LIQUID COMPOSITION, IN PARTICULAR INK, FOR CONTINUOUS BINARY DIE PRINTING WITH UNLATCHED DROPS, USE

专利摘要:
A liquid composition, such as an ink composition, liquid at room temperature, said liquid composition being a liquid composition specifically for printing by a binary deviated continuous jet printing technique wherein said liquid composition forms during the printing of the drops which are not charged by an electric field, which each have a zero electric charge, which each form a dipole under the effect of an electric field, and which are then deflected by said electric field, characterized in that said liquid composition comprises a solvent comprising one or more organic solvent (s) and optionally water, said solvent having generally a dielectric constant less than 15; a binder; one or more dyes and / or pigments; and in that said liquid composition has an electrical conductivity at 20 ° C of less than 200 μS / cm, preferably less than 150 μS / cm, more preferably less than 100 μS / cm. Use of this liquid composition in a printer or print head implementing said printing technique. A process for treating and / or marking a substrate by projection on said substrate of said liquid composition by said printing technique. Substrate, provided with a marking or treatment obtained by drying and / or absorption of said liquid composition.
公开号:FR3046418A1
申请号:FR1650093
申请日:2016-01-06
公开日:2017-07-07
发明作者:Saint-Romain Pierre De
申请人:Dover Europe SARL；
IPC主号:

专利说明:

