Patent Description:
The importance of aqueous inkjet technology in industrial applications on non-absorbing substrates is increasing rapidly as alternative for UV-curable technology, especially in applications where the toxicology of monomers, photoiniators and degradation products formed during curing are a concern.

Indoor decoration is a typical field of technology where smell and volatiles have to be avoided. Resin based aqueous inkjet technology avoid these problems by design as they are fully polymer based. In the prior art, several approaches have been disclosed for the design of resin based inks. The majority of the inks are latex based such as in <CIT>. However, latex based inks often encounter ink jetting reliability problems related to spontaneous film formation at the inkjet head nozzle or colloid chemical instability due to interaction of the latex with the pigment dispersion. Therefore, an encapsulation based approach has been disclosed, making use of core shell systems, where the shell avoids premature film formation.

Encapsulation based technologies making use of core shell systems as disclosed in <CIT> and <CIT>, avoid film formation at the nozzle of the inkjet head, but often require a high activation temperature, making the technology suitable for temperature tolerant applications such as textile printing but not fit for use for printing on temperature sensitive substrates such as poly(olefins).

The problem of compatibility with temperature sensitive substrates has been addressed by inks comprising encapsulated polymeric β-keto-esters or amides as disclosed in the patent application <CIT>. Reliability in ink jet systems for industrial applications is of utmost importance, including the chemical stability of the ink components. Encapsulated β-keto-esters still hold the risk of hydrolysis upon prolonged storage. Therefore, there is still a need for further optimization of the chemical stability of the encapsulated polymer. Now it has been found that encapsulated polymers functionalized with at least three functional groups selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM> ,<NUM>-dialdehyde show excellent physical properties, while being hydrolytically fully stable by design.

It is the objective of the present invention to provide a solution to the above stated problems. The objective has been achieved by providing a fluid set as defined in claim <NUM>.

It is another embodiment of the invention to provide a printing method using the fluid set of claim <NUM> as defined in claim <NUM>.

Other features, elements, steps, characteristics and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the present invention. Specific embodiments of the invention are also defined in the dependent claims.

The fluid set according to the invention comprises:.

The fluid can be <NUM>) a primer or pre-treatment liquid, which is applied before the jetting of the aqueous inkjet ink of the fluid set; <NUM>) an overcoat, which is applied after the jetting of the aqueous inkjet ink of the fluid set; <NUM>) an inkjet ink which is jetted together with the aqueous inkjet ink of the fluid set and comprising a colorant.

The aqueous inkjet ink of the fluid set according to the invention, comprises a colorant and a polymeric particle, the polymeric particle comprises an oligomer or polymer having at least <NUM> repeating units comprising a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde with the proviso that the active methylene is functionalized with at least one hydrogen.

Preferably the oligomer or polymer having at least <NUM> repeating units comprising a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde is obtainable by polymerization of a monomer according to general formula I
<CHM>
wherein
R<NUM> to R<NUM> are independently selected from the group consisting of a hydrogen, 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 with the proviso that one of R<NUM> to R<NUM> is functionalized with a functional group selected from the group consisting of an acrylate, a methacrylate, an acrylamide, a methacrylamide, a styrene, vinyl ether, a vinyl ester, an itaconate, a fumarate, a maleate and a maleimide and said monomer according to general formula I is a monofunctional monomer.

Any of R<NUM> and R<NUM> may represent the necessary atoms to form a five to eight membered ring.

In a preferred embodiment, R<NUM> and R<NUM> are selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, an unsubstituted alkyl or aryl group being more preferred, a C1 to C4 alkyl group being the most preferred. In a particularly preferred embodiment at least one of R<NUM> and R<NUM> represents an alkyl group, a methyl group being the more preferred.

In a particularly preferred embodiment, R<NUM> is functionalized with a functional group selected from the group consisting of an acrylate, a methacrylate, an acrylamide, a methacrylamide, a styrene, vinyl ether, a vinyl ester, an itaconate, a fumarate, a maleate and a maleimide, an acrylate, a methacrylate, an acrylamide, a methacrylamide and a styrene group being more preferred, an acrylamide, a methacrylamide and a styrene group being the most preferred.

Typical monomers functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde are given in Table <NUM> without being limited thereto.

In a preferred embodiment the oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde, comprise at least <NUM> functional groups, more preferably at least <NUM> and most preferably at least <NUM> functional groups.

The oligomer or polymer according to the present invention preferably has a weight average molecular weight of at least <NUM>, more preferably <NUM> and most preferably between <NUM> and <NUM>.

The polymer according to the present invention can be a homopolymer or a copolymer of different repeating units.

The oligomers or polymers according to the present invention can be prepared by addition polymerization of ethylenically unsatured monomers, polycondensation and ring opening polymerization, addition polymerization being particularly preferred. In the most preferred embodiment, free radical polymerization of ethylenically unsatured monomers is used to prepare the resins according to the present invention. In another embodiment of the present invention, the molecular weight of the resins according to the present invention is controlled using RAFT agents, ATRP, nitroxyl radical technology or transfer agents, preferably thiols.

The particles comprising the oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde are preferably dispersed in the aqueous vehicle of the inkjet ink. The particles are dispersed in the aqueous medium of the inkjet ink preferably by using dispersants or surfactants.

The particles preferably have an average particle size of no more than <NUM> as determined by dynamic laser diffraction. The nozzle diameter of inkjet print heads is usually <NUM> to <NUM>. Hence preferably, the average particle size is from <NUM> to <NUM>, more preferably from <NUM> to <NUM>. When the average particle size of the particle is smaller than <NUM>, excellent resolution and dispersion stability with time are obtained.

