EP1234008A1 - Composition d'encre pour impression par jet d'encre - Google Patents

Composition d'encre pour impression par jet d'encre

Info

Publication number
EP1234008A1
EP1234008A1 EP00973088A EP00973088A EP1234008A1 EP 1234008 A1 EP1234008 A1 EP 1234008A1 EP 00973088 A EP00973088 A EP 00973088A EP 00973088 A EP00973088 A EP 00973088A EP 1234008 A1 EP1234008 A1 EP 1234008A1
Authority
EP
European Patent Office
Prior art keywords
ink
polymer
cross
composition
composition according
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.)
Withdrawn
Application number
EP00973088A
Other languages
German (de)
English (en)
Inventor
Hugh Alexander Allen
Richard Vincent Robert Martin
Christine Anne Lear
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coates Brothers and Co Ltd
Original Assignee
Coates Brothers and Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Coates Brothers and Co Ltd filed Critical Coates Brothers and Co Ltd
Publication of EP1234008A1 publication Critical patent/EP1234008A1/fr
Withdrawn legal-status Critical Current

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

Definitions

  • the present invention relates to a composition for an ink-jet ink.
  • Ink-jet printing has been used both for home/office as well as industrial and commercial applications such as coding, cable marking, wide-format poster and vinyl sheet printing, and business forms.
  • organic solvent-based systems have been used.
  • environmental and health and safety concerns make it desirable to minimise the organic solvent content.
  • systems which are substantially aqueous based present other problems.
  • the print is not very durable or water-fast, particularly on non-absorbent surfaces such as plastics substrates.
  • the organic solvent-based systems can still have durability problems.
  • UV-curing systems using a variety of UV-curing systems, has also been described in EP-A-465 039, EP-A-540 203, US-A-4 303 924 and US-A-5 270 368. Whilst this is one solution to the problem of lack of print durability, use of organic solvents is preferably minimised or avoided for the reasons mentioned above. Moreover, the use of a UV source is undesirable for reasons of cost and complexity.
  • WO 95/29944 which comprises an aqueous emulsion of an emulsion polymerised acid functional oligomer having a T g below 50 °C having cross-linker functional groups, the resulting emulsified product being an olefinic hydrophobic polymer having a T g of at least 25 °C.
  • Typical polymers are copolymers of butyl acrylate and methyl methacrylate, the cross-linker functional groups being diacetone acrylamide groups.
  • the cross-linking agent is, typically, adipic acid dihydrazide.
  • the compositions also contain a non-acid functional, non-cross-linking comonomer.
  • JP-A-7026196 discloses surface treatment compositions for use as printing inks, paints and sealants, for plastics, metal, paper or glass substrates. These contain an emulsion of a resin having an aldo or keto group and a carboxyl group, obtained by emulsion polymerisation of an ethylenically unsaturated compound in the presence of a water- soluble resin that is obtained by neutralising a resin containing aldo or keto groups and carboxy groups using ammonia or an organic amine. The composition also contains a cross-linking agent having at least two hydrazine residues.
  • US-A-5 567 747 describes a different drying mechanism which employs an oxidatively drying system of epoxy ester, cyclodextrin and a catalytic drier in the formulation of a flexographic printing ink.
  • a problem is that, once dry, such emulsions have very poor resolubility i.e. they do not easily re-dissolve in the original ink. In ink jet printers which have very small diameter nozzles, this can lead to clogging of the nozzles with dried ink over a period of time.
  • Air-drying self cross-linking acrylic silicone copolymers have been proposed for use in water-based ink-jet ink formulations in JP-A- 10-316908 and JP-A-10-140058. These references respectively relate to systems incorporating a water-solubilising polymer and systems with an oil-emulsion as a resolubilising agent.
  • the present invention now provides a water-based ink-jet ink composition
