WO2003011989A1 - Solvent-free liquid pigment ink for ink-jet printing - Google Patents

Solvent-free liquid pigment ink for ink-jet printing Download PDF

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Publication number
WO2003011989A1
WO2003011989A1 PCT/FR2002/002680 FR0202680W WO03011989A1 WO 2003011989 A1 WO2003011989 A1 WO 2003011989A1 FR 0202680 W FR0202680 W FR 0202680W WO 03011989 A1 WO03011989 A1 WO 03011989A1
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WO
WIPO (PCT)
Prior art keywords
ink
compound
pigment
ink according
photoinitiator
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PCT/FR2002/002680
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French (fr)
Inventor
Elodie Jego
Denis Perisse
Pierre Cocagne
Original Assignee
Armor
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Application filed by Armor filed Critical Armor
Publication of WO2003011989A1 publication Critical patent/WO2003011989A1/en

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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
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • 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
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

  • the present invention relates to the field of liquid pigment inks, in particular those intended for ink jet printing.
  • Such inks are made up of a black or colored pigment, which is suspended in a vehicle.
  • This vehicle generally comprises at least one compound which can be oxidized or crosslinkable by UV, that is to say capable of polymerizing by solidifying by exposure to air or to ultraviolet radiation, and a volatile, organic or aqueous solvent.
  • the role of the solvent is to give the ink composition the fluidity or viscosity necessary to be easily “ejected” from the nozzle of the print head, and also to prevent, during stops, that the ink does not take up en masse by clogging the canals.
  • the solvent After printing, that is to say the deposit of ink on the surface of a support, the solvent must be removed by evaporation and / or penetration into said support if the latter is more or less porous. This drying must be rapid, which implies either the presence of a small amount of solvent in the ink composition, or a high volatility of the latter.
  • Japanese patent JP07041712 describes an ink preparation of this type, prepared by dispersion in water of a UV crosslinkable compound, such as a (meth) acrylic monomer.
  • the object of the present invention is therefore to overcome all of these drawbacks by proposing an ink having the necessary fluidity at the time of ejecting the print head and not likely to clog the channels of the ejection nozzle during interruptions or prolonged stops.
  • the composition of this ink must not contain any solvent to be evaporated (neither volatile organic nor aqueous), and be compatible with current technologies of inkjet printing, for operation at room temperature, especially in cases where it is neither intended nor possible to heat the print head itself.
  • the ink must also be stable over time, mainly during storage, the dispersion remaining perfectly homogeneous, without any sedimentation of the pigment particles, or polymerization (solidification of the ink).
  • the ink after depositing on the support to be printed and drying, must have an excellent mechanical resistance, in particular to scratches as well as a good resistance to water.
  • liquid pigment ink which comprises a pigment in suspension in a vehicle based on a first monomeric or (meth) acrylic oligomer compound crosslinkable by UV, in the presence of a quantity of photoinitiator corresponding to this first compound and which is characterized in that it does not contain an aqueous or volatile organic solvent, and in that the vehicle contains at least one second monomer or oligomer compound, crosslinkable by UV, without additional addition of photoinitiator, the second compound being compatible with said first compound, and of viscosity less than or equal to that of the latter, and being added in proportions such that the final viscosity of the ink is less than about 20 mPa.s at a temperature between 15 and 35 ° C approximately.
  • the polymerization of the monomers or oligomers constituting the vehicle does not take place in the narrow channels of the nozzle, the crosslinking occurs only after printing, when they are exposed to ultraviolet radiation.
  • the first compound is advantageously a monomer or oligomer very reactive to UV, such as the compounds comprising for example from one to six acrylic groups.
  • the second compound serves as a sort of diluent for the first compound, so as to lower if necessary the overall viscosity of the vehicle carrying the pigment, for good "ejection" of the ink from the nozzle of the print head and is also itself reactive to UV, like said first monomeric or oligomeric compound.
  • the compounds which may fall into the category of said second compound must be compounds compatible with the first compound, in particular from the point of view of miscibility.
  • the second compound is also a (meth) acrylic, or vinyl, preferably mono- or di-functional, monomer or oligomer or a mixture of several of these monomers or oligomers.
  • the ink according to the present invention comprises approximately 9 to 20% by weight of the first monomeric or (meth) acrylic oligomer compound, from 0.2 to 4% of photoinitiator, up to 6% by weight of pigment and from 70 to 85% by weight of the second compound.
  • the amount of photoinitiator can advantageously be less than 3 or 4% by weight, or even less than 1% by weight in the final ink composition, but always greater than or equal to approximately 0.2% to ensure minimum reactivity. If the viscosity of the final ink is less than 20 mPa.s, or even 15 mP.s, or less, the said first and second monomeric or oligomeric compounds can be identical (i.e. the vehicle n 'consists of only one and the same monomer or oligomer), and the amount of photoinitiator does not exceed 1% by weight of the final ink.
  • the pigment consists of finely divided particles (of the order of 20 to 500 nm) of organic pigments of different colors, possibly supplemented with titanium dioxide and / or carbon black.
  • These pigment particles are, in the present invention, preferably covered with a coating material which is a polymer, which makes it possible to obtain particles which are practically unitary, that is to say non-agglomerated.
  • This polymer is advantageously soluble, at least partially, in the second compound so as to "unfold" it around the grain of pigment, this in order to allow better maintenance in suspension in the vehicle.
  • the coating material may for example be based on a cellulosic (for example ethylcellulose), aldehyde, (meth) acrylic, vinyl (vinyl chloride, vinyl acetate), polypropylene or polyethylene polymer.
  • the pigment ink composition according to the present invention may also contain a slip agent and / or a spreading agent.
  • This additive can be present in an amount less than or equal to 3%, preferably 1% by weight.
