WO 2018/143960
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`PCT/US2017/015903
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`1
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`inkiet Printing System
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`Background
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`roost}
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`lnkjet printing with aqueous inks is increasingly being used to print on non
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`porous flexible and rigid media for signage and other printing eppiioations.
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`it is recognized
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`that inkjet printing of aqueous inks on nonporous media is substantiaiiy ditterentthan inkjet
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`appiieations fortraditional porous paper—based media. On porous papers, ink drying occurs
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`primarily by ink penetration into the media pore structure, and eontrot of image quality
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`aspects is a strong function otthe rate of ink penetration into the media. Thus, optimization
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`otthe penetration rate is used for attributes such as opticai density and coior—to—coior bieed.
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`0n nonporous media, there is no penetration of the ink into the media, i.e. the coiorant
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`remains on the surface of the media, and image quality detects resulting from wetting and
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`ink migration across the nonporous surface are more difficult to control, especially at high
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`printing speeds.
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`{0002}
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`Durability of aqueous inks on nonporous substrates poses a chaiienge.
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`inks
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`need to wet and adhere to a broad range ot’ substrates, have good abrasion and scratch
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`resistance, resist attack by water, cleaning iiuids, and solvents, and have good outdoor
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`weatherehility. There have been great improvements in the durability of aqueous ink—let
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`inks through incorporation of certain ink—jet compatible iatex polymer dispersions made by
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`emulsion polymerization. When printed as part of an ink—jet ink, a latex component of the
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`ink can form a tiim on a media surface, entrapping and protecting the colorant within the
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`hydrophobic print tiim.
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`Brief Description of the Figures
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`{0003}
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`Figure 1
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`is a schematic diagram of a printing system for use in an example of
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`a method of printing.
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`Detaited Description
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`{0904}
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`Before the iatex polymers, ink compositions, methods and related aspects of
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`the disciosure are disciosed and described, it is to he understood that this disciosure is not
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`restricted to the particular process features and materials disciosed herein because such
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`process features and materiais may vary somewhat.
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`it is also to he understood that the
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`terminology used herein is used for the purpose of describing particular examples. The
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`terms are not intended to be limiting because the scope is intended to he iimited by the
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`appended claims and equivalents thereof.
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`{0005]
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`it
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`is noted that, as used in this specification and the appended eiairns,
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`the
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`singuiarterms "a," "an," and "the” ineiude piurai rei'erents uniess the context eieariy dietates
`otherwise.
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`As used herein, ”oo—peiyrner" reters to a poiymer that is poiyrnerized tron: at
`{0000}
`ieast two monomers.
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`{0007}
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`A certain monomer may be described herein as constituting a oertain weight
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`percentage of a poiyrner. This indicates that the repeating units formed from the said
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`monomer in the poiynter constitute said weight percentage of the poiyrner,
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`{0008}
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`ii’ a standard test is mentioned herein, unless otherwise stated, the version of
`
`the test to he referred to is the most recent at the time of tiiing this patent appiieation.
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`[0000}
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`As used herein, the term "about" is used to provide tiexihiiity to a numerieai
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`range endpoint by providing that a given vaiue may be a iittie above or a iittie beiow the
`
`endpoint. The degree of tiexibiiity of this term can be dictated by the partiouiar variehie.
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`{00010}
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`As used herein, “iatex,” “iatex poiyrner," or “iatex partieies" reterto the peiymerie
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`masses synthesized from individuai niorion‘ters, which can be dispersed in a iiquid vehioie
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`forming a iatex dispersion. The term “iatex” generaiiy refers to iiguid and peiyrnerie partioies
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`that are dispersed within the iiquid. However, when a iatex (ie. a tatex dispersion ineiudihg
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`iatex poiymer partioies) is formuiated within an ink, the iiouid becomes part of the iiouid
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`vehieie of the ink, and thus, iatex polymer can he described based on the iatex particle or
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`iatex poiyr‘ner soiids that remain dispersed in the iiduid vehioie.
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`{00011}
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`The term "monomer ernuision" refers to an organic: monomer or monomer mix
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`that is ernuisitied in an aqueous or water phase. Once the organic monomer or monomer
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`mix is poiymerized, a iatex peiymerdispersion is termed.
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`{00012}
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`The term “iatex poiyrner dispersion" or "iatex dispersion" inoiudes both iatex
`
`partieuiates as weii as the adueous medium in which the iatex partiouiates are dispersed.
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`More specifieaiiy, a iatex dispersion is a iiguid suspension comprising a iiduid (such as
`
`water and/or other iiquids) and poiymerie partieuiates from 20 ntn to 500 nm (preterabiy
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`from 100 nm to 300 nm) in size (average partioie size), and having a weight average
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`nioieouiar weight from about 10,000 MW to 2,000,000 MW (preferably trem about 100,000
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`MW to 300,000 i‘v’iw). Such poiymerie partieuietes can comprise a piuraiity of monomers
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`that are typioaiiy randomiy poiyi’nerized, and can aiso be erossiinked. When erossiinked,
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`the moieoutar weight can he even higher than that cited above. The average partieie size
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`(ed. voiume or intensity weighted average particie size) may be determined by dynamic
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`iig ht scattering.
