WO2024132405A1 - Liquide de prétraitement contenant une résine pour impression à jet d'encre et procédé d'enregistrement - Google Patents

Liquide de prétraitement contenant une résine pour impression à jet d'encre et procédé d'enregistrement Download PDF

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WO2024132405A1
WO2024132405A1 PCT/EP2023/083355 EP2023083355W WO2024132405A1 WO 2024132405 A1 WO2024132405 A1 WO 2024132405A1 EP 2023083355 W EP2023083355 W EP 2023083355W WO 2024132405 A1 WO2024132405 A1 WO 2024132405A1
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poly
polymer
copolymers
treatment liquid
aqueous
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PCT/EP2023/083355
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English (en)
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Hubertus Van Aert
Bingyu YANG
Jens Lenaerts
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Agfa Nv
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    • 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
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • 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
    • 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
    • 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
    • C09D11/12—Printing inks based on waxes or bitumen
    • 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
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink

Definitions

  • Resin containing pre-treatment liquid for inkjet printing and recording method Resin containing pre-treatment liquid for inkjet printing and recording method.
  • the pre-treatment liquid is a composition capable of receiving ink and holding colorants in the ink to a greater degree than a substrate not treated with a pre-treatment liquid.
  • the pre-treatment liquid is capable of holding colorants at or near the surface of a substrate so that optical density and colour gamut of the printed image may be improved compared to a porous substrate that is not treated with the pre-treatment liquid.
  • the colorant in aqueous inkjet inks for inkjet printing can be a dye or a pigment.
  • Pigment based inks have the advantage of providing images with a higher light fastness than dye based inks.
  • reactive binder technology has been introduced into the inks but also into the pre-treatment liquids.
  • W02014/039306A discloses a pre-treatment for digital printing on substrates comprising an aqueous cationic polyurethane dispersion, coagulating acids, and a reactive crosslinking moiety.
  • US2009/0226678 discloses an ink set comprising a fixing liquid for making pigments of inkjet inks fixed, comprising a polymer fine particle synthesized from an alkyl (meth)acrylate and/or cyclic alkyl (meth) acrylate, and a reactant being a block isocyanate, an oxazoline-containing polymer, or a polycarbodiimide.
  • WO2018/138069 discloses a pre-treatment liquid comprising capsules composed of a polymeric shell surrounding a core, the core comprising one or more chemical reactants capable of forming a reaction product upon application of heat and/or radiation.
  • the shell is stabilized by cationic dispersing groups which were linked to the shell by means of copolymerizable surfactants.
  • the chemical reactants are preferably blocked isocyanates.
  • the dispersing groups being solely cationic groups provide only moderate storage stability in the presence of cationic fixing agents of the pre-treatment liquid such as multivalent metal salts or water soluble polymers.
  • Latex based approaches have been disclosed in the patent literature (see WO201 8/114314A, US 2013/0245157A1 and EP3275949A1), having binding capability to fulfil some requirements on physical properties for several applications.
  • latex based inkjet inks do generally not improve simultaneously water resistance and rub resistance of printed images on low absorbing substrates such as corrugated card board, liners, folding board etc.
  • latex based inkjet inks have a tendency for film formation in the nozzles of the print head and in the ink supplies, leading to reliability problems during printing. In industrial applications, system reliability and especially jetting reliability is of utmost importance. Therefore, there was still a need for more optimal resin technologies [0011]
  • Polymerisable polymers having reactive functional groups such as in
  • LIS2019/0023922 are known to have reactivity towards typical shell monomers used in interfacial polymerization such as isocyanates, especially from a moderate alkaline pH onwards. This reactivity towards shell monomers, limits the latitude for encapsulation of these polymers based on interfacial polymerization, which is a concern for industrialization and scalability. Latitude in the industrialization of the core shell particles is of key importance to avoid loss in production, leading to significant economic and ecological losses.
  • Fig. 1 Pattern used for inkjet printing during the evaluation of the image quality of images obtained with pre-treatment compositions.
  • the pattern contains solid areas and negative text with different size ranging from 1 pt to 16 pt.
  • an aqueous pretreatment liquid comprising a fixing agent and a resin particle having an average particle size of 1 pm or less, the resin particle comprising a first polymer and a second polymer, the second polymer is a polyalkylene oxide-graft-polymer obtained by polycondensation or addition polymerization, the polyalkylene oxide-graft having an number average chain length of 20 or more alkylene oxide units.
  • the first and second polymer are different.
  • the presence of a polyalkylene oxide graft of at least 20 units gives the resin particles an increased colloidal stability due to steric repulsion of the particles, leading to an improved storage stability of the pre-treatment liquid.
  • the first polymer comprises cationic dispersing groups, such as quaternary ammonium groups which gives the resin particles an additional electrostatic stabilisation.
  • the resin particle in the pre-treatment liquid for inkjet printing according to the invention comprises a first polymer, including polyureas, polyurethanes, polyesters, polycarbonates, polyamides, poly(acrylates), poly(vinyl ethers), poly(vinyl esters), polysulphonamides, melamine based polymers, silica based sol-gel polymers or mixtures thereof such as in US603149B1 , with polyureas and polyurethanes being especially preferred, polyurea being the most preferred.
  • a first polymer including polyureas, polyurethanes, polyesters, polycarbonates, polyamides, poly(acrylates), poly(vinyl ethers), poly(vinyl esters), polysulphonamides, melamine based polymers, silica based sol-gel polymers or mixtures thereof such as in US603149B1 , with polyureas and polyurethanes being especially preferred, polyurea being the most preferred.
  • the colloidal stability of the resin particles in the vehicle of the pretreatment liquid according to the invention can be further improved via the incorporation of a dispersing group covalently bonded to the first polymer and/or are by using dispersants or surfactants preferably added during or after the formation of the capsule.
  • the incorporation of a dispersing group covalently bonded to the first polymer is preferably performed by reacting a compound containing at least two functional groups capable of reacting with primary and secondary amines from a compound containing a dispersing group such as a quaternary ammonium group. The presence of the primary and secondary amines makes that the compound is a polyamine crosslinker.
  • the first polymer in the resin particles according to the invention are preferably obtainable by reacting a polyamine crosslinker comprising at least two primary or secondary amines and a quaternary ammonium group, with a compound containing at least two functional groups capable of reacting with the primary and secondary amines of the crosslinker.
  • the functional groups are an epoxide, an isocyanate, a 0-keto- ester, a [B-keto-amide, an anhydride, a 1 ,3-diketone, a chloroformate, a sulfochloride, an acid halide, an enol ester, an oxalate ester or an aziridine, an isocyanate being most preferred.
  • Other preferred functional groups are acid halides, chloroformates, enol esters, oxalate esters, N- hydroxysuccinimide active esters, t-butyl carbamates/carbonates, and other active esters.
  • Polymeric curing agents having active ester groups are also commercially available e.g. from Dai Nippon Ink & Chemicals, eg. Epicion EXB 9451 (Cas nr. 931106-68-2) and Epicion HPC 8000-65T (CAS nr.1352138-02-3).
  • Active ester based initiators to prepare (co)polymers having an active ester group capable of reacting with the polyamine curing agent e.g. as the structure described in patent J P2001206946.
  • Copolymer of an active ester functional monomer such as: NHS-PEO8-maleimide (CAS nr.289888-73- 9).
  • polyisocyanates Different chemistries can be used as suitable polyisocyanates.
  • the polyamine comprising at least two primary or secondary amines and a quaternary ammonium group
  • an organic solvent soluble isocyanato based resin such as a polyisocyanate (e.g. biuret, allophanate or isocyanurate trimer based structures).
  • a polyisocyanate e.g. biuret, allophanate or isocyanurate trimer based structures.
  • biuret functional polyisocyanates such as Desmodur N3200 or Desmodur N75 BA are preferred.
  • the chemistry of the polyisocyanate has a significant effect on the particle formation during the high shear treatment and interfacial polymerization.
  • the type of polyisocyanate used influences e.g. reactivity towards the polyamine, the solubility in the organic solvent and the viscosity.
  • Suitable polyisocyanates are monomeric isocyanates, biuret structures, urethione, allophanate, isocyanurate trimer, isocyanate adducts or (partially) modified polyisocyanates.
  • modified polyisocyanates are hydrophilic isocyanates such as polyether modified polyisocyanates, e.g Bayhydur 3100, Bayhydur 305, Bayhydur XP2451/1.
  • the type of isocyanate present in the polyisocyanate is also important for the adhesion properties of the pre-treatment composition to the substrate and the physical properties of the overcoat varnish.
  • Hexamethylene diisocyanate (HDI) offers a higher flexibility than isophorone diisocyanate (IPDI) isocyanates.
  • Suitable isocyanate containing compounds are isocyanato monomer based copolymers prepared by radical copolymerization. The copolymerization can be performed in the organic solvent which is used to make the oleophilic phase.