The particles are preferably present in an aqueous inkjet ink, but can also be present in a primer or overcoat. The amount of particles in the inkjet ink is of no more than <NUM> wt. %, preferably between <NUM> and <NUM> wt. % based on the total weight of the ink. It was observed that above <NUM> wt. % jetting was not always so reliable.

In a preferred embodiment, the oligomer or polymer according to the present invention is encapsulated to form an aqueous dispersion, preferably by polymerization, more preferably by using interfacial polymerization. Encapsulation increases the storage stability of the aqueous inkjet due to the formation of a polymeric barrier, i.e. the polymeric shell of the capsule, between the oligomer or polymer and the other compounds in the aqueous inkjet ink.

The capsules preferably have an average particle size of no more than <NUM> as determined by dynamic laser diffraction for the same reason explained above.

The capsules are dispersed in the aqueous medium of the inkjet ink preferably using a dispersing group covalently bonded to the polymeric shell or are dispersed by using dispersants or surfactants preferably added during or after the formation of the capsule. The dispersing group covalently bonded to the polymeric shell is preferably selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphoric acid ester or salt thereof, a phosphonic acid or salt thereof.

The dispersing group can be used in combination with a polymeric dispersant in order to accomplish steric stabilization. For example, the polymeric shell may have covalently bonded carboxylic acid groups that interact with amine groups of a polymeric dispersant. However, in a more preferred embodiment, no polymeric dispersant is used and dispersion stability of the inkjet ink is accomplished solely by electrostatic stabilization. For example, a slightly alkaline aqueous medium will turn the carboxylic acid groups covalently bonded polymeric shell into ionic groups, whereafter the negatively charged capsules have no tendency to agglomerate. If sufficient dispersing groups are covalently bonded to the polymeric shell, the capsule becomes a so-called self-dispersing capsule.

These negatively charged capsule surfaces can also be advantageously used during inkjet printing. For example, a second liquid such as a pre-treatment liquid containing a cationic substance, being a cationic polymer or multivalent salt, can be used to precipitate the anionic capsules in the inkjet ink printed on top of the second liquid. By using this method an improvement in image quality can be observed due to the immobilisation of the capsules.

There is no real limitation on the type of polymer used for the polymeric shell of the capsule. Preferably, the polymer used in the polymeric shell is preferably cross-linked. By crosslinking, more rigidity is built into the capsules allowing a broader range of temperatures and pressures for handling the capsules in both the ink making and in the inkjet printer.

Preferred examples of the polymeric shell material include polyureas, polyesters, polycarbonates, polyamides, melamine based polymers and mixtures thereof, with polyureas being especially preferred.

The encapsulated oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde is surrounded with a polymeric shell, can be prepared using both chemical and physical methods. Suitable encapsulation methodologies include complex co-acervation, liposome formation, spray drying and polymerization methods.

In the present invention preferably a polymerization method is used, as it allows the highest control in designing the capsules. More preferably interfacial polymerization is used to prepare the capsules of the invention. This technique is well-known and has been reviewed by <NPL>) and by <NPL>)).

In interfacial polymerization, such as interfacial polycondensation, two reactants meet at the interface of the emulsion droplets and react rapidly.

In general, interfacial polymerisation requires the dispersion of an oleophilic phase in an aqueous continuous phase or vice versa. Each of the phases contains at least one dissolved monomer (a first shell component) that is capable of reacting with another monomer (a second shell component) dissolved in the other phase. Upon polymerisation, a polymer is formed that is insoluble in both the aqueous and the oleophilic phase. As a result, the formed polymer has a tendency to precipitate at the interface of the oleophilic and aqueous phase, hereby forming a shell around the dispersed phase, which grows upon further polymerisation. The capsules according to the present invention are preferably prepared from an oleophilic dispersion in an aqueous continuous phase.

Typical polymeric shells of the capsules according to the invention and formed by interfacial polymerisation are selected from the group consisting of polyamides, typically prepared from di- or poly-acid chlorides as first shell component and di- or oligoamines as second shell component, polyurea, typically prepared from di- or oligoisocyanates as first shell component and di- or oligoamines as second shell component, polyurethanes, typically prepared from di- or oligoisocyanates as first shell component and di- or oligoalcohols as second shell component, polysulfonamides, typically prepared from di- or oligosulfochlorides as first shell component and di- or oligoamines as second shell component, polyesters, typically prepared from di- or oligo-acid chlorides as first shell component and di- or oligoalcohols as second shell component and polycarbonates, typically prepared from di- or oligo-chloroformates as first shell component and di- or oligoalcohols as second shell component. The shell can be composed of combinations of these polymers.

In a further embodiment, polymers, such as gelatine, chitosan, albumin and polyethylene imine can be used as second shell components in combination with a di- or oligo-isocyanate, a di- or oligo acid chloride, a di-or oligo-chloroformate and an epoxy resin as first shell component.

In a particularly preferred embodiment, the shell is composed of a polyurea or a combination thereof with a polyurethane. In a further preferred embodiment, a water immiscible solvent is used in the dispersion step, which is removed by solvent stripping before or after the shell formation. In a particularly preferred embodiment, the water immiscible solvent has a boiling point below <NUM> at normal pressure. Esters are particularly preferred as water immiscible solvent.

A 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 <NUM> when mixed in a one over one volume ratio.

