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    • 专利摘要:
    A nonaqueous ink composition for continuous deviated ink jet printing comprising: - a vehicle comprising one or more organic solvent (s) liquid (s) liquid at room temperature; one or more dyes and / or pigment (s); a binder comprising at least one binder resin consisting of a cellulose derivative having a weight average molecular weight Mw greater than or equal to 120 kDa. A method of marking a substrate by spraying said substrate with said ink composition by a liquid jet printing technique. Substrate, provided with a marking obtained by drying and / or absorption of said ink composition.
    公开号:FR3058150A1
    申请号:FR1660562
    申请日:2016-10-31
    公开日:2018-05-04
    发明作者:Pierre de Saint Romain
    申请人:Dover Europe SARL；
    IPC主号:
    专利说明:

    DESCRIPTION
    TECHNICAL AREA
    The invention relates to an ink composition for marking supports and objects of all kinds, the properties of which are particularly well suited to marking or printing by liquid jet, known as printing or marking "by ink jet. »Of a very wide variety of supports, substrates and objects, and in particular supports, substrates and flexible objects.
    PRIOR STATE OF THE ART
    Inkjet printing is a well-known technique which allows printing, marking, or decorating all kinds of objects, at high speed, and without contacting these objects with the printing device, variable messages at will, such as bar codes, sales deadlines, etc. even on uneven surfaces.
    Inkjet printing techniques fall into two main types, namely:
    the technique known as “drop on demand” (“Drop on demand” or “DOD” in English) and the technique called “continuous jet” (“Continuous InkJet” or “CIJ” in English).
    The projection by “drop on demand” jet can be done by so-called “bubble” ink jet, by “piezoelectric” ink jet, by “valve” ink jet, or finally by jet "Hot Melt" or phase change ink.
    In the case of bubble inkjet, the ink is vaporized in the vicinity of the nozzle, and this vaporization causes the ejection of the small quantity of ink situated between the resistor which vaporizes the ink and the nozzle. In the case of the piezoelectric inkjet, a sudden variation in pressure caused by an actuator set in motion by the electrical excitation of a piezoelectric crystal or ceramic, and located in the vicinity of the nozzle, causes the ejection of a drop of ink.
    In the case of the "Hot Melt" inkjet, the ink is solvent-free and it is carried beyond its melting point.
    Drop-on-demand printing can therefore be done at room temperature, this is the case with piezoelectric inkjet, valve inkjet, or bubble inkjet, or at high temperature, for example at from 60 ° C to 130 ° C approximately, this is the case of the ink jet called "Hot Melt" ("HM") or with phase change.
    Projection by continuous deflected jet consists of sending ink under pressure into a cavity containing a piezoelectric crystal, from which the ink escapes through an orifice (nozzle) in the form of a jet.
    The piezoelectric crystal, vibrating at a determined frequency, causes pressure disturbances in the ink jet, which oscillates and breaks up progressively into spherical droplets. An electrode, called a "charging electrode", placed on the path of the jet, where it breaks, makes it possible to give these drops an electrostatic charge, if the ink is conductive. The drops thus charged are deflected, deflected, in an electric field and allow printing.
    The uncharged, therefore undeflected, deflected drops are collected in a gutter where the ink is sucked up, then recycled to the ink circuit.
    For all the techniques, technologies, of ink jet printing, including the technique of printing by jet of binary deviated continuous liquid, with uncharged drops known as the “SPI” technique, the viscosity of the inks is very low at ink projection temperature, typically from 1 to 10 cPs (mPa.s), or 15 cPs, or 20 cPs, and all these printing techniques which implement ink jet projection can therefore be qualified low viscosity ink deposition technologies.
    The projection of ink by jet ensures contactless marking at high scrolling speed on objects which are not necessarily planar and with the possibility of changing messages at will.
    The ink compositions, suitable for projection by jet, in particular for projection by continuous deflected jet, must satisfy a certain number of criteria inherent in this technique, relating, inter alia, to the viscosity, the solubility in a solvent for the cleaning, the compatibility of the ingredients, the correct wetting of the supports to be marked, etc., and the electrical conductivity in the case of the deflected continuous jet.
    In addition, these inks must dry quickly, be able to flow or remain stationary in the vicinity of the nozzle without clogging it, with a high stability of orientation of the jet while allowing easy cleaning of the print head.
    The limits as to the viscosity which these inks can have are dictated, on the one hand, by the pressure which is necessary to project the drops of ink at a sufficient speed through a nozzle of small diameter, and on the other hand, by the relationship between the viscosity and the surface tension of the liquid which dictates the rate at which the drops will form. A high viscosity will necessarily lead to high pressures to obtain the speed of projection of the drops, as well as to greater distances between the nozzle and the place where the drops form.
    There is a simple relationship between the viscosity η of the ink, the jet speed Vj, the pressure P, the surface tension σ, the density of the ink p, and the diameter d of the nozzle. According to this relation, P is proportional to p.Vj 2 + 32.qpVj / d 2 + 2.o / d.
    The ingredients that make up current inks, for the ink jet of the deviated continuous jet type, are organic or mineral products; these are dyestuffs, such as dyes or pigments, resins or binders, in one or more more or less volatile solvent compound (s) or in water, optionally one or more several salt (s) providing conductivity (commonly called conductivity salts), as well as various additives.
    The ingredients that make up current inks for drop-on-demand inkjet (“DOD”) are also organic or mineral products; dyes or pigments, resins or binders, in one or more more or less volatile solvent compound (s) or in water, in proportions other than those of inks for deviated continuous inkjet, but without the need for electrical conductivity.
    In the case of "Hot-Melt" inkjet inks, the inks do not contain liquid solvents at ambient temperature but organic liquids at the spraying temperature already specified above, such as waxes and low molecular weight resins. These low molecular weight waxes and resins are generally chosen so that the viscosity of the ink at the spraying temperature is from 2 to mPa.s.
    The solvent for inkjet inks, with the exception of “HotMelt” inkjet inks, most often consists of a mixture comprising, on the one hand, a majority amount of volatile solvent compounds and not very viscous, in order to allow the markings to dry very quickly, and to adjust the viscosity to the desired value, for example from 1 to 10 cPs (mPa.s), or 15 cPs, or 20 cPs, and, d on the other hand, more viscous and less volatile solvent compounds, slower drying, in a smaller amount, to avoid drying of the ink in the nozzle during the shutdown phases of the printing apparatus (see patents or patent applications US-A-4,155,767, WO-A-92 14794,
    WO-A-92 14795 and US-A-4,260,531).
    The volatile solvent compounds used most often are alcohols, ketones or low molecular weight esters, as indicated in patents US-A-4,567,213, and US-A-5,637,139. Among these solvent compounds, there may be mentioned essentially methanol, ethanol, 1- and 2-propanol, acetone, methyl ethyl ketone (“MEK”), methyl isobutyl ketone, ethyl acetate, and tetrahydrofuran.