  • Suitable monomers to make an isocyanato functional copolymer via addition polymerization are e.g. isocyanatoethylmethacrylate, 2-isocyanatoethyl acrylate, 3- isocyanatopropyl 2-propenoate and 1-(1-lsocyanato-1-methylethyl)-3- isopropenylbenzene (TMI monomer Allnex).
  • a copolymer of methylmethacrylate and 1-(1-lsocyanato-1-methylethyl)-3- isopropenylbenzene can be obtained in ethyl acetate and consequently can be used in the preparation of the resin particle dispersion of the invention.
  • the compound reacting with the polyamine comprising at least two primary or secondary amines and a quaternary ammonium group are epoxy containing resins.
  • examples are bisphenol A diglycidyl ether based epoxy resins, copolymers of epoxy functional monomers such as glycidyl methacrylate (GMA), glycidyl acrylate, allyl glycidyl ether, 4-vinylcyclohexene oxide or (3,4- epoxycyclohexyl)methyl acrylate and epoxydised oils, such as epoxidized soybean oil.
  • the compound reacting with the polyamine comprising at least two primary or secondary amines and a quaternary ammonium group are polyazeridines.
  • Suitable polyazeridines are NeoAdd Pax 521 (ie. a 80% solution in ethyl acetate) supplied by Covestro and polyazeridines as described in the patent application WO 2020/020714 by DSM IP Assets B.V.
  • the compound reacting with the polyamine comprising at least two primary or secondary amines and a quaternary ammonium group are alkoxy silane functional polymers such as SiliXan Lab 1039 M1 supplied by SiliXan GmbH (50% in butyl acetate) and copolymers of siliane monomers.
  • the compound reacting with the polyamine comprising at least two primary or secondary amines and a quaternary ammonium group can be resins having acrylate or acrylamide groups and which are able to react via a Michael addition.
  • resins can be prepared by modification of hydroxyfunctional polymers using isocyanato ethyl acrylate or by modification of maleic anhydride copolymers with a hydroxy-functional acrylate, such as hydroxybutyl acrylate.
  • the compound reacting with the polyamine comprising at least two primary or secondary amines and a quaternary ammonium group can be copolymers with monomers having an active methylene group, e.g. a p-keto-ester, a p-keto-amide, an anhydride or a 1 ,3-diketone, such as diacetone acrylamide or 2- (acetoacetoxy)ethyl methacrylate.
  • an active methylene group e.g. a p-keto-ester, a p-keto-amide, an anhydride or a 1 ,3-diketone, such as diacetone acrylamide or 2- (acetoacetoxy)ethyl methacrylate.
  • Ri, R2, R3, R4 and R5 are independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group and a substituted or unsubstituted aryl or heteroaryl group
  • L, Li and L2 represent independently a divalent linking group having no more than 15 carbon atoms
  • A represents a structural moiety comprising at least two functional groups selected from the group consisting of a primary and a secondary amine
  • A1 and A2 independently represent a structural moiety comprising at least one functional group selected from the group consisting of a primary and a secondary amine
  • X- is a counter ion to compensate the positive charge of the quaternary ammonium group.
  • linking groups L, Li and L2 is according to Formula III, IV orV:
  • Q is O or NH and R is an alkyl or substituted alkyl group.
  • R1 is substituted or unsubstituted alkyl
  • a preferred method of producing the resin particles to be used in the pretreatment liquid according to the invention is by means of interfacial polymerization (see below).
  • Interfacial polymerisation requires the emulsion of an oleophilic phase in an aqueous continuous phase or vice versa.
  • the oleophilic phase is preferably obtained by using a substantially water immiscible organic solvent and dissolving the second polymer together with the compound comprising two functional groups capable of reacting with a primary or secondary amine.
  • the functional groups being preferably an epoxide, an isocyanate, a p-keto-ester, a p-keto-amide, an anhydride, a 1 ,3-diketone, a chloroformate, a sulfochloride, an acid halide, an enol ester, an oxalate ester or an aziridine.
  • a polyamine comprising at least two primary or secondary amines and a quaternary ammonium group, is preferably added in the aqueous phase.
  • the polyamine comprising at least two primary or secondary amines and a quaternary ammonium group, may react at the interface between the oleophilic and the aqueous phase with the compound containing at least two functional groups capable of reacting with the primary or secondary amines of the crosslinker, forming the first polymer in the resin particle.
  • the functional groups are an epoxide, an isocyanate, a p-keto-ester, a p-keto-amide, an anhydride, a 1 ,3-diketone, a chloroformate, a sulfochloride, an acid halide, an enol ester, an oxalate ester or an aziridine.
  • the resin particles of the invention comprise also particles which do not have a separate dispersed phase but having a polymeric shell showing a gradient in crosslinking degree which is higher at the surface than inside the particle.
  • the oleophilic phase comprises a polyisocyanate together with the second polymer and the aqueous phase comprises the cationic polyamine comprising at least two primary or secondary amines and a quaternary ammonium group. Upon reaction between these two compounds, a urea bond is formed.
  • the primary amine groups will firstly react in most cases except in alkylation reactions where the secondary amine groups react faster.
  • the formed polyamine crosslinker will have consequently a lower reactivity towards the compound containing at least two functional groups capable of reacting with the primary and secondary amines of the crosslinker in an interfacial reaction. This enables to add the polyamine crosslinker during the dispersion step and not get too fast reaction. Since the cationic crosslinker also offers electrostatic stabilisation to the obtained resin particle, no huge amounts of surfactant are required to stabilize the particles during the preparation step. This reduces foam formation during the preparation of the particles.
  • Polyamine crosslinking agents comprising at least two primary or secondary amines and a quaternary ammonium group are not readily available.
  • Typical polyamines to be used in the preparation of the polyamine crosslinker comprising at least two primary or secondary amines and a quaternary ammonium group are listed in Table 1 :
  • Table 1 Polyamines which may be used as reagents for preparing polyamine crosslinking agents.
  • polyamines can be reacted with a cationic epoxy compound, such as glycidyltrimethylammonium chloride, ie. CAS nr. 3033-77-0 (e.g. GMAC supplied by Sachem).
  • a cationic epoxy compound such as glycidyltrimethylammonium chloride, ie. CAS nr. 3033-77-0 (e.g. GMAC supplied by Sachem).
  • epoxy compounds are glycidyldimethyldodecylammonium chloride, glycidyltriethylammonium chloride, glycidyldimethyloctylammonium chloride, N,N-dimethyl-N-(phenylmethyl)-oxiranemethanaminium chloride, (2,3-Epoxypropyl)tris(2-hydroxyethyl)ammonium chloride, N,N-dimethyl-N- (oxiranylmethyl)-oxiranemethanaminium, chloride, a,a'- [[octadecyl(oxiranylmethyl)iminio]di-2,1-ethanediyl]bis[w-hydroxy-poly(oxy- 1 ,2-ethanediyl), chloride, N,N,N-trimethyl-oxiranepropanaminium bromide, N-ethyl-N,N-bis(2-hydroxyethyl)
  • Reaction e.g. of TETA with one equivalent of GMAC will lead to a mixture of products.
  • the primary amine groups will react faster than the secondary amine groups.
  • the GMAC is slowly added to the TETA, in order to get more mono-functionalised polyamine (e.g. Formula V) than bis(GMAC) adduct (e.g. Formula VI).
  • Reaction of PA-1 with GMAC leads to the product according to Formula VI and VII.
  • the polyamine should still have unreacted NH or NH2 groups, in order to be reactive towards the compound containing at least two functional groups such as an epoxide, an isocyanate, a p-keto-ester, a p-keto-amide, an anhydride, a 1 ,3- diketone, a chloroformate, a sulfochloride, an acid halide, an enol ester, an oxalate ester or an aziridine.
  • functional groups such as an epoxide, an isocyanate, a p-keto-ester, a p-keto-amide, an anhydride, a 1 ,3- diketone, a chloroformate, a sulfochloride, an acid halide, an enol ester, an oxalate ester or an aziridine.
  • R8, R9 and R10 is a substituted or non-substituted alkyl, aryl, alkyl aryl group
  • the cationic charge density of the polyamine crosslinker can be increased by modifying the polyamine with more than 1 equivalent of cationic reagent. Another way of increasing charge density is by decreasing the pH before, during or after the resin particle dispersion preparation in order to form more quaternary amines due to protonation. [0055] Instead of reacting a cationic reagent with the polyamine, one can react also reagents having a tertiary amine group such as listed in Table 3. Table 3: Acrylates and acrylamides containing a tertiary amine group
  • Products like dimethyl amino propyl acrylamide can also be quaternized with reagents like 3-Chloro-2-hydroxypropyltrimethyl ammonium chloride, in order to obtain products with a higher charge density: 2-hydroxy-N,N,N,N',N'-pentamethyl-N'-[3-[(1 -oxo-2- propenyl)amino]propyl]-1 ,3-propanediaminium, dichloride (CAS nr. 110226-36-3).