LIQUID COMPOSITION, IN PARTICULAR INK, FOR CONTINUOUS BINARY DIE PRINTING WITH UNLATCHED DROPS, USE OF THE SAME, MARKING METHOD, AND BRAND SUBSTRATE.
DESCRIPTION
TECHNICAL FIELD The invention relates to a liquid composition, such as an ink composition, for the printing, and / or the treatment, and / or the marking and / or coding of substrates, supports and objects of all kinds , in particular textile substrates, the properties of which are specifically adapted to the printing, and / or processing, and / or marking and / or coding of a very large variety of substrates, supports and objects of all kinds, by the binary deviated continuous liquid jet printing technique, with uncharged drops.
The liquid composition, such as an ink composition, according to the invention is preferably a volatile solvent composition.
More precisely, this technique of binary deviated continuous jet printing is a technique in which the liquid composition forms during the printing of the drops which are not charged by an electric field, which each have a zero electric charge, which form each a dipole under the effect of an electric field, and which are then deflected by said electric field.
For convenience, this printing technique will be referred to in the following technical "SPI". The invention also relates to the use of this liquid composition, such as an ink composition, according to the invention, in a printer or a printing head implementing the liquid jet printing technique, In particular, the invention relates to a method for printing, and / or processing, and / or marking and / or coding of a substrate, support, or object, in particular in textile, by projection on this substrate, support, or object, such as a textile substrate, of said liquid composition such as an ink composition by the technique of liquid jet printing, called "SPI technique" ". The invention finally relates to a substrate, support, or object, in particular made of textile, provided with printing and / or treatment and / or marking and / or coding obtained by drying and / or absorption (in the substrate, support or object), the liquid composition such as an ink composition according to the invention.
The technical field of the invention is, in general, that of liquid jet printing in particular by ink jet.
PRIOR ART Inkjet printing is a well-known technique which allows the printing, marking, or decoration of all kinds of objects, at high speed, and without contact of these objects with the printing device, variable messages at will, such as barcodes, sell-by dates, etc. even on non-planar supports.
Inkjet printing techniques are divided into two main types: the so-called "drop on demand" or "DOD" technique, and the so-called "continuous jet" technology. "(Continuous InkJet" or "CIJ" in English).
Jet projection "on demand" can be made by "bubble" inkjet, by "piezoelectric" ink jet, by "valve" ink jet or by jet jet. Ink says "Hot Melt" or phase change.
In the case of the bubble ink jet, the ink is vaporized in the vicinity of the nozzle and this vaporization causes the ejection of the small amount of ink between the resistor that vaporizes the ink and the nozzle. In the case of the piezoelectric inkjet, a sudden change in pressure caused by an actuator set in motion by the electrical excitation of a crystal or a piezoelectric ceramic and located in the vicinity of the nozzle, causes the ejection of a drop of ink.
In the case of the "Hot Melt" ink jet, the ink is solvent-free and is carried beyond its melting point. On-demand drop printing can therefore be done at room temperature, such as piezoelectric ink jet, valve ink jet or bubble ink jet, or at high temperature, for example. For example, at around 60 ° C. to 130 ° C., this is the case of the so-called "Hot Melt" (HM) or phase-change ink jet. The deviated continuous jet projection consists in 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 specific frequency, causes pressure disturbances in the ink jet, which oscillates and gradually breaks up into spherical droplets. An electrode, called the "charge 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 in an electric field and allow printing. The uncharged drops, therefore not deflected, are recovered in a gutter where the ink is sucked and then recycled to the ink circuit.
For all types of inkjet technology, the viscosity of the inks is very low at the projection temperature, typically 1 to 10 cPs or 15 cPs, and these technologies can therefore be referred to as ink deposition technologies. low viscosity.
The jet ink projection ensures high speed non-contact marking of scrolling on non-planar objects and with the possibility of changing messages at will.
Ink compositions, which are suitable for jet projection, especially for deviated continuous jet projection, must satisfy a certain number of criteria inherent in this technique, relating, inter alia, to the viscosity, the solubility in a solvent for cleaning. , the compatibility of the ingredients, the correct wetting of the media to be marked, etc., and the electrical conductivity in the case of the deviated continuous jet.
In addition, these inks must dry quickly, be able to pass through the nozzle without clogging, with a great stability of orientation of the jet while allowing easy cleaning of the print head.
The very diverse fields of application of these ink compositions require various ink formulations, adapted to the wide variety of substrates to be marked (metal, plastics, glass, etc.) and meeting a very wide variety of industrial constraints. . In particular, the water resistance of the marking can be an important requirement.
The ingredients that make up the current inks, for the deviated continuous jet type ink jet, are organic or mineral products; these are dyestuffs, such as dyes or pigments, resins or binders, in one or more volatile solvent (s) or in water, optionally one or more salts (s). ) of conductivity, as well as various additives.
The dyestuffs 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 be opaque or not. They bring to the ink its color, its opacity, or particular optical properties, such as fluorescence (see US Pat. Nos. 4,153,593, US-A-4,756,758, US Pat. 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 sufficient ink conductivity so that there is no need to add a conductivity salt. The dyes known under the name C. I. Solvent Black 27, 29, 35 and 45 are in this case.
Substrates, supports, white or light colors are marked with black or color inks, and the dyes or pigments of these inks are based on dyes or organic or inorganic pigments most often transparent.
Substrates, black or dark-colored, are marked with inks containing opaque pigments, the most common being titanium oxide.
The binder (s) or resin (s) is (are) generally for the most part solid (s) and polymeric compound (s) and their choice is dictated by their solubility in the selected solvents and by their compatibility with dyes and other additives, but also and especially according to the properties 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-95/29287).
Their primary function is to provide the ink with adhesion on the maximum of supports or on specific supports, for example non-porous. They also make it possible to give the ink the appropriate viscosity for the formation of the drops from the jet and they bring to the ink, or rather to the marking obtained, most of its properties of resistance to physical and / or chemical attack. .
The solvent of these inks consists most frequently of a mixture comprising, on the one hand, a major amount of volatile and low-viscosity solvent compounds, in order to allow the labels to be dried very quickly and to adjust the viscosity to the value. For example, from 2 to 10 mPa.s, and on the other hand, more viscous and less volatile solvents with slower drying, in a lesser amount, to avoid drying the ink in the nozzle during the phases. stopping the printing apparatus (see US Pat. Nos. 4,155,767, WO-A-92,14794, WO-A-92,147,55 and US-A-4,260,531).
The volatile solvent compounds used most often are alcohols, ketones or low molecular weight esters, as indicated in US-A-4,567,213 and US-A-5,637,139. there may be mentioned essentially methanol, ethanol, 1- and 2-propanol, acetone, methyl ethyl ketone ("MEK"), and methyl isobutyl ketone.
The less volatile solvent compounds having in particular a function of drying retarder are most often ketones, such as cyclohexanone, glycol ethers, cited in US-A-4,024,096 and US-A-4,567,213, ethers and acetals, such as furan or dioxane, mentioned in US-A-4 155 767, dimethylformamide or dimethylsulfoxide (US-A-4 155 895), lactones (EP-A-0 034 881), N-methyl pyrrolidone (EP-A-0 735 120), glycols (WO-A-96 23 844), and even aliphatic hydrocarbons (US-A-4 166 044) or water , alone or in combination with other solvents, mentioned above, reference is made in this respect to US-A-4 153 593, GB-A-2 277 094 and FR-A-2 460 982.
In general, the main or majority solvent compounds of the inks for deviated continuous jet projection must meet a certain number of criteria, in particular: their volatility must be sufficient for the ink to dry rapidly on the support to be marked, but not too big, so as not to evaporate too quickly in the printer, especially during shutdowns; their solvent power, vis-à-vis the binders of the ink, dyes or pigment dispersions and vis-à-vis the printing media, must allow to give the dry ink, good adhesion; their effects on human health, namely their toxicity, harmfulness, irritancy and flammability, must be reduced; they must make it possible to maintain sterile ink possibly intended to be ingested; finally, they must have the capacity to maintain dissolved and dissociated ionic species such as salts that give the ink its electrical conductivity.
The additives include dispersants which allow the dispersion of pigments, surfactants which modify the wetting or penetrating power of the ink (US-A-5 395 431), in particular those which modify or regulate the static or dynamic surface tension, such as that the Fluorad® FC 430 3M® Company, the agents that inhibit the corrosion induced by the salts that bring the conductivity (see EP-A-0 510 752, US-A-5 102 458), or the additives which protect the ink against the proliferation of bacteria and other microorganisms: they are biocides, bactericides, fungicides and others, particularly useful in water-containing inks, buffer pH regulators (see EP -A-0 735 120), antifoaming agents.
The salt (s) of possible conductivity (s) provide (s) to the ink the conductivity necessary for the electrostatic deflection. In this regard, reference may be made to US-A-4,465,800.
Among the salts that provide the conductivity, are used all kinds of ionizable species, soluble and dissociable in the solvent medium of the ink.
For inks where the majority solvent component of the solvent is water, the conductivity input to the ink is generally not a problem, since most water-soluble products are ionizable species.
But the aqueous medium does not allow a wide variety of formulations, because the solvent power of water is limited, and the rate of evaporation of water is too slow to take advantage of the high speed of printing that allows the inkjet.
On the contrary, there is a wide variety of organic solvent compounds which have a high dissolving power with respect to many polymers and dyes, which makes it possible to formulate a very large number of fast-drying inks with excellent adhesion to all kinds of substrates.
In contrast, in these organic media, an electrical conductivity is obtained only when the solvent compounds are sufficiently dissociating, that is to say when their dielectric permittivity and their dipole moment are sufficiently high.
More precisely, the electrical conductivity is provided to the ink by salts, generally conductivity salts. But these salts can provide electrical conductivity to the ink only if the solvents are dissociating with respect to the species present in the ink to give ions.
Solvent compounds whose dielectric constant is less than about 15 are usually considered unsuitable for providing the ink with the conductivity necessary for deviated continuous jet projection.
In other words, the solvents must have a high dielectric constant greater than 15 to be sufficiently dissociative for the ions and give the ink sufficient conductivity.
It is generally recognized that the minimum conductivity that an ink must possess for this type of jet projection is of the order of 500 μS / cm.
In addition, salts can contribute negatively to the stability of the ink.
Consequently, in order to be projected by the deviated continuous jet technique, the inks can be formulated with a solvent comprising only solvent compounds dissociating or comprising a majority of such dissociating solvent compounds.
In other words, non-dissociating low dielectric constant solvents can not be used in ink compositions for the conventional "ICJ" technique.
Thus, EP-A0-1 858 990 (WO-A1-2006 / 097502) teaches that ink solvents for the deviated continuous jet printing technique must have a dielectric constant greater than about 15 to dissociate the species sufficiently. such as salts and provide sufficient conductivity to the inks.
The document EP-AO-1 200 530 (WO-A1-01 / 09255) teaches that the 1-3 dioxolane whose dielectric constant is 7.1 has insufficient dissociation capacity and must be associated with another solvent which is more dissociative for to provide the inks for the deviated continuous jet printing technique with the necessary electrical conductivity.
US-B2-8,282,724 teaches that ethylal whose dielectric constant is 2.5 has insufficient dissociating power and must be associated with another more dissociative solvent to provide the inks for the continuous jet printing technique deviated conductivity electric necessary.