The core contains the oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde. These are usually incorporated into the capsules by dissolving it in the organic solvent having low miscibility with water and having a lower boiling point than water. A preferred organic solvent is ethyl acetate, because it also has a low flammability hazard compared to other organic solvents.

However, in some cases the organic solvent may be omitted. For example, the organic solvent can be omitted when the oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde have a viscosity of less than <NUM> mPa.

The method for preparing a dispersion of capsules preferably includes the following steps:.

The capsule dispersion can then be completed into the aqueous inkjet ink, by addition of e.g. colorants, water, humectants, surfactant and the like.

In a preferred embodiment, the capsules are self-dispersing capsules. In order to make capsules self-dispersing, anionic dispersing groups, such as carboxylic acids or salts thereof, sulfonic acids or salts thereof, phosphoric acid esters or a salts thereof or a phosphonic acids or salts thereof, are coupled to the polymeric shell of the capsule to guarantee the dispersion stability.

A preferred strategy to incorporate anionic stabilizing groups into the polymeric shell of a capsule makes use of carboxylic acid functionalized reactive surfactants that are capable of reacting with isocyanates. This leads to an amphoteric type of surfactant containing at least partially secondary or primary amines. Other reactive surfactants functionalized with a sulfonic acid or salt thereof, a phosphoric acid ester or a salt thereof or a phosphonic acid or salt thereof can be used.

Several amphoteric surfactants, being mixtures of surfactants partially having secondary amines but also comprising tertiary amines are commercially available. Prohibitive foam formation in inkjet inks based on capsules made by using the commercially available amphoteric surfactants was encountered in an inkjet printer. Foaming caused problems in the ink supply and also in the degassing for trying to remove air from the ink, thus leading to unreliable jetting. Therefore, surfactants according to Formula (I) of <CIT> are preferably used during the encapsulation process of the oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde.

The capsules according to the invention are dispersed into an aqueous medium. The aqueous medium consists of water, but may preferably 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 inkjet ink to be prepared, to obtain better penetration in porous substrates or to prevent fast drying of ink at the nozzle of the inkjet head. Preferable water-soluble organic solvents are polyols (e.g., ethylene glycol, glycerin, <NUM>-ethyl-<NUM>-(hydroxymethyl)-<NUM> ,<NUM>-propanediol, tetraethylene glycol, triethylene glycol, tripropylene glycol, <NUM>,<NUM>,<NUM>-butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butyleneglycol, <NUM> ,<NUM>-hexanediol, <NUM> ,<NUM>-hexanediol, <NUM> ,<NUM>-pentanediol, <NUM>,<NUM>-pentanediol, <NUM>,<NUM>-dimethyl-<NUM> ,<NUM>-prapanediol, <NUM>-methyl-<NUM>,<NUM>-pentanediol, <NUM>-methyl-<NUM> ,<NUM>-pentanediol, <NUM>-methyl-<NUM> ,<NUM>-butanediol, and <NUM>-methyl-<NUM> ,<NUM>-propanediol), amines (e.g., ethanolamine, and <NUM>-(dimethylamino)ethanol), monohydric alcohols (e.g., methanol, ethanol, and butanol), alkyl ethers of polyhydric alcohols (e.g., diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether), <NUM>,<NUM>'thiodiethanol, amides (e.g., N,N-dimethylformamide), heterocycles (e.g., <NUM>-pyrrolidone and N-methyl-<NUM>-pyrrolidone), and acetonitrile.

The colorants in the aqueous inkjet ink according to the invention can be dyes such as dispersed dyes, acid dyes, reactive dyes and can be pigments, or a combination thereof. Preferably, the colorant in the inkjet ink according to the invention is a pigment. Pigmented inks deliver images with an extended stability against light fading and improved water and solvent resistance.

The pigments of the ink 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<NPL>.

Suitable pigments are disclosed in paragraphs [<NUM>] to [<NUM>] of <CIT>.

The pigment particles are dispersed in an aqueous medium by means of a polymeric dispersant or a surfactant. Self-dispersible pigments may also be used. If combined with the particles or capsules according to the invention and having anionic dispersing groups, anionic surfactants may be preferably used as dispersant for the pigment. The latter prevents interaction of the polymeric dispersant with the dispersing groups of the particles or capsules included in the inkjet ink, since dispersion stability of the pigment is accomplished by the same technique of electrostatic stabilization as employed for the capsules.

A self-dispersible pigment is a pigment having on its surface covalently bonded anionic hydrophilic groups, such as salt-forming groups or the same groups used as dispersing groups for the capsules, that allow the pigment to be dispersed in an aqueous medium without using a surfactant or a resin. Suitable commercially available self-dispersible colour pigments are, for example, the CAB-O-JET™ 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 <NUM> and <NUM>, more preferably between <NUM> and <NUM> and particularly preferably between <NUM> and <NUM>. Most preferably, the numeric average pigment particle size is no larger than <NUM>. The average particle size of pigment particles is determined with a Brookhaven Instruments Particle Sizer BI90plus based upon the principle of dynamic light scattering. The sample is diluted with water to a pigment concentration of <NUM> wt%. The measurement settings of the BI90plus are: <NUM> runs at <NUM>, angle of <NUM>°, wavelength of <NUM> and graphics = correction function.

Suitable white pigments are given by Table <NUM> in [<NUM>] of <CIT>. The white pigment is preferably a pigment with a refractive index greater than <NUM>. The white pigments may be employed singly or in combination. Preferably titanium dioxide is used as pigment with a refractive index greater than <NUM>. Suitable titanium dioxide pigments are those disclosed in [<NUM>] and in [<NUM>] of <CIT>.