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`[000131
`
`The term "non—porous" when referring to a substrate, such as a media
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`substrate,
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`inciudes surfaces that can have relatively poor water permeability and
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`5
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`absorption. Vihyi, poiypropyiene, poiyethyiehe and other piastic sheets or tiirns, metais,
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`ooated offset media, giass, certain woods, and other simiiar substrates are considered to
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`he non—porous. The term “non-porous media” refers to print media which has a Bristcw
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`Test of iess than 2 mi/m2 at a oontaot time of iess than 0.5 s. The Bristow Test is known in
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`the art and is summarized heiow. A test specimen of defined dimensions is affixed to the
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`to
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`smooth rirn eta wheei tree to rotate at a defined constant speed in contact with a stationary
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`test fiuid appiicator pressing against the test specimen with a defined pressure. The test
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`fioid appiicator consists of a test soiution storage con‘ipartrnent affixed above a t by ‘iEm—rnm
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`test tiuid deiivery siot, the stat being positioned so that the tong dimension is perpendicoiar
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`to the direction of rotation of the rim of the wheei, and paraiiei to the wheei axis. A defined
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`quantity of test fiuid is piaced through the fluid reservoir, onto the fluid deiivery siot. With
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`the wheei with the test specimen affixed rotating at constant speed, the test soiution
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`appiicator is brought into contact with the rotating test specimen and heid in piaoe under
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`defined pressure. The test fluid is transferred from the test soiution appiicator onto the test
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`specimen in a hand whose width, controiied by the appiicator siot width is approximateiy
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`20
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`15 mm, and whose iength is function of the absorptive Characteristics of the test fiuid
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`interaction with the test specimen under the defined test conditions. The amount of iiqoid
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`absorbed per unit area of test specimen is caisuiated from the voitime of test fioid originaiiy
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`pieced in the appiicator, and the average width and iength of the hand created on the test
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`specimen by the transferred test timid. The time avaiiabie for the iiouid absorption is
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`caicuiated from the voiurne of test fiuid originaiiy piaced in the appiicator and appiicator
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`geometry.
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`{00014}
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`As used herein, “ink vehicie" refers to the iiqoid fiuid in which a iatex poiyrner
`
`and a pigment are piaced to form an ink.
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`ink vehicies may inciude a mixture of a variety of
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`different agents,
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`inoiuding,
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`tor exampie, surfactants, soivents, ce-soivents, buffers,
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`biocides, viscosity modifiers, sequestering agents, stabiiizing agents, huniectants and
`water.
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`{00015}
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`The term “decap” is a measure of how tong a printing nozzie may remain
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`inactive before piugging and how many inkjet architecture firings are required to re
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`estabiish proper drop ejection.
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`{00015}
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`The term “(meth)aeryiate” is weii understood in the art to refer to both aeryiates
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`and niethacryiates. For exampte, “eyciohexyi (meth)acryiate” refers to eyciehexyi acryiate
`
`and/er cyciohexyi niethacryiate.
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`Likewise,
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`the term “cycicaiiphatic (meth)aoryiate
`
`monomer" denotes a cyctcatiphatic acryiate monomer and/or a oycioaiiphatic methacryiate
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`5
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`monomer; and the term “aromaticnneth)aciyiate moncrner” denotes an aromatic acryiate
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`monomer and/or an aromatic methacryiate monomer.
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`{0001?}
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`The term “(n‘ieth)acryiamide” is weii understood in the art to refer to both
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`acrytamides and methacryiamides. For exampie, the term "cycicaiiohatie (meth)acryiamide
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`mcnenter” denotes
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`a
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`cyeioaiiphatie aeryiantide monomer and/or a eyctoatipnatic
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`niethacryiamide monomer; and the term “aromatic (meth)aciyiamide monomer" denotes
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`an aromatic acryiamide monomer and/or an aromatic rnethacrytaniide monomer.
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`{00918}
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`As used herein, a piuraiity of
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`items, structurai eiements, composttionai
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`etements, andfor materiais may be presented in a common iist for convenience.
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`i-iowever,
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`these iists shcuid be construed as though each member ot’ the iist is individuaity identified
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`15
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`as a separate and unique member. Thus, no individuai member of such tist shcuid be
`
`construed as a de tacto eduivaient of any other member of the same iist soiety based on
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`their presentation in a common group without indications to the contrary.
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`{00919}
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`Concentrations, amounts, and other numericat data may be expressed or
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`presented herein in a range format.
