) SO,H H0 NH~ NH~ NN~NN OH SO,H Rod HO,S SO,H HO,SJ~ O,H ~
'',~':,' ''~'~.'~ ''-''''"''.' ' ~, (~nown from DE-A-2 001 960 31 HO~S-CN~C Blu~
N~-CN~-CN~-NN ~ O ~ ~ ~ .
CN~ Cl SO~ 2 ~ R CO-CNS_CN~_COON . .
COON c~2 ¦
~nown from US-A-4 629 788) -~
ULing the dyos described in Examples 1 to 31 in multicolor printing, eithor in a ~ingle pae~ or in succession in conjunction with a color separat2on, ma~os ~:
it poesible to produce in this way an infinite number of mixed colore which have the same good application profiles (water reeietance, brilliance).
HOECHST ARTIENGESE~SCHAFT ~OE 92/F 417 Dr.~U
DESCRIPTION
Water-resi~tant ink formulation The ink;et printing process i8 the only one of the non-contact printing proceeees which makee it possible to produce colored imagos rapidly, guietly and in high re~olution. The procoss is usually carried out with aqueou~ lnk~, which are sprayed as small droplets directly on to the substrate. Thore is a continuous form of the proces~, in which the ~nk i~ pressed at a unlform rate through a nozzle and the ~et is directed on to the paper, or into an ink collector, by an eloctrlc fisld depending on the pattorn to be printod, and there is an interrupted ink~et or drop-on-demand process, in which the ink iB expulsed only where a colored dot le to appoar, the latter form of the proce~s employlng a piezoelectric cryetal or a heated hollow needle (bubble or thermal ~et procese) to exert pressure on the ~nk eyetem and 80 e~ect an ink droplot. Thoee techniques are described in Text. Chem. Color 19(8), 23-29 and 21 (6), 27-32.
It iB aleo known that by adding thickeners, for examplo glycerole, or other organ$c aide it ie poeeible to influence the pr~nting specification of wat-r-~olublo anionic dyes on paper (cf. tho Japano~e patent application publicatione sho-62-39665, he~-1-103482 and hei-2-36278 and aleous-~-5,196,0s7. Furthermore, sho-63-260477 discloeee coatings of special papere which are ~aid to enhance the print guality of moet aqueous inke.
Non- of the cited referencee, however, provides a eolutlon to the problem of the water faetness of paper printed with water-eoluble dyee. Colored ink~et prints in particular have hitherto had the disadvantage of a remarkably poor water faetness.
7~ i It i8 an object of the pre~ent invent~on to ~ake available a formulation of wator-~olublo, preforably anionic, dye~ which produces print~ of high water fastnes~ and water droplot fa~tne~s on paper by the ink~et proco~ or ~omo othor minimal add-on spray~ng technique. `~
It has been found that this ob~ect i8 surprlsingly achieved by adding a commercially availablo wallpaper stripper to the water-solublo dye.
Commercially available wallpaper strippers are mixturo0 which essentially contain one or more compounds from the group of the fatty alcohol polyglycol ethors, oxo fatty alcohol polyglycol ether~, alkyl polyglycol ethers and ethyleno oxide-propylene oxido block polymors and, a~ a diluent, a C1-C~-alcohol, u~ually i~opropanol.
The present invention accordingly provldos an lnk formulation consisting essentlally of a) at least one water-soluble dye, b) at least one fatty alcohol polyglyool ether, oxo fatty alcohol polyglycol ether, al~yl polyglycol ether or ethylene oxlde-propylene oxlde block polymer or a mixture thereof, and c) water, with or wlthout d) further, customary additlves.
a) Suitable for the in~ formulation of the iuventlon i~
any wator-soluble, preferably anionic, dye, which preferably contain~ one or more sulfo and/or carboxyl groups and may oontain fiber-reactive groups. The dyes in questlon can belong not only to the class of the flber-reactlve dyes but also to the class of the azolc dyes,the class of the dlrect dye~, the class of the vat dyes or the class of the acld dyes, which can be for example azo dyee, copper complex, cobalt complex or chromium complex azo dyes, copper phthalocyanine or nic~el ~-` -phthalocyanine dye~, anthraguinone, copper formazan or 2 ~ h ~, r~ 2 3 triphendioxazine dyee. These dyes have boen de0crlbed in the literature in large numbere and are ln evory reepect conversant to the pereon ekilled in the art.