Also special colorants may be used, such as fluorescent pigments for special effects in clothing, and metallic pigments for printing a luxury look of silver and gold colours on textiles.

Suitable polymeric dispersants for the pigments 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. Copolymeric dispersants preferably have the following polymer compositions:.

Suitable dispersants are DISPERBYK™ dispersants available from BYK CHEMIE, JONCRYL™ dispersants available from JOHNSON POLYMERS and SOLSPERSE™ dispersants available from Lubrisol. A detailed list of non-polymeric as well as some polymeric dispersants is disclosed by <NPL>.

The polymeric dispersant has preferably a number average molecular weight Mn between <NUM> and <NUM>, more preferably between <NUM> and <NUM>.

The polymeric dispersant has preferably a weight average molecular weight Mw smaller than <NUM>,<NUM>, more preferably smaller than <NUM>,<NUM> and most preferably smaller than <NUM>,<NUM>.

The pigments are preferably present in the range of <NUM> to <NUM> %, more preferably in the range of <NUM> to <NUM> % by weight and most preferably in the range of <NUM> to <NUM> % by weight, each based on the total weight of the inkjet ink. For white inkjet inks, the white pigment is preferably present in an amount of <NUM>% to <NUM>% by weight of the inkjet ink, and more preferably <NUM>% to <NUM>%. An amount of less than <NUM>% by weight cannot achieve sufficient covering power.

The aqueous inkjet ink according to the invention contains water, but may include one or more water-soluble organic solvents. Suitable organic solvents are described in § A.

The aqueous inkjet ink according to the invention may also contain humectants. 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-<NUM>-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 inkjet ink in an amount of <NUM> to <NUM> wt. % based on the total weight of the liquid.

The aqueous inkjet ink according to the invention may contain a surfactant. Any known surfactant may be used but preferably a glycol surfactant and/or an acetylene alcohol surfactant. The use of the acetylene glycol surfactant and/or the acetylene alcohol surfactant further reduces bleeding to improve printing quality, and also 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 <NUM>, <NUM>, <NUM>, <NUM>-tetramethyl-<NUM>-decine-<NUM>, <NUM>-diol, alkylene oxide adducts of <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-decine-<NUM>, <NUM>-diol, <NUM>,<NUM>-dimethyl-<NUM>-decin-<NUM>-ol, and alkylene oxide adducts of <NUM>,<NUM>-dimethyl-<NUM>-decin-<NUM>-ol. These are available, for example, from Air Products (GB) as Olfine (registered trademark) <NUM> series and E series, such as Olfine E <NUM>, or from Nissin Chemical Industry as Surfynol (registered trademark) <NUM> and Surfynol <NUM>.

The inkjet ink composition according to the invention may further comprise an extra resin. This resin is often added to the inkjet ink formulation to further achieve a good adhesion of the pigment to the substrate. The resin is a polymer and suitable resins can be acrylic based resins, a urethane-modified polyester resin or a polyethylene wax.

The concentration of the resin in the inkjet ink according to the invention is at least <NUM> wt. % and preferably lower than <NUM> wt. %, more preferably lower than <NUM> wt.

In a preferred embodiment, the inkjet ink according to the invention is part of an inkjet ink set, more preferably part of a multi-colour inkjet ink set including a plurality of inkjet inks according to the invention. The inkjet ink set preferably includes at least a cyan inkjet ink, a magenta inkjet ink, a yellow inkjet ink and a black inkjet ink. Such a CMYK-inkjet ink set may also be extended with extra inks such as red, green, blue, violet and/or orange to further enlarge the colour gamut of the image. The inkjet ink set may also be extended by the combination of the full density inkjet inks with light density inkjet inks. The combination of dark and light colour inks and/or black and grey inks improves the image quality by a lowered graininess.

In a preferred embodiment, the inkjet ink set also includes a white inkjet ink. This allows obtaining more brilliant colours, especially on transparent substrates, where the white inkjet ink can be applied either as a primer or on top of the colour inkjet inks when the image is viewed through the transparent substrate.

The viscosity of the inkjet ink according to the invention is preferably smaller than <NUM> mPa. s at <NUM> and at a shear rate of <NUM>-<NUM>, more preferably between <NUM> and <NUM> mPa. s at <NUM> and at a shear rate of <NUM>-<NUM>. The surface tension of the inkjet ink according to the invention is preferably in the range of about <NUM> mN/m to about <NUM> mN/m at <NUM>, more preferably in the range of about <NUM> mN/m to about <NUM> mN/m at <NUM>.

The fluid according to the invention comprises a compound functionalized with at least two functional groups selected from the group consisting of a primary amine and a secondary amine, a primary amine being more preferred. Said compound functionalized with at least two functional groups selected from the group consisting of a primary amine and secondary amine, can be selected from a di- or multifunctional low molecular weight compound and an oligomer or polymer.

In a more preferred embodiment, said amino functionalized compound is a low molecular weight compound having a functionality having a functionality of <NUM> to <NUM>, more preferably <NUM> to <NUM> and most preferably is di- or trifunctional. These compounds being more available into the market.

Typical amine functionalized ink additives are given in Table <NUM> without being limited thereto.

In a more preferred embodiment, said compound functionalized with at least two functional groups selected from the group consisting of a primary amine and secondary amine is a polymer is functionalized with at least <NUM>, more preferably at least <NUM> and most preferably at least <NUM> functional groups, selected from the group consisting of a primary amine and a secondary amine, a primary amine being more preferred.