However, it is still necessary that the volatility of these solvent compounds be sufficient for the ink to dry rapidly on the support to be marked,
However, there are very few solvents that are both volatile and dissociative.
These volatile and dissociating solvent compounds are almost exclusively ketones and low molecular weight alcohols such as acetone, methyl ethyl ketone, methanol and ethanol, and the use of some of these solvent compounds, such as methanol, is undesirable because of their toxicity.
Esters which have comparable volatilities to ketones and low molecular weight alcohols have dielectric constants of less than 10, and can not be used as the sole components of the ink solvents.
Finally, the marking, coding or printing inks based on volatile solvent compounds must contain a majority of dissociating solvent compounds to be projected by the continuous deviated jet printing technique, which considerably reduces the possible choices for these solvent compounds and, consequently, also reduces the possible choices for binders and dyes, and ultimately considerably limits the possible ink formulations.
In addition, a liquid jet printing technique has been recently developed, which we will call for convenience in the following, and in order to avoid repetitions, the "SPI" technique which is the abbreviation of "Super Piezo InkJet".
This technique "SPI" is different from the technique called "drop on demand" or "DOD" in English language, as the technology called "continuous jet" ("Continuous InkJet" or " ICJ "in the English language).
The "SPI" technique can be defined, for simplicity, as a binary "CIJ" deviated continuous jet printing technique in which, unlike the continuous jet printing technique deviated where the projected drops for printing each have a load net electric non-zero, the drops are not charged by an electric field, each have a zero net electric charge and each form a dipole under the effect of an electric field, and are then deflected by this field.
By "binary" is meant: that there is a first trajectory of the drops for printing, and a second trajectory of the drops for recycling the ink. In this second trajectory of the drops, the drops are recovered in a gutter where the ink is sucked, then recycled to the ink circuit. that a message of N pixels in height requires a print head with N nozzles.
It is important to note that, while in the "CIJ" deflected continuous jet printing technique, the deflected drops are printed, in the so-called "SPI" technique, on the contrary, the non-deflected drops are printed. .
The "SPI" technique is thus widely described in the following documents [1] and [2] to which reference is made herein explicitly and which are introduced in the present description in their entirety.
WO-A2-2005 / 070676 (corresponding to documents FR-A1-2 851 495 and US-B2-7,192,121) [1], describes how drops are formed in this technique by means of a print head provided with an internal simulation system.
More specifically, this document relates, according to claim 1, to an inkjet printer comprising: a print head with one or more nozzles having a head body accommodating in particular for each nozzle, a hydraulic path of the ink comprising , a stimulation chamber in hydraulic communication with one of the printing nozzles emitting an ink jet under pressure along an axis of this nozzle, internal means for stimulating the jet of ink emitted by the nozzle mechanically coupled to the nozzle; ink housed in the stimulation chamber, these means acting on the jet emitted by the nozzle to break the jet in a controlled manner, and means for recovering the ink which is not received by a printing substrate, a electrical control signal generator receiving a control signal and delivering stimulation signals to the stimulating means, an arrangement of charge electrodes defining around the nozzle axis upstream and downstream regions; al, the downstream zone being further from the nozzle than the upstream zone, upstream and downstream electrodes of this arrangement being connected to sources of electrical potential so as to maintain in one of the zones a potential equal to that of the ink in the body of the print head, and in the other of these areas a potential different from that of the ink in the body of the print head, a deflection electrode arrangement located axially downstream of the charge electrode arrangement characterized in that the electrical control signal generator supplies the stimulating means with signals causing the jet to be intermittently intermittently broken into an upstream break position in the upstream zone. , to intermittently form a drop, thus separating the jet into a drop and a section and also causing the controlled breaking of the jet or sections of the jet continuously in a positive direction. it is downstream breaking, the continuous jet emitted by the nozzle thus being transformed after the downstream zone into a continuous stream of electrically charged and uncharged ink drops.
This document also relates, according to claim 13, to a method of printing a support by means of said printer in which an ink jet emitted by a nozzle of the printer is split in order to form first drops which will strike a substrate for forming points and sections, characterized in that, the jet or the sections resulting from splitting the jet into first drops and sections into second drops, the second drops resulting from the latter fraction being directed towards the gutter, are further fractionated; .
Finally, this document relates, according to claim 14, to an ink jet printer head comprising: a print head with one or more nozzles having a head body (1) housing in particular for each nozzle, a hydraulic path of the ink comprising, a stimulation chamber in hydraulic communication with one of the printing nozzles emitting a jet of ink under pressure along an axis of this nozzle, internal means for stimulating the ink jet emitted by the nozzle mechanically coupled to the ink housed in the stimulation chamber, these means acting on the jet emitted by the nozzle to break the jet in a controlled manner, and means for recovering the ink which is not received by a substrate of an electrical control signal generator receiving a control signal and delivering stimulation signals to the stimulating means, an arrangement of charging electrodes defining upstream and downstream zones around the axis of the nozzle; 1, the downstream zone being further from the nozzle than the upstream zone, upstream and downstream electrodes of this arrangement being connected to sources of electrical potential so as to maintain in one of the zones a potential equal to that of the ink in the body of the print head, and in the other of these areas a potential different from that of the ink in the body of the print head, an axially located deflection electrode arrangement downstream of the charge electrode arrangement characterized in that the control electric signal generator supplies the stimulation means with signals causing the jet to be intermittently intermittently broken into an upstream break position in the upstream zone, and also causing the controlled breaking of the jet or sections of the jet continuously to a downstream breaking position, the continuous jet emitted by the nozzle thus being transformed after the downstream zone into a coaxial train. ntinu of electrically charged and uncharged ink drops.
Document FR-A1-2 906 755 (corresponding to documents WO-A1-2008 / 040777 and US-B2-8,162,450) [2] describes how the drops are sorted in this technique under the effect of a variable field.
More specifically, this document relates, according to claim 1, to a method for deflecting a liquid jet comprising: forming a conductive liquid jet exiting at a predetermined speed (v) through a nozzle of a pressure chamber along a path hydraulic system (A), the generation of an electric field (E) variable along the hydraulic path (A) by putting under potential a succession, in the direction of the hydraulic trajectory (A), of several electrodes of deflection isolated between them and forming a network which extends along an electrode plane parallel to the hydraulic path (A) over a network length (L), in which the potential applied to each electrode of the network is variable and the potential applied to all the electrodes of the network is zero spatial and temporal means, the deflection of the jet by the electric field (E) by the mobilization of charges within the jet.
Improvements to the technique described in documents [1] and [2] are described in the following documents [3], [4], and [5], to which reference is made here and which are introduced in this description in their entirety:
Document FR-A1-2 952 851 (corresponding to documents WO-A1-2011 / 061331 and US-B2-8,540,350) [3] describes how to avoid interactions between neighboring nozzles by compensating for mechanical crosstalk.
More specifically, this document relates to a continuous ink jet printer comprising a print head which is characterized in that it comprises means for compensating a mechanical crosstalk between adjacent chambers, these means transmitting simultaneously to the transmission to a stimulated chamber, a stimulation pulse, a mechanical crosstalk compensation pulse on each of the lines serving a chamber actuator adjacent to the stimulated chamber.
In particular, claim 1 of this document relates to a continuous inkjet printer comprising a print head comprising: a plurality of stimulation chambers, aligned along an axis of alignment of the chambers, a planar diaphragm whose parts form a wall of each of the stimulation chambers, a plurality of nozzles respectively each in hydraulic communication with one of the stimulation chambers, at least one charging electrode and one deflection electrode located downstream of the nozzles, a plurality of actuators each electromechanical unit being mechanically respectively connected to each of the diaphragm portions forming a wall of each of the stimulation chambers, a plurality of stimulation lines each intended to transmit stimulation pulses respectively to each of the different actuators, a data processing device to print receiving a signal carrying imp data rhyming and delivering according to these data stimulation pulses to the stimulation lines, characterized in that it further comprises means for compensating a mechanical crosstalk between adjacent chambers, these means transmitting simultaneously to the transmission to a stimulated chamber , a pacing pulse on a pacing line, a mechanical crosstalk compensation pulse on each of the lines serving a room actuator adjacent to the paced chamber.
This document also relates, according to claim 2, to a print head of a continuous inkjet printer comprising: a plurality of stimulation chambers, aligned along an axis of alignment of the chambers, a planar diaphragm of which portions form a wall of each of the stimulation chambers, a plurality of nozzles respectively each in hydraulic communication with one of the stimulation chambers, at least one charging electrode and one deflection electrode located downstream of the nozzles, a plurality electromechanical actuators each being mechanically respectively connected to each of the diaphragm portions forming a wall of each of the stimulation chambers, a plurality of stimulation lines each intended to transmit stimulation pulses respectively to each of the different actuators, characterized in that it furthermore comprises means for compensating a mechanical crosstalk between adjacent chambers, these means transmitting simultaneously to the transmission to a stimulated chamber, a stimulation pulse on a stimulation line a mechanical crosstalk compensation pulse on each of the lines serving a room actuator adjacent to the stimulated chamber.
Finally, this document relates, according to claim 7, to a method for reducing the consequences of mechanical crosstalk between adjacent stimulation chambers of a print head of a continuous ink jet printer having a plane diaphragm whose parts a wall of each of the stimulation chambers, at least one charging electrode and a deflection electrode located downstream of the nozzles, and electromechanical actuators for stimulating each chamber and a plurality of stimulation lines each intended to transmit pulses of stimulation to each of the different actuators, characterized in that simultaneously with the sending of a stimulation pulse to an actuator of a stimulated chamber, is sent to each of the chambers adjacent to the stimulated chamber compensation pulses to each of the actuators chamber adjacent to the stimulated chamber.
The document FR-A1-2 971 199 (corresponding to the documents WO-A1-2012 / 107461 and US-A1-2013 / 307891) [4], describes a print control method in which a change of the polarity is effected. between two adjacent nozzles.