of the abovementioned dyee usable for the ink formulation of the invention, the fiber-reactive dyoe are u~ed with preference. Fiber-reactive dyee aro organic dyee which contain 1, 2, 3 or 4 fiber-reactive radicals of the aliphatic, aromatic or heterocyclic eerioe. Thee~ dyoe are doscribed in the litoraturo ln large nu~bsre. They can belong to a wide range of dye claeese, for exampl~
the claee of the monoazo, dieazo, polyazo and metal complex azo dyee, such ae 1:1 copper, 1:2 chromium and 1:2 cobalt complex monoazo and dieazo dyee, and alao the eerise of the anthraguinons dyse, copper and cobalt phthalocyanine dyse, coppor formazan dyee, azomsthino, n$troaryl, dioxazine, triph ndioxazine, phenazine and etilbene dyee. Fibsr-roactive dyee are dy-e with a "fiber-reactive" group, i.e. a group capabls of reacting with the hydroxyl groupe of tho cslluloeo to form a covalent chsmical bond. The fiber-roactivo radical can be bondod to the dyo radical diroctly or via a bridgs msmbor; it is preferably bondod to the dyo radical diroctly or via a poeeibly monoalkylated amino group, for exa~plo a group of the formula -NH-, -N(CH3)-, -N(C,H5)-or -N(C3H7)-, or via an aliphatic radical, euch ae methylono, othylono, propylono or an alkylone radical of 2 to 8 carbon atome which ie intorrupted by one or two oxy and/or amino groupe, or via an amino-containing bridge msmber, for example v$a a phsnylamino group.
Fiber-reactive radicale are for oxampls: vinyleulfonyl, ~-chloroothyleulfonyl, p-eulfato~thylsulfonyl, ~-acotoxyothyleulfonyl, ~-phosphatoothyleulfonyl, p-thioeulfatoothyleulfonyl, N-mothyl-N-(p-eulfatoothyl-eulfonyl)amino, acryloyl, -CO-CCl.CH2, -CO-CH.CH-Cl, -CO-CCl.CHCl, -CO-CCl.CH-CH3, -CO-CBr.CH2, -CO-CH.CH-Br, -CO-CBr.CH-CH3, -CO-CCl.CH-COOH, -CO-CH.CCl-COOH, -CO-CBr-CH-COOH, -CO-CH.CBr-COOH, -CO-CCl.CCl-COO~, -C0-CBr=CBr-C00~, ~-ehloro- or ~-bromo-proplonyl, 3-phenyl~ulfonylpropionyl, 3-mothyl~ulfonylpropionyl, 3-chloro-3-phenyl 8ul fonylpropionyl, 2,3-diehloro-propionyl, a, 3-dibromopropionyl, 2-fluoro-2-ehloro-3,3-difluorocyclobutane-2-carbonyl, 2,2,3,3-tetrafluoro-cyclobutane-1-carbonyl or -l-~ulfonyl, ~-(2,2,3,3-tetr~-fluorocyclobut-l-yl)acryloyl, a- or ~-mothyleulfonyl-acryloyl, propiolyl, ohloroacotyl, bromo~eotyl, 4-(~-chloroethyl~ulfonyl)butyryl, 4-vinyl~ulfonylbutyryl, 5-(~-chloroethyl~ulfonyl)valeryl, 5-vinylnulfonylvaleryl, 6-(~-ehloroethyl~ulfonyl)caproyl, 6-vinyl~ulfonylc~pro~l, 4-fluoro-3-nitrobenzoyl, 4-fluoro-3-nitrophenyl~ulfonyl, 4-fluoro-3-mothyl~ulfonylbenzoyl, 4-fluoro-3-cyano-benzoyl, 2-fluoro-5-methylsulfonylbenzoyl, 2,4-dichloro-triazin-6-yl, 2,4-dichloropyrimidin-6-yl, 2,4,5-tri-chloropyrimidin-6-yl, 2,4-dichloro-5-nitro- or -5-methyl-or -5-carboxymethyl- or -5-earboxy- or -5-cy~no- or -5-vinyl- or -5-~ulfo- or -5-mono-, -di- or -triehloro-mothyl- or -5-methyl~ulfonyl-pyrimidin-6-yl, 2,5-di-chloro-4-methyl0ulfonylpyrimidin-6-yl, 2-fluoro-4-pyri-midinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimi-dinyl,2,6-difluoro-5-methyl-4-pyrimidinyl,2,5-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-m-thyl-6-ehloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-ehloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-eyano-4-pyri-mldinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-tri-fluoro-4-pyrimidinyl, 5-ehloro-6-ehloromethyl-2-fluoro-4-pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimldlnyl, 2-fluoro-5-bromo-6-ehloromethyl-4-pyrimidinyl, 2,6-d$-fluoro-5-ehloromothyl-4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-ehloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-ehloro-4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromothyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-n$tro-4-pyrimidinyl, 2-fluoro-5-trifluoromothyl-4-pyrimidinyl, 2-fluoro-5-ph-nyl- or -5-methyl~ulfonyl-4-pyrimidinyl, 2-~luoro-5-c~rbox~mido-4-pyriDldinyl, ? ~i'?