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`it is to be understood that such a range format is used
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`mereiy for convenience and brevity and thus shouid be interpreted tiexibiy to inciude not
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`just the numericat vatues expiicitiy recited as the end points ot the range, but aiso tc inciude
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`ati the individuat numericat vaiues or sub—ranges encompassed within that range as it' each
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`numericai vaiue and sub—range is expiicitiy recited. As an iiiustration, a numericai range of
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`"about t wt% to about 5 wt%“ shcuid be interpreted to inctude netiust the expiicitiy recited
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`vaiues of about 1 wt% to about 5 wt%. but aisc inciude individuai vaiues and subranges
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`within the indicated range. Thus, inciuded in this numericai range are individuai vaiues
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`such as 2, 3.5, and It and sub—ranges such as from 1—3, from 2—4, and from 3—5, etc. This
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`same princtpte appiies to ranges reciting a singie numericai vaiue. Furthermore, such an
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`interpretation shoutd appty regardtess ot the breadth of the range or the characteristics
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`being described.
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`{00020}
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`Uniess otherwise stated, any 1feature described herein can be combined with
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`any aspect or any other feature described herein
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`{00021}
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`The present inventors have found that the printing systems described herein
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`provide inkjet-printed images having improved durabiiity atong with maintenance of cotour
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`of the initjet
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`ink composition The present inventors have aiso found that print head
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`reiiahiiity (eg. decap performance) and riuidio efficiency can be improved using the printing
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`systems described herein.
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`{00022}
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`in an aspect there is provided an inkjet printing system comprising:
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`an aqueous pre—treatment fluid comprising a cationic poiyrner and a pre—
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`treatment vehicie;
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`an aqueous inkjei ink composition comprising a iatex poiymer, a pigment and
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`an ink vehioie; and
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`an aqueous inkjet overcoat composition comprising a iatex poiyiner, a wax and
`an overcoat vehicie.
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`{00923}
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`in an aspect there is provided an inkjet printing system comprising:
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`an aqueous pie—treatment ftuid comprising a cationic poiyrner and a pre—
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`treatment vehieie;
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`an aqueous inkjet ink composition comprising a iatex poiymer comprising a
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`(meth)aoryiete or (rneth)acryiamide poiyrner or oopoiyrner, a pigment and an ink vehicie;
`and
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`an aqueous in kjet overcoat composition comprising a iatex poiymer comprising
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`a (methiaoryiate or (meth)aoryiamide polymer or oopoiymer, a wax and an overcoat
`vehicie.
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`{00024}
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`in an aspect there is provided a method or printing comprising:
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`providing a non—porous substrate;
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`appiying an aqueous pre—treatment tiuid comprising a cationic poiyrner and a
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`pie—treatment vehicie to the nonporous substrate to form a ore—treatment iayer;
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`inkjet printing an aqueous init composition comprising a iatex polymer, 3
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`pigment and an ink vehicie to the non—porous substrate to form an ink iayer; and
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`inkjet printing an aqueous overcoat composition comprising a iatex potymer, a
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`wax and an overcoat vehicie to the non-porous substrate to form an overcoat iayer.
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`{06025}
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`in an aspect there is provided a method or printing comprising:
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`providing a non—porous substrate;
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`appiying an aqueous pee—treatment iiuid comprising a cationic poiymer and a
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`pie-treatment vehicie to the non—porous substrate to form a gore-treatment iayer disposed
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`on the non—porous substrate;
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`inkie‘t printing an aqueous ink composition comprising a iatex polymer, a
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`pigment and an ink vehicle to the non—porous substrate to form an ink iayer disposed on
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`the pretreatment iayer; and
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`int-{jet printing an aqueous overcoat composition comprising a iatex poiymer, a
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`wax and an overcoat venicie to the non~porous substrate to form an overcoat iayer
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`disposed on the ink iayer.
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`initjei: Printing System
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`[00025]
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`Described herein is an initjet printing system comprising:
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`an aqueous ore—treatment fiuio comprising: a cationic polymer and a pre—
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`treatment vehicie;
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`an aqueous inkjet ink composition comprising a tatex poiymer, a pigment and
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`an inkvehicie; and
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`an aqueous inkjet overcoat composition comprising a iatex poiyn’ier, a wax and
`an overcoat vehicie.
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`{00927}
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`in some exampies, the Latex poiyrner of the ink composition is different to the
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`iatex potymer of the overcoat composition.
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`Aqueous Pre~Treatment Fluid
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`{00028}
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`The aqueous pro—treatment fiuid comprises a cationic poiymer and a pre—
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`treatment vehicie.
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`in some exampies, the aqueous pro—treatment ftuid comprises a cationic
`
`poiymer, a ore—treatment vehicie and a surfactant.