The polymer can be dissolved in the fluid or can be present as a dispersed or emulsified polymer particle. Typical polymers, useful in the design of the fluid as a primer, are selected from the group consisting of poly(allylamine), poly(vinylamine), poly(vinylamine-co-vinylformamide), chitosan, homo- or copolymers of <NUM>-aminomethyl-styrene or salt thereof, <NUM>-aminoethyl-acrylate or salt thereof, <NUM>-aminoethyl-methacrylate or salt thereof, <NUM>-aminopropyl-acrylamide or salt thereof, <NUM>-aminopropyl-methacrylamide or salt thereof, poly(lysine) or copolymers thereof and the like.

In a preferred embodiment, the fluid comprises at least one resin particle, functionalized with at least <NUM>, more preferably at least <NUM> and most preferably at least <NUM> functional groups selected from the group consisting of a primary amine and a secondary amine, a primary amine being more preferred. The use of a functionalized resin particle instead of a functionalized compound in the fluid has the advantage of an improved rheological behaviour leading to an improved jetting reliability and colloidal stability of the fluid. This is of great importance if the fluid has to be jetted in the image forming method by means of an inkjet head or valve-jet head, for example if the fluid is a primer (pre-treatment liquid), an aqueous inkjet ink or an overcoat which is image wise applied.

The amino functionalized resin particle can be prepared by derivatisation of amino functionalized polymers, followed by dispersing of said derivative in an aqueous environment, optionally followed by crosslinking of the particle. Preferred starting polymers are homo- or co-polymers of vinyl amine or allylamine. Typical examples include poly(allylamine), poly(vinylamine), poly(vinylamine-co-vinylformamide), chitosan, homo- or copolymers of <NUM>-aminomethyl-styrene or salt thereof, <NUM>-aminoethylacrylate or salt thereof, <NUM>-aminoethyl-methacrylate or salt thereof, <NUM>-aminopropyl-acrylamide or salt thereof, <NUM>-aminopropyl-methacrylamide or salt thereof, poly(lysine) or copolymers thereof and the like. The weight average molecular weight of the starting polymers is preferably at least <NUM>, more preferably at least <NUM> and most preferably at least <NUM>.

Other synthetic strategies include derivatisation of carboxylic acid functionalized acrylic polymers with azeridine followed by emulsification and optionally crosslinking, emulsion or mini-emulsion polymerization of optionally protected amino functionalized monomers, optionally followed by deprotection, post derivatisation of reactive latexes, comprising reactive monomers such as <NUM>-chloromethyl-styrene and sol gel based polycondensations based on amino functionalized alkoxysilanes.

In a preferred embodiment, said amino functionalized resin particles are crosslinked. Crosslinked particles give more formulation latitude. Indeed, due to crosslinking, resin particles will be more resistant to water soluble organic solvents present in the vehicle of the ink. In a further preferred embodiment at least <NUM> mol%, more preferably at least <NUM> mol% and most preferably at least <NUM> mol% of the repeating units in the polymer resin particle are functionalized with a functional groups selected from the group consisting of a primary amine and a secondary amine.

The amines can be at least partially neutralized with an acid such as hydrochloric acid, methane sulfonic acid, p. -toluene sulfonic acid, phosphoric acid, sulfuric acid and carboxylic acids such as acetic acid, citric acid and lactic acid.

The fluid may comprise additives which are specific for the functioning of the fluid.

If the fluid as part of the fluid set according to the invention functions as a primer, the fluid may further comprise a flocculating agent which reacts with the colorant of the aqueous ink of the fluid set. The flocculating agent induces a viscosity increase, a precipitation or an immobilization of the colorant of the ink when the aqueous ink comes into contact with the fluid acting as primer.

The flocculating agent is preferably a resin or a multivalent metal ion. Suitable examples of multivalent metal ions are water-soluble metal salts formed from bi- or higher valent metal cations, such as magnesium, calcium, strontium, barium, zirconium, and aluminum, and anions, such as a fluoride ion (F-), a chloride ion (Cl-), a bromide ion (Br-), a sulfate ion (SO<NUM><NUM>-), a nitrate ion (NO<NUM>-), and an acetate ion (CH<NUM>COO-).

These polyvalent metal ions have a function of aggregating the colorant, more specifically the pigment, by acting on the carboxyl groups on the surface of the pigment in the inkjet ink, or on the dispersed polymer of capsules contained in the ink. As a result, the colorants of the ink are fixed resulting in a decreased color bleeding and beading. Therefore, it is preferred that the surface of the pigment in the ink and/or the dispersed polymer of the capsules, if contained in the ink, have an anionic group, preferably a carboxyl group.

The resin as a flocculating agent can be selected from the group of starches; cellulosic materials such as carboxymethyl cellulose and hydroxymethyl cellulose; polyurethanes, polysaccharide ; proteins such as gelatine and casein; water-soluble naturally occurring polymers such as tannin and lignin; and synthetic water-soluble polymers such as polymers comprising polyvinyl alcohol, polymers comprising polyethylene oxide, polymers formed from acrylic acid monomers, and polymers formed from maleic anhydride monomers. Other suitable resins are acrylic polymers as described in <CIT>[<NUM>-<NUM>]. Preferably the resin is a cationic resin, more preferably a cationic charged polyurethane. The resin content is preferably not more than <NUM> wt. % relative to the total mass of the fluid acting as primer (<NUM> mass%).