2 ~
2-fluoro-5-carbom~tho~ 4-pyrimidlnyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl, 2-fluoro-6-carboxamido-4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl, 2-fluoro-6-cyano-5 4-pyrimidinyl, 2, 6-difluoro-5-msthylsulfonyl-4-pyrimidinyl, 2-fluoro-5-~ulfonamido-4-pyrimidlnyl, 2-fluoro-5-chloro-6-carbomothoxy-4-pyrimldinyl, 2,6-difluoro-5-trifluoromothyl-4-pyrlmidlnyl, 2,4-bi~-(methylEIulfonyl)pyrimidln-4-yl, 2,5-bis(mothylaulfonyl)-10 5-chloropyrimidin-4-yl, 2-methyl~ulfonylpyrimidin-4-yl, 2-phenyl~ulfonylpyrimidin-4-yl, 2-methylculfonyl-5-chloro-6-mothylpyrimidin-4-yl, 2-methyl~ulfonyl-5-bromo-6-mothylpyrimidin-4-yl, 2-methyl~ulfonyl-5-chloro-6-ethylpyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-methylpyrimidin-4-yl, 2-mothyl~ulfonyl-5-nitro-6-methylpyri mi din-4-yl, 2,5,6-tri~mothyl~ulfonyl-pyrimidin-4-yl, 2-mothyl~ulfonyl-5,6-dimethylpyrlmldin-4-yl, 2-ethyl~ulfonyl-5-chloro-6-methylpyrimidin-4-yl, 2-methyl~ulfonyl-6-chloropyrim din-4-yl, 2,6-bl~(methyl-aulfonyl)-5-chloropyrimidin-4-yl, 2-methyleulfonyl-6-carboxypyrimidin-4-yl, 2-methyl~ulfonyl-5-sulfopyri-midin-4-yl, 2-methyl~ulfonyl-6-carbomethoxypyrimidln-4-yl, 2-methyl~ulfonyl-5-carboxypyrimidin-4-yl, 2-mothyl-~ulfonyl-5-cyano-6-methoxypyrimidin-4-yl, 2-methylcul-fonyl-5-chloropyrimidln-4-yl, 2-sulfoethylculfonyl-6-methylpyrimidin-4-yl, 2-methyl~ulfonyl-5-bro~opyriml-d$n-4-yl, 2-phenyl~ulfonyl-S-chloropyrimidln-4-yl, 2-carboxymethylculfonyl-5-chloro-6-methylpyrimidin-4-yl, 2,4-dichloropyrimidine-6-carbonyl or -6-culfonyl, 2,4-di-chloropyrimidine-5-carbonyl or -5-sulfonyl, 2-chloro-4-methylpyrimidino-5-carbonyl, 2-methyl-4-chloropyri-midine-5-carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine-5-carbonyl, 2,4,6-trichloropyrimidine-5-carbonyl, 2,4-dichloropyr~
dine-5-~ulfonyl, 2,4-dichloro-6-methylpyrimidine-5-car-bonyl or -5-~ulfonyl, 2-methyl~ulfonyl-6-chloropyrimldin-4-yland-5-carbonyl, 2,6-bi~(mothylsulfonyl)pyrimidin-4-or -5-carbonyl, 2-ethyl~ulforlyl-6-chloropyrimidine-5-carbonyl, 2,4-bis(mothyl~ulfonyl)pyrimidine-5-~ulfonyl, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-Eulfonyl or -5-carbonyl, 2-chloroqulnoxaline-3-carbonyl, 2- or 3-monochlorogu$noxaline-6-carbonyl, 2- or 3-monochloro-quinoxaline-6-oulfonyl, 2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloroquinoxaline-5- or -6-sulfonyl, 1,4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-~ulfonyl or -carbonyl, 2,4,6-trichloroqu$nazolins-7- or -8-sulfonyl, 2- or 3- or 4-(4',5'-dichloropyridaz-6~-on-1'-yl)phenylsulfonyl or -carbonyl, ~-(4',5'-dichloropyridaz-6'-on-1'-yl)pro-pionyl, 3,6-dichloropyrldazine-4-carbonyl or -4-sulfonyl, 2-chlorobenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-aryl~ulfonyl- or 2-alkylsulfonylbenzo-thiazole-5- or -6-carbonyl or -5- or -6- 8ul fonyl, such a8 2-methylsulfonyl or 2-ethylsulfonylbenzothiazole-5- or -6-sulfonyl or -carbonyl, 2-phenylsulfonylhenzo-thiazole-5- or -6-sulfonyl or -carbonyl and the corre~-ponding 2-sulfonylbenzothiazole-5- or -6-carbonyl- or -~ulfonyl derivatives with eulfo groups in the fused-on benzene ring, 2-chlorobenzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chlorobenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-l-methylbenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-4-mothylthiazole(1,3)-5-carbonyl or -4- or -5-~ulfonyl, a~monium-containing triazine rings, ~uch as 2-trimethyla~monium-4-phenyl-amino- and -4-(o, m- or p-~ulfophenyl)amino-6-triazinyl, 2-(1,1-dimethylhydrazinium)-4-phenyla~ino- and -4-(o-, m-or p-Rulfophenyl)amino-6-triazinyl, 2-(2-i~opropylidene-1,1-dimethyl)hydrazinium-4-phenylamino- and -4-(o-, m- or p-sulfophenyl)amino-6-triazinyl, 2-N-aminopyrrolidinium-, 2-N-aminopiperidinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)~mino-6-triazinyl, 4-phenylamino- or 4-(~ulfophenylamino)-6-triazinyl which contain~ 1,4-bie-azabicyclol2.2.2] octane or 1,2-bisazabicyclo[0.3.3]
~. . .