  • amphoteric reagents can be reacted with a polyamine, e.g. A/-(2-carboxyethyl)-A/,A/-dimethyl-3-[(1-oxo-2- propenyl)amino]-1-propanaminium, inner salt (CAS nr. 79704-35-1).
  • a polyamine e.g. A/-(2-carboxyethyl)-A/,A/-dimethyl-3-[(1-oxo-2- propenyl)amino]-1-propanaminium, inner salt (CAS nr. 79704-35-1).
  • Another reaction type which can be used to make a polyamine comprising at least two primary or secondary amines and a quaternary ammonium group is the reaction of an aldehyde with the polyamine forming an imine, e.g. using 2-(dimethylamino)acetaldehyde (CAS nr. 52334-92-6), or derivatives of 2-(dimethylamino)acetaldehyde, e.g. the reaction product with Reagens 65.
  • 2-(dimethylamino)acetaldehyde CAS nr. 52334-92-6
  • derivatives of 2-(dimethylamino)acetaldehyde e.g. the reaction product with Reagens 65.
  • the cationic polyamine crosslinkers could be derived from protonated tertiary amines. Polyamines with secondary and primary amines can also become cationic at low pH, but are less preferred if the pH of the jettable liquids have a pH of 5 or higher.
  • regular polyamines such as: Spermidine, Diethylenetriamine, N,N'-Bis(2- aminoethyl)-1 ,3-propanediamine, Triethylenetetramine, Tetraethylenepentamine, N,N'-Bis(3-aminopropyl)ethylenediamine, Pentaethylenehexamine, Bis(hexamethylene)triamine, Bis(3- aminopropyl)amine, Bis(3-aminopropyl)methylamine, Bis(2- aminoethyl)methylamine, Tris(2-aminoethyl)amine, Tris(3- aminopropyl)amine.
  • regular polyamines such as: Spermidine, Diethylenetriamine, N,N'-Bis(2- aminoethyl)-1 ,3-propanediamine, Triethylenetetramine, Tetraethylenepentamine, N,N'-Bis(3-aminopropyl)ethylenediamine, Pentaethylenehexamine, Bis(hexamethylene)triamine
  • polyamines can also be modified by means of an epoxy amine reaction using the following reagents, e.g.: N,N-Dimethyl-2- oxiranemethanamine and N,N-dimethyl-2-Oxiranepropanamine.
  • Derivatives of poly(saccharides) and cellulose are esters and ethers as disclosed in https://en.wikipedia.org/wiki/Cellulose. They comprise cellulose acetate, cellulose triacetate, Cellulose propionate, Cellulose acetate propionate (CAP), Cellulose acetate butyrate (CAB), Nitrocellulose (cellulose nitrate), Cellulose sulfate, methylcellulose, ethylcellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose.
  • this second polymer and a monomer such as a polyisocyanate are mixed prior to the high shear treatment of the interfacial polymerization.
  • the second polymer should then be preferably soluble in the organic solvents forming the oleophilic phase in the interfacial polymerization (see ⁇ A.1.4.) or should have at least segments which are soluble or swellable in the organic solvents.
  • the incorporation of the polyalkylene oxide grafts can be accomplished by means of copolymerization of polyether diols.
  • the incorporation of hydrophilic grafts can be accomplished by graft copolymers of methacryl terminated polyethylene glycol. Examples are a polyethylene glycol functional polyacrylate copolymer such as Byk LPG21241 , or polyethylene glycol based block copolymers which are well soluble in the organic phase (ethyl acetate).
  • Such graft or block copolymers contain then besides the water compatible polyether chains also segments which are insoluble in water (e.g.
  • Suitable polyether diols in the present invention are Ymer N90 or Tegomer D 3403, i.e. a-[2,2-bis(hydroxymethyl)butyl]-u)-methoxy-Poly(oxy- 1 ,2-ethanediyl). These diols can be prepared from trimethylol propane oxetane (TMPO). A possible synthesis procedure is described by Fock, J.; Mohring, V., Polyether-1 ,2- and -1 ,3-diols as macromonomers for the synthesis of graft copolymers, 1. Synthesis and characterization of the macromonomers. Die Makromolekulare Chemie 1990, 191 (12), 3045- 3057. In general, also other polyether 1 ,2- or 1 ,3-diols can be used.
  • TMPO trimethylol propane oxetane
  • the length of the polyalkylene oxide chain incorporated in the second polymer determines the colloidal stability of the resin particles of the invention in a pre-treatment liquid formulation.
  • a shorter polyether chain such as with Ymer N 180 or Ymer N 120 is less preferable than a longer polyether chain as with Ymer N90.
  • Suitable poly(urethanes) as second polymer can be obtained by polymerization of di- or polyisocyanates with diols.
  • Typical di-isocyanates can be selected from the group consisting of isophorone diisocyanate (IPDI), 4, 4’ -dicyclohexylmethane diisocyanate (H12MDI), 2,4,4’-trimethyl- 1 ,6-hexamethylene diisocyanate (TMDI), hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate (PDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI) and diphenylmethane diisocyanate (MDI).
  • IPDI isophorone diisocyanate
  • H12MDI 4, 4’ -dicyclohexylmethane diisocyanate
  • TMDI 2,4,4’-trimethyl- 1 ,6-hexamethylene
  • Diols can be low molecular weight compounds but oligomeric diols are particularly preferred.
  • Typical oligomeric diols can be selected from the group consisting of polyester polyols, polyether polyols, polyamide polyols, polyacrylate polyols, polycarbonate polyols and polyolefine polyols.
  • a suitable polyacrylate graft copolymers the acrylate monomer(s) are copolymerized with a polyalkylene oxide containing macromer, such as methoxypolyethylene glycol monomethacrylate (CAS registry number 26915-72-0) e.g. Bisomer S 20 W, Visiomer MPEG 2005MAW or Visiomer MPEG 5005MAW.
  • a polyalkylene oxide containing macromer such as methoxypolyethylene glycol monomethacrylate (CAS registry number 26915-72-0) e.g. Bisomer S 20 W, Visiomer MPEG 2005MAW or Visiomer MPEG 5005MAW.
  • macromers are: methoxypolyethylene glycol acrylate (CAS registry number 32171-39-4) , polyethylene glycol monoacrylate (CAS registry number 26403-58-7), polyethylene glycol acrylate (CAS registry number 26915-72-0), polyethylene glycol monomethacrylate (CAS registry number 25736-86-1), Polyethylene glycol) maleimide (CAS registry number 58914-60-6) and N- polyethylene glycol)acrylamide (CAS registry number 39839-67-3).
  • methoxypolyethylene glycol acrylate CAS registry number 32171-39-4
  • polyethylene glycol monoacrylate CAS registry number 26403-58-7
  • polyethylene glycol acrylate CAS registry number 26915-72-0
  • polyethylene glycol monomethacrylate CAS registry number 25736-86-1
  • Polyethylene glycol) maleimide CAS registry number 58914-60-6
  • N- polyethylene glycol)acrylamide CAS registry number 39839-67-3
  • Suitable acrylates as second polymer are obtained by polymerization of monomers selected from the group consisting of ethylacrylate, butylacrylate, methylmethacrylate, ethylmethacrylate, methyl acrylate, butylmethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, stearyl acrylate, stearyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isopropyl acrylate, isopropyl methacrylate and copolymers of acrylic or methacrylic monomers with monomers selected from the group consisting of alpha-methylstyrene, vinylacetate, vinyl versatate, butadiene, isoprene, acrylonitrile, methacrylonitrile
  • the second polymer preferably has a weight average molecular weight (M w ) between 500 g/mol and 400.000 g/mol, more preferably between 1000 g/mol and 100.000 g/mol and most preferably between 2000 g/mol and 50.000 g/mol.
  • M w weight average molecular weight
  • the resin particles to be used in the pre-treatment liquid which is preferably jettable, have an average particle size of no more than 1 pm as determined by dynamic laser diffraction.
  • the nozzle diameter of inkjet print heads is usually 20 to 35 pm. Reliable inkjet printing is possible if the average particle size of the capsules is five times smaller than the nozzle diameter. An average particle size of no more than 1 pm allows jetting by jetting heads having the smallest nozzle diameter of 20 pm. In a more preferred embodiment, the average particle size of the capsules is ten times smaller than the nozzle diameter. Hence preferably, the average particle size is from 0.05 to 1 pm. When the average particle size of the particle is smaller than 1 pm, excellent resolution and dispersion stability with time are obtained.
  • the resin particles are preferably present in the pre-treatment liquid in an amount of no more than 45 wt.%, preferably between 1 and 25 wt.% based on the total weight of the liquid. It was observed that above 30 wt.% jetting was not always so reliable.
  • the resin particles in the pre-treatment liquid according to the invention can be prepared using both chemical and physical methods. Suitable methodologies include complex co-acervation, liposome formation, spray drying and polymerization methods.