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`Cationic Polymer
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`{00029}
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`As used herein, the term "cationic potymer” refers to an ionic poiymer where
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`the specific ions are cationic in nature, eg. a customized poiyamine. Poiymerio cationic
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`poiymei‘s, aiso referred to as cationic poiyeiectroiytes, may contain either guanidinium or
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`fuiiy ouaternized ammonium functionaiities, such as ouaternized poiyamine copciymers.
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`in
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`some exampies, the cationic potymer does not contain primary or secondary ammonium
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`functionaiities, such as poiyaiiyiamine or poiyethyiene imine, due to yeiiowing issues in
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`outdoor exposure. Genereiiy, the weight average rnoiecuiar weight (MW) of the cationic
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`poiyrner aiiows viscosity iess than 25 cP at 25° C, as measured on a Brookfieid viscometer,
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`Typicat Why are less than 500,090, for exarnpie tess than 50.000.
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`in some exarnptes,
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`cationic poiyniers can have high charge densities to improve fixing efficiencies. As such,
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`cationic charge densities can he higher than 1000 microeouivaients per gram cationic
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`functionaiity, for example higherthan 4090 microequivaients per gram.
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`in some exarnoies,
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`the aqueous ore-treatment tiuid comprises a cationic ooiymer in an amount in the range of
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`about (3.1 wt% to about 25 wt%, for exampie, 0.5 wt% to about ti) wt%, for examoie €15
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`wt% to about 5 wt%, or about t wt% to about 2.5 wt% by totai weight of the aqueous pre—
`treatment fluid.
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`{00030}
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`Ciasses ot cationic poiyrners that can be used inciude,
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`for examoie,
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`quaternized poiyamines, dicyandiamide boiycations, diatiytdimethyi ammonium chioride
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`copoiyrners,
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`duaternized
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`dimethyiarnincetnyir‘meth)acryiate
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`ooiymers,
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`quaternized
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`vinyiimidizoi poiymers, aikyi guanidine boiymers, aikoxyiated poiyethyiene imines, and
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`to
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`mixtures thereof. it is to be understood that one or more ooiycations may be used, and that
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`any desirabie combination otthe ooiycations can be used. One or more ions oftbe cationic
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`poiyeiectroiytes may be ion~exchanged for a nitrate, acetate, rnesyiate, or other anion. An
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`exampie of a suitabie cationic poiymer is Fioquat® FL2350, a duaternized poiyarnine
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`derived from eeichiorohydrin and dirnethyi amine, commerciaiiy avaiiabie from SNF inc.
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`Surfactant
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`{00831}
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`The aqueous ore—treatment
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`ttuid may comprise nonnichic, cationic, and/or
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`anionic surfactants.
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`in some examnies, the surfactant may be present in an amount
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`ranging trom (3.01 wt% to 10 wt% by totai weight of the pretreatment tiuid, tor exampie
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`0.01 wt% to 5 wt%. Cationic and nonionic surfactants are generaiiy used, as many anionic
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`surfactants can give soiubiiity issues in the presence of a cationic ooiymer. For examoie,
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`suitabie surfactants may be seiected torrn aikyi poiyethyiene oxides,
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`aikyi ohenyi
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`ooiyethyiene oxides, ooiyethyiene oxide biock coboiymers, acetyienic poiyethyiene oxides,
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`ooiyethyiene oxide (di)esters, dimethicone copoiyois, t’iuoroaikyi boiyethyiene oxides, and
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`the iike.
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`in some exampies,
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`the aqueous gore-treatment fluid can inciude a cationic
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`surfactant, nonionic surfactant, tiuorosurfactant, siiicone surfactant. and mixtures thereof.
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`in some exambies, the aqueous ore-treatment fluid can inctude a nonicnic siiicone and/or
`fiuorosurfactant.
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`Additives
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`{00032}
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`in some examoies the aqueous ore—treatment fluid may comprise additives
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`such as biccides (such as NuoseptTM (NudexTM inc), UcarcideTM {Union carbide Corp“),
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`VancideTM (RT.
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`‘y’anderbiitTM Co), F’roxeiT-M (LonzaW), and combinations thereof),
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`viscosity modifiers, materiais for pH adjustment. sequestering agents (such as EDTA
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`(ethyiene diamine tetraacetic acid», preservatives, and the like.
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`Pie—treatment Vehicie
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`()0
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`[OOQBSI
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`The aqueous pre—treatment iiuid comprises a pre—treatment vehicie.
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`in some
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`exampies, the pre—treatrhont vehicio comprises water and a oo—soivent.
`
`in some exampies
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`the aqueous preutreatment fluid comprises a co—soivent in an amount of about t to about
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`50 wt% by totai weight ofthe pre—treatn’ient fiuici, for exampie from about t to about 40 wt%
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`oithe pre—treatn'ient tiuiri, or about 5 to about 30 wt% otthe totai weight oithe ore—treatment
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`fluid.
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`[000341
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`in some examples, the pretreatment vehicle comprises a cc—scivent having a
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`betting point ranging from 160° C to 250° C.