    The less volatile solvent compounds having in particular a function of drying retarder are most often ketones, such as cyclohexanone, glycol ethers, cited in documents US-A-4,024,096 and US-A-4,567,213, ethers and acetals, such as furan or dioxane, mentioned in document US-A-4,155,767, dimethyl formamide or dimethylsulfoxide (US-A-4,155,895), lactones (EPAO 034 881), Nmethyl pyrrolidone (EP-A- 0 735 120), glycols (WO-A-96 23844), and even aliphatic hydrocarbons (US-A-4,166,044) or even water, alone or in combination with other solvent compounds, mentioned above, in this regard, refer to documents US-A4,153,593, GB-A-2 277 094 and FR-A-2 460 982.
    Additives include:
    - plasticizers which soften the film of dry ink which can improve the adhesion and cohesion of the ink on the marked support.
    dispersants which allow the dispersion of pigments. Such dispersants stabilize the pigments by steric effect and / or by electrostatic effect depending on whether they are ionizable or not, and according to the polarity of the solvent.
    agents which inhibit corrosion induced by certain salts, such as the salts which provide conductivity (so-called conductivity salts) described below, such as chlorides (see documents EP-A-0 510 752, US-A-5,102,458).
    additives that protect the ink against the proliferation of bacteria and other microorganisms: these are biocides, bactericides, fungicides and others, particularly useful in inks containing water.
    pH regulating buffers (see EP-A-0 735 120). anti-foaming agents.
    The inks for inkjet printing can also include surfactants or surfactants which modify the wetting or penetrating power of the ink (cf. US Pat. No. 5,395,431), in particular those which modify or regulate the static or dynamic surface tension such as Fluorad 'FC 430 from 3M. Such products regulate the size of the impacts of the drops. Thanks to them, the impacts of the drops all have the same diameter whatever the nature, cleanliness or regularity of the support.
    The additives also include, in the case of inks for printing by deviated continuous ink jet, optionally one or more salts called conductivity salts.
    The conductivity salt (s), if any, provide the conductivity (s) necessary for the electrostatic deflection to the ink. On this subject, reference may be made to document US-A-4,465,800. However, it can be noted that in certain cases, other constituents of the ink such as the dyes already provide sufficient conductivity to the ink so that there is no need to add a conductivity salt.
    The coloring matters are called “dyes or pigments”, depending on whether they are respectively soluble or insoluble in the solvent used.
    Pigments, by nature insoluble, are therefore dispersed and may or may not be opaque. They bring the ink its color, its opacity, or particular optical properties, such as fluorescence (see patents or patent applications US-A-4,153,593, US-A-4,756,758, US-A-4,880,465, EP-A -0 289 141, US-A-5,395,432,
    GB-A-2 298 713). In some cases, the dyes also provide enough conductivity to the ink so that there is no need to add a conductivity salt. The dyes known under the name C.l. Solvent Black 27, 29, 35 and 45 are in this case.
    The binder (s) or resin (s) is (are) generally for the most part (s) solid (s) and polymeric compound (s) and their choice is dictated by their solubility in the selected solvents, by their compatibility with the dyes and the other additives, their capacity to allow the good electrostatic charge of the drops but also according to the properties which they bring to the ink film, once dry (see patents or patent applications US-A -4,834,799, GB-A-2,286,402, US-A-5,594,044, US-A-5,316,575,
    WO-A-96/23844, WO-A-95 / 29,287).
    Their primary function is to provide the ink with adhesion on the maximum number of supports or on specific supports, for example non-porous. They also make it possible to give the ink the viscosity suitable for the formation of the drops from the jet and they bring to the marking obtained, the essential of its properties of resistance to physical and / or chemical aggressions such as resistance to friction and more generally abrasion.
    The polymers used with organic solvents are synthetic or natural, they can be either linear polymers, such as rosin resins, shellac, acrylic, methacrylic, styrene, vinyl, cellulose, and phenolic resins, polyamides, polyurethanes, melamines, or even polyesters; or branched polymers such as dendrimers (see US-B2-6, 221,933).
    Pre-polymers crosslinkable by radiation, for example by ultraviolet or electron beams are used in the ink compositions and are subjected to crosslinking after deposition on the support.
    For the formulations in aqueous phase, the polymers are either soluble linear polymers, or dispersions, also called latex. The polymers of these dispersions can be linear or crosslinkable during drying.
    The polymers or resins used in jet spray inks are generally polymers of relatively low molecular weight for two main reasons:
    if the molecular weights of the polymers or resins are too high, the viscosity provided by these polymers or resins is very high and their quantity is very low, and in particular too low to properly coat the coloring matters of the inks. This is true for all inkjet printing technologies.
    if the molecular weights of the polymers or resins are too high, the electrostatic charges of the drops are not stable and the printing is of poor quality or even impossible, because the separation of the drops at the time of their charging is not facilitated and is unstable. This is true for the inkjet printing technique of the deviated continuous jet type.
    It is generally recognized that there is an upper limit for the molecular weight of a polymer or resin contained in an ink composition for printing by the continuous deflected jet technique, above which the printing by the continuous deflected jet technique is not satisfactory, if not impossible.
    Thus, US Pat. No. 6,106,600 shows that nitrocelluloses with a mass greater than 25,000 Da pose problems in binary continuous jet printers.
    US-B2-7,279,511 specifies that acrylic or styrene-acrylic resins must have molecular weights of less than 100 kDa, or preferably less than 50 kDa and even less than 20 kDa, in order to be used satisfactorily in compositions of ink for continuous deflected inkjet printing.
    US-B2-7,740,694 specifies that the polyvinyl butyral resins must have molecular weights of 40 to 80 kDa to be able to be used satisfactorily in ink compositions for printing by continuous ink jet deviation.
    US-B2-8,278,371 specifies that only vinyl chloride copolymers with a molecular weight of less than 30 kDa can be used in ink compositions for printing by deviated continuous ink jet. Similarly, according to this patent, only polyesters whose molecular mass is between 10 and 50 kDa, or acrylic resins whose molecular mass is less than 65 kDa, can be used in ink compositions for printing. by continuous ink jet deflected.
    US-B2-8,952,078 specifies that acrylic, epoxy, ketone, nitrocellulosic, polyesters, or PVC resins must have a molecular weight between 1.5 and 70 kDa to be used in ink compositions for printing by continuous ink jet deflected.
    Patent US-B2-9,034,090 specifies that cellulosic resins, such as hydroxypropyl celluloses, which can be used in ink compositions for printing by deviated continuous ink jet, have a molecular mass of between 10 and 120 kDa and preferably between 40 and 80 kDa.
    Without wishing to be bound by any theory, it would seem that the upper limit values of the molecular weights which the resins or polymers used in the binders for inkjet printing may have are linked to the dynamics of the breakage of the jet and to the elongational viscosity of fluids.
    In this regard, we can refer to the following article on this subject: Journal of Non-Newtonian Fluid Mechanics 222 (2015) 171-189.
    Expressed simply, when the (cylindrical) jet leaving the nozzle must, under the effect of surface tension, form drops, it is subjected to a deformation in stretching, and no longer in shearing as in the pipes and nozzle. When the molecular weights of the polymers are too large, the drops form but are linked together by a wire of liquid which prevents any individual electrical charge for each drop. This phenomenon is called "bead on string".