  • a polymerization method is used, as it allows the highest control in designing the resin particles. More preferably interfacial polymerization is used to prepare the resin particles of the invention. This technique is well-known and has been reviewed by Zhang Y. and Rochefort D. (Journal of Microencapsulation, 29(7), 636-649 (2012) and by Salitin (in Encapsulation Nanotechnologies, Vikas Mittal (ed.), chapter 5, 137-173 (Scrivener Publishing LLC (2013)).
  • interfacial polymerization such as interfacial polycondensation
  • two reactants meet at the interface of the emulsion droplets and react rapidly.
  • interfacial polymerization requires the emulsion of an oleophilic phase in an aqueous continuous phase or vice versa.
  • the oleophilic phase is preferably obtained by using a substantially water immiscible organic solvent.
  • Each of the phases contains at least one dissolved reagent (a first ‘monomer’) that is capable of reacting with another reagent (a second ‘monomer’) dissolved in the other phase to form the first polymer of the resin particle.
  • the first polymer is formed that is insoluble in both the aqueous and the oleophilic phase.
  • the formed polymer has a tendency to precipitate at the interface of the oleophilic and aqueous phase.
  • a partial or complete shell is formed around the dispersed phase comprising the second polymer, which grows upon further polymerisation.
  • the particles according to the present invention are preferably prepared from an oleophilic emulsion in an aqueous continuous phase.
  • interfacial polymerization is performed and a first polymer (see A.1.1.) is formed at the interface.
  • a first polymer see A.1.1.
  • the functional groups are preferably an epoxide, an isocyanate, a p-keto-ester, a 0-keto- amide, an anhydride, a 1 ,3-diketone, a chloroformate, a sulfochloride, an acid halide, an enol ester, an oxalate ester or an aziridine, an isocyanate being most preferred.
  • This compound is preferably present in the oleophilic phase.
  • This compound reacts with a reagent in the aqueous phase such as water or a crosslinker preferably being a polyamine comprising a primary and secondary amine group together with a quaternary group.
  • polyamines are preferred whereas polyols show a much slower reaction rate.
  • the polyamine crosslinker can be omitted as water can react with the isocyanate moiety and can form an amine. This in-situ formed amine can then further react with another isocyanate moiety present in the polyisocyanate. So even without adding a polyamine crosslinker a crosslinked first polymer can be obtained.
  • the concentration of the polyisocyanate, the added second polymer and in particular, the ratio of water immiscible solvent phase/aqueous phase determines the oleophilic droplet sizes during the high shear treatment.
  • the amount of the isocyanate groups in the polyisocyanate, their reactivity and the concentration of the reagent in the aqueous phase, preferably a polyamine crosslinker, determines the crosslinking density of the first polymer in the resin particle.
  • the type of solvent forming the oleophilic phase in the interfacial polymerization is important to obtain an industrial scalable process.
  • an organic solvent is used with a low boiling point which can be easily removed, such as ethyl acetate or methylene chloride.
  • the organic solvent has a boiling point lower than that of water.
  • polyisocyanate has a significant effect on the resin particle formation.
  • Suitable polyisocyanates can be monomeric isocyanates, biuret structures, urethione, allophanate, isocyanurate trimer, isocyanate adducts or (partially) modified polyisocyanates.
  • modified polyisocyanates are hydrophilic isocyanates such as polyether modified polyisocyanates, e.g Bayhudur 3100, Bayhydur 305, Bayhydur XP2451/1.
  • isocyanates The reactivity of isocyanates is dependent on the structure. Aromatic isocyanates are more reactive than aliphatic isocyanates. Reactivity is further reduced by steric hindrance in isocyanate groups.
  • the structure of the polyisocyanate will also determine the final mechanical properties of the shell. A polyisocyanate with a lot of sp 3 hybridized carbon atoms in its structure will result in a more flexible shell than a polyisocyanate with little sp 3 carbon atoms.
  • Ionic polyisocyanates can also be used but are less preferred due the reduced solubility in organic solvents such as ethyl acetate, e.g Bayhydur XP2547 or Bayhydur XP2700.
  • the polyisocyanates can be based on the following monomeric isocyanates: isophorone diisocyanate (IPDI), 4,4’- dicyclohexylmethane diisocyanate (H12MDI), 2,4,4’-trimethyl-1 ,6- hexamethylene diisocyanate (TMDI), hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate (PDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI) and diphenylmethane diisocyanate (MDI).
  • IPDI isophorone diisocyanate
  • H12MDI 4,4’- dicyclohexylmethane diisocyanate
  • TMDI 2,4,4’-trimethyl-1 ,6- hexamethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • PDI pentamethylene diisocyanate
  • the first polymer is composed of a polyurea or a combination thereof with a polyurethane.
  • a substantial water immiscible solvent is used in the dispersion step, which is removed by solvent stripping before or after the shell formation.
  • the water immiscible solvent has a boiling point below 100°C at normal pressure. Esters and ketones are particularly preferred as water immiscible solvent.
  • a substantial water immiscible solvent is an organic solvent having low miscibility in water.
  • Low miscibility is defined as any water solvent combination forming a two-phase system at 20°C when mixed in a one over one volume ratio.
  • a preferred organic solvent is ethyl acetate, because it also has a low flammability hazard compared to other organic solvents.
  • a preferred method of producing the resin particles as part of the pretreatment liquid according to the invention is to prepare an aqueous dispersion of the resin particles, preferably by means of interfacial polymerisation.
  • This method for preparing a dispersion of particles according to the invention preferably includes the following steps: a) preparing a second polymer according to the present invention in a substantially water immiscible solvent such as to form an non-aqueous solution; b) adding a compound containing at least two functional groups capable of reacting with the primary and secondary amines of the crosslinker, the functional groups being an epoxide, an isocyanate, a p-keto-ester, a 0- keto-amide, an anhydride, a 1 ,3-diketone, a chloroformate, a sulfochloride, an acid halide, an enol ester, an oxalate ester or an aziridine, an isocyanate being most preferred, to the non
  • the resin particle dispersion can then be completed into a pre-treatment liquid formulation, by addition of e.g. water, humectants, surfactants, solvents and the like.
  • One or more organic solvents may be added for a variety of reasons. For example, it can be advantageous to add a small amount of an organic solvent to improve the dissolution of a compound in the pre-treatment liquid to be prepared, to obtain better penetration in porous substrates or to prevent fast drying at the nozzle of the inkjet head.
  • Preferable water- soluble organic solvents are polyols (e.g., ethylene glycol, glycerin, 2- ethyl-2-(hydroxymethyl)-1 ,3-propanediol, tetraethylene glycol, triethylene glycol, tripropylene glycol, 1 ,2,4-butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butyleneglycol, 1 ,6-hexanediol, 1 ,2- hexanediol, 1 ,5-pentanediol, 1 ,2-pentanediol, 2,2-dimethyl-1 ,3- prapanediol, 2-methyl-2,4-pentanediol, 3-methyl-1 ,5-pentanediol, 3- methyl-1 ,3-butanediol, and 2-methyl-1 ,3-propanediol), N-hydroxye
  • the aqueous pre-treatment composition according to the invention comprises a fixing agent.
  • the fixing agent serves to crash, precipitate or destabilize the ink colorants and hence fix them to the substrate. This leads to an improved image quality (less bleeding, less coalescence).
  • the fixing agent is preferably a water-soluble multivalent metal salt or a cationic polymer.
  • the polyvalent metal salt may be present in the pre-treatment composition to improve inkjet print quality.
  • the polyvalent metal salt may be any water-soluble polyvalent metal salt.
  • the polyvalent metal salt may include calcium chloride (CaCI2), magnesium chloride (MgCI2), magnesium sulfate (MgSO4), aluminium chloride (AICI3), calcium nitrate (Ca(NO3)2), magnesium nitrate (Mg(NO3)2), magnesium acetate (Mg(CH3COO)2), zinc acetate (Zn(CH3COO)2) calcium propionate (Ca(C2H5COO)2), or a combination thereof.
  • the polyvalent metal salt may include a metal cation selected from calcium, copper, nickel, magnesium, zinc, barium, iron, aluminium, chromium, or another polyvalent metal.
  • Polymeric cationic polymers suitable as fixing agent in the pre-treatment composition contain either guanidinium or fully quaternized ammonium functionalities, such as quaternized polyamine copolymers.
  • Mw weight average molecular weight
  • Typical Mw are less than 500.000, and in one aspect, less than 50.000.
  • Suitable classes of cationic polymers include, but are not limited to, quaternized polyamines, dicyandiamide polycations, diallyldimethyl ammonium chloride copolymers, quaternized dimethylaminoethyl(meth)acrylate polymers, quaternized vinylimidizol polymers, alkyl guanidine polymers, alkoxylated polyethylene imines, and mixtures thereof.
  • the aqueous medium of the pre-treatment liquid contains water, but may preferably include one or more water-soluble organic solvents. Suitable solvents which can be incorporated in the pre-treatment liquid are described in ⁇ A.1.
  • the pre-treatment composition according to the invention may comprise a wax.
  • the wax may improve the durability of the ink and pre-treatment package during corrugation.