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`in some examples, the pro—treatment vehicie
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`comprises a co—soivent having a boiling point ranging from 170° C to 220° C), for exampie
`from 170° C to 215° C.
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`{00635}
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`in some exampies, the co~soivent may be seiecteo form organic co—scivents
`
`inciuding aiiohatic aicohois, aromatic aicohois, diots, gtycoi ethers, poiygiycoi others.
`
`caproiactarns, forniamides, acetamioes, and tong chain aicohois.
`
`in some exampies, the
`
`oo—soivent may be seiecteci form primary aiiphatio aicohois, secondary aiiphatic aicohois,
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`1,2—aicohois,
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`1,3naioohois,
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`t,4—aioohois,
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`1,5—aiochcis, ethyiene giycoi
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`aikyi ethers,
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`propyiene giycoi aikyi ethers, higher homoiogs (Ce-(312) of pciyethyiene giycoi aikyi ethers,
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`pyrroiidincnes, Nuaikyi caprciactams, unsubstituted oaproiaotams, both substituted and
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`unsubstituted torntamicies,
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`both
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`substituted
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`and
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`unsubstituted
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`acetamides,
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`and
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`combinations thereof.
`
`{00036}
`
`in some exarnpies, the co—soivent
`
`is seiectett from an aiiphatic aicohoi, for
`
`exampie a primary aiiphatio aicchci. a secondary aiiphatic aicohoi or a tertiary aiiphatic
`
`aioohci. The aiiphatic aicohoi may be a diet.
`
`in some exainpies, the cowsoivent is an
`
`aiiphatic aicchoi containing t0 carbons or iess, for exampie 8 carbons or iess or 6 carbons
`
`or toss.
`
`in some exampies, the first soivent is an aiiphatic aicohoi being a diet containing
`
`10 carbons or less, for exampie 8 carbons or iess or 8 carbons or less.
`
`{00637}
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`in some exampies,
`
`the co—soivent
`
`is seiected from the group comprising
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`1,2—propanedioi, 1,2—butanedioi, ethyiehe giycoi, 2~rnethyi~2,4~pentaneuioi, t,3~butanedioi,
`
`2—methyi—t,3npropanedioi and t,3—propaneciioi.
`
`in some exampies the co—soivent
`
`is
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`seiecteo from the group comprising 1,2—propanedioi, 1,2—butaneriioi, ethyiene giyooi, 2—
`
`methyi—2,4—pentanedioi, and 1,3—butaneoici.
`
`in some exampies the first soivent is seiected
`
`from the group consisting of t ,Zupropanedioi, 1,2—butanedioi. ethylene giycoi, 2—methyiu2,4—
`
`pentanedioi, 1,3—butanedioi, 2—methyini,3-propanedioi and 1,3—propanedioi.
`
`in some
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`PCT/U82017/015903
`
`examptes the eo-selvent is seiected from the group consisting of 1,2—eropanedloi. 1,2—
`
`hutenedioi, ethyiehe giyeoi, 2—methyi~2,4~pentenedioi, and 1,3-hutehediot.
`
`in some
`
`exarnpies the co—seivent is 1,2vhutenediol.
`
`{06338}
`
`in some exempies, the aqueous pretreatment fluid comprises:
`
`about 0.1 wt% to sheet 25 wt% or a cationic potyrher by tetei weight etthe preu
`
`treatment fluid; and
`
`e gore-treatment vehioie comprising water and about t to about 50 wt% by totei
`
`weight of the pretreatment tluid of a ce—soivent having a boiling point in the range of about
`WC) ”(3 to about 215 ”C3.
`
`Aqueous inkjet ink Compositien
`
`The aqueous inkjet ihh composition comprises a ietex noiymer, a pigment and
`{00939}
`an ink vehicle.
`
`5
`
`10
`
`Latex Paiymer of the inkjet ink composition
`
`15
`
`{00046}
`
`The inkjet ink cemposition comprises a tatex poiymer.
`
`{00041}
`
`Latex potynters can he prepared using any of a number et methods known in
`
`the art, inciuding but not iimited to emuision potymerizetion techniques where ce—menemers
`
`are dispersed and peiymerized in a discontinuous phase of en emuision, The tatexes can
`
`atse be dispersions of potymer prepared by ether techniques known to these in the art.
`
`20
`
`{00942}
`
`The monomers used in the ietexes can he vinyi monomers.
`
`in some exemeies,
`
`the monomers from which the tatex poiyrner is formed are selected from vinyl monomers,
`
`eerytete monomers, methacryiate monerners, styrene monomers, ethyiene, vinyi chtoride,
`
`vinylidene ehtoride, rneteete esters, fairnerate esters, itacenete esters and combinations
`
`thereof.