octane bonded in quaternary fashion in the 2-position via a nitrog~n bond, 2-pyridinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl) amino-6-triazinyl and corresponding 2-onium-6-triazinyl radicals which aro substituted in the 4-poeit$on by alkylamino, 6uch as methylamino, ethyl~m~no :: : :: :~
2 ~ ~ ~ 7 ~ 3 or ~-hydroxyethylamino, or alkoxy, ~uch a~ methoxy or ethoxy, or aryloxy, auch as phenoxy or sulfophenoxy b) Useful fatty alcohol polyglycol ethor~ aro thoao whlch are derlved from a fatty alcohol unlt having 8 to 30, preferably 12 to 18, ln partlcular 14 to 16, carbon atoms, for example octyl, pslargonyl, capryl, undecyl, dodocyl, tridocyl, myristyl, pentadecyl, palmltyl, heptadecyl, atoaryl and oloyl alcohol, ln partlcular also those fatty alcohols derived from natural product~ ~uch as coconut oil fatty acid, tallow fatty acld, tall oil fatty acid, palm oil fatty acld, linseed oll fatty acid, castor oil fatty acid and rizinonic acid The polyglycol ether unlt~ are preparable for example by condensation of ethylene oxide with the fatty alcohols mentioned and advantagoously consist of 2 to 50, preferably 2 to 20, ln particular 5 to 15, ethylene oxide unitc ~ ;
Oxo fatty alcohol polyglycol others are fatty alcohol 20 polyglycol other~ ac mentionod abovo which carry a froe -hydroxyl group on a carbon atom of the fatty acid chain or contaln a carbonyl group Uceful polyal~yl glycol etherc are C,-C30-al~yl, proferably Cl~-Cl,-al~yl, ln partlcular Cl~-Cl,-al~yl, polyglycol othorc ha~ing 2 to 50, proforably 2 to 20, in particular 5 to 15, ethylone oxide unitc, for oxamplo the i~
reaction product of 1 1 of iaotridecyl alcohol wlth 7 to 9 mol of othyl-ne oxide Ucoful thylon oxido-propylono oxido bloc~ polymorc aro those ~ ich contain 10 to 80 % by mole, preferably 10 to 40 ~ by mole, ethylene oxide and 90 to 20 % by mole, preferably 90 to 60 %
by mole, proQylene oxide. The blodk polymers should advantagecusly gi~o cloar colutiona ln wator ln tho concentratlon range uced according to tho invontlon Tho HLB (hydrophilic-lipophilic balanco) value of the-e bloc~ polymerc ic ( 2 3 greater than 2, preferably greater t~an 4. Partlcular preference is given to block polymers having an HLB ~alue between 8 and 15.
Al~o of partieular intere~t are mixture~ of one or more of the aforementioned (oxo)Eatty alcohol polyglycol ethers, alkyl polyglycol ethers and/or ethylene oxide-propylene oxide bloc~ polymer~.
d) The dye ~olutions may con ~in aids which are customarily present in ink~ for ink~et printers, for example antiaggregants, ~uch as N-methylpyrrolldone, dimethylformamide and dimethylacotamide, wettlng agonts, such ae ionic or nonlonic ~urfactant~, triethanolamine as buffer, and glycols such as diethylene glycol as viscosity controllers. -When the commercially available wallpaper ctripper used contains one or more of the compound~ mentioned ln b), the ink formulation of the lnvention will contain the diluent, too. This diluent, u~ually isopropanol, has no advantageou~ effect within the meaning of the pr~sent -~
invention, but it does not have an adverse effect either, provided its level in tho ink formulation does not exceod 10% by weight.