  • a slip agent gives the ink improved scratch resistance performance, it also improves the spreading of the ink.
  • a spreading agent mainly contributes to reducing the surface tension.
  • slip agents are silicone acrylates, polyether / silicone copolymers or also polysiloxane / polyether copolymers. These latter slip agents also allow the superposition of several layers of ink.
  • the process for preparing the ink composition according to the present invention comprises a first step of dispersing the pigment particles in said second compound in a "ball mill” with fine beads, in a way “sorting out” or unfolding the polymer of coating the pigment particles. Under the effect of shear forces, this step is generally slightly exothermic, the coating polymer becomes more malleable after a few minutes and is partially dissolved in said second compound. Cooling is usually necessary before starting the second step, which consists in adding to this dispersion the mixture of the first compound with the corresponding amount of photoinitiator, a mixture carried out beforehand and carefully stored away from light. Finally, the slip and / or spreading agent is optionally incorporated into the ink.
  • Example 1 with volatile organic solvent
  • the pigment, coated with a type N ethylcellulose polymer, is first suspended in a solution of glycol ethers in a 15% pigment / 85% ratio glycol ethers (dispersion A).
  • This ink composition has good machinability on the MIT piezoelectric printhead.
  • the machinability test consists of operating the print head under impulse for 15 minutes, stopping it for 10 minutes, then restarting it for 5 minutes, stopping it for 15 minutes and finally restarting it for 5 minutes.
  • the ink obtained has a good gloss, but with a tendency to yellowing. Its reactivity to UV is weak, its adhesion poor, and its mechanical resistance is weak. This composition also has the disadvantage of containing 70 to 85% of volatile organic solvents, which must then be evaporated.
  • Example 2 Compared to Example 1, the solvents based on glycol ethers are replaced by monomers or oligomers reactive to UV.
  • the same pigment is "ground” (mixed) with various monomers or oligomers (in the ratio 15% of pigment, 85% of monomer or oligomer): urethane monoacrylate, hexane diacrylate 1,6-diol, l 'tetrahydrofurfuryl acrylate, a mixture of octyl and decyl acrylates (ODA).
  • various monomers or oligomers in the ratio 15% of pigment, 85% of monomer or oligomer: urethane monoacrylate, hexane diacrylate 1,6-diol, l 'tetrahydrofurfuryl acrylate, a mixture of octyl and decyl acrylates (ODA).
  • the dispersion in the ODA is chosen for its very low viscosity (2 to 3 mPa.s) which makes it possible to have a low viscosity of the final ink while retaining a high proportion of pigment.
  • dispersion B The dispersion 15% of pigment in 85% of ODA constitutes dispersion B:
  • the chlorinated polyester is here tested to improve the adhesion, in particular for its good compatibility with vinyl supports.
  • the other two types of "first compound" are chosen for their good viscosity / reactivity compromise.
  • ODA is a very good reactive diluent, which is perfectly suited as a second compound.
  • ODA is a very good reactive diluent, which is perfectly suited as a second compound.
  • the best adhesion / scratchability compromise is obtained with the ink of composition d).
  • Example 3 (comparative): with volatile organic solvent
  • the coating of the pigment is here a polymer based on vinyl aceto-chloride, hard polymer, which has a good affinity with the supports in plastic materials.
  • This pigment is dispersed in glycol acetates (in the respective weight ratio 15/85) to form dispersion C.
  • Example 4 The major drawback of this composition is that it contains solvents (here around 22% by weight).
  • Example 4 The major drawback of this composition is that it contains solvents (here around 22% by weight).
  • Example 3 The same pigment as that of Example 3 is used and is dispersed in ODA.
  • Pigment 2.8 to 4.2% + coating: 2.8 to 4.2% (vinyl resin)
  • first compound urethane monoacrylate: 9.5 to 14.1% photoinitiator: 0.5 to 0, 7% slip agent: 0.2 to 0.3%
  • second compound ODA 84.1 to 76.4%
  • Example 5 Taken from example 4, a standard ink according to the invention is prepared, with a pigment identical to that of example 3, dispersed in ODA.
  • This standard ink has the following composition:
  • This ink has a final viscosity of 9.35 mPa.s at 25 ° C.
  • inks according to the invention are prepared by modifying, with respect to the above standard ink serving as a reference, the nature of the first compound, monomer or oligomer.
  • first compounds have been tested:
  • the viscosity of these inks is between 9.5 and 12 mPa.s (at 25 ° C). The tests carried out show that these five inks have excellent mechanical resistance (scratchability) as well as good resistance to water (more particularly ink 5d containing the acrylated oligomer.
  • the inks 5c, 5d and 5e also exhibit excellent resistance to chemical agents such as fuel oil, gasoline and other solvents (alcohols, ketones, esters).
  • the solvent-free pigment ink according to the present invention can be used for printing by ink jet with piezoelectric or thermal excitation, on any porous or non-porous support, such as textiles, metals, ceramics, glass, wood, paper and plastic supports (eg PVC). TABLE 1

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention concerns a liquid pigment ink, free of aqueous or volatile organic solvent, comprising a pigment suspended in a vehicle based on a first (meth)acrylic monomer or oligomer compound, UV-curable in the presence of a photoinitiator. The vehicle contains at least a second UV-curable monomer or oligomer compound, compatible with the first compound, and of viscosity not higher than that of the latter, which is added in proportions such that the final viscosity of the ink is about 20 mPa's at a temperature ranging between about 15 and 35 °C. Said solvent-free ink is in particular designed for ink-jet printing.

Description

Encre pigmentaire liquide sans solvant, pour impression par jet d'encre Solvent-free liquid pigment ink for inkjet printing
La présente invention concerne le domaine des encres pigmentaires liquides, notamment celles destinées à l'impression par jet d'encre.The present invention relates to the field of liquid pigment inks, in particular those intended for ink jet printing.