  • a water-based ink-jet ink composition comprising:-
  • composition has a viscosity at 25 °C of no more than 50 centipoise, preferably no more than 30 centipoise, more preferably no more than 15 centipoise, and especially preferably no more than 5 centipoise.
  • Ink-jet inks necessarily have a room temperature viscosity far below that of normal printing inks.
  • systems based on acrylic emulsions are particularly advantageous.
  • Ink-jet inks have a very low room temperature viscosity and it can be difficult to make ink formulations with sufficient levels of resin to achieve satisfactory dry film properties.
  • the emulsion form of these air-drying cross- linker systems gives them inherently low viscosity at high solids levels making them ideally suited to ink-jet ink formulation.
  • ink-jet inks according to the invention are very storage stable. This stability is especially enhanced when they are formulated to be alkaline, e.g. having a pH of from 7.5 to 10.0, more preferably from 8.0 to 9.5.
  • Component (a) is a polymer emulsion, specifically an emulsion of an oligomer or polymer having reactive groups capable of being cross-linked by the cross-linking agent (b) when the composition dries.
  • it is an acrylic-type polymer emulsion.
  • the reactive group(s) comprise reactive carbonyl groups (e.g. having keto or aldehyde functionality) but, in principle, they may be chosen from a wide range of groups, such as epoxy (preferably glycidyl) and hydroxyalkyl (preferably Ci to d 2 e.g. hydroxyethyl) methacrylates and acrylates.
  • Other monomer units incorporated in the oligomer or polymer of emulsion (a) may be chosen from a wide range of possibilities to import other desirable properties, such as to provide stability and film forming properties, for example one or more selected from carboxyl functional monomers (e.g. acrylic acid, methacrylic acid, itaconic acid, crotonic acid), acrylate esters (e.g. ethyl acrylate, butyl acrylate, ethylhexyl acrylate.), methacrylate esters (e.g.
  • carboxyl functional monomers e.g. acrylic acid, methacrylic acid, itaconic acid, crotonic acid
  • acrylate esters e.g. ethyl acrylate, butyl acrylate, ethylhexyl acrylate.
  • methacrylate esters e.g.
  • the oligomer or polymer in emulsion (a) preferably has a weight average molecular weight of from 500 to 5,000,000, more preferably from 3,000 to 3,000,000, these molecular weights being those determined using the method of gel permeation chromatography, using an appropriate known polymer as standard.
  • the cross-linking agent (b) may comprise a di- or polyamine and/or di- or polyhydrazide, such as oxalic acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, isophorone diamine or 4,7-dioxadecene - 1,10-diamine, or selected from derivatives of dibasic acids (e.g.
  • adipic dihydrazide succinic dihydrazide, phthalic acid dihydrazide dialkylamine derivatives of polyalkyl glycols, and alkyl di- or triamines such as isophorone diamine.
  • suitable cross-linking agents (b) are polyisocyanates, melamine and glycoluril.
  • the amount of the oligomer or polymer material per se from emulsion (a) is present at from 5% to 40%, more preferably from 10% to 35%, by weight of the total ink composition.
  • the amount of the cross-linking agent (b) is determined by the ratio of reactive equivalents, which can typically be from 4: 1 to 1 :4 or, more preferably, from 2:1 to 1 :2.
  • compositions according to the present invention is the resolubilising polymer (c).
  • the polymer (c) is included in the composition for the purpose of ensuring resolubilisation of any partially dried ink, e.g. around the ink jet print head nozzle, in order to keep the apparatus clean and the ink free-flowing. It is preferably included in the ink in an amount of from 0.5% to 10%, more preferably from 1% to 8%, by weight of the total composition.
  • the resolubilising polymer is preferably a water-soluble polymer, more preferably a polymer containing carboxylic acid groups which is soluble only when these groups are neutralised with an alkali such as ammonia or a volatile amine like dimethylethanolamine or monoethanolamine.