More specifically, this document describes, according to claim 1, a print control method of a continuous ink jet printer with a print head, or a print head of a printer. such printer for printing a pattern on a print medium moving relative to the head, the head comprising: a multi-nozzle drop generator comprising: a body comprising: • stimulation chambers each adapted to receive the ink under pressure, • ejection nozzles, each in communication with a stimulation chamber and each able to eject an ink jet along its longitudinal axis, the nozzles being aligned along an alignment axis and arranged in a same plane, actuators, each mechanically coupled to a stimulation chamber, and adapted to cause on command pulse breaking a jet ejected by a nozzle in communication with said chamber at a distance Lbr from the plane of the nozzles, a deflection assembly arranged below the nozzles and having from upstream to downstream: • a shielding electrode, • a first dielectric layer adjacent to the shielding electrode, • at least one pair of deflection electrodes each deflection electrode being framed on both sides by a dielectric layer, the method according to which: information is determined on the relative position of the support with respect to the head, the electrodes of an electrode are supplied with an alternating voltage; same pair in phase opposition between them, pulses are sent to the actuators to form, from the breaking of a jet ejected by a nozzle in communication with the chamber to which is mechanically coupled said actuator at a distance Lbr from the plane of nozzles, drops not capable of being electrically charged by the deflection electrodes or jet sections subjected to the electrostatic influence of the deflection electrodes the lexion, the pulses are controlled so as to minimize the total electrical charge on the jet sections, which is contained within the electrostatic influence volume of the deflection electrodes.
This document also relates, according to claim 9, to a binary continuous inkjet printer for implementing said control method.
The document FR-A1-2 975 632 (corresponding to the documents WO-A1-2012 / 163830 and US-A1-2014 / 168322) [5] describes how to increase the printing speed from 2 to 10 m / s thanks to the generator of drops.
More specifically, this document describes, according to claim 1, a method for printing a continuous ink jet multi-nozzle printer or a print head of such a printer in order to print a pattern. on a printing medium moving relative to the head, the head comprising: a multi-nozzle drop generator comprising a body comprising: • one or more pressurized chambers each capable of receiving ink under pressure, • nozzles ejection in hydraulic communication with a pressurized chamber and each able to eject an inkjet having a speed Vj along its longitudinal axis (A), the nozzles being aligned along an alignment axis and arranged in the same plane, actuators, able to cause on command of a pulse breaking a jet ejected by a nozzle to form a succession of drops, the method according to which the support has with respect to the head, a speed Vs, the distance between pixels consecutive in the direction of displacement of the support is Dii, and according to which is formed by breaking jet drops of a first category and drops of a second category, the drops of the first category each having a first volume, all the first volumes being substantially equal to each other, the drops of the second category having second volumes not necessarily equal to each other, but all the drops of the second category having a volume which is not equal to the volume of a drop of the first category; differentiates the trajectories followed by the drops of first and second categories by applying to at least one of the drop categories a deflection force capable of differentiating the trajectories of the drops of the first category and the drops of the second category, the trajectory of the drops of first category meeting the print medium and the trajectory of the second category drops encountering a retrieval of these drops, we create information on the moments where the successive pixels to print scroll in a position where they are likely to be printed, for the printing of a black pixel followed by a white pixel is formed a drop of first category, and a drop of second category, the accumulated duration of formation of these droplets of first and second categories being equal to or greater than the running time of a pixel.
In documents [1], [2], [3], [4] and [5], there is no description of the specific inks used in the printers, print heads and processes of these documents, nor any suggestion as to the criteria to guide the choice of these inks.
There is therefore a need for ink compositions, and more generally for liquid compositions, which are specifically adapted to the so-called "SPI" technique as defined above and which can be used in particular in processes methods, printheads and printers described in documents [1], [2], [3], [4], and [5], and explicitly set forth hereinabove.
The object of the present invention is to meet, inter alia, the need for compositions for marking, coding or printing any ink jet medium, and to provide liquid compositions which are specifically adapted to the technique known as " SPI ", as defined above, which may be used in particular in the methods, methods and printers described in documents [1], [2], [3], [4] , and [5] explicitly stated above in the present description.
Another object of the present invention is to provide a liquid composition, in particular a volatile ink composition, for the marking, coding or printing of all supports, by a deviated continuous jet printing technique in which the possible choices for the solvent compounds of this composition is considerably broadened in order to have a very wide latitude in the formulation of these liquid compositions.
In particular, an object of the present invention is to provide a liquid composition, in particular a volatile ink composition, for the marking, coding or printing of all supports, by a deviated continuous jet printing technique. , in which low dielectric constant solvents, non-dissociating, can be used without the quality of the print is degraded.
STATEMENT OF THE INVENTION
This and other objects are achieved according to the invention by a liquid composition, such as an ink composition, which is liquid at room temperature, specifically for printing by a jet printing technique. binary deviated continuous circuit in which said liquid composition forms, when printing drops which are not charged by an electric field, which each have a zero electric charge, which each form a dipole under the effect of an electric field, and which are then deflected by said electric field, characterized in that said liquid composition comprises: a) a solvent comprising one or more compound (s) organic solvent (s) and optionally water, said solvent having overall (as a whole) a dielectric constant less than 15; b) a binder; c) one or more dyes and / or pigments; and in that: d) said liquid composition has an electrical conductivity at 20 ° C of less than 200 μS / cm, preferably less than 150 μS / cm, more preferably less than 100 μS / cm. Generally, the solvent comprises at least one organic solvent compound having a dielectric constant of less than 15, and optionally also one or more organic solvent compound (s) having a dielectric constant greater than or equal to 15 and / or some water.
It should be noted that the dielectric constant of a solvent mixture can ideally be measured or, failing that, can be estimated by the average of the dielectric constants of the constituents and weighted by their mass proportions.
Note further that the electrical conductivity is measured with a commercial apparatus and according to principles well known to those skilled in the art, for example described in the site: http://fr.wikipedia.org/wiki/Conductim% C3% A9trie.
Electrical conductivity can be measured according to the following standard: ASTM D1125-14: "Standard Test Methods for Electrical Conductivity and Resistivity of Water".
Electrical conductivity can be measured, for example, with a commercially available conductivity meter from Radiometer®.
In what follows when it comes to viscosity, it can be measured according to the following standard: DIN 53019-1: "Measurements of viscosities and flow curves by means of rotational viscometers".
The dynamic viscosities can be measured for example by means of a viscometer with coaxial cylinders, such as the viscosimeter with coaxial cylinders of the "Couette" type of Contraves®.
In what follows, when it comes to particle sizes, they can be measured according to the following standard: ISO 22412: 2008.
The particle sizes can be measured for example by means of a particle size analyzer from Malvern® using the technique of "Quasi Elastic Light Scattering (QELS)", also called "photon autocorrelation".
In what follows, when it comes to molecular weight, it can be measured by GPC (or size exclusion chromatography) using polystyrene standards.
The term "liquid composition" covers both inks and fluids called "functional fluids". A functional liquid may be any liquid allowing the deposition of a substance having a particular function, for example and without being exhaustive: a dyeing function, medicinal, waterproofing, fixing, refractory, conductive, insulating, anti-counterfeiting, especially for meadow -treatments and post-treatments of textiles.
It can generally be considered that a functional liquid is different from an ink in that an ink is in principle colored, while a functional liquid is not necessarily.
The pre-treatments of the aforementioned textiles, may be generally defined as treatments that serve to prepare the textile before printing, either to help fixing or to prevent it in places. The post-treatments of the aforementioned textiles can be varied and are well known to those skilled in the art.
By "ambient temperature" is generally meant a temperature of 5 ° C to 30 ° C, preferably 10 ° C to 25 ° C, more preferably 15 ° C to 24 ° C, more preferably 20 ° C to 23 ° C. ° C. It is understood that the ink is liquid at atmospheric pressure.
The term "binary" is well known in this field of the art and has been clearly defined above.
The liquid composition according to the invention is a liquid composition specifically for printing by a very specific printing technique, namely a binary deviated continuous jet printing technique, in which the liquid composition forms at the time of the invention. printing drops that are not charged by an electric field, each have a zero electric charge, each form a dipole under the effect of an electric field, and are then deflected by said electric field.
This technique is referred to as "SPI" for convenience.
The liquid composition according to the invention is a composition for any SPI technique, namely for all methods, methods, "SPI", and it can be implemented in all printers and printheads operating according to this technique. .
Thus, it is expressly stated that the liquid composition according to the invention is a composition for methods, methods, printers and printing heads as described in documents [1], [2], [3], [4] ] or [5] cited above; for the methods, methods, printers and print heads of these documents as explicitly set out hereinabove; and for any method, method, printer, or print head defined by the combination of features of at least two methods, methods, printers or print heads as described in documents [1], [2], [3] ], [4] or [5] described above; or defined by the combination of at least two methods, methods, printers or print heads as explicitly set forth hereinabove. By way of combination, mention may be made of the combination of documents [1] and [2] or documents [1] and [2] and of one or more of documents [3] to [5].
This means that the ink composition according to the invention is intrinsically formulated for printing by this specific "SPI" technique and is therefore intrinsically different from a liquid composition for the "DOD" printing technique. the conventional "CIJ" printing technique, namely a "CIJ" technique.
More exactly, the liquid composition according to the invention is first of all a liquid composition for printing by a deflected continuous jet printing technique "CIJ", and from this simple fact, it is clearly different from a liquid composition for printing by "DOD" drop-on-demand printing technique.
Then, the liquid composition according to the invention forms during the printing of the drops which are not charged by an electric field, each have a zero electrical charge, each form a dipole under the effect of an electric field, then that the compositions for the conventional "CIJ" technique form charged drops.
Finally, the liquid composition according to the invention is printed using an electric field to deflect the drops, which again clearly differentiates it from a liquid composition for the DOD technique.
The liquid composition according to the invention is characterized in that it also has all the characteristics a), b), c) and d).
A liquid composition, such as an ink composition, which has all of the features a), b), c) and d) has never been described or suggested by the prior art.
It has been found that the liquid composition according to the invention, which has both these four characteristics, is particularly suitable for the specific printing technique known as "SPI" defined above.
These characteristics further differentiate the liquid composition according to the invention from the liquid compositions for the "DOD" printing technique or the conventional "ICJ" printing technique and give the liquid composition according to the invention advantageous properties with respect to liquid compositions for "DOD" printing technique or "CIJ" printing technique. Thus, according to characteristic a), the liquid composition, such as an ink composition, according to the invention comprises a solvent comprising one or more organic solvent compound (s) and optionally water, said solvent having generally a dielectric constant less than 15. Generally, the solvent comprises at least one organic solvent compound having a dielectric constant of less than 15, and optionally further one or more organic solvent compound (s) ) having a dielectric constant greater than or equal to 15 and / or water.
Liquid compositions, such as ink compositions for the "ICJ" printing technique, do not include such a solvent generally having a dielectric constant of less than 15.