The fluid acting as a primer may also comprise colorants, more specifically white colorants to obtain vivid colored images when the primer is overprinted with the aqueous inkjet ink of the fluid set according to the invention on dark or colored substrates like card board, black colored textile,. or transparent substrates. More specifically the fluid acting as a primer preferably comprises white pigments. Suitable white pigments are given by Table <NUM> in [<NUM>] of <CIT>. The white pigment is preferably a pigment with a refractive index greater than <NUM>. The white pigments may be employed singly or in combination. Preferably titanium dioxide is used as pigment with a refractive index greater than <NUM>. Suitable titanium dioxide pigments are those disclosed in [<NUM>] and in [<NUM>] of <CIT>. Titanium dioxide (TIO<NUM>) pigment useful in the present invention may be in the rutile or anatase crystalline form. Processes for making TiOs are described in greater detail in "<NPL>), the relevant disclosure of which is incorporated by reference herein for all purposes as if fully set forth.

The titanium dioxide particles can have a wide variety of average particle sizes of about <NUM> micron or less, depending on the desired end use application of the fluid. For applications demanding high hiding or decorative printing applications, the titanium dioxide particles preferably have an average size of less than about <NUM>. Preferably, the particles have an average size of from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, and still more preferably from about <NUM> to about <NUM>.

For applications demanding white colour with some degree of transparency, the pigment preference is "nano" titanium dioxide. "Nano" titanium dioxide particles typically have an average size ranging from about <NUM> to about <NUM>, preferably from about <NUM> to about <NUM>, and more preferably from about <NUM> to about <NUM>. A fluid comprising nano titanium dioxide can provide improved chroma and transparency, while still retaining good resistance to light fade and appropriate hue angle. A commercially available example of an uncoated nano grade of titanium oxide is P-<NUM>, available from Degussa (Parsippany N.

In addition, unique advantages may be realized with multiple particle sizes, such as opaqueness and UV protection. These multiple sizes can be achieved by adding both a pigmentary and a nano grade of TIO<NUM>.

The titanium dioxide pigment may also bear one or more metal oxide surface coatings. These coatings may be applied using techniques known by those skilled in the art. Examples of metal oxide coatings include silica, alumina, aluminasilica, boria and zirconia, among others. These coatings can provide improved properties including reducing the photoreactivity of the titanium dioxide. Metal oxide coatings of alumina, aluminasilica, boria and zirconia result in a positive charged surface of the TiOs pigments and hence are particularly useful in combination with the compound functionalized with at least two functional groups selected from the group consisting of a primary amine and a secondary amine, which has a positive charge at usual pH of a primer. No additional surface treatment of the pigment, is then required.

Commercial examples of such coated titanium dioxides include R700 (alumina-coated, available from E. DuPont deNemours, Wilmington Del. ), RDI-S (alumina-coated, available from Kemira Industrial Chemicals, Helsinki, Finland), R706 (available from DuPont, Wilmington Del. ) and W-<NUM> (a silica alumina treated nano grade titanium dioxide from Tayco Corporation, Osaka Japan).

When the fluid acting as a primer is jetted via an inkjet head or valve jet head, other additives may be added such as the ones described in § A.

The fluid as part of the fluid set according to the invention may also function as an aqueous inkjet ink in the formation of an image, also called co-reactive inkjet ink due to its ability to react with the first aqueous inkjet ink of the set.

The fluid acting as an inkjet ink preferably comprise the colorants as described in § A. and additives as described in § A.

If the fluid as part of the fluid set according to the invention functions as an overcoat which is coated or printed on top of the jetted aqueous inkjet ink according to the invention, the fluid may further comprise a resin. Suitable resins can be acrylic based resins, a urethane-modified polyester resin or a polyethylene wax.

The polyurethane resin may be incorporated in the fluid formulation acting as an overcoat as a dispersion and may be selected from the group consisting of aliphatic polyurethane dispersions, aromatic polyurethane dispersions, cationic polyurethane dispersions, non-ionic polyurethane dispersions, aliphatic polyester polyurethane dispersions, aliphatic polycarbonate polyurethane dispersions, aliphatic acrylic modified polyurethane dispersions, aromatic polyester polyurethane dispersions, aromatic polycarbonate polyurethane dispersions, aromatic acrylic modified polyurethane dispersions, for example, or a combination of two or more of the above.

Some examples of suitable polyurethane dispersions are NEOREZ R-<NUM>, NEOREZ R-<NUM>, and NEOREZ R-<NUM> (DSM NeoResins); BAYHYDROL UH <NUM>, BAYHYDROL UH XP <NUM>, BAYHYDROL UH XP <NUM>, and BAYHYDROL UA XP <NUM> (Bayer Material Science); DAOTAN VTW <NUM>/35WA, DAOTAN VTW <NUM>/36WA, DAOTAN VTW <NUM>/36WA, DAOTAN VTW <NUM>/42WA, DAOTAN VTW <NUM>/36WA (Cytec Engineered Materials Inc. , Anaheim CA); and SANCURE <NUM>, SANCURE <NUM>, SANCURE <NUM> (Lubrizol Corporation), for example, or a combination of two or more of the above.

Acrylic based resins include polymers of acrylic monomers, polymers of methacrylic monomers, and copolymers of the aforementioned monomers with other monomers. These resins are present as a suspension of particles having an average diameter of about <NUM> to about <NUM>. The acrylic latex polymer is formed from acrylic monomers or methacrylic monomer residues. Examples of monomers of the acrylic latex polymer include, by way of illustration, acrylic monomers, such as, for example, acrylate esters, acrylamides, and acrylic acids, and methacrylic monomers, such as, for example, methacrylate esters, methacrylamides, and methacrylic acids. The acrylic latex polymer may be a homopolymer or copolymer of an acrylic monomer and another monomer such as, for example, a vinyl aromatic monomer including, but not limited to, styrene, styrene butadiene, p-chloromethylstyrene, divinyl benzene, vinyl naphthalene and divinylnaphthalene.