  • any suitable wax may be used in the pre-treatment composition.
  • the wax may be polyethylene waxes, petroleum waxes, paraffin waxes, carnauba waxes, polypropylene waxes, crystalline and microcrystalline waxes, amide waxes (oleamide, stearamide, erucamide, cyclic amide, etc... ), and combinations thereof.
  • the wax may be a high density polyethylene wax.
  • the wax may be a micronized polypropylene wax, for example Mju:Wax 4810 available from Cerona GmbH.
  • polyethylene wax includes high density polyethylene (HDPE) wax, which has a density ranging from about 0.93 g/mL to 0.97 g/mL.
  • HDPE high density polyethylene
  • modified paraffin wax particles includes paraffin wax that has been modified to improve solubility in water, e.g., via emulsification.
  • the modified paraffin wax may be surface modified, chemically modified, etc.
  • wax examples include those of the JONCRYL Wax series (such as JONCRYL Wax 22, JONCRYL Wax 26, and JONCRYL Wax 120 available from BASF Corp.), those of the AQUACER series (such as AQUACER 498, AQUACER 501 , AQUACER 505, AQUACER 513, AQUACER 530, AQUACER 531 , AQUACER 535, AQUACER 537, AQUACER 539, and AQUACER 552 available from BYK- Gardner, Columbia, Md. ) and Liquilube 404E from Lubrizol .
  • AQUACER series such as AQUACER 498, AQUACER 501 , AQUACER 505, AQUACER 513, AQUACER 530, AQUACER 531 , AQUACER 535, AQUACER 537, AQUACER 539, and AQUACER 552 available from BYK- Gardner, Columbia, Md.
  • the wax may have i) a high melting temperature T and/or ii) a small average particle size.
  • the wax may have a high T such as one that is equal to or greater than about 100°C.
  • the T of the wax may range from about 100°C to about 150°C.
  • the T of the wax may range from about 110°C to about 135°C.
  • the wax may have an average particle size (in terms of effective diameter assuming that the individual wax particles are not perfectly spherical) ranging from 0.03 pm to 15 pm.
  • the wax particles may have an average particle size of 0.05 pm to 10 pm, more preferably from 0.09 pm to 0.50 pm (D50). If the particle size exceeds these upper limits, jetting reliability problems of the pre-coat composition are likely to occur.
  • the wax may be present in the pre-treatment liquid in an amount ranging from 3 to 25 wt. %, more preferably from 5 to 20 wt. %, relative to the total solids weight of the pre-treatment composition.
  • the pre-treatment liquid according to the invention may also contain humectants.
  • Humectants are preferably incorporated in a pre-treatment liquid, especially if this liquid has to be applied by means of a jetting technique such as inkjet or valve jet. Humectants prevent the clogging of nozzles. The prevention is due to its ability to slow down the evaporation rate of the inkjet ink, especially the water in the liquid.
  • the humectant is preferably an organic solvent having a higher boiling point than water.
  • Suitable humectants include triacetin, N-methyl-2-pyrrolidone, glycerol, urea, thiourea, ethylene urea, alkyl urea, alkyl thiourea, dialkyl urea and dialkyl thiourea, diols, including ethanediols, propanediols, propanetriols, butanediols, pentanediols, and hexanediols; glycols, including propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, diethylene glycol, tetraethylene glycol, and mixtures and derivatives thereof.
  • a preferred humectant is glycerol.
  • the humectant is preferably added to the pre-treatment liquid formulation in an amount of 0.1 to 20 wt.% based on the total weight of the liquid.
  • the pre-treatment liquid may contain a surfactant.
  • a surfactant Any known surfactant may be used but preferably a glycol surfactant and/or an acetylene alcohol surfactant and /or a polysiloxane surfactant is used.
  • the use of the acetylene glycol surfactant and/or the acetylene alcohol surfactant and/or the polysiloxane surfactant further reduces bleeding to improve printing quality, and also improves the drying property in printing to allow highspeed printing.
  • the acetylene glycol surfactant and/or the acetylene alcohol surfactant is preferably one or more selected from 2, 4, 7, 9-tetramethyl-5-decine-4, 7- diol, alkylene oxide adducts of 2,4,7, 9-tetramethyl-5-decine-4, 7-diol, 2,4- dimethyl-5-decin-4-ol, and alkylene oxide adducts of 2,4-dimethyl-5-decin- 4-oL
  • Olfine registered trademark
  • Surfynol registered trademark
  • Liquid set comprising a pre-treatment liquid and an aqueous inkjet ink.
  • the liquid set according to the invention comprises the pre-treatment as described in ⁇ A. and an aqueous inkjet ink including at least an aqueous medium and a colorant.
  • the aqueous inkjet ink as part of the liquid set according to the present invention includes at least a) an aqueous medium; and b) a colorant, the colorant preferably being a pigment.
  • the aqueous medium of the ink contains water, but may include one or more water-soluble organic solvents.
  • the aqueous inkjet ink comprises a resin and or a wax. Suitable waxes are described in ⁇ A.4.
  • the aqueous inkjet ink may further comprise a surfactant, a humectant, a biocide, a resin and a thickener as an additive.
  • the pigments in the aqueous inkjet ink in the liquid set according to the invention may be black, white, cyan, magenta, yellow, red, orange, violet, blue, green, brown, mixtures thereof, and the like.
  • a colour pigment may be chosen from those disclosed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley - VCH, 2004. ISBN 3527305769.
  • Suitable pigments are disclosed in paragraphs [0128] to [0138] of WO 2008/074548.
  • the pigment particles are dispersed in an aqueous medium using a polymeric dispersant, a surfactant or a combination thereof.
  • Self- dispersible pigments can also be used. The latter prevents interaction of the polymeric dispersant with the dispersing groups of binders or capsules which may be included in the inkjet ink (see below).
  • a self-dispersible pigment is a pigment having on its surface covalently bonded anionic hydrophilic groups or salt-forming groups, that allow the pigment to be dispersed in an aqueous medium without using a surfactant or a resin.
  • EP1220879A discloses pigments having attached a) at least one steric group and b) at least one organic ionic group and at least one amphiphilic counterion, wherein the amphiphilic counterion has a charge opposite to that of the organic ionic group that are suitable for inkjet inks.
  • EP906371A discloses suitable surface-modified coloured pigment having attached hydrophilic organic groups containing one or more ionic groups or ionizable groups.
  • Suitable commercially available self- dispersible colour pigments are, for example, the CAB-O-JETTM inkjet colorants from CABOT.
  • Pigment particles in inkjet inks should be sufficiently small to permit free flow of the ink through the inkjet-printing device, especially at the ejecting nozzles. It is also desirable to use small particles for maximum colour strength and to slow down sedimentation.
  • the average pigment particle size is preferably between 0.050 and 1 pm, more preferably between 0.070 and 0.300 pm and particularly preferably between 0.080 and 0.200 pm. Most preferably, the numeric average pigment particle size is no larger than 0.150 pm.
  • the average particle size of pigment particles is determined with a Brookhaven Instruments Particle Sizer BI90plus based upon the principle of dynamic light scattering.
  • Suitable white pigments are given by Table 2 in [0116] of WO 2008/074548.
  • the white pigment is preferably a pigment with a refractive index greater than 1.60.
  • the white pigments may be employed singly or in combination.
  • titanium dioxide is used as pigment with a refractive index greater than 1.60.
  • Suitable titanium dioxide pigments are those disclosed in [0117] and in [0118] of WO 2008/074548.
  • Suitable polymeric dispersants are copolymers of two monomers but they may contain three, four, five or even more monomers.
  • the properties of polymeric dispersants depend on both the nature of the monomers and their distribution in the polymer.
  • Co-polymeric dispersants preferably have the following polymer compositions:
  • alternating polymerized monomers e.g. monomers A and B polymerized into ABABABAB
  • block copolymers e.g. monomers A and B polymerized into AAAAABBBBBB wherein the block length of each of the blocks (2, 3, 4, 5 or even more) is important for the dispersion capability of the polymeric dispersant;
  • graft copolymers consist of a polymeric backbone with polymeric side chains attached to the backbone
  • Suitable dispersants are DISPERBYKTM dispersants available from BYK CHEMIE, JONCRYLTM dispersants available from BASF and SOLSPERSETM dispersants available from Lubrizol.
  • MC CUTCHEON Functional Materials, North American Edition. Glen Rock, N. J.: Manufacturing Confectioner Publishing Co., 1990. p.110-129.
  • the polymeric dispersant has preferably a number average molecular weight Mn between 500 and 30000, more preferably between 1500 and 10000.
  • the polymeric dispersant has preferably a weight average molecular weight Mw smaller than 100,000, more preferably smaller than 50,000 and most preferably smaller than 30,000.
  • the pigments are preferably present in the range of 0.01 to 15 %, more preferably in the range of 0.05 to 10 % by weight and most preferably in the range of 0.1 to 5 % by weight, each based on the total weight of the inkjet ink.