. . . -. , Preference for the purpo~es of the pre~ent invention is given to an ink formulation containing 25 3 to 10% by weight, preferably 4 to 6% by weight, of component a), 1 to 10% by weight, preferably 2 to 5% by weight, of component b), 94 to 77% by weight, preferably 92 to 86% by weight, of component c), and 0 to 5% by weight, preferably 2 to 3% by weight, of component d) with the proviso that the percentages of tho components a) to d) add up to 100% by weight.
The present invention also provides a proces~ for dyeing ;
:
i 2 3 g or printing paper with water-~oluble, preferably anionic, dyoe, in particular reactive dyos~ ueing ~he in~et process or some other cus~y min~E~ add-on spraying tK~ique, which comprisee dyoing or prlnting with an ink formulation according to the invontion.
Proference i8 given to u~ing aqueoue reactivo dye solutions which may contain antiaggregante. For the inkjet procees ~t ~ ad~antagooue to uso domlnoralized roactive dye~ in order that tho lifotimos of the fine nozzlos may be prolongod, but by ink~ot it ie aleo po~siblo to apply dyo proparatione containing up to 50 by woight of electrolyto salt.
The a~ueoue dye solution is admixed with a mixture of the above-doscribod components b) and, if usod, d). Slnce many commorcially avallablo noutral to weakly ba~ic wallpaper strippors contain tho co~pounde mentioned undor component b) ln such a mixing ratio as is ~uitablo for the purposes of the present inventlon, lt le advantageous for roaeons of convenienco to add ~uch a wallpaper strlppor to the aqueous dye solutlon dlroctly. An amount of from 0.5 to 20% by weight, proferably from 3 to 10% by weight, of tho wallpapor strippor, basod on the total weight of tho in~ formulatlon, is advantngeous.
In many casos it le advantagoous for the a~uoous dyo solution first to bo hoatod togethor with componont b) or tho wallpapor stripper and thon to cool down with vigorous stirring in ordor that adoquato mixlng and dieassociation of possible dye conglomerates may be obtained.
~hen the ompty ink cartridgo is charged wlth the lnk formulatlon of the lnvontlon. It le also possiblo to ueo usod in~ cartrldgos aftor thoy have boen rinsod out with wator or somo othor suitable cloaning agont until tho runoff wae colorloss.
In tho caee of multicolor printing, a plurality of ink ~ r rl~ 2 3 cartridgeo can be connected ln eeriee, which are controllable by the preeent-day customary mean~ for the purpo~e of croating the print on the moving ehoet of material. It ie aleo pos~iblo to uee modern multichamber inkjet cartridges, whsreby a plurality of colore can bo applied at tho eame time in a eingle paes.
The preeent invention aleo providee for the U80 of an lnk formulation according to the invention for ink~et printing or for eome other non-contactlng printing proceee with water-soluble dyee on paper. It wae found that the brillianco of the dyoe ueod i8 not impa~red by the $nk formulation and that tho brilliant, etrong printe obtained have very good water faetneee and water droplet faetnese.
The Examplee which follow cerve to illuctrato tho invention. The parte mentioned thorein are parte by weight and the percentages too are by weight, unlees otherwiee etated. Parte by weight relato to parto by volume ae the kilogram relatee to the liter. The water roeistance wae toetod undor running wator.
Examplo 1 Tho com~orcial ink cartridge of a DOD (drop-on-demand~
inkjot printer of the piezoeloctric type i8 cleanod with wator and charged by moane of a eyringo with an ink formulation containing 6S by woight of a rod dye of tho formula ,~3--N O H N H - C 0 HO350H2CH2c025 N~`503H
.. , . . . ~, , . . " - . ~ . . ~ . . . .. . . . .
known from EP-A-158233 (USA-4 581 036 and -4 585 459), 3%
by weight of iootridecyl alcohol otherlfiod with 8 ethylens oxide unito, and 91% by welght of water. Ths mixture can be heated to speed up oolution. Th~o ink formulation brings about brilliant red printo of excellent water reoiotance.
Example 2 A commercial ink cartridge of a bubble ~nk~st pr~nter of the thermal jet type io cleaned wlth water and charged by means of a syrlnge with an ink formulation containing 6%
by weight of the dye C.I. Roactive Yellow 37 of the formula -S0~H
SO2CH2CH20SO~H
and 3~ by weight of coconut fat alcohol etherified with 8 ethylene oxide un$to, and 91% by weight of water. The mixture can be hoatod to apeod up oolution. This ink formulation bringo about brilliant yollow printo of excollent water reolotance.
Example 3 A commercial ink cartridge of a DOD (drop-on-domand) inkjet printer of the piezoolectric type io cleaned with wator and charged with an ink formulation containing 6%
by weight of a turguoioe dye of the formula ~ . , , . .. ~, . . . . . . . ... .. . . . . . .