De telles encres sont constituées d'un pigment noir ou de couleur, qui est en suspension dans un véhicule. Ce véhicule comprend généralement au moins un composé oxydable ou reticulable aux U.V., c'est-à-dire capable de polymériser en se solidifiant par exposition à l'air ou aux rayonnements ultra-violets, et un solvant volatil, organique ou aqueux. Le rôle du solvant est de conférer à la composition d'encre la fluidité ou viscosité nécessaire pour être facilement "éjectée" de la buse de la tête d'impression, et également d'éviter, lors des arrêts, que l'encre ne prenne en masse en colmatant les canau .Such inks are made up of a black or colored pigment, which is suspended in a vehicle. This vehicle generally comprises at least one compound which can be oxidized or crosslinkable by UV, that is to say capable of polymerizing by solidifying by exposure to air or to ultraviolet radiation, and a volatile, organic or aqueous solvent. The role of the solvent is to give the ink composition the fluidity or viscosity necessary to be easily "ejected" from the nozzle of the print head, and also to prevent, during stops, that the ink does not take up en masse by clogging the canals.
Après l'impression, c'est à dire le dépôt de l'encre à la surface d'un support, le solvant doit être éliminé par évaporation et/ou pénétration dans ledit support si celui- ci est plus ou moins poreux. Ce séchage doit être rapide, ce qui implique soit la présence de solvant en faible quantité dans la composition d'encre, soit une grande volatilité de ce dernier.After printing, that is to say the deposit of ink on the surface of a support, the solvent must be removed by evaporation and / or penetration into said support if the latter is more or less porous. This drying must be rapid, which implies either the presence of a small amount of solvent in the ink composition, or a high volatility of the latter.
Mais la présence de solvants organiques volatils pose des problèmes de pollution de l'environnement et de toxicité.However, the presence of volatile organic solvents poses problems of environmental pollution and toxicity.
C'est pourquoi des compositions d'encres pour impression par jet d'encre dans lesquelles le solvant volatil a été en partie remplacé par de l'eau ont été récemment mises au point. Le brevet japonais JP07041712 décrit une préparation d'encre de ce type, préparée par dispersion dans l'eau d'un composé reticulable aux UV, tel qu'un monomère (méth)acrylique.This is why ink compositions for inkjet printing in which the volatile solvent has been partly replaced by water have been recently developed. Japanese patent JP07041712 describes an ink preparation of this type, prepared by dispersion in water of a UV crosslinkable compound, such as a (meth) acrylic monomer.
Cependant de telles encres présentent l'inconvénient de renfermer une grande quantité d'eau qu'il faut ensuite aussi évaporer, ce qui pose des difficultés importantes, à cause de la chaleur latente de vaporisation élevée de l'eau. Toutes les difficultés évoquées ci-dessus sont en outre accentuées dans les cas où la surface d'impression est importante (par exemple si la surface atteint plusieurs mètres carrés). Le but de la présente invention est donc de pallier l'ensemble de ces inconvénients en proposant une encre possédant la fluidité nécessaire au moment de l'éjection de la tête d'impression et ne risquant pas de colmater les canaux de la buse d'éjection lors des interruptions où des arrêts prolongés. La composition de cette encre ne doit renfermer aucun solvant à évaporer (ni organique volatil, ni aqueux), et être compatible avec les technologies actuelles de l'impression par jet d'encre, pour un fonctionnement à température ambiante, notamment dans les cas où il n'est pas prévu, ni possible, de chauffer la tête d'impression elle-même.However, such inks have the disadvantage of containing a large amount of water which must then also be evaporated, which poses significant difficulties, because of the latent heat of high vaporization of the water. All the difficulties mentioned above are further accentuated in cases where the printing surface is large (for example if the surface reaches several square meters). The object of the present invention is therefore to overcome all of these drawbacks by proposing an ink having the necessary fluidity at the time of ejecting the print head and not likely to clog the channels of the ejection nozzle during interruptions or prolonged stops. The composition of this ink must not contain any solvent to be evaporated (neither volatile organic nor aqueous), and be compatible with current technologies of inkjet printing, for operation at room temperature, especially in cases where it is neither intended nor possible to heat the print head itself.
L'encre doit en outre être stable dans le temps, principalement durant le stockage, la dispersion restant parfaitement homogène, sans aucune sédimentation des particules de pigment, ni polymérisation (prise en masse de l'encre). De plus l'encre, après dépôt sur le support à imprimer et séchage, doit présenter une excellente résistance mécanique, notamment aux rayures ainsi qu'une bonne résistance à l'eau.The ink must also be stable over time, mainly during storage, the dispersion remaining perfectly homogeneous, without any sedimentation of the pigment particles, or polymerization (solidification of the ink). In addition, the ink, after depositing on the support to be printed and drying, must have an excellent mechanical resistance, in particular to scratches as well as a good resistance to water.
Ces buts sont atteints par l'encre pigmentaire liquide selon la présente invention, qui comprend un pigment en suspension dans un véhicule à base d'un premier composé monomère ou oligomère (méth)acrylique reticulable par U.V., en présence d'une quantité de photoinitiateur correspondant à ce premier composé et qui est caractérisée en ce qu'elle ne contient pas de solvant aqueux ni organique volatil, et en ce que le véhicule renferme au moins un second composé monomère ou oligomère, reticulable par U.V., sans ajout supplémentaire de photoinitiateur, le second composé étant compatible avec ledit premier composé, et de viscosité inférieure ou égale à celle de ce dernier, et étant ajouté dans des proportions telles que la viscosité finale de l'encre soit inférieure à environ 20 mPa.s à une température comprise entre 15 et 35° C environ.These objects are achieved by the liquid pigment ink according to the present invention, which comprises a pigment in suspension in a vehicle based on a first monomeric or (meth) acrylic oligomer compound crosslinkable by UV, in the presence of a quantity of photoinitiator corresponding to this first compound and which is characterized in that it does not contain an aqueous or volatile organic solvent, and in that the vehicle contains at least one second monomer or oligomer compound, crosslinkable by UV, without additional addition of photoinitiator, the second compound being compatible with said first compound, and of viscosity less than or equal to that of the latter, and being added in proportions such that the final viscosity of the ink is less than about 20 mPa.s at a temperature between 15 and 35 ° C approximately.