`
`in some exemeies, monomers from which the latex peiymer is formed may
`
`25
`
`cemprise ethyi ecrylete; ethyi metheeryiete; henzyi eeryiete; henzyt methacryiete; prepyi
`
`acryiate; nropyi methecrytete; iso—propyi eeryiete; iso—propyi metheeryiete; hutyt ecrytete;
`
`butyi methaerytete; hexyi acnyiete; hexyi methacryiate; ectedecyi methecrytete: octedecyi
`
`aeryiete;
`
`ism‘yi methacryiate:
`
`lauryi
`
`acrytate;
`
`hydroxyethyt
`
`acrylate;
`
`hydroxyethyi
`
`methaeryiete;
`
`hydroxyhexyl
`
`eeryiete:
`
`hydrexyhexyi methacryiete;
`
`hydrexyoctadeeyi
`
`30
`
`aerytate; hydrexyoetedecyi methacrylate;
`
`hydrexyieuryt methecryiate;
`
`hydrexyleulyi
`
`aei‘yiate;
`
`phenethyt
`
`aerytete;
`
`phenethyi me‘theerytete; 6-phenythexyi
`
`ecryiete;
`
`6-
`
`phenythexyi metheeryiete; phenyliauryi eeryiete; phenylieuryt methecryiste; 3—nitrophenyi~
`
`S-hexyi metheeryiete; 3~nitrophenyi~tS-oetadeeyi ecryiete; ethyieneglyeoi dicyciopentyi
`
`

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`WO 2018/143960
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`PCT/U82017/015903
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`1.0
`
`other acryiate; vinyi ethyl ketone: vinyi cropyi Ketone: vinyi hexyi keione; vinyl octyi ketone;
`
`vihyi
`
`hutyi
`
`ketone;
`
`cyciohexyi
`
`acryiate;
`
`methoxysiiane;
`
`acryioxyoropyniethyidiinetnoxysiiane;
`
`trifiuoromethyi
`
`styrene;
`
`tritiuorometnyi aciyiate;
`
`tritiuorotnethyi methacryiate;
`
`tetraiiucropropyi actyiate;
`
`tetrafioorcpropyi methaciyiate;
`
`5
`
`heptafioorcbiityi methaciyiate;
`
`iSO'bti'tyi acryiate;
`
`iso—ioutyi methacryiate; 2~ethyihexyi
`
`acryiate; B—ethyihexyi methacryiate;
`cci’nbinations thereof.
`
`iso—octyi
`
`acryiate;
`
`iso—cctyi methacryiate; and
`
`{00043}
`
`in some examoies, the iaiex poiymer is formed from monomers seiected i'roin
`
`styrenes, Ct
`
`to C8 aikyi methacryiaiee, Ct
`
`to €38
`
`aikyi acryiates, ethyiene giycoi
`
`10
`
`methacryiatec and ditnethacryiates, methacryiic acids, aciyiic acids, and combinations
`
`thereof. Exampies of iatex ooiymers that can be used inciude those prepared using a
`
`monomer emuision of styrene, hexyi methacryiate, ethyiene giycci dii‘nethaci‘yiate, and
`
`methacryiic acid, which are copoiymerized to form the iatex.
`
`{00044}
`
`in some exampies, the monomerc from which the iaiex poiyrner is formed
`
`15
`
`inciude acid monomers, such ac (meth)acryiio acid monomers. Acidic monomers that can
`
`he pciymerized in forming iatexes incitida, without iimitaiion, acryiic acid, methacryiic acid,
`
`ethacryiic acid, dimethyiacwiic acid, maieic anhydride, maieic acid, vihyisuifonate,
`
`cyanoacryiic acid, vihyiacetic acid, aiiyiacetic acid, ethyiidineacetic acid, orcpyiidiheacetic
`
`acid, crotonoic acid, tomaric acid, itaconic acid, sorbic acid, angeiic acid, cinnamic acid,
`
`20
`
`styryiacnriic acid, citraconic acid, giutaconic acid, aconitic acid, phehyiacwiic acid,
`
`acryicxypropicnic
`
`acid,
`
`accnitic
`
`acid,
`
`phenyiacryiic
`
`acid,
`
`acryicxypropionic
`
`acid,
`
`vinyibenzoic
`
`acid, N—Vinyisuccinamidic
`
`acid, mesaccnic
`
`acid, methacroyiaianine,
`
`acryioyihydroxygiycine,
`
`suiicethyi methacr‘yiic acid, suiiccrooyi acryiic acid, styrene
`
`suitonic
`
`acid,
`
`suifoethyiacryiic
`
`acid, Zumethacryicyioxymethane—i-suitohic
`
`acid,
`
`3—
`
`25
`
`methacryoyioxypropane—t -suitonic
`
`acid,
`
`3u(vihyioxy)propaheu’i —suifonic
`
`acid,
`
`ethyienesuifonic acid, vinyi suiiiiric acid, 4—vinyiphenyi suifuric acid, ethyiene phosphonic
`
`acid, vinyi phosphoric acid, vinyi hertzoic acid, Z-acryiamioo-z—rnethyi—i~cropanasuifonic
`
`acid, combinations thereof, derivatives ihereot’, and mixtures thereof.