In addition, according to characteristic d), the liquid composition according to the invention has an electrical conductivity at 20 ° C. of less than 200 μS / cm, preferably less than 150 μS / cm, more preferably less than 100 μS / cm. while liquid compositions for the "ICJ" printing technique have electrical conductivity at 20 ° C, greater than or equal to 500 μS / cm, preferably greater than 500 μS / cm.
The liquid composition according to the invention generally has a viscosity of 2 to 10 mPa.s.
It has been surprisingly demonstrated, by looking for liquid compositions that are specifically suitable for the so-called "SPI" technique, that precisely because of the so-called "SPI" technique for which the liquid compositions according to the invention are When designed, these compositions could have advantageous features over liquid compositions for the "DOD" printing technique or the "ICJ" printing technique.
It has also been demonstrated, surprisingly, that the liquid compositions according to the invention, while allowing a very wide latitude in their formulation, in particular as regards the solvent, remain printable even at low electrical conductivities, namely less than 200 μS / cm, preferably less than 150 μS / cm, more preferably less than 100 μS / cm.
In the conventional "ICJ" printing technique, the net charge taken by the drops is induced by an electrostatic effect on the surface of the jet in the same way as the charge of a capacitor.
This charge depends on the charging voltage duration and also depends on the electrical conductivity of the ink. The net electric charge brought varies in time until a final asymptotic value is obtained. When the conductivity is insufficient, this final value is not obtained in time and this load will strongly depend on the moment when the breaking of the jet occurs.
On the contrary, in the so-called "SPI" technique, since the net charge of the drops is zero, the accuracy of the moment when the break is produced is not critical.
It has thus been demonstrated, according to the invention, that liquid compositions such as inks, of much lower electrical conductivity than liquid compositions for the conventional "CIJ" technique can be used in giving markings or impressions. excellent qualities.
As already mentioned above, the electrical conductivity at 20 ° C. of the liquid composition according to the invention is no longer greater than or equal to 500 μS / cm, as that of the liquid compositions for conventional "CIJ" printing, but less than 200 pS / cm.
As already mentioned above, electrical conductivity is provided to liquid compositions, such as ink compositions, for the conventional "ICJ" printing technique with salts. But these salts can provide conductivity only if the solvents are dissociating for the ions and these salts have a negative impact on the stability of the liquid composition.
Solvents of the liquid compositions, such as ink compositions, for the conventional "ICJ" printing technique must have a high dielectric constant greater than 15 to be sufficiently dissociative for the ions.
According to the invention, since the electrical conductivity of the liquid composition is low, solvent compounds with a low dielectric constant of less than 15 become usable when they are not used with compositions for conventional ICJ.
The choice for these solvent compounds is considerably broadened. In particular, the number of volatile solvent compounds that can be selected is considerably increased, since these volatile solvent compounds no longer have to be chosen as was previously the case only among the only high dielectric constant solvent compounds.
These solvent compounds can thus be chosen according to criteria other than their dielectric constant, such as their absence of harmfulness.
In addition, the amount of conductivity salt in the liquid composition according to the invention is generally less than the amount of conductivity salts in the compositions for conventional ICJ (see below), which eliminates the negative effects on stability. of the liquid composition due to these salts. In other words, the compositions according to the invention are compositions which contain less salts and which are therefore more stable.
Advantageously, less polar solvent compounds than ketones, water, amides or alcohols may be used and may thus make it possible to obtain compositions, formulations, the harmfulness of which is lower than that of the compositions which contain ketones or amides for example.
In the technique of "CIJ", the liquids of high densities, densities, are not printable because the force of deflection of electrical origin is insufficient to divert drops of strong mass, because of an effect of inertia. Conversely, it has been demonstrated according to the invention, that in the so-called "SPI" technique, the printed drops are those which are not deflected, and drops of high densities in the range according to the invention. invention are therefore printable.
Advantageously, the liquid composition according to the invention may comprise solid particles, such as pigment particles or particles of polymer binder in dispersion.
Preferably, the maximum size of the solid particles is from 2 to 10 μιτι, preferably from 2 to 5 μιτι.
The average or maximum size of the particles is measured using a laser granulometer, either by quasi-elastic light scattering as with the Zetasizer Nano-S® from Malvern®, or by light diffraction as with the Mastersizer® from Malvern®.
Here again, it is a characteristic which differentiates the liquid composition according to the invention from the liquid compositions for the "DOD" printing technique or the conventional "CIJ" printing technique. gives the liquid composition according to the invention advantageous properties with respect to liquid compositions for the "DOD" printing technique or the conventional "ICJ" printing technique.
Indeed, the solid particles, such as contain the liquid compositions for the conventional "ICJ" printing technique have a much smaller maximum size, less than 2 μιτι.
In the conventional "ICJ" printing technique, the net charge taken by the drops depends on the perfect synchronism between the slot of the electric charge field and the moment when the break occurs. The large particles disrupt the breakage and make it random, resulting in a variable load onboard, resulting in poor positioning of the drops after deflection and therefore a bad impression.
On the contrary, in the so-called "SPI" technique, since the net charge of the drops is zero, the accuracy of the breaking moment is not critical. It has therefore been demonstrated, according to the invention, that solid particles, such as pigments, much larger than in the liquid compositions for the conventional "CIJ" technique can be used in the liquid composition according to the invention. without any problem when printing and giving markings or treatments of excellent qualities. The maximum size of the solid particles of the liquid composition according to the invention is no longer limited by the size of the nozzle.
Moreover, the sedimentation problems observed with large particles become manageable in the compositions according to the invention by adjusting their viscosity.
In other words, according to the invention, the "large" solid particles become "printable" while they were not with the compositions for conventional ICJ.
Advantageously, when the liquid composition according to the invention further comprises at least one soluble polymer (for example as a binder polymer), then said polymer has a weight average molecular weight of more than 70,000 Daltons, preferably 75,000 to 200,000 Daltons, more preferably 800,000 to 200,000 Daltons.
Here again, it is a characteristic which differentiates the liquid composition according to the invention from the liquid compositions for the "DOD" printing technique or the conventional "CIJ" printing technique. gives the liquid composition according to the invention advantageous properties with respect to liquid compositions for the "DOD" printing technique or the "ICJ" printing technique.
Indeed, the polymers that contain the liquid compositions for the printing technique by "CIJ" have a molecular weight that does not exceed 70000 Daltons.
In a manner analogous to that described above for large solid particles, the solid composition according to the invention can contain polymers with very long chains without problems occurring during printing and giving markings or treatments of excellent qualities.
In other words, according to the invention, the very long-chain polymers become "printable" while they were not with the compositions for conventional ICJ.
The solvent comprises one or more solvent compound (s), chosen from organic solvent compounds and optionally water.
It should be noted that the ink composition according to the invention generally comprises a very small amount of water, generally less than 10% by weight, preferably less than 5%, more preferably less than 1% by weight, relative to the total weight of the ink composition.
The ink composition according to the invention can even be considered as essentially free from water (0% water).
In fact, the water present is only the water supplied as an impurity in the various components of the ink. The higher the purity of the chosen components, the lower the water content.
The low content or absence of water in the ink composition according to the invention promotes the formation of the ink film when the binders and other dyes in the composition are insoluble in water, thus improving the strength and adhesion of the ink.
Advantageously, the one or more organic solvent compound (s) of the solvent is (are) chosen from, for example, alcohols, in particular low molecular weight alcohols, for example alcohols. aliphatics such as ethanol; ketones preferably of low molecular weight; alkylene glycol ethers; esters of alkylene glycols and esters of alkylene glycol ethers, such as acetates; dimethylformamide; 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 diethyl carbonates; and their mixtures.
Preferably, this or these organic solvent (s) compound (s) has the property of dissolving the other ingredients of the ink, including the binder, dyestuffs, additives, etc..
The alcohols will preferably be chosen from linear or branched aliphatic alcohols of 1 to 8 carbon atoms, such as methanol, ethanol, propanol-1, propanol-2, n-butanol, butanol- 2, tert-butanol, etc.
The ketones will preferably be chosen from ketones of 3 to 10 carbon atoms, such as acetone, butanone (methyl ethyl ketone), pentanone 2 (methyl propyl ketone), methyl 3 butanone-2 (methyl isopropyl ketone) and 4-methylpentanone-2 (methyl isobutyl ketone).
The alkylene glycol ethers are preferably chosen from monoalkyl (C 1 -C 6 alkyl) or dialkyl (C 1 -C 6 alkyl) ethers of alkylene glycol having 1 to 10 carbon atoms in the alkylene chain, preferably they are ethers of ethylene or propylene glycol, such as methoxy-propanol.
The alkylene glycol esters and the alkylene glycol ether esters are preferably chosen from the esters of these 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.
Examples include methoxypropyl acetate, butyldiglycol acetate, and the like.
The esters are preferably chosen from low molecular weight esters such as formates, acetates, propionates or butyrates of alcohols with 1 to 10 carbon atoms.
The acetals are preferably selected 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 the organic solvent compounds listed above those whose dielectric constant is less than 15.
The organic solvent compounds whose dielectric constant is less than 15 can be found for example in the following table: http://www.atomer.fr/l/lbcsu.html or in the following table http: //www.stenutz .eu / chem / solv23.php.
Or, a list of the most common solvents with their dielectric constant can be found at this address: http://depts.washington.edu/eooptic/linkfiles/dielectric chart% 5Bl% 5D.pdf.
Similarly, one skilled in the art can easily identify among the solvent compounds listed above those which are volatile and those which are non-volatile.
By "volatile organic solvent compound" is generally meant that this compound has an evaporation rate greater than 0.5 on the scale where the butyl acetate has an evaporation rate of 1.
According to a preferred embodiment, the solvent of the liquid composition, such as an ink composition, according to the invention comprises a major amount by weight relative to the total weight of the solvent (50% by weight relative to the weight total or more solvent) of at least one organic solvent compound having a dielectric constant of less than 15; preferably the solvent comprises 90% by weight or more, more preferably 95% by weight or more, more preferably 100% by weight based on the total weight of the solvent of said organic solvent compound having a dielectric constant of less than 15, that is, the solvent is constituted by said organic solvent compound having a dielectric constant of less than 15.
The solvent of the liquid composition according to the invention when it is not constituted by said organic solvent compound having a dielectric constant less than 15 according to the invention may optionally further comprise one or more solvent compound (s) ) organic (s) having a dielectric constant greater than or equal to 15 and / or water.
The solvent of the liquid composition, such as an ink composition, according to the invention according to the preferred embodiment described above may then comprise in addition a minor amount by weight relative to the total weight of the solvent (less than 50% by weight relative to the total weight of the solvent) of at least one organic solvent compound having a dielectric constant greater than or equal to 15 and water; preferably the solvent comprises less than 10% by weight, more preferably less than 5% by weight, based on the total weight of the solvent, of said solvent compound having a dielectric constant greater than or equal to 15 and water.