    Inks for printers that use the drop-on-demand printing technique (“DOD”) are not necessarily subject to this limitation as to the molecular weight of the polymers or binder resins, because the effects of the higher molecular weights on the breaking of the jet are, in this technique, unlike the continuous deflected jet, taken advantage of. Indeed, in this technique, the bonding of the drops together according to the “bead on string” phenomenon avoids the dispersion of smaller drops.
    There is therefore, in view of the foregoing, a significant limitation on the molecular weight which the resins or polymers which can be used as a binder for inks for the deviated continuous inkjet printing technique may have.
    Regardless of the limitations that exist on the molecular weight of the resins or polymers of the binders of these inks, there are also limitations on the viscosity that these inks may possess.
    This limit is also due to the physics of the jet, and depends on the speed of the jet, the dimensions of the nozzle and the vibration frequency of the piezoelectric crystal.
    In this regard, the following document may be cited in particular: Annu. Rev. Fluid Mech. 2013.45: 85-113.
    Many patents refer to viscosity values that inks may have for inkjet printing.
    Thus, US-A-4,207,577 relates to opaque ink compositions for inkjet printing, and indicates that the viscosities of these inks can be between 1.5 and 25 mPa.s preferably between 1.8 and 7.5 mPa.s.
    Patent US-A-5,710,195 relates to opaque ink compositions, nonpigmented for inkjet printing, which contain a combination of film-forming resins chosen from nitrocelluloses, alkyd resins, vinyl acetate copolymers. vinyl chloride and styrene-acrylic resins. According to the claims, these inks have viscosities between 1 and 20 mPa.s, but does not cite any example which demonstrates this.
    US-Bl-6,869,986 relates to ink compositions for printing by the technique of the deviated continuous ink jet, and indicates that these compositions must have viscosities between 2 and 10 mPa.s.
    US-B2-7,279,511, US-B2-7,520,926, US-Bl-6,444,019, US-Bl-6,645,280, US-Bl-6,726,756, US-B2-7,147,801, and US-B2-7,148,268 relate to ink compositions for inkjet printing and all give the same limits as to the viscosity that these inks can have, namely from 1.6 to 7 mPa.s or 1.6 to 10 mPa.s.
    There is therefore, in light of the above, a need for ink compositions for printing by liquid jet, and more particularly for printing by continuous deflected jet, which are suitable for printing by jet of liquid and more particularly for printing by deflected continuous jet, for a range of viscosities or molecular weights of resins, polymers, of the binder of these inks, more extensive than the range of viscosities or molecular weights of ink compositions for liquid jet printing currently used and which are described in particular in the documents of the prior art cited above.
    More precisely, there is in view of the above, a need for ink compositions for printing by liquid jet, and more particularly for printing by continuous deflected jet, which are suitable for jet printing of liquid and more particularly to continuous jet deviation printing, for a range of viscosities or molecular mass of resins, polymers, of the binder of these inks, for which printing by liquid jet was generally considered to be impossible or not satisfactory, especially in the documents of the prior art cited above.
    In other words, there is in view of the above, a need for ink compositions for printing by liquid jet, and more particularly for printing by continuous deflected jet, which are suitable for jet printing of liquid and more particularly to printing by continuous deflected jet, for a viscosity or a molecular mass of the resins, polymers, of the binder of these inks, greater than the viscosity or the molecular mass for which the printing by liquid jet was generally considered to be impossible or unsatisfactory, in particular in the documents of the prior art cited above.
    By compositions suitable for printing by liquid jet and more particularly for printing by deflected continuous jet, it is generally understood that the use of these ink compositions in printers implementing this technique is possible without incidents, and that the printing, marking obtained is of good quality.
    In other words, there is a need for ink compositions for liquid jet printing, and more particularly for deviated continuous jet printing, which are suitable for liquid jet printing and more particularly to printing by deflected continuous jet, which overcomes the limitations commonly accepted in the prior art, relating to the viscosity or the molecular mass of the resins, polymers, of the binder of these inks.
    Still in other words, there is a need for ink compositions for liquid jet printing, and more particularly for deviated continuous jet printing which offer much more extensive formulation possibilities than before, as explained in particular in the documents of the prior art cited above.
    The object of the invention is to provide an ink composition for printing by liquid jet, and more particularly for printing by deflected continuous jet, which meets, among other things, all the needs, requirements and criteria indicated above, and which does not have the drawbacks, defects, limitations and disadvantages of the compositions of the prior art, and which overcomes the problems of the compositions of the prior art.
    STATEMENT OF THE INVENTION
    This object, and others still are achieved, according to the invention, according to a first embodiment, by a non-aqueous ink composition for printing by continuous deflected ink jet comprising:
    a vehicle comprising one or more organic solvent compound (s) liquid (s) at room temperature;
    one or more dye (s) and / or pigment (s);
    a binder, comprising at least one binder resin consisting of a cellulose derivative of weight average molecular weight Mw greater than or equal to 120 kDa.
    This object, and still others are achieved, in accordance with the invention, according to a second embodiment, by a non-aqueous ink composition for printing by deviated continuous ink jet comprising:
    a vehicle comprising one or more organic solvent compound (s) liquid (s) at room temperature;
    one or more dye (s) and / or pigment (s);
    a binder, comprising at least one binder resin consisting of a cellulose derivative;
    characterized in that the composition has a viscosity greater than 10 mPa.s at 20 ° C measured at a shear rate less than 1000 s -1 .
    The technique of continuous deflected jet printing also includes the technique of binary continuous deflected jet printing, with uncharged drops known as the “SPI” technique.
    For convenience, and for simplicity, the binder resin consisting of a cellulose derivative, is also called cellulose resin.
    Advantageously, the cellulose derivative can be chosen from cellulose esters and cellulose ethers, such as nitrocelluloses, cellulose acetates, cellulose acetobutyrates, cellulose acetopropionates, ethyl celluloses, methyl cellulose, carboxymethyl-celluloses, hydroxypropyl-celluloses, and hydroxypropylmethyl-celluloses.
    By ambient temperature is generally meant a temperature of 5 ° C to 30 ° C, preferably from 10 ° C to 25 ° C, more preferably from 15 ° C to 24 ° C, better still from 20 ° C to 23 ° C .
    It is understood that the ink is liquid at atmospheric pressure.
    Again, it should be noted that by molecular weight is meant the average molecular weight "by weight" Mw, and not the molecular weight "by number" or "in z".
    This molecular mass can be determined by steric exclusion chromatography known as “GPC”, with calibrations by calibration with polystyrene or poly (methyl methacrylate) standards, or by absolute determination by measurement of light scattering, for example.
    It turns out that this molecular weight by weight is closest to that of the maximum of the mass distribution. All the details on these notions of molecular weights can be found in the introductory textbooks on macromolecular chemistry.
    The ink composition according to the invention both according to the first embodiment and according to the second embodiment, differs fundamentally from the ink compositions for printing by liquid jet of the prior art.
    Thus, according to the first embodiment, the ink composition according to the invention differs fundamentally from ink compositions for printing by liquid jet of the prior art in that it contains a specific binder resin constituted a cellulose derivative of average molecular weight by specific weight Mw greater than or equal to 120 kDa. This molecular weight is higher than what is usually accepted for this application in ink compositions for printing by liquid jet.