  • an alkali such as ammonia or a volatile amine like dimethylethanolamine or monoethanolamine.
  • Examples of truly water-soluble resolubilising polymers include sulphopolyesters, polyvinyl pyrrolidones and polyvinyl alcohols.
  • polymers which may be rendered water soluble by virtue of their carboxylic acid functionality e.g. maleic resins, fumaric resins, styrenated maleic anhydride resins, polyamide resins, acrylic copolymer resins and acrylic emulsions. Any of the foregoing polymers may be used alone or in combination.
  • the resolubilising resin Whilst the selection of the resolubilising resin is limited only by the compatibility with the self-cross-linking emulsion, a particularly useful choice is from the very wide range of commercially available acrylic copolymer resins and emulsions. Pigment may easily be ground into these acrylic polymers to produce stable dispersions with high colour strength and gloss. These materials typically have an acid value of from 100 to 300, preferably from 150 to 250, mg/mole KOH.
  • the resins have a weight average molecular weight between 1,500 and 20,000, preferably between 5,000 and 15,000. Examples include Joncryl 678 and Joncryl 683 (ex S. C. Johnson), Morez 100 and Morez 300 (ex Morton).
  • the emulsions have a weight average molecular weight between 25,000 and 55,000, preferably between 35,000 and 45,000.
  • Examples include Joncryl 142 (ex S. C. Johnson), Neocryl BT-26 (ex Zeneca) and Lucidene 196 (ex Morton).
  • compositions according to the present invention preferably contain from 60% to 85%, more preferably from 70% to 80%, by weight of water.
  • compositions of the present invention necessarily have a low viscosity of 25 °C, i.e. no more than 50 centipoise (cP), preferably no more than 30 centipoise, and more preferably no more than 15 centipoise, for drop on demand (DOD) printing and no more than 5 cP for continuous printing.
  • cP centipoise
  • DOD drop on demand
  • compositions having air-drying cross-linking systems which have been used for non-ink-jet applications, typically contain other materials and/or are formulated differently, so that they have a higher viscosity than an ink-jet ink, which must have a very low viscosity.
  • the ink-jet inks according to the present invention can easily be formulated by the person skilled in the art to have the required low viscosity.
  • the basic air-drying emulsion itself will normally have a relatively low viscosity and the amount of the water and/or choice of, and amounts of, co-solvent and/or the total amount of solids, can easily be adjusted to achieve a particular desired viscosity.
  • ink-jet ink composition encompasses both compositions which already contain colourant and those without colourant, being a base to which an ink manufacturer can add one or more colourants of choice.
  • ink-jet ink compositions according to the present invention will normally already contain colourant.
  • colourants may be considered as falling into two classes, namely dyes, which are substantially soluble in the ink composition, and pigments, which are dispersed in the ink composition in the form of fine particles, if necessary with the aid of a suitable dispersant.
  • colourant also includes materials which endow a non-visible optical property (e.g. fluorescence) to the ink.
  • dyes are employed, these may be selected from a wide range of classes, so long as they are soluble in the ink vehicle. Suitable types of dye include acid dyes, basic dyes, reactive dyes and those solvent dyes which are water-soluble or water-dispersible. A wide range of appropriate commercially available types will be well known to those skilled in the art.
  • the object of this invention is to produce prints with a high degree of resistance properties.
  • dyes have relatively poor resistance properties, for example to water and to light.
  • a pigment will therefore normally be chosen as the colourant.
  • Pigments may be selected from a wide range of classes including azo pigments (monoarylide, diarylide, naphthol, benzimidazolone, metal salt reds), phthalocyanines, quinacridones and dioxazines, for example Pigment Red 57:1, Pigment Red 52:2, Pigment Red 48:2, Pigment Blue 15:3, Pigment Green 7, Pigment Yellow 83, Pigment Yellow 13, Pigment White 6, Pigment Black 7.