Preferably, the solvent is free (0%) of organic solvent compounds having a dielectric constant greater than or equal to 15 and water.
Advantageously, the compound (s) organic solvent (s) whose dielectric constant is less than 15 is (are) chosen from volatile organic solvent compounds.
Preferably, the solvent is constituted by one or more volatile organic solvent compound (s), more preferably the solvent consists of one or more organic solvent compound (s) (s). ) volatile (s) whose dielectric constant is less than 15.
Among the preferred volatile organic solvent compounds whose dielectric constant is less than 15, mention may be made of dioxolane, methylal, diethoxymethane (or ethylal), esters such as ethyl, propyl or isopropyl acetates, or butyl, and dimethyl carbonate.
The solvent of the liquid composition according to the invention may consist of one or more of these preferred volatile organic solvent compounds whose dielectric constant is less than 15, for example the solvent of the liquid composition according to the invention may consist of with ethyl acetate, or with dioxolane, or with a mixture of dioxolane and ethylal, or with a mixture of dioxolane and dimethyl carbonate.
In the composition according to the invention, the solvent generally represents at least 20% by weight of the total weight of the liquid composition, preferably the solvent represents from 30% to 90% by weight, more preferably from 60% to 80% by weight. by weight, the total weight of the liquid composition.
In order to be colored or opaque, the liquid composition, for example ink, according to the invention also comprises dyestuffs such as dyes and pigments.
The dye (s) and / or pigment (s) may be chosen from all the dyes or pigments that are suitable for the intended use, known to those skilled in the art, some of these pigments or dyes. have already been mentioned above.
These dyes and pigments may in particular be chosen from dyes and pigments already known to those skilled in the art for the formulation of inks for the continuous flow printing technique "CIJ".
It has been seen above that the solid particles such as the pigments that may contain the liquid composition according to the invention may have specific particle sizes.
The said dye (s) may be chosen from the dyes known under the name "C.I. Solvent Dyes ", and said one or more of said pigment (s) can be chosen from conventional known organic and inorganic pigments, in particular from the pigments known under the name" C.I. Pigments ", and among the solid particles not referenced in the" Color Index "(Cl) such as particles of metals or alloys or mixtures of metals such as copper and / or silver particles, particles of metal oxides, ceramic particles, particles of refractory mineral compounds, and the particles of any other inorganic compound, preferably said one or more of said pigment (s) is (are) chosen from titanium oxide and carbon black. As examples, the most common pigments and dyes include C.l. Solvent Black 3, 7, 27, 28, 29, 35, 48, 49, C.I. Solvent Blue 38, 44, 45, 70, 79, 98, 100, 129, C.I. Solvent Red 8, 49, 68, 89, 124, 160, 164, C.I. Solvent Yellow 83: 1,126,146, 162, C.I. Solvent Green 5, the C.I. Solvent Orange 97, the C.I. Solvent Brown 20, 52, C.I. Solvent Violet 9, dispersions of Pigment Blue 15: 1, 15: 3, 60, 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.
Preferred dyes are C.I. 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% by weight. total of the liquid composition.
A dye with the lowest solubility in water, which is insoluble in water, will preferably be selected.
By water-insoluble dye is generally meant a dye which, added to 1% by weight in demineralised water, does not visibly stain the water in the eye.
The liquid composition according to the invention may further comprise a binder consisting of one or more binder polymers.
These binder polymers may be chosen from those already known to those skilled in the art for formulating inkjet inks type CIJ.
It has been seen above that the polymers which may contain the liquid composition according to the invention may have specific molecular masses.
Advantageously, this or these binder polymer (s) can be chosen from (meth) acrylic, vinyl, ketone, hydroxyaromatic, cellulosic, styrene, epoxy polymers, polyurethanes, styrene-acrylates, alkoxysilanes, and combinations of two or more thereof.
Advantageously, the binder represents from 1% to 45% by weight, preferably from 5% to 25% by weight, more preferably from 10% to 20% by weight, of the total weight of the liquid composition according to the invention in solid matter.
The liquid composition, for example ink, according to the invention may, in addition, comprise one or more plasticizer (s) (of the polymer (s) of the binder) chosen (s), for example, from the plasticizers known to those skilled in the art and chosen according to the binder used.
Plasticizers, phthalates, adipates, citrates and citric acid esters, alkyl phosphates, glycerol, lactic oleic, polypropylene glycol, triglycerides of fatty acids, levulinic acid; and their mixtures.
The plasticizer (s) is (are) generally present in a proportion of at least 0.05%, preferably from 0.1% to 20% by weight, of the total weight of the liquid composition, by example of ink.
The composition according to the invention may, in addition, optionally comprise at least one conductivity salt, unless another ingredient of the ink such as a dye, pigment, or other, is itself an ionizable compound such as a salt which can bring conductivity when it is dissociated, and gives sufficient conductivity to the ink so that there is no need to add a salt of conductivity proper, this is particularly the case of the compounds known under the name "Cl Solvent Black 27, 29, 35 and 45 ", already mentioned.
However, it will sometimes be necessary to include in the liquid composition, for example ink, according to the invention at least one conductivity salt itself, different ionizable compounds, such as dyes, pigments and other ingredients cited upper.
By "salt conductivity" is generally meant a salt that provides electrical conductivity to the liquid composition, for example ink.
This salt of conductivity may thus be chosen from alkali metal salts such as lithium, sodium, potassium, alkaline earth metal salts such as magnesium and calcium, and simple ammonium salts or quaternary; these salts being in the form of halides (chlorides, bromides, iodides, fluorides), perchlorates, nitrates, thiocyanates, formates, acetates, sulphates, propionates, trifluoroacetates, triflates (trifluoromethanesulfonates), hexafluorophosphates, hexafluoroantimonates, tetrafluoroborates, picrates, carboxylates and sulfonates etc.
If the markings obtained with the liquid composition, for example ink, according to the invention must be resistant to water, we will choose this or these salt (s) of conductivity among those which are insoluble in water (c). that is to say generally, whose solubility in water is less than 0.5% by weight), such as fatty-chain quaternary ammoniums and hexafluorophosphates or hexafluroantimonates.
This at least one conductivity salt will therefore be present, if necessary, in the liquid composition so as to impart to the composition the above conductivity: preferably, its (their) amount is 0, 01% to 10% by weight, more preferably 0.01% to 1% by weight, and more preferably 0.01% to 0.05% by weight of the total weight of the liquid composition.
Since the liquid composition according to the invention has a conductivity generally lower than liquids, such as inks, for the "ICJ" technique the amount of conductivity salt which may be added will generally be lower than in these liquids for the "ICJ". ".
The composition according to the invention may, in addition, comprise one or more additive (s) chosen (s) among the compounds which improve the solubility of some of its components, the print quality, the adhesion, or the control wetting the liquid, for example ink, on different supports.
The additive (s) may be chosen, for example, from anti-foaming agents, chemical stabilizers, UV stabilizers; surfactants, agents inhibiting corrosion by salts, in particular by conductivity salts, bactericides, fungicides and biocides, 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 antifoam stabilizers or surfactants. Those skilled in the art can easily identify from these additives those which are necessary for the application according to the medium to be marked. The invention also relates to the use of the liquid composition, such as an ink composition, according to the invention, as described above, in a printer or print head using employs a binary deviated continuous jet printing technique, wherein said liquid composition forms upon printing drops which are not charged by an electric field, each having a zero electrical charge, which each form a dipole under the effect of an electric field, and which are then deflected by said electric field.
This printing technique is therefore the so-called "SPI" technique.
This technique, this printer and this print head are as described in documents [1], [2], [3], [4], or [5] cited above or in any combination thereof. These include printers and print heads of these documents taken alone or in combination as explicitly set forth herein. The subject of the invention is also a process for printing, and / or processing, and / or marking and / or coding of substrates, supports or objects, for example, porous or non-porous, by projection onto these substrates, carriers or objects of a liquid composition, such as an ink composition, by a binary deviated continuous jet printing technique, wherein said liquid composition forms upon printing drops which are unloaded by an electric field, each having a zero electric charge, which each form a dipole under the effect of an electric field, and which are then deflected by said electric field, characterized in that said liquid composition, such as an ink composition, is the liquid composition, such as an ink composition according to the invention, as described above.
This printing technique is therefore the so-called "SPI" technique.
This technique is as described in documents [1], [2], [3], [4], or [5] cited above taken alone or in combination through methods, methods, printers and heads. impression implementing this technique. These include the technique of printing these documents alone or in combination as explicitly stated above in the present through the presentation of methods, methods, printers and printheads implement this technique. The invention also relates to a substrate, support or object, for example porous or nonporous provided with printing, and / or treatment, and / or marking and / or coding obtained by drying and / or absorption (in the substrate or support) of the liquid composition, such as an ink composition, according to the invention, as described above.
Said printing, and / or said treatment, and / or said marking and / or said coding generally comprises essentially all nonvolatile solids, such as the pigment of the liquid composition and / or the binder, and is obtained by evaporation and / or absorption into the substrate of essentially all of the other volatile or migrating constituents of the liquid composition, for example the ink composition, such as the vehicle.
This substrate may be metal, for example, aluminum, steel (beverage cans); glass (glass bottles); ceramic; a material containing cellulose such as cellophane, paper, possibly coated or glossy, cardboard or wood; an organic polymer, in particular a thermoplastic polymer ("plastic"), especially in the form of a film, chosen for example from PVDC, PVC, polyesters, PET, polyolefins, such as polyethylenes (PE) polypropylenes (PP); poly (methyl methacrylate) PMMA also called "Plexiglas"; Fabric ; textile; natural or synthetic rubber; or any other non-porous or porous substance; or composite of many of the foregoing materials.
The substrate may be cotton, fiber, viscose, polyester, wool, or a mixture thereof.
Impressions, and / or treatments, and / or markings and / or codings of excellent quality are obtained on all the substrates, and in particular on the flexible or very flexible substrates.
DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS The invention will be better understood on reading the following description of embodiments of the invention, given by way of illustrative and non-limiting examples.
Examples 1 to 4:
In all these examples, ink compositions according to the invention are prepared.
These ink compositions comprise the ingredients mentioned in Table I, in the proportions mentioned in Table I.
These compositions are generally prepared by simple mixing of the ingredients.
The dielectric constants of the constituent solvents, the conductivity of the compositions (in pS / cm) and the viscosity (in mPa.s = cPs) were also reported in Table I according to the ink compositions, and it was finally specified whether the inks whether or not suitable for printing by the continuous deviated jet ("CIJ") technique or the so-called SPI technique.
TABLE I - INK COMPOSITIONS
Electrical conductivity was measured with a commercially available conductivity meter from Radiometer®.
The dynamic viscosities were measured using a viscosimeter with coaxial cylinders of the "Couette" type of Contraves®.
The nature of the components of the inks is specified below:
The compositions of Examples 1 to 4 gave suitable prints on plastic films in a prototype printer employing the so-called "SPI" technique having a nozzle diameter of 40 μm.
It has also been found that it was impossible to implement the compositions of Examples 1 to 4 in a printer implementing the so-called "CIJ" technique and a fortiori to obtain a suitable printing.