    According to the second embodiment, the ink composition according to the invention differs fundamentally from the ink compositions for printing by liquid jet of the prior art in that it contains a specific binder resin consisting of a cellulose derivative and in that it has a specific viscosity greater than 10 mPa.s at 20 ° C and a shear rate less than 1000 s -1 . This viscosity is higher than the viscosity which is usually accepted for this application in ink compositions for printing by liquid jet.
    No document of the prior art describes or suggests an ink composition for printing by liquid jet having all the specific characteristics of the ink composition according to the invention, as well as according to the first mode of embodiment as in the second embodiment.
    Thus, no document of the prior art describes or suggests the effective use of a cellulosic resin of weight average molecular mass greater than 120 kDa in a printing technique by continuous deflected jet.
    Likewise, no document of the prior art describes or suggests the effective use of a cellulosic resin at viscosities higher than 10 mPa.s at 20 ° C. in a printing technique by continuous deflected jet.
    The invention is notably based on the surprising observation that, on the one hand, the cellulose resins have a sufficiently pseudoplastic, shear-thinning behavior, so that the viscosity at the nozzle is low enough to be sprayable without requiring exaggerated pressures, and on the other hand, that even at these high viscosities, there is no negative consequence on the breaking of the jet in drops and their electrical charge.
    This observation is all the more surprising since the high viscosities at low shear speed slow the progression of the pressure disturbance leading to the breaking of the jet and result in load and print quality defects.
    In other words, according to the invention, it has been brought to light, quite unexpectedly, that all the cellulosic resins behave, in terms of rheology (see the single FIGURE) differently from all the other resins synthetic in particular of all those obtained by polyaddition of unsaturated monomers (for example acrylic or methacrylic vinyl monomers), or by polycondensation such as polyesters, polyamides or polyurethanes, for example.
    Thus, the viscosity of various resins, commonly used as binders in inks for inkjet printing, was measured using a rheometer from the company Rheosense® (San Ramon, CA 94583, USA) . This rheometer is capable of measuring the viscosity of fluids at shear rates from a few s 1 to several hundreds of thousands of
    The curves obtained are presented in the single Figure.
    It can be seen in this Figure that all the cellulosic polymers (namely the cellulosic polymers cited in the examples), have a pseudoplastic, shear-thinning behavior, very marked because their viscosity in the vicinity of 10 6 s 1 is less by a factor of 3 to 4 to that at 1000 s -1 .
    The other polymers, non-cellulosic, of comparable molecular mass have an almost Newtonian behavior and see their viscosity reduced only by a few%, at most 20% from 4 to 6.10 5 s -1 .
    It seems that all polymers of cellulosic type have this same pseudoplastic (or shear thinning) behavior.
    It is generally known to those skilled in the art that inks based on non-cellulosic resins with a molecular mass greater than 80 kDa are generally unsuitable for printing by the continuous deflected jet technique, for the reason explained above. failure to break the jet, similar to the “bead on string” phenomenon
    According to the invention, it has surprisingly been found that inks based on cellulose resins do not have this defect whatever the molecular mass of the cellulose resin, and whatever the viscosity of this ink.
    According to the invention, it has been demonstrated, in a completely surprising manner, that all the cellulosic resins were perfectly suitable for spraying in non-aqueous ink compositions, even at molecular weights greater than or equal to 120 kDa , or in inks that have viscosities higher, or even significantly higher than 10 mPa.s.
    It did not clearly follow from the known applications of such cellulosic resins dissolved in organic solvents that they can be used successfully as binders in ink compositions capable of being sprayed by continuous jet deflected to such molecular weights and / or to such viscosities.
    In particular, it was absolutely not obvious and predictable in the light of the prior art that cellulosic resins could be as different from non-cellulosic resins as regards their rheological behavior.
    Thus, the patents cited above neither describe nor suggest the use of cellulosic resins of molecular masses greater than or equal to 120 kDa in solution in a suitable organic solvent, for use in inks for jet printing. ink.
    These patents do not present any exemplary embodiment comprising cellulosic resins of molecular masses greater than or equal to 120 kDa in solution in an organic solvent.
    These patents neither mention nor suggest the use of such cellulosic resins in the binder of nonaqueous ink compositions for printing by deviated continuous ink jet, at viscosities higher than 10 mPa.s.
    There is no indication in these documents, which could have suggested that unexpected, advantageous properties could be obtained, by dissolving cellulosic resins of molecular mass greater than or equal to 120 kDa, to formulate inks for jet printing. deviated continuous ink, or using cellulose resins in ink compositions whose viscosity is greater than 10 mPa.s at 20 ° C.
    In conclusion, the ink compositions according to the invention provide new possibilities for formulating inks for printing by deviated continuous ink jet, including binary deviated continuous ink jet printing, with uncharged drops. called "SPI" technique, compared to the prior art.
    The ink compositions according to the invention do not have the drawbacks of the ink compositions of the prior art as shown in particular by the documents cited above, and they provide a solution to the problems posed by the compositions of the art prior.
    The ink composition according to the invention is a non-aqueous composition, which generally means that the ink composition according to the invention comprises a very low proportion of water.
    Thus, the ink composition according to the invention generally comprises less than 0.5% by weight of water, preferably less than 0.1% by weight of water, more preferably less than 0.05% by weight water based on the total weight of the ink; better still the vehicle, for example the solvent, and the ink composition can be considered to be essentially free of water (0% by weight of water).
    The water supplied being present as an impurity in the various components of the ink, the greater the degree of purity of the selected components, the lower the water content.
    In fact, one could say that the ink according to the invention does not contain added water but only the water supplied as an impurity by the various constituents of the ink.
    In the same way, the vehicle of the ink composition according to the invention is generally non-aqueous in the sense given above, in other words this vehicle is essentially or exclusively organic and it only comprises organic solvent compounds.
    The binder of the ink composition according to the invention, preferably consisting of at least one binder resin consisting of a cellulose derivative, preferably of weight-average molecular mass greater than 120 kDa, generally represents from 0.1 to 30% by weight, preferably from 1 to 25% by weight, more preferably from 3 to 20% by weight, better still from 3 to 10% by weight, of the total weight of the ink composition.
    Advantageously, the binder can comprise at least 10% by weight, preferably at least 50% by weight of said at least one binder resin consisting of a cellulose derivative, preferably of weight average molecular weight greater than 120 kDa.
    Preferably, the binder can be formed (100% by weight) by said at least one binder resin consisting of a cellulose derivative, preferably of weight average molecular weight greater than 120 kDa.
    In addition to the at least one binder resin consisting of a cellulose derivative, preferably of weight average molecular mass greater than 120 kDa, and in the case where the binder is not constituted solely by said binder resin, the binder of the ink composition according to the invention may also comprise one or more other binder resin (s) chosen generally from resins soluble at room temperature in the organic solvent compound (s) (s) of the ink composition.
    By resins soluble at room temperature in the organic solvent (s) of the ink composition, it is generally understood that these resins are soluble at room temperature in all proportions in this or these organic solvent (s) (s).