~ ~ ~ 1 7 2 3 N
~ (S~NH) ~ SO~CH2CH20SO~H)~
known from Example 2 of DE-A-l 179 317 (US-A-3 268 548), 3% by weight of an othylene oxlde propyleno oxld- block polymer havlng an ethylene oxlde con~ent of 20%, and 91%
by welght of water. The mixture can be hoated to ~peed up solution. This lnk formulatlon bring~ about brilli~nt turquoi~e print0 of excellent water roei~tance.
Examplo 4 A commercial lnk cartridge of a DOD (drop-on-demand) ink~et printer of the thermal type (bubble ~-t) is cleaned w~th water and chargod wlth an ink formulatlon whlch as well as water contalns 6% of a red dye of the formula C l HO3SOH2CH2CO~S ~ N OH N 1 N~1 N ~ SO H
HO~S ~ SO~H
known from EP-A O 094 055 (CA-A-l 221 360), 2% of a mixture of a coconut fat alcohol contalnlng predomlnantly Cl2-C,~ unlts and etherifled wlth 5 to 20 ethylene oxlde unlts, 1% of N-methylpyrrolldone (NMP) and 2% of lsopropyl alcohol. The mlxture can be heated to speed up solutlon. Thi~ ln~ formulatlon brlhgs about brllliant red prlnts of oxcollent wator resi~tance.
~xample 5 A commerclal lnk cartrldge of a DOD (drop-on-demand) 2 ~ ~
ink~et printer of the piozoelectric type Sbub~le ~et) i~
cleaned with water and charged with an ink formulatlon which a~ well a~ water contains 6% of a blue ~ye of formula O N H 2 . ' .
~,SO3H
O HN~ so2cH2cH2oso3H
known as ~ I Roactiv0 Blue 19, 2% of isotridecyl alcohol having an ethylene oxide number of 8, 1% of dimethyl-formamide and 1% of oleyl alcohol having an ethylene oxide number of 6 The mixture can be heated to speed up solution This ink formulation brings about brilliant blue prints of excollent water resistance Examples 6 to 3 6 To prepare further dyeings by the process of the lnvention, paper $~ printed with an ink~et printor, for oxampl- analogously to one of the mothods describod in the above ombodiment examplos, uslng 6% strongth agu~ous solutlons of ono or re of the ~nown dye~ lnd~cated below in the table examplos (the dyos are wrltten ln the form of free acidS howev-r, thoy ar- u~od ln the form of their alXali metal ~alt~) containing 3 to 5% of a commercial wallpaper stripper, for oxample T~3 from ARA-Chemie Clear, strong print~ are obtained in the hue indicated for the resp-ctive table example and with tho good fastn-ss proportle~ of the r-~p-ctlve dye, ln partlcular goodwater fa~tnoso propertl-s ':'~ ":
,,: ' ~;
.., . ~: ., ... ;.
',`'' .'.;'.'",' ~''' ,' '7 ~ 3 : :
_ -. --Ex. calt) Hue l ¦
I . I : -: "' 6 SO~H OH C I SO3H Scarlet II H~ H O, S~LN H--~N~N H ~
C H :s I ;
I '~ ~ ~
(known from C~ Patent 350,390) 1 : ~
. ._. I ::
. 7SO,H OH Scarlet l : :~
C H oJ~ H o3~L ~X~lrxc ~ ¦ : :
I
(known from DE-A-1 813 438, ~x. 1) 8SO~H HO NH-CO ~ X Red ¦
~N = N~ l : ~
h O 3 S~S O 3 H l : ~ - :
3 ~
I '' ' ~ ~' (known from DE-B-1 191 059) ¦
Red ' S O ~ H I I N~k I :
~N = N~ Cl ¦
H O 3 S~S O 3 H I
(k~own from ~olour Index a~ C.I. Reactive Red 11) .
~;~ : . . : : : ~
7 ~ 3 -- I
Ex. salt) ~ue l . . I
O H Red I NH-CO-CH, l ¦ J ~N H C 0~ ~
CHz-OSO~H
(known from DE-B-1 126 647) 11 S 0 3 H N l Yellow ,~N =N ~ NH J~N~J--NH2 HO~jS SO~jH NH-CO-NH2 (known from Colour Index as C.I. Reactive Yellow 152) 12 H O N H 2 Navy ,~N-- N~N-- N ~3L
l C H 2 - O S O , H
CH2-OSO,H
(known from Colour Index a~ C.$. Reactivo ~lack 5) .
. ................... . .
salt) Pue :
13 HO NH~ ~C I Red S 2~ H 0 3~5 0 3 H
(known from JP-B-63-23287) 14 SO3H CH~ Yellow [~ ~N I
SOIH OH CH2-OSO,H :
I
(known from Colour Index a~ C.I. React~ve Yellow 37) ~ -I
SO~H Yellow ~ `
,0--N =N ~N H 2 C H 2 N H - C O - C H, ¦(bnown from ~P-3-0 073 ~B1) `~ t~ 3 _ .