Some examples of suitable acrylic latex polymer suspensions are, JONCRYL <NUM> and JONCRYL <NUM> (BASF Corporation, Port ArthurTX); CARBOSET GA-<NUM>, CARBOSET CR-<NUM>, CARBOSET CR-<NUM>, CARBOSET CR-<NUM>, CARBOSET CR-<NUM>, CARBOSET CR-<NUM>, CARBOSET CR-<NUM>, and CARBOSET GA-<NUM> (Lubrizol Corporation); NEOCRYL A-<NUM>, NEOCRYL A-<NUM>, NEOCRYL A-<NUM>, NEOCRYL A-<NUM>, NEOCRYL XK-<NUM>, and NEOCRYL XK-<NUM> (DSM); and BAYHYDROL AH XP <NUM>, BAYHYDROL AH XP <NUM>, BAYHYDROL A <NUM>, and BAYHYDROL A2651 (Bayer), for example, or a combination of two or more of the above.

The concentration of the resin in the fluid acting as an overcoat is at least <NUM> wt. % and preferably lower than <NUM> wt. %, more preferably lower than <NUM> wt.

The overcoat can be applied onto the jetted aqueous inkjet ink by a coating technique or printed using a printing technique such as: gravure printing, flexographic printing, offset printing or inkjet printing. In a particular preferred embodiment, the varnish is printed using inkjet printing.

The fluid set according to the invention is suitable to be used in an inkjet image recording method. The inkjet recording method according to the invention comprises the steps of:.

In a preferred inkjet recording method, the method comprises the steps of:.

In another preferred inkjet recording method, the method comprises the steps of: a) forming an image by ink jetting the fluid set onto a substrate, preferably a non-porous substrate. The fluid of the fluid set comprises a compound functionalized with at least two functional groups selected from the group consisting of a primary amine and a secondary amine, a primary amine being more preferred and preferably a colorant. More preferably, the compound is a resin particle. The aqueous inkjet ink of the fluid set according to the invention comprises the dispersion of particles containing an oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde more preferably the ink comprising a dispersion of capsules composed of a polymeric shell surrounding a core, the core containing an oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde. The jetting of the fluid set in forming the image, can be performed by jetting the fluid and the aqueous inkjet ink sequentially or simultaneously; and b) drying the jetted fluid set by applying heat such as to obtain a temperature of the jetted ink of at least <NUM>, more preferably at least <NUM>.

In another preferred inkjet recording method, the method comprises the steps of: a) jetting the aqueous inkjet ink of the fluid set according to the invention onto a substrate, preferably a non-porous substrate. The ink comprises the dispersion of particles containing an oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde, more preferably the ink comprises a dispersion of capsules composed of a polymeric shell surrounding a core, the core containing an oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde. Optionally the inkjet ink can be dried by applying heat to a dry or semi-dry condition; and b) applying the fluid according to the invention as an overcoat onto the jetted aqueous inkjet ink. The fluid comprises a compound functionalized with at least two functional groups selected from the group consisting of a primary amine and a secondary amine, a primary amine being more preferred. The fluid can be coated by any suitable coating method or printed using a printing technique such as: gravure printing, flexographic printing, offset printing or inkjet printing. In a particular preferred embodiment, the fluid is jetted using inkjet printing and the compound functionalized with at least two functional groups selected from the group consisting of a primary amine and a secondary amine is a resin particle. c) drying the applied fluid set by applying heat such as to obtain a temperature of the jetted ink of at least <NUM>, more preferably at least <NUM>.

In another preferred inkjet recording method, two or three of the preferred methods described above can be combined.

The substrate in the inkjet recording method may be porous, such as e.g. textile, paper, leather and card board substrates, but is preferably a non-absorbing substrate such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl chloride, polyesters like polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polylactide (PLA) or polyimide.

The substrate may also be a paper substrate, such as plain paper or resin coated paper, e.g. polyethylene or polypropylene coated paper. There is no real limitation on the type of paper and it includes newsprint paper, magazine paper, office paper, wallpaper but also paper of higher grammage, usually referred to as boards, such as white lined chipboard, corrugated board and packaging board.

The substrates may be transparent, translucent or opaque. Preferred opaque substrates includes so-called synthetic paper, like the Synaps™ grades from Agfa-Gevaert which are an opaque polyethylene terephthalate sheet having a density of <NUM>/cm<NUM> or more.

Examples of the heating process to dry the fluid set according to the invention, or at least dry the fluid or aqueous inkjet ink, include, but are not limited to, heat press, atmospheric steaming, high-pressure steaming, THERMOFIX. Any heat source can be used for the heating process; for example, an infrared ray source is employed.

The drying step can be performed at the ambient air, but the heating step to achieve a temperature of the applied fluid set or at least one of the fluid or aqueous inkjet ink of at least <NUM>, more preferably <NUM>, must be performed by using a heat source. Examples of suitable heat sources include equipment for forced-air heating, radiation heating such as IRradiation, including NIR- and CIR radiation, conduction heating, highfrequency drying, and microwave drying.