  • pigments include the following from the Irgalite range (ex CIBA): Rubine L4, Bordeaux CM, Red 2BP, Blue LG, Green GLN, Yellow B3R and yellow LBG; as well as Tioxide RHD6 (ex Tioxide) and Special Black 250 (ex Degussa).
  • the total amount of colourant in the composition is typically from 1% to 15%, preferably from 2% to 10%, by weight of the total composition.
  • Ink-jet ink compositions according to the present invention may contain other optional components such as organic solvents, surfactants, slip and scratch resistance additives, anti-foams and biocide.
  • One or more organic solvents such as alcohols and polyols (e.g. ethyl alcohol and isopropyl alcohol), glycols (e.g. propylene glycol, diethylene glycol), glycol ethers (e.g. methoxypropanol) and glycol ether acetates (e.g. methoxylpropyl acetate) may be included to adjust drying speed and improve wetting on low surface energy plastic surfaces.
  • the total amount of organic solvent is from 1 % to 10%) by weight of the total composition.
  • surfactants may therefore be included in the formulation to reduce the surface tension of the composition to aid in the wetting of low surface energy, non-absorbent surfaces, especially plastics surfaces.
  • useful surfactant classes include anionic surfactants (e.g. sulphosuccinates), non-ionic surfactants (e.g. acetylenic diols, polyethylene/polypropylene oxides) and fluorosurfactants.
  • anionic surfactants e.g. sulphosuccinates
  • non-ionic surfactants e.g. acetylenic diols, polyethylene/polypropylene oxides
  • fluorosurfactants e.g. acetylenic diols, polyethylene/polypropylene oxides
  • the total amount of surfactant is from 0.1 to 5% by weight of the total composition.
  • the surface slip, scratch and rub resistance of the dried ink film can be improved by the addition of low levels of surface active materials such as silicones and waxes. Generally speaking, if present, the total amount of these additives together will be between 0.1 and 5% by weight of the total composition.
  • foam can be a problem in water-based ink-jet inks, particularly where the ink is agitated during use such as in continuous printing.
  • This can be controlled by the use of anti-foams and defoamers, either silicone-based or silicone-free.
  • anti-foams and defoamers either silicone-based or silicone-free.
  • a wide variety of chemistries and products are commercially available.
  • the total amount of anti-foam is from 0.1% to 1.0% by weight of the total composition.
  • the aqueous environment provides an ideal breeding ground for microbes.
  • a biocide is therefore included in the composition to extend the shelf life e.g. a 1,2-benziso- thiozolyn-3-one type biocide such as Proxel CF (ex Zeneca), at a level of less than 1%, normally no more than 0.1%), by weight of the total composition.
  • the black pigment is pre-dispersed into the resin solution in a bead mill.
  • the black pigment is pre-dispersed into the resin solution in a bead mill.
  • Adhesion to polythene corona discharge treated to a surface energy of 38 dynes/cm
  • fast-moving air excellent (no ink removal using adhesive tape).
  • Adhesion to polythene corona discharge treated to a surface energy of 38 dynes/cm
  • fast-moving air excellent (no ink removal using adhesive tape).
  • the ink reticulates on the polythene surface.
  • Joncryl 683 (ex SCJohnson Polymer) 2 (neutralised to a pH of 9.0-9.5 with ammonia) 13.00%
  • the black pigment is pre-dispersed into the resin solution in a bead mill
  • Adhesion to polythene corona discharge treated to a surface energy of 38 dynes/cm
  • fast-moving air excellent (no ink removal using adhesive tape).
  • Neocryl BA-820-B (ex Zeneca Resins) ' 21.20% 20%) Solids solution in de-ionised water of alkali soluble emulsion, Neocryl BT-26 2 (ex Zeneca Resins) (neutralised to a pH of 9.0-9.5 with monoethanolamine) 12.90% Flexiverse Blue 15 : 3 aqueous dispersion (ex Sun Chemical) 8.50%
  • Raw Materials An emulsion of an acrylic co-polymer including reactive keto-functionality, and a polyamine or polyhydrazide cross-linker.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