Ex . ~alt) Hue ¦
16 SOsH (~) Blue ¦
H s S N ~ N ~ H
N~ N I H2 ~ 0 5 0 3 H
(known f rom EP-B- O 02 8 7 8 8 ) _ 17 ~ju ~ COOH Black N--N~ \I = N ~Il ~L S 0 3 H ¦
C H 2 - 5 s H ¦
' ~
Blaclc 3 I ) 18 5 o H l S O ~ H Reddi sh ,~ N = N ~ N =N ~N H ~`N~N H~ brown ~
5 0, H ~ -(known from DE-A-2 733 109, Ex. 2) . ~
., :. ::, 3 : ~
- 18 - :
13x. ~alt) ~ue N~ N ~
(known from EP-A- O 228 348) ~ `
2 0 Ni~ ( - ) Blu--¦ RC SJ~ 11~503U ( ~3 S O, - C H, - C H I - O S O
(1~nown from ISP-A-O 144 766) .
BlU~
N~ ~N 1 S O ~ H
` `~ ~ `
(Icnown from l~P-A- O 099 721) : ~
. . ._ .
Ex. Dye u~ed (in the form of an alkali motal Huo I .~ , 2 2 ~ H ~ ( - ) Blue N ~C u~ ~ 5 0 ~ N ~3 H ~ ~
~ C ~ I
~ I '.'.' (known from DE-A-2 342 197, Ex. 2) 23 SO~H Yellow N-N ~ NN-C0 ~ NX
(known from DE-B-l 191 059) ~:
.-24 Cl Yellow ~ N = N--Ç3N H~N~ H~ . ¦
H O 3 S O - C H 2 - c H 2 I ~' ' ' ''"' ~`''~ ' ~
(known from European Patont Appli~ation Publication No. 0 056 975) SO3H N~N S03H Yellow ~[~ N = N ~3N H~`N~N H~ ~ .
HO,S SO3H NH-CO-NH2 (known from Colour Index C.I. Rea~tive Orango 91) -:' ' _ . :
Ex. ~alt) Hue . . .
~0--N NN-CO-CN, I I HZ ) Z Y--llo (7H2)2 HO,SO-CH2-cH2-SOi (known from EP-A-0 457 715) 27 N~N Red S O ~ H H O N H--~`N~N H ~
$~ N= N ~ ~1~2 S O 3 H H O ~ S S O ~, H 7 H
~' '".'' ~ :,' ' ' _ (known from EP-A-0 022 575) 28 cl R~d H O N H l~N~ N H - ( Cl H 2 ) 2 ,~N=N~l~ o 1 2 H 0 ~ S S 0 ~ H ( C H I ) 2 CH2-OSO"H C I -CH2-CH2 ~' ,~', L (known from EP-A-0 144 766, Ex. 5) 7 ~ 3 ~alt) _ ~ ~ :
29 Cl Red I i :
~ J-- ¦ ., ¦ S ~ H0,5~5O~H
CH2-OSO,H ¦
L (known from EP-B-0 094 055) SO,H H0 NH~ NH~ NN~NN OH SO,H Rod HO,S SO,H HO,SJ~ O,H ~
'',~':,' ''~'~.'~ ''-''''"''.' ' ~, (~nown from DE-A-2 001 960 31 HO~S-CN~C Blu~
N~-CN~-CN~-NN ~ O ~ ~ ~ .
CN~ Cl SO~ 2 ~ R CO-CNS_CN~_COON . .
COON c~2 ¦
~nown from US-A-4 629 788) -~
ULing the dyos described in Examples 1 to 31 in multicolor printing, eithor in a ~ingle pae~ or in succession in conjunction with a color separat2on, ma~os ~:
it poesible to produce in this way an infinite number of mixed colore which have the same good application profiles (water reeietance, brilliance).
Claims (11)
1. An ink formulation consisting essentially of a) at least one water-soluble dye, at least one fatty alcohol polyglycol ether, oxo fatty alcohol polyglycol ether, alkyl polyglycol ether or ethylene oxide-propylene oxide block polymer or a mixture thereof, and c) water, with or without d) further, customary additives.
2. The ink formulation of claim 1 wherein the water-soluble dye contains one or more sulfo or carboxyl groups or a combination thereof.
3. The ink formulation of claim 1 or 2 wherein the water-soluble dye contains one or more fiber-reactive groups.
4. The ink formulation of at least one of claims 1 to 3 wherein component b) comprises one or more fatty alcohol polyglycol ethers or oxo fatty alcohol polyglycol ethers composed of a fatty alcohol or oxo fatty alcohol of 8 to 30, preferably 12 to 18, carbon atoms and 2 to 50, preferably 2 to 20, ethylene oxide units.