La polymérisation des monomères ou oligomères constituant le véhicule n'a pas lieu dans les canaux étroits de la buse, la réticulation ne se produit qu'après l'impression, lorsqu'ils sont exposés aux rayonnements ultra-violets.The polymerization of the monomers or oligomers constituting the vehicle does not take place in the narrow channels of the nozzle, the crosslinking occurs only after printing, when they are exposed to ultraviolet radiation.
Aucun solvant volatil n'étant présent, il n'y a pas d'étape de séchage, ni de problèmes vis à vis de l'environnement.No volatile solvent being present, there is no drying step, nor environmental problems.
Le premier composé est avantageusement un monomère ou oligomère très réactif aux U.V., tels que les composés comportant par exemple de un à six groupements acryliques. Le second composé sert en quelque sorte de diluant au premier composé, de façon à abaisser si nécessaire la viscosité globale du véhicule portant le pigment, pour une bonne "éjection" de l'encre de la buse de la tête d'impression et est également lui-même réactif aux U.V., comme ledit premier composé monomère ou oligomère.The first compound is advantageously a monomer or oligomer very reactive to UV, such as the compounds comprising for example from one to six acrylic groups. The second compound serves as a sort of diluent for the first compound, so as to lower if necessary the overall viscosity of the vehicle carrying the pigment, for good "ejection" of the ink from the nozzle of the print head and is also itself reactive to UV, like said first monomeric or oligomeric compound.
Les composés pouvant entrer dans la catégorie du dit second composé doivent être des composés compatibles avec le premier composé, notamment du point de vue de la miscibilité. Avantageusement, le second composé est également un monomère ou oligomère (méth)acrylique, ou vinylique, de préférence mono- ou di-fonctionnel ou un mélange de plusieurs de ces monomères ou oligomères.The compounds which may fall into the category of said second compound must be compounds compatible with the first compound, in particular from the point of view of miscibility. Advantageously, the second compound is also a (meth) acrylic, or vinyl, preferably mono- or di-functional, monomer or oligomer or a mixture of several of these monomers or oligomers.
Comme exemples de monomères ou oligomères pour ce second composé sont cités les composés suivants : l'acrylate de 2-éthylhexyle, l'acrylate d'octyle, l'acrylate de nonyle, l'acrylate de décyle, l'acrylate d'isodécyle, l'acrylate de lauryle, l'acrylate de stéaryle, le (méth)acrylate de phénoxyéthyle, l'acrylate de nonylphénol éthoxylé, l'acide bis acrylique, le (méth)acrylate de tétrahydrofurfuryle, l'acrylate d'isobomyle, l'acrylate de cyclohexyle, l'acrylate de tertiobutyle, l'acrylate de 2-(2 éthoxy) éthyle, le N-vinyl caprolactame, le di(meth)acrylate d'hexane-l,6-diol, le diacrylate de dipropylèneglycol, le diacrylate de tripropylèneglycol, le diacrylate de tétraéthylèneglycol, le triacrylate de triméthylolpropane, le diméthacrylate d'éthylène glycol, le méthacrylate d'allyle, le diméthacrylate de triéthylène glycol, le diméthacrylate de tétraéthylène glycol, le diméthacrylate de polyéthylène glycol 200, le diméthacrylate de 1,4 butane diol, le diméthacrylate de diéthylène glycol, le diméthacrylate de 1,3 butylène glycol, le diacrylate de polyéthylèneglycol 400, l'acrylate d'uréthane, la N-vinylpyrrolidone, le pentacrylate de dipentaérythritol. De manière préférée, l'encre selon la présente invention comprend approximativement de 9 à 20 % en poids du premier composé monomère ou oligomère (méth)acrylique, de 0,2 à 4 % de photoinitiateur, jusqu'à 6 % en poids de pigment et de 70 à 85 % en poids du second composé. La quantité de photoinitiateur peut avantageusement être inférieure à 3 ou 4 % en poids , ou même inférieure à 1 % en poids dans la composition d'encre finale, mais toujours supérieure ou égale à 0,2 % environ pour assurer une réactivité minimale. Si la viscosité de l'encre finale est inférieure à 20 mPa.s, ou même 15 mP.s, ou moins, les dits premier et second composés monomères ou oligomères peuvent être identiques (c'est-à-dire que le véhicule n'est constitué que d'un seul et même monomère ou oligomère), et la quantité de photoinitiateur ne dépasse pas 1 % en poids de l'encre finale.As examples of monomers or oligomers for this second compound are cited the following compounds: 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, stearyl acrylate, phenoxyethyl (meth) acrylate, ethoxylated nonylphenol acrylate, bis acrylic acid, tetrahydrofurfuryl (meth) acrylate, isobomyl acrylate, cyclohexyl acrylate, tert-butyl acrylate, 2- (2 ethoxy) ethyl acrylate, N-vinyl caprolactam, hexane-1,6-diol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, allyl methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate 200 dimethacrylate, 1 , 4 butane diol, diethylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, polyethylene glycol 400 diacrylate, urethane acrylate, N-vinylpyrrolidone, dipentaerythritol pentacrylate. Preferably, the ink according to the present invention comprises approximately 9 to 20% by weight of the first monomeric or (meth) acrylic oligomer compound, from 0.2 to 4% of photoinitiator, up to 6% by weight of pigment and from 70 to 85% by weight of the second compound. The amount of photoinitiator can advantageously be less than 3 or 4% by weight, or even less than 1% by weight in the final ink composition, but always greater than or equal to approximately 0.2% to ensure minimum reactivity. If the viscosity of the final ink is less than 20 mPa.s, or even 15 mP.s, or less, the said first and second monomeric or oligomeric compounds can be identical (i.e. the vehicle n 'consists of only one and the same monomer or oligomer), and the amount of photoinitiator does not exceed 1% by weight of the final ink.