`
`{00045}
`
`in
`
`some exampies,
`
`the iatex ooiymer comprises
`
`a
`
`(methiacryiate or
`
`30
`
`(meth)acryianiide poiymer or copoiymer.
`
`in some examoies, the iatex ooiymer comprises
`
`a (meth)acryiate or (meth)acryiate cccciymar. A (meth)acryiate or (meth)acryiamide
`
`cccciymar may contain a (meih)acryiate/(meth)acryiainide component in addition to other
`
`components, such as other vinyi monomer components. For exampie, the iatex coiyn’ier
`
`may comprise a coooiymer ot a (meth)acryiate monomer and another vihyi monomer, for
`
`35
`
`exampie another vihyi monomer seiected from styrenes, Ct to (33 aikyi methacryiaies, Ci
`
`

`

`WO 2018/143960
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`PCT/U82017/015903
`
`1.1
`
`to C8 alkyi aoryiaies, etnyiene glycol metnacryiates and dimeihaoryiates, methacryiic acios,
`
`aoryiic acids, and combinations thereof. For exampie, the iatex poiymer may comprise a
`
`copeiymer of a (metn)aoryiemide monomer and another vinyi monomer, for exampie
`
`another vinyi monomer seieoteo from styrenes, (31 to (3% aikyi methaoryiates, C1 to (:8
`
`5
`
`aiiryi acryiates, etnyiene giyooi mothaoryiates and dimothaoryiates, metnaoryiic acids,
`
`acryiic acids, and Combinations thereof.
`
`{00045}
`
`in some exampies, tne iatex poiymer comprises a (meih)aoryiete poiymer being
`
`a poiymer comprising (metiflacryiate monomers or a (metmacryiate oopoiymer being a
`
`oopoiymer comprising (meth)acryiate monomers.
`
`in some exampies, the iatex poiymer
`
`10
`
`comprises a (meth)aoryiate oopoiymer comprising (metancryiate monomers.
`
`{00047}
`
`in some exampies, the (metnfiacryiate monomers are seiected from aiiphaiic
`
`(meth)acryiaie monomers, aromatic (mermacryiate monomers and combinations thereof.
`
`{00048}
`
`in some exampies, aiiphetio (meth)acryiate monomers comprise iinear aiipnatic
`
`(meth)acryiate monomers and/or oycioaiiphatic (meth)aoryiate monomers.
`
`15
`
`{00049}
`
`in
`
`some
`
`examples,
`
`iinear
`
`(metn)aoryiaie monomers
`
`comprise
`
`aikyi
`
`(metn)acryiate monomers (for example C1 to (38 eikyi (meih)acryiate monomers).
`
`in some
`
`exampies,
`
`tne iinear (metn)acryiate monomers oomprise aikyi metnecryiete monomers
`
`(eg. (31 to £38 aikyi meinacryiate monomers).
`
`in some exampies, the iinear (meth)acryiate
`
`monomers comprise eikyi methacryiete monomers (so.
`
`(31 to (38 aikyi metnaciyiate
`
`20
`
`monomers) and aikyi acryiate monomers (C1 to C38 aikyi acryiate monomers).
`
`{00050}
`
`in some examples, the latex poiymer comprises a copoiymer comprising aikyi
`
`(metn)acryiate reg. Ct to C8 aikyi (metn)acryiate monomers) and styrene monomers.
`
`in
`
`some exampies, the iatex poiymer comprises a oopoiymer comprising aikyi (metn)acryiate
`
`25
`
`(eg. Ct to £38 aikyi (metn)acryiate monomers), styrene monomers and (metmacryiio acid
`monomers.
`
`{00051}
`
`in some exampies, the iatex poiymer comprises a (meth)acryiamirie ooiymer
`
`being a poiymer comprising (meth)acryiamide monomers ora (maimaoryiamioe copoiymer
`
`being a copoiymer comprising {mermacryiamide monomers.
`
`in some exampies, the iatex
`
`3Q
`
`comprises
`poiymer
`monomers.
`
`a
`
`(meth)acryiemide
`
`oopoiymer
`
`comprising
`
`(mermacryiamide
`
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`

`WO 2018/143960
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`PCT/U82017/015903
`
`1.2
`
`{00052}
`
`in some examples, the (metn)acrylamide monomers are seiec‘ted from aiiphatic
`
`(metn)acryiamide monomers, aromatic (metn)acrylamide monomers and combinations
`thereof.
`
`{06353}
`
`in some exampies, aliphatic (meth)acryiamide monomers comprise iinear
`
`aiiphatic (meth)acryiamide monomers and/or cycioaiiphatic (meth)acryiamide.