5. The ink formulation of at least one of claims 1 to 3 wherein component b) comprises one or more alkyl polyglycol ethers composed of an alkyl group of 8 to 30, preferably 12 to 18, carbon atoms and 2 to 50, preferably 2 to 20, ethylene oxide units.
6. The ink formulation of at least one of claims 1 to 3 wherein component b) comprises one or more ethylene oxide-propylene oxide block polymers containing from 10 to 80 % by mole, preferably from 10 to 40 % by mole, of ethylene oxide and from 90 to 20 % by mole, preferably from 90 to 60 % by mole, of propylene oxide and having an HLB value greater than 2.
7. The ink formulation of at least one of claims 1 to 3 wherein component b) is a mixture of one or more fatty alcohol polyglycol ethers, oxo fatty alcohol polyglycol ethers, alkyl polyglycol ethers and/or ethylene oxide-propylene oxide block polymers.
8. The ink formulation of at least one of claims 1 to 7, containing 3 to 10% by weight, preferably 4 to 6% by weight, of component a), 1 to 10% by weight, preferably 2 to 5% by weight, of component b), 94 to 77% by weight, preferably 92 to 86% by weight, of component c), and 0 to 5% by weight, preferably 2 to 3% by weight, of component d) with the proviso that the percentages of the components a) to d) add up to 100% by weight.
9. A process for dyeing or printing paper with water-soluble, preferably anionic dyes, in particular reactive dyes, using the ink-jet process or come other customary minimal add-on spraying technique, which comprises dyeing or printing with an ink formulation as claimed in at least one of claims 1 to 8.
10. The process of claim 9 wherein the ink formulation is prepared by adding from 0.5 to 20% by weight, preferably from 3 to 10% by weight, of a customary neutral or weakly basic wallpaper stripper, based on the total weight of the ink formulation, to an aqueous dye solution.
11. The use of an ink formulation as claimed in at least one of claims 1 to 8 for ink-jet printing or some other non-contact printing process with water-soluble dyes on paper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4242868.8 | 1992-12-18 | ||
| DE4242868A DE4242868A1 (en) | 1992-12-18 | 1992-12-18 | Waterproof ink formulation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2111723A1 true CA2111723A1 (en) | 1994-06-19 |
Family
ID=6475694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002111723A Abandoned CA2111723A1 (en) | 1992-12-18 | 1993-12-17 | Water-resistant ink formulation |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0602551A1 (en) |
| JP (1) | JPH06279720A (en) |
| KR (1) | KR940014701A (en) |
| BR (1) | BR9305087A (en) |
| CA (1) | CA2111723A1 (en) |
| DE (1) | DE4242868A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10027236A1 (en) * | 2000-05-31 | 2001-12-06 | Wack O K Chemie Gmbh | Method and test liquid for the detection of acidic flux residues on electronic assemblies |
| US6852153B2 (en) * | 2002-09-24 | 2005-02-08 | Hewlett-Packard Development Company, L.P. | Nonionic additives to control puddling in inkjet inks |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3614462A1 (en) * | 1985-04-30 | 1986-10-30 | Canon K.K., Tokio/Tokyo | Recording fluid and its use in ink jet recording processes and ink jet printing processes |
| US4853036A (en) * | 1986-11-25 | 1989-08-01 | Canon Kabushiki Kaisha | Ink for ink-jet recording and ink-jet recording process using the same |
| US5019166A (en) * | 1989-06-22 | 1991-05-28 | Xerox Corporation | Thermal ink jet compositions |
| US5139574A (en) * | 1991-01-28 | 1992-08-18 | Xerox Corporation | Ink compositions |
| US5211747A (en) * | 1991-05-16 | 1993-05-18 | Xerox Corporation | Ink jet ink compositions containing desizing agents |
-
1992
- 1992-12-18 DE DE4242868A patent/DE4242868A1/en not_active Withdrawn
-
1993
- 1993-12-09 EP EP93119887A patent/EP0602551A1/en not_active Withdrawn
- 1993-12-16 BR BR9305087A patent/BR9305087A/en not_active Application Discontinuation
- 1993-12-17 CA CA002111723A patent/CA2111723A1/en not_active Abandoned
- 1993-12-17 KR KR1019930028299A patent/KR940014701A/en not_active Application Discontinuation
- 1993-12-17 JP JP5318745A patent/JPH06279720A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0602551A1 (en) | 1994-06-22 |
| JPH06279720A (en) | 1994-10-04 |
| BR9305087A (en) | 1994-06-28 |
| KR940014701A (en) | 1994-07-19 |
| DE4242868A1 (en) | 1994-06-23 |
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