  • the white pigment is preferably present in an amount of 3% to 40% by weight of the inkjet ink, and more preferably 5% to 35%. An amount of less than 3% by weight cannot achieve sufficient covering power.
  • the aqueous ink comprises a pigment which is encapsulated by means of a cross-linked polymeric shell.
  • Encapsulated pigments provide printed images having improved physical properties such as water resistance and dry rub resistance with respect to pigments dispersed by means of un-cross-linked polymers.
  • Suitable encapsulated pigments are provided by Lubrizol as Diamond HSDX-dispersions and by Fujifilm as RxD pigment dispersions such as APD1000 and APD400 premium dispersions.
  • the aqueous ink according to the invention comprises water as a vehicle.
  • the aqueous vehicle may further include one or more water-soluble organic solvents.
  • the one or more organic solvents may be added for a variety of reasons. For example, it can be advantageous to add a small amount of an organic solvent to improve the dissolution of a compound in the ink composition to be prepared or to prevent fast drying of the ink at the nozzle of the inkjet head. Examples of useful water soluble organic solvents can be found in ⁇ A.1.4. B.2.3. Resin
  • the inkjet ink composition according to the invention may comprise a resin suspension.
  • the resin is often added to the inkjet ink formulation to achieve a good adhesion of the pigment to the substrate.
  • the resin is preferably a polymer and suitable resins can be acrylic based resins, a urethane resin or a wax.
  • the concentration of the resin in the inkjet ink according to the invention is at least 1 wt.% and preferably lower than 30 wt.%, more preferably lower than 20 wt.% with respective to the total weight of the ink.
  • the inkjet ink composition according to the invention may comprise a capsule.
  • Capsules, more preferably, nanocapsules are often incorporated in inkjet ink formulations to encapsulate colouring agents (US2009227711A, JP2004075759) or to encapsulate reactive ingredients which can cross-link.
  • Particularly useful are the nanocapsules disclosed in WO201 5158649 [0037-0110]:
  • the nanocapsules have a polymeric shell surrounding a core containing reactive chemistry.
  • the shell material includes polyureas, polyurethanes, polyesters, polycarbonates, polyamides, melamine based polymers and mixtures thereof, with polyureas and polyurethanes being especially preferred.
  • nanocapsules are selfdispersable and include a dispersing group covalently coupled to the shell polymers.
  • the core of the nanocapsules in WO201 5158649 [0037-0110] and WO2016165970 [0051-0138] comprise reactive chemistry which is able to form a reaction product upon application of heat and/or light, allowing a wide variety of substrates to be addressed.
  • Other suitable reactive chemistry is the one which is activated upon radiation as described in WO2015158649 [0068-0110],
  • the resins are preferably present in the inkjet ink in an amount of no more than 30 wt.%, preferably between 5 and 25 wt.% based on the total weight of the ink. It was observed that above 30 wt.% jetting was not always so reliable. B.2.4. Additives
  • the ink composition may contain a surfactant.
  • a surfactant Any known surfactant may be used but preferably a glycol surfactant and/or an acetylene alcohol surfactant and /or a polysiloxane surfactant is to be used.
  • the use of the acetylene glycol surfactant and/or the acetylene alcohol surfactant and/or the polysiloxane surfactant improves the drying property in printing to allow high-speed printing.
  • the acetylene glycol surfactant and/or the acetylene alcohol surfactant is preferably one or more selected from 2, 4, 7, 9-tetramethyl-5-decine-4, 7- diol, alkylene oxide adducts of 2,4,7, 9-tetramethyl-5-decine-4, 7-diol, 2,4- dimethyl-5-decin-4-ol, and alkylene oxide adducts of 2,4-dimethyl-5-decin- 4-oL
  • Olfine registered trademark
  • E1010 such as Olfine E1010
  • Evonik formerly Air Products (GB)
  • a biocide may be added to the ink composition to prevent unwanted microbial growth, which may occur over time.
  • the biocide may be used either singly or in combination.
  • Suitable biocides for the ink-jet ink of the present invention include sodium dehydroacetate, 2-phenoxyethanol, sodium benzoate, sodium pyridinethion-1 -oxide, ethyl p-hydroxybenzoate and 1 ,2-benzisothiazolin-3-one and salts thereof.
  • Preferred biocides are ProxelTM GXL and ProxelTM Ultra 5 available from ARCH UK BIOCIDES and BronidoxTM available from COGNIS.
  • a biocide is preferably added to the aqueous medium in an amount of 0.001 to 3 wt.%, more preferably 0.01 to 1.0 wt. %, each based on the total weight of the liquid.
  • the inkjet recording method including the pre-treatment liquid according to the invention is suitable for making images onto substrates, such as the one intended for packaging applications.
  • the substrate in the inkjet recording method may be porous, such as e.g. textile, paper and leather.
  • Porous substrates include paper, card board, white lined chipboard, corrugated board, packaging board, folding board, wood, ceramics, stone, leather and textile.
  • the papers can be a single layer of a multilayer paper.
  • the paper may be brown Kraft, White Top or bleached board.
  • the paper may be manufactured from chemical, wood, or recycled fibre.
  • the paper may be a liner intended for printing on page wide web presses and converted into corrugated boxes.
  • the liner paper may be used as a double face liner and may be converted directly in a corrugator or laminated onto a double face liner after corrugation.
  • the paper may also be boards used for boxes and other packaging applications.
  • the pre-treatment liquid according to the invention is also useful for printing on non-absorbing substrates such as polyethylene, polypropylene, polycarbonate, polyvinyl chloride, polyesters like polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polylactide (PLA), polymethylmethacrylate or polyimide.
  • non-absorbing substrates such as polyethylene, polypropylene, polycarbonate, polyvinyl chloride, polyesters like polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polylactide (PLA), polymethylmethacrylate or polyimide.
  • the substrates may be transparent, translucent or opaque.
  • Preferred opaque substrates includes so-called synthetic paper, like the SynapsTM grades from Agfa-Gevaert which are an opaque polyester sheet having a density of 1.10 g/cm 3 or more.
  • the pre-treatment liquid according to the present invention is suitable for treating different substrates, porous and non-porous ones.
  • the treatment by the pre-treatment liquid according to the invention provides a fixing of the colorants of an ink which is jetted onto the applied pre-treatment composition to form the printed image.
  • the fixing strongly limits the colour bleeding, increases the sharpness of the image, provides a good spreading of the inkjet ink and increases the water and solvent resistance of the printed images.
  • All well-known conventional methods can be used for coating or impregnating the substrate by the pre-treatment composition. Examples of the method include air knife coating, blade coating, roll coating, flexographic coating, gravure coating and spraying. More preferably the pre-treatment composition is applied by means of a jetting technique, such as an inkjet technique. The pre-treatment composition is then preferably applied using an inkjet head or valve jet head.
  • This means of applying the pre-treatment composition which is preferably according to an image, has the advantage that the amount of required pretreatment composition is substantially lower than with coating methods. This reduces material cost and decreases the required time for drying the applied amount of pre-treatment composition. High jetting reliability of the pre-treatment liquid is obtained because the resin particles do not show film formation in inkjet head nozzles and supply equipment.
  • Suitable ink jet head types for applying the pre-treatment composition are piezoelectric type, continuous type, thermal print head type, Memjet-type or valve jet type.
  • the liquid is preferably at least partially dried before printing the image onto the treated substrate.
  • Substrates to which the pre-treatment composition has been applied may be (partially) dried and optionally undergo a heat treatment, before the subsequent ink jetting step with the colorant containing ink.
  • the drying step can be performed at the air, but the heating step must be performed by using heat sources; examples include equipment for forced-air heating, radiation heating such as IR-radiation, including NIR-, CIR- and SWIR radiation, conduction heating, high-frequency drying, and microwave drying.
  • Examples of the heating process include, but are not limited to, heat press, atmospheric steaming, high-pressure steaming, and THERMOFIX. Any heat source can be used for the heating process; for example, an infrared ray lamp is employed.
  • the pre-treatment composition is not substantially dried before the image is printed by means of the jetting of the aqueous ink jetting step.
  • an aqueous inkjet ink comprising a colorant is applied to the substrate, preferably onto the parts where the pre-treatment composition has been applied on.
  • the colorant is preferably a pigment.
  • a preferred method of applying the aqueous inkjet ink is by means of an ink jetting technique.
  • a preferred ink jet head for the jetting of the pre-treatment composition and inkjet ink is a piezoelectric inkjet head.
  • Piezoelectric inkjet jetting is based on the movement of a piezoelectric ceramic transducer when a voltage is applied thereto. The application of a voltage changes the shape of the piezoelectric ceramic transducer in the print head creating a void, which is then filled with pre-treatment composition. When the voltage is again removed, the ceramic expands to its original shape, ejecting a drop of ink from the inkjet head.
  • the jetting of the aqueous inkjet ink is not restricted to piezoelectric inkjet printing.