A preferred ink jet head for the inkjet printing system to jet the inkjet ink and optionally the fluid acting as primer and/or overcoat 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 ink or liquid. When the voltage is again removed, the ceramic expands to its original shape, ejecting a drop of ink from the ink jet head. However, the jetting of the aqueous inkjet ink and optionally the fluid according to the present invention 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 MEM-jet type head and a valve jet type.

All compounds are supplied by TCI Europe unless otherwise specified.

The solvent resistance is tested by wiping <NUM> times with a Q-tip over the coatings or printed images using isopropanol and methyl ethyl ketone as solvent or water.

A score of <NUM> means complete dissolution of the coating or image layer. A score of <NUM> means clear visible damage upon wiping. A score of <NUM> means minor visual damage upon wiping. A score of <NUM> means no or hardly noticeable damage on the coating or image.

<NUM> phenoxyethyl acrylate and <NUM> <NUM>-[(<NUM>-vinylphenyl)methyl]pentane-<NUM>,<NUM>-dione were dissolved in <NUM> ethyl acetate. <NUM> dodecyl mercaptan and <NUM> WAKO V59 were added and the mixture was flushed with nitrogen. The polymerization was allowed to continue for <NUM> hours at <NUM>. An additional <NUM> WAKO V59 was added and the polymerization was allowed to continue for <NUM> hours at <NUM>. The reaction mixture was allowed to cool down to room temperature and <NUM> n-hexane was added. INVPOL-<NUM> precipitated from the medium and was isolated by filtration. <NUM> (y: <NUM>%) of INVPOL-<NUM> was isolated.

<NUM> phenoxyethyl acrylate and <NUM> N-(<NUM>-benzoyl-<NUM>-oxo-butyl)prop-<NUM>-enamide were dissolved in <NUM> ethyl acetate. <NUM> dodecyl mercaptan and <NUM> WAKO V59 were added and the mixture was flushed with nitrogen. The polymerization was allowed to continue for <NUM> hours at <NUM>. The reaction mixture was allowed to cool down to room temperature and <NUM> n. -hexane was added. INVPOL-<NUM> precipitated from the medium and was isolated by filtration. <NUM> (y: <NUM>%) of INVPOL-<NUM> was isolated.

A solution of <NUM> of INVPOL-<NUM> and <NUM> Desmodur N75 BA in <NUM> ethyl acetate was added to a solution of <NUM> Lakeland ACP70 and <NUM> triethyl amine in <NUM> water under sonification for <NUM> minutes. <NUM> water was added and the ethyl acetate was removed under reduced pressure. Water was evaporated to obtain <NUM> of the INVCAP-<NUM> dispersion in water. <NUM> N-methyl-morpholine was added and the mixture was heated to <NUM> for <NUM> hours. The mixture was allowed to cool down and the INVCAP-<NUM> dispersion was used in the formulation of INVINK-<NUM>.

The average particle size was measured using a ZetasizerTM Nano-S (Malvern Instruments, Goffin Meyvis). The average particle size was <NUM>.

This example illustrates the increase in solvent resistance by using an ink set, comprising an aqueous ink having a <NUM>,<NUM>-diketone (KETO-<NUM>) based resin, and an aqueous liquid acting as an over-print varnish and comprising an amino functionalized alkoxysilane homopolymer.

The inventive ink INVINK-<NUM> and comparative ink COMPINK-<NUM> were prepared by mixing the components according to Table <NUM>. PU-<NUM> has been prepared as PU-<NUM>, disclosed in <CIT>. All weight percentages are based on the total weight of the ink jet ink.

Overcoat INVOV-<NUM> was prepared by mixing the components according to Table <NUM>. All weight percentages are based on the total weight of the overcoat.

The inks INVINK-<NUM> and COMPINK-<NUM> were coated on poly(propylene) (Priplak, supplied by Antalis), using a <NUM> micron wired bar, and dried for <NUM> minutes at <NUM> in an oven. The coatings were evaluated for water and solvent resistance. On top of the coating of INVINK-<NUM>, a coating of <NUM> micron of INVOV-<NUM> was applied and dried for <NUM> minutes at <NUM> in an oven. The solvent resistance of the coatings was measured according to the method described above. Before measuring the solvent resistance, the coatings were stored at room temperature for <NUM> days. The inventive ink INVINK-<NUM> was stored for <NUM> days at <NUM> and coated again as described above. The solvent resistance of the coating was measured again according to the method described above. Before measuring the solvent resistance, the coatings were stored at room temperature for <NUM> days. The results are summarized in table <NUM>.

From table <NUM>, it becomes apparent that applying a fluid set according to the present invention significantly improves the chemical resistance, in comparison with a poly(urethane) based resin ink (COMPINK-<NUM>) and that the set remains stable, even after <NUM> days storage at <NUM>.

The inventive ink INVINK-<NUM> was prepared by mixing the components according to Table <NUM>. All weight percentages are based on the total weight of the ink.

INVINK-<NUM> and INVOV-<NUM> were applied and tested the same way as in Example <NUM>. The results are summarized in Table <NUM>.

Claim 1:
A fluid set comprising a fluid comprising a compound functionalized with at least two functional groups selected from the group consisting of a primary amine and a secondary amine, and an aqueous inkjet ink comprising a colorant and a polymeric particle comprising an oligomer or polymer comprising at least three repeating units functionalized with a functional group selected from the group consisting of a <NUM>,<NUM>-diketone, a β-keto-aldehyde and a <NUM>,<NUM>-dialdehyde, with the proviso that the active methylene is functionalized with at least one hydrogen.