    This or these other binder resin (s) can be chosen, for example, from resins soluble in ketone solvents such as polyacrylates, polymethacrylates, polystyrenes and their copolymers, epoxy, epoxyphenolic resins, melamines, polyurethanes, polyamides and rosin derivatives.
    The vehicle generally represents from 30 to 95% by weight, preferably from 30 to 90% by weight, more preferably from 60 to 80% by weight, of the total weight of the ink composition according to the invention.
    As already stated above, the vehicle preferably comprises one or more organic solvent compound (s) liquid (s) at room temperature and optionally water at the condition that the quantity of water respects the conditions indicated above.
    The organic solvent compound (s) of the ink composition according to the invention may (may) be any organic solvent compound capable of dissolving cellulosic resins, and in particular cellulosic resins of molecular weights weight averages greater than or equal to 120 = kDa, according to the invention.
    Advantageously, the vehicle comprises a majority quantity by weight, relative to the total weight of the vehicle (50% by weight of the total weight of the vehicle or more, or even up to 100% by weight of the total weight of the vehicle), of one or several volatile organic solvent compound (s), and a minority proportion by weight, relative to the total weight of the vehicle, of one or more organic solvent compound (s) non-volatile (s).
    Preferably, the vehicle consists of one or more volatile organic compound (s) solvent (s).
    By “volatile organic solvent compound”, it is generally understood that this compound has an evaporation rate greater than 0.5 on the scale where the butyl acetate has an evaporation rate equal to 1.
    The said organic solvent compound (s) forming part of the vehicle is (are) chosen, for example, from alcohols, in particular, low molecular weight alcohols, for example, alcohols aliphatics such as ethanol; ketones preferably of low molecular weight; alkylene glycol ethers; alkylene glycol esters and esters of alkylene glycol ethers, such as acetates; dimethyl formamide; N-methyl pyrrolidone; acetals; esters; linear or cyclic ethers; aliphatic, cyclic or linear hydrocarbons; aromatic hydrocarbons; and carbonates such as propylene carbonate, ethylene carbonate and dimethyl and diethylcarbonates; and their mixtures.
    The alcohols will preferably be chosen from linear or branched aliphatic alcohols of 1 to 8 carbon atoms, such as methanol, ethanol, propanoll, propanol2, nbutanol, butanol2, tertbutanol, etc.
    The ketones will preferably be chosen from ketones of 3 to 10 carbon atoms, such as acetone, butanone (methyl ethyl ketone or "MEK"), pentanone2 (methylpropyl ketone or "MPK"), methyl-3 butanone -2 (methyl-isopropyl ketone or "MiPK") and methyl4 pentanone2 (methylisobutylketone or "MiBK").
    The alkylene glycol ethers are preferably chosen from monoalkyl ethers (C1 to C6 alkyl group) or dialkyl ethers (C1 to C6 alkyl groups) of alkylene glycol comprising 1 to 10 carbon atoms in the alkylene chain, preferably these are ethylene or propylene glycol ethers, such as methoxypropanol.
    The alkylene glycol esters and the esters of alkylene glycol ethers are preferably chosen from the esters thereof with saturated aliphatic carboxylic acids of 1 to 6 carbon atoms, such as formic acid. , acetic acid, propionic acid, butyric acid, valeric acid and caproic acid.
    Mention may be made, for example, of methoxypropyl acetate, butyldiglycol acetate, etc.
    The esters are preferably chosen from low molecular weight esters such as formates, acetates, propionates or butyrates of alcohols of 1 to 10 carbon atoms.
    The acetals are preferably chosen from low molecular weight acetals such as ethylal and methylal.
    The ethers are preferably chosen from low molecular weight ethers such as dioxolane or tetrahydrofuran.
    Those skilled in the art can easily identify among these solvent compounds those which are volatile and those which are non-volatile.
    A preferred vehicle according to the invention comprises a majority amount by weight (50% by weight or more) relative to the total weight of the vehicle, preferably consists of one or more selected solvent compound (s) ) among ketones with 3 to 10 carbon atoms, such as acetone, butanone (methyl ethyl ketone or “MEK”), pentanone-2 (methylpropyl ketone or “MPK”), methyl-3 butanone-2 (methyl 3058150 isopropyl ketone or "MiPK") and 4-methyl pentanone-2 (methyl isobutyl ketone or "MIBK").
    A particularly preferred vehicle comprises a majority amount by weight relative to the total weight of the solvent for MEK, preferably consists of MEK.
    This preferred vehicle may also comprise one or more other solvent compound (s) other than the ketone (s) in a minor total amount by weight (less than 50% by weight), relative to the total weight of the vehicle, for example in an amount of 0.1% to 25% by weight, preferably from 0.1 to 20% by weight, more preferably from 5% to 15% by weight, relative to the weight total of the vehicle, in order to optimize the properties of the inks. This minority solvent compound (s) may be chosen from esters, ethers of ethylene glycol or propylene glycol, and acetals.
    The ink composition according to the invention may optionally contain coloring materials such as dyes and pigments.
    The dye (s) and / or pigment (s) can (be) chosen (s) from all the dyes or pigments suitable for the desired use, known to those skilled in the art, some of these pigments or dyes have already been mentioned above.
    Dyes and pigments will generally be chosen from the dyes and pigments known under the name of "C.l. Solvent Dyes "and" C.l. Pigments ”.
    By way of examples, the most common pigments and dyes, mention may be made of C.l.
    Solvent Black 3, 7, 27, 28, 29, 35, 48, 49, C.l. Solvent Blue 38, 44, 45, 70, 79, 98, 100, 129, C.l. Solvent Red 8, 49, 68, 89, 124, 160, 164, C.l. Solvent Yellow 83: 1, 126, 146, 162, C.l. Solvent Green 5, C.l. Solvent Orange 97, C.l. Solvent Brown 20, 52, C.l. Solvent Violet 9, the dispersions of Pigment Blue 15: 1, 15: 3, 60, of Pigment Green 7, of Pigment Black 7, of Pigment Red 48: 2, 144,149,166, 185, 202, 208, 214, 254, of Pigment
    Violet 19, 23, from Pigment Yellow 17, 83, 93, 139,151, 155,180,191, from Pigment Brown 23, 25, 41, or from Pigment White 6.
    The preferred dyes are C.l. Solvent Black 27 and C.l. Solvent Black 29.
    The preferred pigments are Pigment white 6, Pigment black 7, Pigment Blue 60,
    Pigment red 202 and Pigment Green 7.
    The total amount of dye (s) and / or pigment (s) is generally from 0.05 to 25% by weight, preferably from 1 to 20%, more preferably from 3 to 10% relative to the total weight of ink composition.
    The ink composition can, in addition, comprise one or more plasticizer (s) (of the resin (s) or polymer (s) of the binder) chosen (s), for example, from the plasticizers known in the art. skilled in the art and chosen according to the binder used comprising a cellulose resin and optionally one or more other polymer (s) and / or resin (s). Mention may be made, as plasticizer, for example, of thermoplastic polyurethanes, phthalates, adipates, citrates and esters of citric acid, alkyl phosphates, glycerol, lactic acid, acid oleic, polypropylene glycol, triglycerides of fatty acids, levulinic acid; and their mixtures.