权利要求:
Claims (23)
[1" id="c-fr-0001]
A liquid composition, such as an ink composition, liquid at room temperature, said liquid composition being a liquid composition specifically for printing by a binary deviated continuous jet printing technique in which said composition of liquid liquid forms when printing drops that are not charged by an electric field, each of which has a zero electric charge, which each form a dipole under the effect of an electric field, and which are then deflected by said field characterized in that said liquid composition comprises: a) a solvent comprising one or more organic solvent (s) and optionally water, said solvent having generally a dielectric constant of less than 15; b) a binder; c) one or more dyes and / or pigments; and in that: d) said liquid composition has an electrical conductivity at 20 ° C of less than 200 μS / cm, preferably less than 150 μS / cm, more preferably less than 100 μS / cm.
[2" id="c-fr-0002]
2. The liquid composition as claimed in claim 1, wherein the one or more organic solvent compound (s) of the solvent is (are) chosen from among the alcohols, in particular the low-weight alcohols. molecular, for example, aliphatic alcohols such as ethanol; ketones preferably of low molecular weight; alkylene glycol ethers; esters of alkylene glycols and esters of alkylene glycol ethers, such as acetates; dimethylformamide; 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 diethyl carbonates; and their mixtures.
[3" id="c-fr-0003]
3. Liquid composition according to claim 1 or 2, wherein the solvent comprises a major amount by weight relative to the total weight of the solvent (50% by weight relative to the total weight of the solvent or more) of at least one organic solvent compound having a dielectric constant of less than 15; preferably the solvent comprises 90% by weight or more, more preferably 95% by weight or more, more preferably 100% by weight based on the total weight of the solvent of said organic solvent compound having a dielectric constant of less than 15.
[4" id="c-fr-0004]
4. Liquid composition according to claim 3, wherein the solvent further comprises a minor amount by weight relative to the total weight of the solvent (less than 50% by weight relative to the total weight of the solvent) of at least one compound organic solvent having a dielectric constant greater than or equal to 15 and water; preferably the solvent comprises less than 10% by weight, more preferably less than 5% by weight, based on the total weight of the solvent, of said organic solvent compound having a dielectric constant greater than or equal to 15 and water.
[5" id="c-fr-0005]
A liquid composition according to any one of the preceding claims, wherein the organic solvent (s) having a dielectric constant of less than 15 are selected from volatile organic solvent compounds.
[6" id="c-fr-0006]
A liquid composition according to any one of the preceding claims, wherein the solvent is one or more volatile organic compound (s), preferably the solvent is one or more a plurality of volatile organic solvent compound (s) having a dielectric constant of less than 15.
[7" id="c-fr-0007]
7. Composition according to any one of claims 5 and 6, wherein the volatile organic solvent compounds whose dielectric constant is less than 15 are chosen from dioxolane, methylal, diethoxymethane (or ethylal), esters such as acetates. ethyl, propyl, isopropyl, or butyl, and dimethyl carbonate.
[8" id="c-fr-0008]
A liquid composition according to any one of the preceding claims, wherein the solvent is at least 20% by weight of the total weight of the liquid composition, preferably the solvent is from 30% to 90% by weight, preferably still from 60% to 80% by weight of the total weight of the liquid composition.
[9" id="c-fr-0009]
9. A liquid composition according to any one of the preceding claims wherein said dye (s) is (are) selected from dyes known as "C.I. Solvent Dyes ", and said one or more of said pigment (s) is (are) chosen from known conventional organic and inorganic pigments, in particular from the pigments known under the name" C.I. Pigments ", and among the solid particles not referenced in the" Color Index "(Cl) such as particles of metals or alloys or mixtures of metals such as copper and / or silver particles, particles of metal oxides, ceramic particles, particles of refractory mineral compounds, and the particles of any other inorganic compound, preferably said one or more of said pigment (s) is (are) chosen from titanium oxide and carbon black.
[10" id="c-fr-0010]
10. A liquid composition according to claim 9, wherein said one or more "Solvent Dyes" is (are) chosen from among the C.I. Solvent Black 3, 7, 27, 28, 29, 35, 48, 49, C.I. Solvent Blue 38, 44, 45, 70, 79, 98, 100, 129, the C.I. Solvent Red 8, 49, 68, 89, 124, 160, 164, C.I. Solvent Yellow 83: 1,126,146,162, C.I. Solvent Green 5, the C.I. Solvent Orange 97, the C.I. Solvent Brown 20, 52, and C.I. Purple Solvent 9, and said one or more "C I. Pigments" is (are) chosen among the dispersions of Pigment Blue 15: 1, 15: 3, 60, Pigment Green 7, Pigment Black 7, Pigment Red 48: 2,144,149,166,185, 202, 208, 214, 254, Violet Pigment 19, 23, Pigment Yellow 17, 83, 93, 139, 151, 155, 180, 191, Pigment Brown 23, 25, 41, or Pigment White 6.
[11" id="c-fr-0011]
11. A liquid 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%, more preferably from 3 to 10% by weight of dye (s) and / or pigment (s) relative to the total weight of the liquid composition.
[12" id="c-fr-0012]
12. A liquid composition according to any one of the preceding claims, wherein the binder is constituted by one or more binder polymer (s), preferably the binder polymer (s) is (are) selected from (meth) acrylic, vinyl, ketone, hydroxyaromatic, cellulosic, styrene, epoxy polymers, polyurethanes, styrene acrylates, alkoxysilanes, and combinations of two or more thereof.
[13" id="c-fr-0013]
The liquid composition of claim 12, wherein the binder is from 1% to 45% by weight, preferably from 5% to 25% by weight, more preferably from 10% to 20% by weight, of the total weight. of the liquid composition.
[14" id="c-fr-0014]
14. A liquid composition according to any one of the preceding claims, further comprising at least one plasticizer (s) in a proportion of at least 0.05%, preferably 0.1 to 20% by weight of the total weight. of the liquid composition.
[15" id="c-fr-0015]
The liquid composition according to any one of the preceding claims, further comprising at least one conductivity salt in an amount of 0.01% to 10% by weight, preferably 0.01% to 1% by weight. and more preferably from 0.01% to 0.05% by weight, of the total weight of the liquid composition.
[16" id="c-fr-0016]
The liquid composition according to claim 15, wherein said conductivity salt is selected 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 (trifluoromethanesulfonates), hexafluorophosphates, hexafluoroantimonates, tetrafluoroborates, picrates, carboxylates and sulfonates.
[17" id="c-fr-0017]
17. A liquid composition according to any one of the preceding claims, further comprising one or more additive (s) selected from antifoam agents; chemical stabilizers; UV stabilizers; surfactants; agents inhibiting corrosion by salts; bactericides, fungicides and biocides; and pH buffers.
[18" id="c-fr-0018]
A liquid composition according to any one of the preceding claims, which when it comprises at least one soluble polymer, is characterized in that said polymer has a weight average molecular weight of more than 70,000 Daltons, preferably 75,000 to 200,000 Daltons, more preferably 800,000 to 200,000 Daltons.
[19" id="c-fr-0019]
19. A liquid composition according to any one of the preceding claims, which when it comprises solid particles, is characterized in that the maximum size of the solid particles is 2 to 10 μm, preferably 2 to 5 μm.
[20" id="c-fr-0020]
20. Use of the liquid composition, such as an ink composition according to any one of claims 1 to 19, in a printer or printhead employing a binary deviated continuous jet printing technique, wherein said liquid composition forms upon printing drops that are not charged by an electric field, each having zero electrical charge, which each form a dipole under the effect of an electric field, and which are then deflected by said electric field.
[21" id="c-fr-0021]
A method for printing, and / or processing, and / or marking and / or coding substrates, supports or objects, for example porous or non-porous, by spraying on these substrates, supports or objects of a liquid composition, such as an ink composition, by a binary deviated continuous jet printing technique, wherein said liquid composition forms upon printing drops which are not charged by an electric field, which each have a zero electric charge, which each form a dipole under the effect of an electric field, and which are then deflected by said electric field, characterized in that said liquid composition, such as an ink composition is the liquid composition, such as an ink composition according to any one of claims 1 to 19.
[22" id="c-fr-0022]
22. Substrate, support, or article, for example porous or non-porous provided with printing, and / or treatment, and / or marking and / or coding obtained by drying and / or absorption of the liquid composition according to any one of claims 1 to 19.
[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, possibly coated or glossy, cardboard or wood; an organic polymer, in particular a thermoplastic polymer ("plastic"), chosen for example from PVDC, PVC, polyesters, PET, polyolefins, such as polyethylenes (PE), polypropylenes (PP); poly (methyl methacrylate) PMMA ("Plexiglas"); Fabric ; textile; natural or synthetic rubber; or any other non-porous or porous substance; or composite of many of the foregoing materials.