Le pigment est constitué de particules finement divisées (de l'ordre de 20 à 500 nm) de pigments organiques de différentes couleurs éventuellement complétés par du dioxyde de titane et/ou du noir de carbone.The pigment consists of finely divided particles (of the order of 20 to 500 nm) of organic pigments of different colors, possibly supplemented with titanium dioxide and / or carbon black.
Ces particules de pigment sont, dans la présente invention, de préférence recouvertes d'un matériau d'enrobage qui est un polymère, ce qui permet d'obtenir des particules pratiquement unitaires, c'est à dire non agglomérées. Ce polymère est avantageusement soluble, au moins partiellement, dans le second composé de façon à le "déplier" autour du grain de pigment, ceci afin de permettre un meilleur maintien en suspension dans le véhicule. Le matériau d'enrobage peut par exemple être à base d'un polymère cellulosique (par exemple l'éthylcellulose), aldéhydique, (méth)acrylique, vinylique (chlorure de vinyle, acétate de vinyle), un polypropylène ou un polyéthylène.These pigment particles are, in the present invention, preferably covered with a coating material which is a polymer, which makes it possible to obtain particles which are practically unitary, that is to say non-agglomerated. This polymer is advantageously soluble, at least partially, in the second compound so as to "unfold" it around the grain of pigment, this in order to allow better maintenance in suspension in the vehicle. The coating material may for example be based on a cellulosic (for example ethylcellulose), aldehyde, (meth) acrylic, vinyl (vinyl chloride, vinyl acetate), polypropylene or polyethylene polymer.
La composition d'encre pigmentaire selon la présente invention peut également renfermer un agent de glissance et/ou un agent d'étalement. Cet additif peut être présent en quantité inférieure ou égale à 3 %, de préférence 1 % en poids. Un agent de glissance confère à l'encre des performances améliorées de résistance aux rayures, il permet également d'améliorer l'étalement de l'encre. Un agent d'étalement contribue principalement à diminuer la tension superficielle. Des exemples d'agents de glissance sont des acrylates de silicone, des copolymères polyéther/silicone ou encore des copolymères polysiloxane/polyéther. Ces derniers agents de glissance autorisent en outre la superposition de plusieurs couches d'encre.The pigment ink composition according to the present invention may also contain a slip agent and / or a spreading agent. This additive can be present in an amount less than or equal to 3%, preferably 1% by weight. A slip agent gives the ink improved scratch resistance performance, it also improves the spreading of the ink. A spreading agent mainly contributes to reducing the surface tension. Examples of slip agents are silicone acrylates, polyether / silicone copolymers or also polysiloxane / polyether copolymers. These latter slip agents also allow the superposition of several layers of ink.
Le procédé de préparation de la composition d'encre selon la présente invention comprend une première étape de dispersion des particules de pigment dans ledit second composé dans un "broyeur" à billes fines, pour en quelque sorte "désenchevêtrer" ou déplier le polymère d'enrobage des particules de pigment. Sous l'effet des forces de cisaillement, cette étape est en général légèrement exothermique, le polymère d'enrobage devient plus malléable après quelques minutes et est partiellement dissous dans ledit second composé. Un refroidissement est habituellement nécessaire avant d'aborder la deuxième étape qui consiste à rajouter à cette dispersion le mélange du premier composé avec la quantité correspondante de photoinitiateur, mélange effectué préalablement et soigneusement conservé à l'abri de la lumière. Enfin, l'agent de glissance et/ou d'étalement est éventuellement incorporé à l'encre.The process for preparing the ink composition according to the present invention comprises a first step of dispersing the pigment particles in said second compound in a "ball mill" with fine beads, in a way "sorting out" or unfolding the polymer of coating the pigment particles. Under the effect of shear forces, this step is generally slightly exothermic, the coating polymer becomes more malleable after a few minutes and is partially dissolved in said second compound. Cooling is usually necessary before starting the second step, which consists in adding to this dispersion the mixture of the first compound with the corresponding amount of photoinitiator, a mixture carried out beforehand and carefully stored away from light. Finally, the slip and / or spreading agent is optionally incorporated into the ink.
Des exemples non limitatifs illustrent ci-après l'invention. Les pourcentages sont tous des pourcentages en poids, par rapport à la composition finale de l'encre.Nonlimiting examples illustrate the invention below. The percentages are all percentages by weight, relative to the final composition of the ink.
Exemple 1 (comparatif): avec solvant organique volatil Le pigment, enrobé d'un polymère d'éthylcellulose de type N, est d'abord mis en suspension dans une solution d'éthers de glycol dans un rapport 15 % de pigment/85 % d'éthers de glycol (dispersion A).Example 1 (comparative): with volatile organic solvent The pigment, coated with a type N ethylcellulose polymer, is first suspended in a solution of glycol ethers in a 15% pigment / 85% ratio glycol ethers (dispersion A).