    The plasticizer (s) is (are) generally present in an amount of at least 0.05%, preferably from 0.1 to 20% by weight, of the total weight of the ink composition.
    The composition according to the invention, if it is to be sprayable by the technique of continuous deflected jet printing, can also, optionally, comprise at least one salt of conductivity, unless another ink ingredient such as dye, pigment, or other, is itself an ionizable compound such as a salt which can provide conductivity when it is dissociated, and gives sufficient conductivity to the ink so that there is no need for add conductivity salt proper, this is particularly the case for the compounds known under the name "Cl Solvent Black 27, 29, 35 and 45 ”, already cited.
    Indeed, the ink according to the invention when it is to be applicable by deflected continuous jet, must have a sufficient electrical conductivity, generally greater than or equal to 5 pS / cm at 20 ° C, preferably greater than or equal to 300 pS / cm at 20 ° C, more preferably greater than or equal to 500 pS / cm at 20 ° C.
    The conductivity of the ink according to the invention may for example be from 300 to 5000 pS / cm at 20 ° C, in particular from 500 to 2000 pS / cm at 20 ° C.
    However, it will sometimes be necessary to include, in the ink composition at least one salt of conductivity proper, different from the ionizable compounds, such as the dyes, pigments and other ingredients mentioned above.
    By "conductivity salt" is generally meant a salt which provides electrical conductivity to the ink composition.
    This conductivity salt can thus be chosen from alkali metal salts such as lithium, sodium, potassium, alkaline earth metal salts such as magnesium and calcium, and simple or quaternary ammonium salts; these salts being in the form of halides (chlorides, bromides, iodides, fluorides), perchlorates, nitrates, thiocyanates, formates, acetates, sulfates, propionates, trifluoroacetates, triflates (trifluoromethane sulfonates) , hexafluorophosphates, hexafluoroantimonates, tetrafluoroborates, picrates, carboxylates or sulfonates etc.
    Since the markings obtained with the ink composition must generally be resistant to water, this or these conductivity salts will be chosen from those which are insoluble in water (that is to say generally, the solubility in water is less than 0.5% by weight), like fatty chain quaternary ammoniums and hexafluorophosphates or hexafluroantimonates.
    This at least one conductivity salt will be (will be) therefore, if necessary, in the ink composition so as to impart the above conductivity to the ink: preferably, its (their) quantity is 0.1 to 20% by weight, preferably still from 0.1 to 10% by weight and better still from 0.1 to 5% by weight, of the total weight of the ink composition.
    The composition according to the invention may, in addition, comprise one or more additive (s) chosen, for example, from compounds which improve the solubility of some of its components, the print quality, the adhesion, or else control of ink wetting on different supports.
    The additive (s) may be chosen, for example, from antifoaming agents; chemical stabilizers; UV stabilizers; surfactants, such as Fluorad® FC430 or BYK UV-3500; agents inhibiting corrosion by salts, in particular by conductivity salts; bactericides, fungicides and biocides; and pH regulating buffers, etc.
    The additive (s) is (are) used at very low doses, generally less than or equal to 5% and sometimes as low as 0.01%, depending on whether it is defoamers , stabilizers or surfactants.
    The invention also relates to a method of marking substrates, supports or objects, for example, porous or non-porous, by spraying onto these substrates, supports or objects with ink by the ink jet printing technique. continuous deviated, the ink projected being an ink composition according to the invention, as described above.
    The marking is carried out by the technique of continuous deflected jet printing. The technique of continuous deflected jet printing also includes the technique of binary continuous deflected jet printing, with uncharged drops known as the “SPI” technique.
    The subject of the invention is also a substrate, support or object, for example, porous or non-porous, provided with a marking obtained by drying and / or absorption (in the substrate or support) of the ink composition, such as described above.
    Said marking essentially comprises the dye or pigment of the ink as well as the binder, and it is obtained by evaporation and / or absorption in the substrate, essentially all of the other constituents of the ink such as the vehicle.
    This substrate can be made of metal, for example, aluminum, steel (beverage cans); glass (glass bottles); ceramic; a material containing cellulose such as cellophane, paper, optionally coated or glazed, cardboard or wood; in an organic polymer, in particular in a thermoplastic polymer (“plastic”), in particular in the form of a film, chosen for example from PVDCs, PVCs, polyesters, PETs, polyolefins, such as polyethylenes (PE ), polypropylenes (PP); poly (methyl methacrylate) PMMA also called "Plexiglas"; Fabric ; natural or synthetic rubber; or any other non-porous or porous substance; or as a composite of several of the previous materials.
    The substrate is in particular a flexible or very flexible substrate such as a plastic film, preferably thin, made of cellophane, polyethylene or polypropylene, in particular bi-oriented polypropylene, poly (vinyl chloride) (PVC), in particular plasticized or poly (vinylidene chloride) (PVDC); or a rubber substrate.
    Markings, prints, of excellent quality are obtained on all substrates, and in particular on flexible or even very flexible substrates.
    BRIEF DESCRIPTION OF THE DRAWING
    The single figure is a graph which gives the measured viscosity (in cPs) of different resins, commonly used as binders for inks for inkjet printing, as a function of the shear rate (s _1 ).
    The viscosity is measured using a rheometer from the company Rheosense® 5 (San Ramon, CA 94583, USA). This rheometer is capable of measuring the viscosity of fluids at shear rates of a few s 1 to several hundred thousand s -1 .
    The invention will be better understood on reading the following description of embodiments of the invention, given by way of illustrative and nonlimiting examples.
    DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
    Examples 1 to 13:
    In all these examples, ink compositions are prepared in accordance with the invention, which all contain, as a binder, a cellulose resin with a molecular mass greater than or equal to 120 kDa, or whose viscosity is greater than 10 mPa.s .
    These ink compositions comprise, in addition to the cellulose resin, other ingredients mentioned in Table I, such as dyes, pigments, and other additives, and optionally another resin different from the cellulose resin, in the proportions mentioned in the Table. I.
    These ink compositions were prepared by mixing the products, ingredients mentioned in Table I below in the proportions indicated in Table I below.
    The viscosities, conductivities, and pressures for 20 m / s of the ink compositions are also given in Table I below.