  • Other inkjet print heads can be used and include various types, such as a continuous type, a thermal print head type, a Memjet-type of head and a valve jet type.
  • Examples of the heating process to dry the inkjet ink according to the invention are listed in ⁇ C.1.
  • the drying step is such that a temperature of the printed images is preferably obtained below 150°C.
  • Dynacoll 7150 is a polyester polyol containing terephthalic ester and isophthalic ester units supplied by Evonik
  • Ymer N90 is 1 ,3 diol polyether, having an average number of 26 EO units per graft from Perstorp
  • Ymer N120 is 1 ,3 diol polyether having an average number of 20 EO units per graft from Perstorp
  • Ymer N180 is 1 ,3 diol polyether having an average number of 10 EO units per graft from Perstorp
  • Reaxis C708 is a bismuth based catalyst supplied by Reaxis BV
  • Reagens 65 is a 65% aqueous solution of 3-chloro-2- hydroxypropyltrmethyl ammonium chloride supplied by Sachem
  • GMAC is a 72% solution of glycidyl trimethylammonium chloride supplied by Sachem
  • CROSS-1 is a cationic crosslinker and is prepared as follows: In a round bottom flask of 500 ml 30.417 g of Tris(2-aminoethyl)amine was diluted with 68.10 g of water. The obtained solution was cooled to 5 °C. A solution of Reagens 65 was slowly added during 20 minutes to the TREN solution. The reaction mixture was stirred during the addition using a magnetic stirrer. After the dosing was completed, the reaction mixture was stirred for another 30 minutes at 5 °C and subsequently heated to 70 °C. The reaction mixture is then heated during 24 hours and afterwards cooled to room temperature. The prepared CROSS1 showed a solids content of 32.7 wt.% after drying at 140 °C for 45 minutes.
  • CROSS-2 is a cationic crosslinker prepared as follows: In a reactor of 120 ml 7.83 g of bis(3-aminopropyl)methylamine and 36.53 g of water were added. The solution of the amine is cooled to 15 °C. Then 15.6 g of Reagens 65 was slowly added in 30 minutes. The reaction mixture was still stirred during 30 minutes and then the reaction mixture was heated to 70 °C and heated overnight during 24 hours. Afterwards the reaction mixture was cooled to room temperature and the concentration was determined (45 minutes drying at 140 °C). The solids content was 31.4%
  • SLIRF1 is a reaction product of glycidyl trimethylammonium chloride and dodecyl amine.
  • This co-polymerisable cationic surfactant is prepared as follows: 10.024 g of dodecyl amine 98% was added to a 100 ml round bottom flask, stirred using a magnetic stirrer and 30 g of water was added. Then 11.433 g of GMAC was added. After stirring during 48 hours at room temperature a clear solution was obtained.
  • SR552 is methoxy terminated polyethylene glycol mono methacrylate having an average number of 11 EO units, from Arkema.
  • Wako V601 is dimethyl 2,2-azobisisobutyrate, supplied by FujiFilm Wako Chemicals Europe GmbH
  • Bisomer S20W is methoxy terminated polyethylene glycol mono methacrylate having an average number of 45 EO units per graft from GEO Specialty Chemicals UK Ltd and in advance freeze dried to remove water
  • Desmodur N3200 is an HDI based polyisocyanurate supplied by Covestro
  • Ultralube GA 1042 is a 35 wt.% HDPE wax dispersion from KEIM- ADDITEC SURFACE GMBH
  • Surfynol 104PG50 is a 50wt.% solution of 2,4,7, 9-Tetramethyl-5- decyne-4,7-diol in propylene glycol from Evonik
  • Kauropal K933 is a 100% non-ionic oxirane, mono(2-propylheptyl) ether from BASF
  • Tego Foamex 822 is a 20% defoaming agent containing an emulsion of a polyether siloxane copolymer in water from Evonik Industries AG.
  • Proxel is a 5wt. % aqueous solution of 1 ,2-benzisothiazolin-3-one available as ProxelTM K from YDS CHEMICALS NV.
  • Aquacer 530 is an aqueous dispersion containing 32 wt.% oxidized HDPE wax from BYK
  • Synperonic PE P105 is a PEO/PPO co-polymeric dispersant having an average Mw of 6500 g/mol and a PPO/PEO weight ratio of approximately 1.00 from Croda •
  • HSDCX1 is a 19.7 wt.% encapsulated Pigment Blue 15:3 dispersion in water from Lubrizol Corporation.
  • PD is 1 ,2-propanediol, manufactured by Dow Chemical
  • the freshly prepared resin particle dispersions were measured by Malvern Zetasizer. Both the average particle size and polydispersity index (PDI) were registered. Subsequently, the resin particle dispersions were visually observed within the period of a few days under room temperature to determine the stability of the dispersions. A stable resin particle dispersion is demonstrated by optically homogeneous appearance of the liquid. Instability of the dispersion is indicated by visual clues such as sedimentation or creaming.
  • PDI polydispersity index
  • Pre-treatment liquids were applied onto a coated corrugated liner XLHD MM X-Liner HD (180 g/m 2 ) from MM Karton using a 4 pm spiral bar.
  • the coated liner was dried at 60°C in an oven for 2 minutes to obtain a pretreated liner.
  • Ink spreading the ink should completely cover the solids in the printed image. A lack of ink spreading is demonstrated by the appearance of white lines in the solid areas. The evaluation was conducted by visually observing the solid areas and by giving a score from 0 (excellent ink spreading, complete coverage) to 3 (poor ink spreading, more than 20 white lines visible in the solid area).
  • Ink fixing the ink should homogenously and intensely cover the solids in the printed image. A lack of ink fixing is demonstrated by the appearance of uneven patterns in the solid areas. The ink fixing was evaluated by visually observing the solid areas and by giving a score from 0 (excellent ink fixing, homogeneous coverage) to 3 (poor ink fixing, strong unevenness observable).
  • Image sharpness the fine text should be readable. A lack of image sharpness is demonstrated by the disappearance of negative text. The image sharpness was evaluated by visually observing the negative texts and by giving a score from 0 (excellent image sharpness, 6 pt clearly readable) to 3 (poor image sharpness, 16 pt partially or totally covered by ink).
  • PU-1 solution was prepared by the following steps. 2171 g of Dynacoll 7150 was dissolved in 2951 g of ethyl acetate at 45 °C in an 12L double jacketed glass reactor. 542.8 g of Ymer N90 dissolved in 856.2 g of ethyl acetate was added to the Dynacol solution. Whereas Ymer N90 is a wax, it was preheated at 90 °C in order to become liquid and easier to handle. After addition of the Ymer into the ethyl acetate solution was allowed to cool to room temperature. A catalyst solution was prepared by dilution of 20.30 g of Reaxis C708 in 182.7 g of ethyl acetate.
  • the polyol solution was transferred to the double jacketed 12 L glass reactor equipped with a coiled condenser and an overhead stirrer. The reactor was flushed with nitrogen and slow nitrogen flow was maintained during stirring and reaction. Subsequently the catalyst was added dropwise via an addition funnel with pressure equalization arm. The oil bath was heated to 75 °C. After appr. 1 hour the reaction mixture reaches a constant temperature of appr. 68 °C. Subsequently 275.8 g of Vestanat IPDI was added via an addition funnel with pressure equalization arm for 90 minutes. Then the oil bath was put to 70 °C and the reaction was allowed to react overnight during appr. 19 hours. After reacting over night, the oil bath was put again to 75 °C for 30 minutes and then cooled to room temperature. The solids content, as determined by drying for 2 hours at 85°C is 45.21 %.
  • PU-3 solution was prepared by the following steps. 111.16 g of Dynacoll 7150 was dissolved in 200.45 g of ethyl acetate at 45 °C in a 500 ml Erlenmeyer. 27.79 g of Ymer N180 was added to the Dynacol solution. A catalyst solution was prepared by dilution of 1.07 g of Reaxis C708 in 9.6 g of ethyl acetate. The polyol solution was transferred to a 3 necked round bottom flask of 500 ml, equipped with a coiled condenser and an overhead stirrer. The flask was flushed with nitrogen and a slow nitrogen flow was maintained during stirring and reaction.
  • the catalyst was added dropwise via an addition funnel with pressure equalization arm.
  • the oil bath was heated to 75 °C. After appr. 1 hour the reaction mixture reaches a constant temperature of appr. 68 °C. Subsequently 19.07 g of Vestanat IPDI was added via an addition funnel with pressure equalization arm for 110 minutes. Then the oil bath was put to 70 °C and the reaction was allowed to react overnight during appr. 19 hours. After reacting over night the oil bath was put again to 75 °C for 30 minutes and then cooled to room temperature. The solids content as determined by drying for 2 hours at 85°C is 46.04%.
  • PU-4 solution was prepared the same way as PU-3 but with 227.49 g of Dynacoll 7150 dissolved in 402.83 g of ethyl acetate at 45 °C in an 1000 ml Erlenmeyer, 56.87 g of Ymer N120 instead of Ymer N180, a catalyst solution prepared by dilution of 2.14 g of Reaxis C708 in 19.34 g of ethyl acetate. The solids content is 43.0%.