Puis divers mélanges sont effectués, avec un monoacrylate d'uréthane comme premier composé réactif aux U.V., et d'un photoinitiateur (l'amino-acétophénone), pour obtenir des compositions d'encre dans les gammes suivantes:Then various mixtures are carried out, with a urethane monoacrylate as the first UV-reactive compound, and with a photoinitiator (amino-acetophenone), to obtain ink compositions in the following ranges:
- dispersion A : 30 à 35 %- dispersion A: 30 to 35%
- monoacrylate d'uréthane : 7 à 15 %- urethane monoacrylate: 7 to 15%
- photoinitiateur : 3 à 4 %- photoinitiator: 3 to 4%
- acétates de glycol : 46 à 60 % (à coefficient d'évaporation élevé)- glycol acetates: 46 to 60% (with a high evaporation coefficient)
Cette composition d'encre présente une bonne machinabilité sur la tête d'impression MIT piézoélectrique. Dans ces exemples, le test de machinabilité consiste à faire fonctionner sous impulsion la tête d'impression pendant 15 minutes, à l'arrêter 10 minutes, puis la remettre en marche 5 minutes, l'arrêter 15 minutes et enfin la remettre en fonction pendant 5 minutes.This ink composition has good machinability on the MIT piezoelectric printhead. In these examples, the machinability test consists of operating the print head under impulse for 15 minutes, stopping it for 10 minutes, then restarting it for 5 minutes, stopping it for 15 minutes and finally restarting it for 5 minutes.
L'encre obtenue présente un bon brillant, mais avec une tendance au jaunissement. Sa réactivité aux U.V. est faible, son adhérence mauvaise, et sa résistance mécanique est faible. Cette composition comporte en outre l'inconvénient de renfermer de 70 à 85 % de solvants organiques volatils, qu'il faut ensuite évaporer.The ink obtained has a good gloss, but with a tendency to yellowing. Its reactivity to UV is weak, its adhesion poor, and its mechanical resistance is weak. This composition also has the disadvantage of containing 70 to 85% of volatile organic solvents, which must then be evaporated.
Exemple 2 (comparatif)Example 2 (comparative)
Par rapport à l'exemple 1, les solvants à base d'éthers de glycol sont remplacés par des monomères ou oligomères réactifs aux U.V.Compared to Example 1, the solvents based on glycol ethers are replaced by monomers or oligomers reactive to UV.
Le même pigment est "broyé" (mélangé) à divers monomères ou oligomères (dans le rapport 15 % de pigment, 85 % de monomère ou oligomère) : le monoacrylate d'uréthane, le diacrylate d'hexane 1,6-diol, l'acrylate de tétrahydrofurfuryle, un mélange d'acrylates d'octyle et de décyle (ODA).The same pigment is "ground" (mixed) with various monomers or oligomers (in the ratio 15% of pigment, 85% of monomer or oligomer): urethane monoacrylate, hexane diacrylate 1,6-diol, l 'tetrahydrofurfuryl acrylate, a mixture of octyl and decyl acrylates (ODA).
Une bonne dispersion est obtenue dans tous les cas. On choisit cependant la dispersion dans l'ODA pour sa très faible viscosité (2 à 3 mPa.s) ce qui permet d'avoir une basse viscosité de l'encre finale tout en gardant une forte proportion de pigment.Good dispersion is obtained in all cases. However, the dispersion in the ODA is chosen for its very low viscosity (2 to 3 mPa.s) which makes it possible to have a low viscosity of the final ink while retaining a high proportion of pigment.
La dispersion 15 % de pigment dans 85 % d'ODA constitue la dispersion B :The dispersion 15% of pigment in 85% of ODA constitutes dispersion B:
Figure imgf000007_0001
Figure imgf000007_0001
Le polyester chloré est ici testé pour améliorer l'adhérence, notamment pour sa bonne compatibilité avec les supports vinyliques. Les deux autres types de "premier composé" sont choisis pour leur bon compromis viscosité/réactivité.The chlorinated polyester is here tested to improve the adhesion, in particular for its good compatibility with vinyl supports. The other two types of "first compound" are chosen for their good viscosity / reactivity compromise.
L'ODA est un très bon diluant réactif, qui convient parfaitement comme second composé. Parmi les 4 encres (a à d) testées, le meilleur compromis adhérence/rayabilité est obtenu avec l'encre de composition d).ODA is a very good reactive diluent, which is perfectly suited as a second compound. Among the 4 inks (a to d) tested, the best adhesion / scratchability compromise is obtained with the ink of composition d).
Cette encre sans solvant présente une meilleure adhérence que celle de l'exemple 1 avec une bonne machinabilité malgré une faible résistance mécanique et une faible réactivité. Exemple 3 (comparatif): avec solvant organique volatilThis solvent-free ink has better adhesion than that of Example 1 with good machinability despite low mechanical strength and low reactivity. Example 3 (comparative): with volatile organic solvent
L'enrobage du pigment est ici un polymère à base d'acéto-chlorure de vinyle, polymère dur, qui présente une bonne affinité avec les supports en matériaux plastiques.The coating of the pigment is here a polymer based on vinyl aceto-chloride, hard polymer, which has a good affinity with the supports in plastic materials.
Ce pigment est dispersé dans des acétates de glycol (dans le rapport pondéral respectif 15/85) pour former la dispersion C.This pigment is dispersed in glycol acetates (in the respective weight ratio 15/85) to form dispersion C.
La composition d'encre suivante est ensuite réalisée :The following ink composition is then carried out:
- dispersion C : 26 %- dispersion C: 26%
- monoacrylate d'uréthane : 60 % - ODA : 10 % - photoinitiateur : 4 %- urethane monoacrylate: 60% - ODA: 10% - photoinitiator: 4%
Les résultats des tests effectués avec cette encre montrent une bonne machinabilité sur les têtes d'impression jet d'encre, notamment celles des constructeurs MIT, DATA PRODUCT et TRIDENT, une meilleure réactivité, un bon brillant, de meilleures résistances mécaniques et une meilleure adhérence, malgré des résultats d'impression ayant une tendance au jaunissement.The results of the tests carried out with this ink show good machinability on the inkjet print heads, in particular those of the manufacturers MIT, DATA PRODUCT and TRIDENT, better reactivity, good gloss, better mechanical strengths and better adhesion , despite printing results with a tendency to yellowing.