`
`{00654}
`
`in
`
`some examples,
`
`iinear
`
`(rneth)acryiamide monomers comprise alkyi
`
`(meth)acryiamide monomers (for example Ct to C8 alkyi (metn)aoryiamide monomers).
`
`in
`
`some exampies, the iinear (metn)aoryiamide monomers comprise aikyi methacryiamide
`
`monomers (eg. Ct to ()8 aikyi methacryiamide monomers).
`
`in some exampies= the iinear
`
`(meth)acryiamide monomers comprise aikyi metnacryiamioe monomers (eg.
`
`(31 to C8
`
`aiityi methacryiamide monomers) and aikyi acryiamide monomers (Ct
`
`to CS aikyi
`
`acryiarnide monomers).
`
`{00055}
`
`in some exampies, the iatex poiymer comprises a copoiymer corriprising alkyi
`
`(meth)acryiamioe reg. Ct to £38 aikyi (nteth)acryiamide) and styrene monomers.
`
`in some
`
`exampies, the iatex poiymer comprises a copoiymer comprising aikyi (meth)acryiamioe
`
`(eg. (:21 to (38 aikyi (meth)aoryiamide monomers), styrene monomers and (meth)acryiic
`acid monomers.
`
`{00655}
`
`in some exampies,
`
`tne iatex ooiymer comprises a copoiyrner comprising
`
`cycioalipnatic (metinacrylate monomers or cycloaliphatic (tractioacryiamioe monomers.
`
`{00057}
`
`The present inventors have found that employing a iatex polymer comprising
`
`cycioaiiphatic (meth)acryiate or (meth)aoryiarnide monomers in the inkjet ink compositions
`
`described herein provides further improvements regarding the curing ottne iatex poiyrners
`
`on, and adhesion to, a wide range of print substrates.
`
`{09058}
`
`in some exampies,
`
`the iatex poiymer comprises a oopoiymer comprising
`
`aromatic (meth)aoryiate monomers or aromatic (meth)acryiamioe monomers.
`
`{00059}
`
`The terms ‘cycioaiiphatic’ and ‘aromatic’ are well understood by the skiiied
`
`person.
`
`{00660}
`
`in some examples, the iatex poiymer is derived from a composition comprising
`
`a cycioaiiphatic monomer and an aromatic monomer, wherein the cycioaiiphatic monomer
`
`comprises a cycioaiiphatic (meth)acryiate monomer or a cycioaiiphatic (meth)acryiamide
`
`monomer and the aromatic monomer comprises an aromatic (meth)acrylate monomer or
`
`an aromatic (meth)acryiarnide monomer. For exampie; the iatex poiymer may comprise a
`
`10
`
`20
`
`30
`
`

`

`WO 2018/143960
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`PCT/U82017/015903
`
`copoiymer of a cycioaiiphatic monomer and an aromatic monomer. wherein the
`
`cycioaiiphatic monomer comprises one or more monomers comprising a cycioaiiphatic
`
`(meth)acryiate monomer or a cycioaiiphatic (metinacryiamioe monomer, and the aromatic
`
`monomer comprises one or more monomers comprising an aromatic (rneth)aoryiate
`
`5
`
`monomer or an aromatic (meth)acryiamide monomer. For exarnpie, the iatex poiymer may
`
`comprise a copoiymer comprising cycioaiiphatic monomer units (eg. cycioaiiphatic
`
`(mettuacryiate and/or cycioaiiphatic (meth)acryiamide units) and aromatic monomer units
`
`(eg. aromatic (meth)acryiate and/or aromatic (meth)aoryiamide units).
`
`{00051}
`
`The present inventors have found that empioying a iatex poiymer comprising a
`
`lo
`
`copoiymer comprising cycioaiiphatio monomers (such as cycioaiiohatic (meth)acryiate or
`
`(meth)acryiamioe monomers)
`
`in combination aromatic monomers (such as aromatic
`
`(meth)acryiate or (rnetihacryiamide monomers) in the inkjet init compositions described
`
`herein provides further improvements regarding the curing of the iatex poiymers on, and
`
`adhesion to, a wide range or print substrates.
`
`15
`
`{00952}
`
`in some exampies, the cycioaiiphatic monomer comprises a cycioaiiphatic
`
`(meth)acryiate monomer or a cycioaiibhatic (meth)acryiamioie monomer.
`
`in some
`
`exampies,
`
`the cycioaiiphatic monomer comprises
`
`a
`
`cycioaiiphatic (meth)aoryiate
`
`monomer.
`
`A cycioaiiphatic (meth)acryiate monomer
`
`is a monomer corriprising a
`
`cycioaiiphatic moiety bonded to, either directiy or inoir'eotiy, a (meth)acryiate moiety (eg.
`
`20
`
`by a carbon chain; for exampie a substituted or unsubstituted carbon chain, for example a
`
`saturated or unsaturated carbon chain, such as a (31-12