Cette invention concerne une composition d"encre à base d"eau pour impression par jet d"encre, composée comme suit: émulsion d"un oligomère ou d"un polymère réticulable comprenant au moins un groupe carbonyle réactif capable de réagir avec un agent de réticulation (b); (b) agent de réticulation qui réticule l"oligomère ou le polymère en (a) au moment du séchage de la composition; et (c) polymère de resolubilisation. Cette composition présente une viscosité à 25 °C de 50 centipoise maximum, de préférence de 30 centipoise maximum et, mieux encore, de 5 centipoise maximum.
EP00973088A 1999-11-16 2000-11-08 Composition d'encre pour impression par jet d'encre Withdrawn EP1234008A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9927105A GB2356403B (en) 1999-11-16 1999-11-16 Ink-jet ink composition
GB9927105 1999-11-16
PCT/GB2000/004277 WO2001036547A1 (fr) 1999-11-16 2000-11-08 Composition d"encre pour impression par jet d"encre

Publications (1)

Publication Number Publication Date
EP1234008A1 true EP1234008A1 (fr) 2002-08-28

Family

ID=10864619

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00973088A Withdrawn EP1234008A1 (fr) 1999-11-16 2000-11-08 Composition d'encre pour impression par jet d'encre

Country Status (4)

Country Link
EP (1) EP1234008A1 (fr)
AU (1) AU1163801A (fr)
GB (1) GB2356403B (fr)
WO (1) WO2001036547A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7897658B2 (en) 2003-10-28 2011-03-01 Cabot Corporation Aqueous coating compositions
US7495042B2 (en) 2003-10-28 2009-02-24 Cabot Corporation Non-aqueous coating compositions
WO2007103542A1 (fr) * 2006-03-09 2007-09-13 E. I. Du Pont De Nemours And Company Ensemble d'encres pour jet d'encre
GB0625530D0 (en) 2006-12-21 2007-01-31 Eastman Kodak Co Aqueous inkjet fluid
CN115160851A (zh) 2016-10-20 2022-10-11 太阳化学公司 用于收缩和非收缩聚合物膜的水基油墨
EP3622111B1 (fr) * 2017-10-18 2021-05-26 Hewlett-Packard Development Company, L.P. Impression sur un textile
EP3720916A4 (fr) * 2017-12-08 2021-10-13 Swimc LLC Polymère de latex ayant une capacité de lavage et une résistance au blocage améliorées
US20230295448A1 (en) 2020-10-14 2023-09-21 Sun Chemical Corporation Aqueous ink compositions
EP4150017B8 (fr) 2021-07-30 2024-04-10 Sun Chemical Corporation Compositions d'encre aqueuses

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000064681A1 (fr) * 1999-04-23 2000-11-02 Sawgrass Systems, Inc. Procede d'impression a jet d'encre a l'aide d'encres reactives

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Publication number Priority date Publication date Assignee Title
US4136076A (en) * 1977-10-25 1979-01-23 Dennison Manufacturing Co. Ink jet printing composition comprising a solvent, a dye stuff, a volatile base, a multi-valent metal and a polymer containing carboxyl groups
JP2540467B2 (ja) * 1988-06-17 1996-10-02 東光株式会社 Ｌｃフイルタ
JP3033093B2 (ja) * 1989-07-25 2000-04-17 セイコーエプソン株式会社 画像記録用インク及び画像記録方法
GB9014299D0 (en) * 1990-06-27 1990-08-15 Domino Printing Sciences Plc Ink composition
US5270368A (en) * 1992-07-15 1993-12-14 Videojet Systems International, Inc. Etch-resistant jet ink and process
US5492952A (en) * 1993-03-22 1996-02-20 Canon Kabushiki Kaisha Ink, ink-jet recording process and apparatus making use of the same
DE69627601T2 (de) * 1995-10-06 2003-12-04 Seiko Epson Corp., Tokio/Tokyo Tintenzusammensetzung für das Tintenstrahlaufzeichnen und Tintenstrahl-Aufzeichnungsverfahren
GB9603667D0 (en) * 1996-02-21 1996-04-17 Coates Brothers Plc Ink composition
JP3982003B2 (ja) * 1997-05-20 2007-09-26 富士ゼロックス株式会社 記録液および画像記録方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000064681A1 (fr) * 1999-04-23 2000-11-02 Sawgrass Systems, Inc. Procede d'impression a jet d'encre a l'aide d'encres reactives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO0136547A1 *

Also Published As

Publication number Publication date
GB2356403A (en) 2001-05-23
GB2356403B (en) 2003-09-03
GB9927105D0 (en) 2000-01-12
AU1163801A (en) 2001-05-30
WO2001036547A1 (fr) 2001-05-25

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