L'inconvénient majeur de cette composition est de renfermer des solvants (ici environ 22 % en poids). Exemple 4 :The major drawback of this composition is that it contains solvents (here around 22% by weight). Example 4:
Le même pigment que celui de l'exemple 3 est utilisé et est dispersé dans l'ODA.The same pigment as that of Example 3 is used and is dispersed in ODA.
Diverses compositions d'encre sont ensuite préparées, elles présentent des proportions variant dans les gammes suivantes :Various ink compositions are then prepared, they have proportions varying in the following ranges:
Pigment : 2,8 à 4,2 % + enrobage : 2,8 à 4,2 % (résine vinylique) premier composé:=monoacrylate d'uréthane : 9,5 à 14,1 % photoinitiateur : 0,5 à 0,7 % agent de glissance : 0,2 à 0,3 % second composé = ODA 84.1 à 76.4 %Pigment: 2.8 to 4.2% + coating: 2.8 to 4.2% (vinyl resin) first compound : = urethane monoacrylate: 9.5 to 14.1% photoinitiator: 0.5 to 0, 7% slip agent: 0.2 to 0.3% second compound = ODA 84.1 to 76.4%
TOTAL 100 % 100 %TOTAL 100% 100%
Exemple 5 : Tirée de l'exemple 4, une encre type selon l'invention est préparée, avec un pigment identique à celui de l'exemple 3, dispersé dans l'ODA. Cette encre type présente la composition suivante :Example 5: Taken from example 4, a standard ink according to the invention is prepared, with a pigment identical to that of example 3, dispersed in ODA. This standard ink has the following composition:
Pigment : 2,86 %Pigment: 2.86%
+ enrobage : 2,86 % (résine vinylique) premier composé=monoacrylate d'uréthane : 9,51 % photoinitiateur : 0,50 % agent de glissance : 0,20 % second composé = ODA 84.07 %+ coating: 2.86% (vinyl resin) first compound = urethane monoacrylate: 9.51% photoinitiator: 0.50% slip agent: 0.20% second compound = ODA 84.07%
TOTAL 100 % Cette encre présente une viscosité finale de 9,35 mPa.s à 25°C.TOTAL 100% This ink has a final viscosity of 9.35 mPa.s at 25 ° C.
D'autres encres selon l'invention sont préparées en modifiant, par rapport à l'encre type ci-dessus servant de référence, la nature du premier composé, monomère ou oligomère. Les "premiers composés" suivants ont été testés :Other inks according to the invention are prepared by modifying, with respect to the above standard ink serving as a reference, the nature of the first compound, monomer or oligomer. The following "first compounds" have been tested:
5a - le triacrylate de triméthylpropane éthoxylé5a - ethoxylated trimethylpropane triacrylate
5b - le tétraacrylate de pentaérythritol éthoxylé5b - ethoxylated pentaerythritol tetraacrylate
5c - le pentaacrylate de dipentaérythritol 5d - un oligomère acrylé (commercialisé par Galstaff sous le nom Monocryl5c - dipentaerythritol pentaacrylate 5d - an acrylated oligomer (marketed by Galstaff under the name Monocryl
903)903)
5e - un diacrylate aliphatique (commercialisé par Henkel sous le nom Photomer 4200).5th - an aliphatic diacrylate (marketed by Henkel under the name Photomer 4200).
La viscosité de ces encres est comprise entre 9,5 et 12 mPa.s (à 25°C). Les tests effectués montrent que ces cinq encres présentent une excellente résistance mécanique (rayabilité) ainsi qu'une bonne résistance à l'eau (plus particulièrement l'encre 5d renfermant l'oligomère acrylé.The viscosity of these inks is between 9.5 and 12 mPa.s (at 25 ° C). The tests carried out show that these five inks have excellent mechanical resistance (scratchability) as well as good resistance to water (more particularly ink 5d containing the acrylated oligomer.
Les encres 5c, 5d et 5e présentent en outre une excellente résistance à des agents chimiques tels que le fuel, essences et autres solvants (alcools, cétones, esters).The inks 5c, 5d and 5e also exhibit excellent resistance to chemical agents such as fuel oil, gasoline and other solvents (alcohols, ketones, esters).
Avec les encres selon les exemples 4 et 5, toutes les propriétés sont améliorées (machinabilité, aspect, réactivité et performances mécaniques) : voir tableau 1.With the inks according to Examples 4 and 5, all the properties are improved (machinability, appearance, reactivity and mechanical performance): see Table 1.
Elles ne contiennent pas de solvant, et une faible teneur en photoinitiateur (inférieure ou égale à 1 %) permet d'éviter le jaunissement.They do not contain any solvent, and a low content of photoinitiator (less than or equal to 1%) makes it possible to avoid yellowing.
L'ensemble des résultats des tests obtenus avec les encres de compositions selon les exemples 1 à 5 ci-dessus sont regroupés dans le tableau 1.All the results of the tests obtained with the inks of compositions according to Examples 1 to 5 above are collated in Table 1.