    S60298-FR / PA-T
    Table I - INK COMPOSITIONS ACCORDING TO THE INVENTION
    Constituents # 1 # 2 # 3 # 4 N ° 5 N ° 6 # 7 # 8 N ° 9 # 10 N ° ll # 12 N ° 13 (percentages by mass) Mw (kDa) Methyl ethyl ketone 87 75.42 94.70 23.62 92 88 84.5 84 87 87.3 88.59 90.5 85.45 Ethanol 14.41 63.87 Neplast 2001® 1 Nitrocellulose Walsroder E840® 236 8 Ethyl cellulose T50 150 3.39 Cellulose acetobutyrate CAB 381-2 130-158 4 5.5 Cellulose acetobutyrate CAB 381-05 105 8 Cellulose acetobutyrate CAB 381-01 66.8 11.8 CAB 551-02 Cellulose Acetobutyrate 68.6 12 10.91 Cellulose acetobutyrate CAB 553-04 69.7 9 Cellulose acetopropionate CAP 482-20 215 2.65 Cellulose acetopropionate CAP 504--02 49.1 9.1 Cellulose acetopropionate CAP 482-05 94.2 8.15 Hydroxypropyl Cellulose Klucel LF® 95 1.39 TegoVariplus SK® resin 3.39 3.48 Solvent Black 29 (Orasol black RLI®) 4 3.39 2.65 4 4 3.6 4 4 3.6 3.26 4 3.64 Dispersion of C.I. Pigment Whlte 6 to 75% in Neocryl B813® resin 6.95 Lithium nitrate 0.70 Viscosity (mPa.s) 16.2 12.5 7.13 7 6.7 16 14.8 18.8 14.8 11.3 12.5 14.5 14.8 Conductivity (pS / cm) 980 840 820 1570 1020 915 830 806 868 809 796 1040 825 Pressure for 20 m / s 4 4.0 3.4 3.0 2.8 3.6 4 4.2 3.6 3.5 3.7 3.5 3.5
    Neplast 2001® is a polymeric plasticizer produced by the company Hagedorn®.
    Walsroder E840® Nitrocellulose resin is a resin available from Dow ”.
    Neocryl® B813 resin is a copolymer of ethyl methacrylates and an acidic monomer giving an acid number of 10 mg KOH / g manufactured by the company DSMNeoresin®. Its Tg (glass transition temperature) is 64 ° C.
    The resins CAB 381-2, 381-05, 382-01, 551-02, and 553-04 are cellulose aceto-butyrates manufactured by the company Eastman®.
    The resins CAP 482-20, 504-02 and 482-05 are cellulose acetopropionates manufactured by the company Eastman®.
    EC T-50 resin is an ethylcellulose manufactured by the company Ashland®.
    Klucel L® resin is a hydroxypropylcellulose manufactured by the company Ashland®. Variplus SK® resin is a polyol resin manufactured by the company Tego®.
    The ink compositions according to Table I were prepared by mixing the various resins, dyes and other additives in the solvent until complete dissolution.
    Molecular masses are molecular weights by weight, measured by GPC calibrated with polymethyl methacrylate standards, or given by the manufacturers as such.
    The pressures indicated are the pressures which were necessary to obtain jet speeds of 20 m / s.
    All of these formulations were tested in a Markem-lmaje® continuous jet printer and resulted in excellent quality prints.
    权利要求:
    Claims (23)
    [1" id="c-fr-0001]
    1. A non-aqueous ink composition for continuous deviated inkjet printing comprising:
    a vehicle comprising one or more organic solvent compound (s) liquid (s) at room temperature;
    one or more dye (s) and / or pigment (s);
    a binder, comprising at least one binder resin consisting of a cellulose derivative of average molecular weight by weight Mw greater than or equal to 120 kDa.
    [2" id="c-fr-0002]
    2. A non-aqueous ink composition for continuous deviated inkjet printing comprising:
    a vehicle comprising one or more organic solvent compound (s) liquid (s) at room temperature;
    one or more dye (s) and / or pigment (s);
    a binder, comprising at least one binder resin consisting of a cellulose derivative;
    characterized in that said composition has a viscosity greater than 10 mPa.s at 20 ° C measured at a shear rate less than 1000 s -1 .
    [3" id="c-fr-0003]
    3. Ink composition according to any one of the preceding claims, in which the cellulose derivative is chosen from cellulose esters and cellulose ethers, such as nitrocelluloses, cellulose acetates, cellulose acetobutyrates, acetopropionates cellulose, ethyl celluloses, methyl celluloses, carboxymethyl celluloses, hydroxypropyl celluloses, and hydroxypropyl methylcelluloses.
    [4" id="c-fr-0004]
    4. Ink composition according to any one of the preceding claims, in which the binder represents from 0.1 to 30% by weight, preferably from 1 to 25% by weight, more preferably from 3 to 20% by weight. , better from 3 to 10% by weight of the total weight of the ink composition.
    [5" id="c-fr-0005]
    5. Ink composition according to any one of the preceding claims, in which the binder comprises at least 10% by weight, preferably at least 50% by weight of said at least one binder resin consisting of a cellulose derivative.
    [6" id="c-fr-0006]
    6. Ink composition according to any one of the preceding claims, in which, in addition to said at least one binder resin consisting of a cellulose derivative, the binder further comprises one or more other binder resin (s) ).
    [7" id="c-fr-0007]
    7. Ink composition according to any one of the preceding claims, in which the vehicle represents from 30 to 95% by weight, preferably from 30 to 90% by weight, preferably from 60 to 80% by weight, by weight. total ink composition.
    [8" id="c-fr-0008]
    8. An ink composition according to any one of the preceding claims, in which the said compound (s) organic solvent (s) of the vehicle is (are) chosen (s), from alcohols, in particular, low molecular weight alcohols, for example, aliphatic alcohols such as ethanol; preferably low molecular weight ketones; alkylene glycol ethers; alkylene glycol esters and esters of alkylene glycol ethers, such as acetates; dimethyl formamide; N-methyl pyrrolidone; acetals; esters; linear or cyclic ethers; aliphatic, cyclic or linear hydrocarbons; aromatic hydrocarbons; and carbonates such as propylene carbonate, ethylene carbonate and dimethyl and diethylcarbonates; and their mixtures.
    [9" id="c-fr-0009]
    9. Composition according to claim 8, in which the vehicle comprises a majority amount by weight (50% by weight or more) relative to the total weight of the vehicle, preferably consists of one or more solvent compound (s) ( s) chosen from ketones of 3 to 10 carbon atoms, such as acetone, butanone (methyl ethyl ketone or “MEK”), pentanone-2 (methylpropyl ketone or “MPK”), methyl-3 butanone -2 (methyl-isopropyl ketone or "MiPK") and 4-methyl pentanone-2 (methyl isobutyl ketone or "MIBK").
    [10" id="c-fr-0010]
    10. Composition according to claim 9, in which the vehicle comprises a majority amount by weight relative to the total weight of the MEK vehicle, preferably consists of MEK.
    [11" id="c-fr-0011]
    11. The composition as claimed in claim 9 or 10, in which the vehicle also comprises one or more other solvent compound (s) other than ketone (s) in a minor total amount by weight (lower 50% by weight), relative to the total weight of the vehicle, for example in an amount of 0.1% to 25% by weight, preferably 0.1% to 20% by weight, more preferably 5% at 15% by weight relative to the total weight of the vehicle, preferably this minority solvent compound (s) are chosen from esters, ethers of ethylene glycol or propylene glycol, and acetals.
    [12" id="c-fr-0012]
    12. An ink composition according to any one of the preceding claims, in which said dye (s) and / or pigment (s) is (are) chosen from dyes and pigments known under the name of " Cl Solvent Dyes "and" Cl. Pigments ”.