  • the reaction mixture was heated to 68 °C and the nitrogen flush was stopped after 4 hours.
  • the reaction mixture was stirred overnight for 16 hours, and subsequently cooled to room temperature.
  • the obtained solids content was 42.48%.
  • PMMA-3 was prepared the same way as PMMA-1 , but with Bisomer S20W instead of SR552.
  • An inventive resin particle dispersion CM-1 was prepared via interfacial polymerization.
  • the oleophilic phase was prepared by mixing: 58.51 g of ethyl acetate, 16.24 g of Desmodur N3200 and 35.92 g of the Pll-1 solution.
  • An aqueous phase was prepared by mixing: 4.84 g of dodecyl trimethylammonium chloride, 6.51 g of CROSS1 , and 84.93 g water.
  • the aqueous phase was brought in a plastic bottle having a wide opening and was placed in an ice bath for 10 minutes.
  • the organic phase was also placed in an ice batch for 10 minutes in advance of the addition.
  • the organic phase was added to the aqueous phase.
  • the organic phase was emulsified in the aqueous phase at 18000 RPM using an Ultraturrax device for 5 minutes.
  • the ethyl acetate was evaporated on a rotary evaporator until a weight of 145 g.
  • the temperature was set to 40 °C and the ethyl acetate was removed under reduced pressure.
  • the evaporation was started at a pressure of 200 mbar and the pressure was gradually decreased till 40 mbar. When too much water was evaporated, this water was compensated by addition up to 145 g in total.
  • the round bottom flask was placed in an oil bath which has a temperature of 40 °C and was heated within 30 minutes to 60 °C.
  • the dispersion was then kept overnight at 60 °C for 16 hours and then cooled to room temperature.
  • the resulting resin particle dispersion CM-1 had a solids content of 30.79 wt.%.
  • the average particle size was 169.4 nm (determined by a Malvern particle sizer), a PDI of 0.10 and no measurable particles fraction above 1pm particle size.
  • the comparative resin particle dispersion CM-3 was prepared the same way as CM-1 , but with the oleophilic phase prepared by mixing: 57.94 g of ethyl acetate, 16.50 g of Desmodur N3200 and 35.84 g of the Pll-3 solution and an aqueous phase prepared by mixing: 4.90 g of Dodecyl trimethylammonium chloride, 3.3 g of CROSS1 and 86.06 g water.
  • the resulting resin particle dispersion CM-3 had a solids content of 28.03 wt.%.
  • the average particle size was 838.40 nm (determined by a Malvern particle sizer), a PDI of 0.79 and having a significant particle fraction above 1 m particle size.
  • the inventive resin particle dispersion CM-4 was prepared the same way as CM-1 , but with the oleophilic phase prepared by mixing: 57.09 g of ethyl acetate, 16.50 g of Desmodur N3200 and 36.50 g of the Pll-1 solution and an aqueous phase prepared by mixing: 4.90 g of Dodecyl trimethylammonium chloride, 3.44g of CROSS2 and 85.92 g water.
  • the resulting resin particle dispersion CM-4 had a solids content of 27.67 wt.%.
  • the average particle size was 159.1 nm (determined by a Malvern particle sizer), a PDI of 0.14 and no measurable particles fraction above 1pm particle size.
  • CM-6 The average particle size was 159.1 nm (determined by a Malvern particle sizer), a PDI of 0.14 and no measurable particles fraction above 1pm particle size.
  • the comparative resin particle dispersion CM-6 was prepared the same way as CM-1 , but with the oleophilic phase prepared by mixing: 57.92 g of ethyl acetate, 16.50 g of Desmodur N3200 and 35.84 g of the Pll-3 solution and an aqueous phase was prepared by mixing: 4.90 g of dodecyl trimethylammonium chloride, 3.55 g of CROSS2 and 85.8 g water.
  • the resulting resin particle dispersion CM-6 had a solids content of 26.00 wt.%.
  • the average particle size was 880.50 nm (determined by a Malvern particle sizer), a PDI of 0.90 and an important particle fraction above 1 m particle size.
  • CM-7 The average particle size was 880.50 nm (determined by a Malvern particle sizer), a PDI of 0.90 and an important particle fraction above 1 m particle size.
  • the comparative resin particle dispersion CM-7 was prepared via interfacial polymerization.
  • the oleophilic phase was prepared by mixing: 60.19 g of ethyl acetate, 17.989 g of Desmodur N3200 and 41.821 g of the PU-4 solution.
  • An aqueous phase was prepared by mixing: 15.001 g of SURF-1 , 3.43g of CROSS2 and 83.82 g water.
  • the oleophilic ethyl acetate phase was brought in a plastic bottle having a wide opening and was placed in an ice bath and cooled for 10 minutes. The aqueous phase also cooled during 10 minutes in an ice batch was added to the oleophilic phase.
  • the emulsification of the aqueous phase and the polymerisation reaction was done the same way as described in CM-1.
  • the resulting resin particle dispersion CM-7 had a solids content of 33.92 wt.%.
  • the average particle size was 247.40 nm (determined by a Malvern particle sizer), a PDI of 0.44 and an important fraction of particles having a particle size above 1 pm.
  • the comparative resin particle dispersion CM-9 was prepared the same way as CM-1 , but with the oleophilic phase prepared by mixing: 59.90 g of ethyl acetate, 16.50 g of Desmodur N3200 and 39.29 g of the PMMA-1 solution and an aqueous phase prepared by mixing: 4,9 g of dodecyl trimethylammonium chloride, 6,51 g of CROSS1 and 78.31 g of water. Before placing the round bottom flask in an oil bath which has a temperature of 40 °C , it was observed that the resin particle dispersion was fully flocculated and partially settled to the bottom. No stable dispersion could be obtained.
  • the inventive resin particle dispersion CM-11 was prepared the same way as CM-1 , but with the oleophilic phase prepared by mixing: 55.07 g of ethyl acetate, 16.50 g of Desmodur N3200 and 44.12 g of the PMMA-3 solution and an aqueous phase was prepared by mixing: 4,90 g of dodecyl trimethylammonium chloride, 6,51 g of CROSS1 and 78.31 g of water.
  • the resulting resin particle dispersion CM-11 had a solids content of 23.96 wt.%.
  • the average particle size was 169.80 nm (determined by a Malvern particle sizer), a PDI of 0.26 and no measurable particles above 1 m particle size.
  • Table 4 Properties of comparative and inventive resin particle dispersions.
  • the resin particle dispersions are stable when the average number of EO-units of the second polymer is 20 or more.
  • the resin particle dispersion CM-7 wherein the cationic dispersing groups are introduced via a co-polymerisable surfactant as described in WO2018/138069A do show an important particle fraction having a particle size above 1 pm.
  • the pre-treatment compositions were prepared by mixing the ingredients given in Table 5. The weight percentages are relative to the total weight of the pre-treatment compositions.
  • the raw materials were used as supplied without any further treatments.
  • CM-3 and CM-6 resin particle dispersions were not suitable to be used for preparation of pre-treatment liquids due to their instability.
  • Table 5 Composition of inventive pre-treatment liquids.
  • PL 1 showed the best accelerated aging test result by being stable for 4 weeks at 60 °C. D.4.2. Aqueous inkjet ink.
  • An aqueous cyan ink was prepared by diluting the wax dispersion with the other ink ingredients according to Table 6, the ingredients expressed in wt.% based on the total weight of the ink. Water was added to complete the ink to the desired pigment concentration.
  • the pre-treatment liquids according to the invention were able to improve the image quality of the image printed onto the liner by significantly better ink spreading and ink fixing with respect to inkjet printed images without a pre-treatment liquid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un liquide de prétraitement aqueux pour l'impression à jet d'encre, comprenant une particule de résine et un agent de fixation. La particule de résine présente un diamètre moyen de 1 µm ou moins et comprend un premier polymère et un second polymère. Le premier polymère est un polymère choisi dans le groupe constitué par la poly(urée), les poly(uréthanes), les poly(amides), les poly(esters), les poly(carbonates), les poly(sulfonamides), les poly(amides), les poly(sulfonamides), les polymères à base de mélamine, les polymères sol-gel à base de silice et leurs combinaisons. Le second polymère est un polymère greffé de poly(oxyde d'alkylène) obtenu par polycondensation ou polymérisation par addition, la greffe de poly(oxyde d'alkylène) présentant une longueur de chaîne moyenne en nombre de 20 motifs d'oxyde d'alkylène ou plus. Le liquide de prétraitement est utile pour l'impression à jet d'encre sur des matériaux d'emballage tels que le carton ou le carton ondulé.
PCT/EP2023/083355 2022-12-19 2023-11-28 Liquide de prétraitement contenant une résine pour impression à jet d'encre et procédé d'enregistrement WO2024132405A1 (fr)

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