L'encre pigmentaire sans solvant selon la présente invention est utilisable pour l'impression par jet d'encre à excitation piézoélectrique ou thermique, sur tous supports poreux ou non poreux, tels que les textiles, les métaux, les céramiques, le verre, le bois, le papier et les supports en matière plastique (ex. P.V.C.). TABLEAU 1The solvent-free pigment ink according to the present invention can be used for printing by ink jet with piezoelectric or thermal excitation, on any porous or non-porous support, such as textiles, metals, ceramics, glass, wood, paper and plastic supports (eg PVC). TABLE 1
Figure imgf000011_0002
Figure imgf000011_0002
Figure imgf000011_0001
Figure imgf000011_0001

Claims

REVENDICATIONS
1. Encre pigmentaire liquide, notamment pour l'impression par jet d'encre, comprenant un pigment en suspension dans un véhicule à base d'un premier composé monomère ou oligomère (méth)acrylique reticulable par U.V., en présence d'une quantité de photoiniateur correspondant à ce premier composé, caractérisée en ce qu'elle ne contient pas de solvant aqueux ni organique volatil, en ce que le véhicule renferme de 70 % à 85 % d'au moins un second composé monomère ou oligomère (méth)acrylique, reticulable par U.V., sans ajout supplémentaire de photoinitiateur, le second composé étant compatible avec ledit premier composé, et de viscosité inférieure ou égale à celle de ce dernier, et étant ajouté dans des proportions telles que la viscosité finale de l'encre soit inférieure à environ 20mPa.s à une température comprise entre 15 et 35° C environ, et en ce qu'elle contient de 0,2 à 0,7 % de photoinitiateur. 1. Liquid pigment ink, especially for inkjet printing, comprising a pigment in suspension in a vehicle based on a first monomeric or (meth) acrylic compound crosslinkable by UV, in the presence of an amount of photoiniator corresponding to this first compound, characterized in that it does not contain an aqueous or volatile organic solvent, in that the vehicle contains from 70% to 85% of at least one second monomer or (meth) acrylic oligomer compound, crosslinkable by UV, without additional addition of photoinitiator, the second compound being compatible with said first compound, and of viscosity less than or equal to that of the latter, and being added in proportions such that the final viscosity of the ink is less than about 20mPa.s at a temperature between about 15 and 35 ° C, and in that it contains from 0.2 to 0.7% of photoinitiator.
2. Encre selon la revendication 1, caractérisée en ce qu'elle comprend approximativement de 9 à 20 % en poids du premier composé jusqu'à 6 % en poids de pigment et de 0,5 à 1 % de photoinitiateur.2. Ink according to claim 1, characterized in that it comprises approximately from 9 to 20% by weight of the first compound up to 6% by weight of pigment and from 0.5 to 1% of photoinitiator.
3. Encre selon l'une quelconque des revendications précédentes, caractérisée en ce que le pigment est constitué de particules recouvertes d'un polymère d'enrobage, le polymère d'enrobage étant soluble au moins partiellement dans ledit second composé.3. Ink according to any one of the preceding claims, characterized in that the pigment consists of particles covered with a coating polymer, the coating polymer being at least partially soluble in said second compound.
4. Encre selon l'une quelconque des revendications précédentes, caractérisée en ce que le photoinitiateur est une aminoacétophénone.4. Ink according to any one of the preceding claims, characterized in that the photoinitiator is an aminoacetophenone.
5. Encre selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend un agent de glissance ou d'étalement.5. Ink according to any one of the preceding claims, characterized in that it comprises a slip or spreading agent.
6. Encre selon l'une quelconque des revendications précédentes, caractérisée en ce que le second composé est un mélange d'acrylate d'octyle et d'acrylate de décyle.6. Ink according to any one of the preceding claims, characterized in that the second compound is a mixture of octyl acrylate and decyl acrylate.
7. Encre selon l'une quelconque des revendications précédentes, caractérisée en ce que le premier composé est un monoacrylate d'uréthane, ayant de préférence des substituants linéaires, ou un di-, tri-, tetra- ou penta-acrylate. 7. Ink according to any one of the preceding claims, characterized in that the first compound is a urethane monoacrylate, preferably having linear substituents, or a di-, tri-, tetra- or penta-acrylate.
8. Encre selon l'une des revendications 1 à 7, caractérisée en ce que le premier composé est un pentacrylate de dipentaérythritol.8. Ink according to one of claims 1 to 7, characterized in that the first compound is a dipentaerythritol pentacrylate.
9. Utilisation de l'encre selon l'une quelconque des revendications précédentes pour l'impression par jet d'encre à excitation piézoélectrique ou thermique. 9. Use of the ink according to any one of the preceding claims for printing by ink jet with piezoelectric or thermal excitation.
PCT/FR2002/002680 2001-08-01 2002-07-26 Solvent-free liquid pigment ink for ink-jet printing WO2003011989A1 (en)

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CN102382506A (en) * 2011-08-02 2012-03-21 周贤永 Water-soluble environmentally-friendly gravure ink and preparation method thereof
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JP5530141B2 (en) * 2009-09-29 2014-06-25 富士フイルム株式会社 Ink composition and inkjet recording method
US10589560B2 (en) * 2017-08-31 2020-03-17 Duplo Corporation Active energy ray curing inkjet ink, printed product, inkjet printing apparatus, and inkjet printing method

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Publication number Priority date Publication date Assignee Title
EP1645605A1 (en) * 2004-10-06 2006-04-12 TETENAL AG & Co. KG. Radiation-curable ink jet ink
EP2420540A1 (en) 2006-11-04 2012-02-22 Xennia Technology Limited Inkjet printing
US8388124B2 (en) 2007-01-29 2013-03-05 Sericol Limited Printing ink
CN102382506A (en) * 2011-08-02 2012-03-21 周贤永 Water-soluble environmentally-friendly gravure ink and preparation method thereof
CN102382506B (en) * 2011-08-02 2013-11-06 周贤永 Water-soluble environmentally-friendly gravure ink and preparation method thereof
CN114410150A (en) * 2022-01-27 2022-04-29 广东阿诺捷喷墨科技有限公司 UV-LED digital ink-jet silver scraping ink and spraying process thereof

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