    [13" id="c-fr-0013]
    13. The ink composition according to claim 12, in which the said “Solvent Dyes” is (are) chosen from C.l. Solvent Black 3, 7, 27, 28, 29, 35, 48, 49, C.l. Solvent Blue 38, 44, 45, 70, 79, 98, 100, 129, C.l. Solvent Red 8, 49, 68, 89, 124, 160,164, C.l. Solvent Yellow 83: 1,126,146,162, C.l. Solvent Green 5, C.l. Solvent Orange 97, C.l. Solvent Brown 20, 52, and C.l. Solvent Violet 9.
    [14" id="c-fr-0014]
    14. The ink composition as claimed in claim 12, in which said “C I. Pigments” is (are) chosen from dispersions of Pigment Blue 15: 1, 15: 3, 60, of Pigment Green 7 , Pigment Black 7, Pigment Red 48: 2, 144, 149, 166, 185, 202, 208,
    214, 254, Pigment Violet 19, 23, Pigment Yellow 17, 83, 93, 139, 151, 155, 180, 191, Pigment Brown 23, 25, 41, or Pigment White 6.
    [15" id="c-fr-0015]
    15. Ink composition according to any one of the preceding claims, comprising in total from 0.05 to 25% by weight of dye (s) and / or pigment (s), preferably from 1 to 20%, preferably still from 3 to 10% by weight of dye (s) and / or pigment (s) relative to the total weight of the ink composition.
    [16" id="c-fr-0016]
    16. An ink composition according to any one of the preceding claims, further comprising one or more plasticizer (s) in an amount of at least 0.05%, preferably 0.1 to 20% by weight of the weight total ink composition.
    [17" id="c-fr-0017]
    17. An ink composition according to any one of the preceding claims, further comprising at least one conductivity salt in an amount of 0.1 to 20% by weight, preferably from 0.1 to 10% by weight, more preferably from 0.1 to 5% by weight of the total weight of the ink composition.
    [18" id="c-fr-0018]
    18. An ink composition according to claim 17, in which said conductivity salt is chosen from alkali metal salts such as lithium, sodium, potassium, alkaline earth metal salts such as magnesium and calcium , and simple or quaternary ammonium salts; these salts being in the form of halides, perchlorates, nitrates, thiocyanates, formates, acetates, sulfates, propionates, trifluoroacetates, triflates (trifluoromethane sulfonates), hexafluorophosphates, hexafluoroantimonates, tetrafluoroborates, picrates, carboxylates, sulfonates.
    [19" id="c-fr-0019]
    19. An ink composition according to any one of the preceding claims, which has a conductivity in the liquid state greater than or equal to 5 pS / cm at 20 ° C, preferably greater than or equal to 300 pS / cm at 20 ° C, preferably still greater than or equal to 500 pS / cm at 20 ° C.
    [20" id="c-fr-0020]
    20. An ink composition according to any one of the preceding claims, further comprising one or more additive (s) chosen from antifoaming agents; chemical stabilizers; UV stabilizers; surfactants; agents inhibiting corrosion by salts; bactericides, fungicides and biocides; and pH regulating buffers.
    [21" id="c-fr-0021]
    21. A method of marking a substrate, support, or object by spraying onto this substrate, support or object, an ink by the technique of printing by deviated continuous ink jet, characterized in that the ink sprayed is an ink composition according to any one of claims 1 to 20.
    [22" id="c-fr-0022]
    22. Substrate, support or object characterized in that it is provided with a marking obtained by drying and / or absorption of the ink composition according to any one of claims 1 to 20.
    [23" id="c-fr-0023]
    23. Substrate, support or object according to claim 22, characterized in that the substrate is made of metal, for example, aluminum, steel; glass; ceramic; a material containing cellulose such as cellophane, paper, optionally coated or glazed, cardboard or wood; an organic polymer, in particular a thermoplastic polymer (“plastic”), chosen for example from PVDCs, PVCs, polyesters, PETs, polyolefins, such as polyethylenes (PE), polypropylenes (PP); poly (methyl methacrylate) PMMA ("Plexiglas"); Fabric ; natural or synthetic rubber; or any other non-porous or porous substance; or as a composite of several of the previous materials.
    S.60298
    1/1
    READ
    Vicosities of oc (sdo) eijSOOSiA resins • ♦ “4 ♦ ♦
    类似技术:
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    同族专利:
    公开号 | 公开日
    EP3470478B1|2021-07-07|
    EP3315565B1|2020-04-29|
    EP3315565A1|2018-05-02|
    US20180208788A1|2018-07-26|
    CN108017956A|2018-05-11|
    FR3058150B1|2020-07-03|
    EP3470478A1|2019-04-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPH10158554A|1996-12-05|1998-06-16|Taiho Ind Co Ltd|Ink for ink jet recording|
    WO2007094252A1|2006-02-15|2007-08-23|Sakata Inx Corp.|Ink composition for continuous-type ink jet recording|
    EP2464696B1|2009-08-14|2014-01-08|Eckart GmbH|Ink jet printer ink comprising effect pigments having high gloss|
    EP2960307A1|2014-06-26|2015-12-30|Markem-Imaje Holding|Ink composition for deflected continuous jet printing, in particular for security markings.|
    JPS5792064A|1980-11-28|1982-06-08|Fuji Photo Film Co Ltd|Aqueous ink for ink jet print|
    FR2885619B1|2005-05-13|2011-02-11|Imaje Sa|LIQUID, FOOD, INGERABLE INK COMPOSITION FOR INKJET PRINTING|
    WO2011103378A1|2010-02-18|2011-08-25|Videojet Technologies Inc.|Wetness indicating ink compositions|
    FR3025801B1|2014-09-16|2018-03-09|Dover Europe Sarl|LIQUID COMPOSITION, IN PARTICULAR INK, FOR CONTINUOUS BINARY DIE PRINTING WITH UNLATCHED DROPS, USE OF THE SAME, MARKING METHOD, AND BRAND SUBSTRATE.|EP3802712A4|2018-06-07|2022-03-09|Videojet Technologies Inc|Dna-tagged inks and systems and methods of use|
    CN109291676B|2018-09-14|2020-12-15|赵忠祥|Manufacturing method of light-aluminum heat transfer film and manufacturing method of ceiling or wallboard|
    EP3916060A1|2020-05-29|2021-12-01|Dover Europe Sàrl|Opaque grey ink jet ink composition|
    CN112961543A|2021-02-04|2021-06-15|广东德康化工实业有限公司|Water-based water-washing gloss oil and preparation method and application thereof|
    法律状态:
    2017-10-31| PLFP| Fee payment|Year of fee payment: 2 |
    2018-05-04| PLSC| Search report ready|Effective date: 20180504 |
    2018-10-30| PLFP| Fee payment|Year of fee payment: 3 |
    2019-10-31| PLFP| Fee payment|Year of fee payment: 4 |
    2020-10-30| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1660562|2016-10-31|
    FR1660562A|FR3058150B1|2016-10-31|2016-10-31|INK COMPOSITION FOR LIQUID JET PRINTING.|FR1660562A| FR3058150B1|2016-10-31|2016-10-31|INK COMPOSITION FOR LIQUID JET PRINTING.|
    EP17198735.7A| EP3315565B1|2016-10-31|2017-10-27|Ink composition for liquid jet printing|
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