类似技术:

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同族专利:

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公开号 | 公开日

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US20170190926A1|2017-07-06|

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EP3190160A1|2017-07-12|

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CN106947323A|2017-07-14|

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FR3046418B1|2020-04-24|

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EP3190160B1|2020-12-23|

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US10597546B2|2020-03-24|

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法律状态:
2017-01-31| PLFP| Fee payment|Year of fee payment: 2 |

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2017-07-07| PLSC| Publication of the preliminary search report|Effective date: 20170707 |

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2018-01-31| PLFP| Fee payment|Year of fee payment: 3 |

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2020-01-30| PLFP| Fee payment|Year of fee payment: 5 |

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2021-01-28| PLFP| Fee payment|Year of fee payment: 6 |

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2022-01-31| PLFP| Fee payment|Year of fee payment: 7 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1650093A|FR3046418B1|2016-01-06|2016-01-06|LIQUID COMPOSITION, ESPECIALLY INKED, FOR CONTINUOUS JET BINARY JET PRINTING WITH UNLOADED DROPS, USE OF SAID COMPOSITION, MARKING METHOD, AND SUBSTRATE MARKED.|

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FR1650093|2016-01-06|FR1650093A| FR3046418B1|2016-01-06|2016-01-06|LIQUID COMPOSITION, ESPECIALLY INKED, FOR CONTINUOUS JET BINARY JET PRINTING WITH UNLOADED DROPS, USE OF SAID COMPOSITION, MARKING METHOD, AND SUBSTRATE MARKED.|

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EP17150379.0A| EP3190160B1|2016-01-06|2017-01-05|Liquid composition, especially ink composition, for printing with a binary deflected continuous jet, with non-charged drops, use of said composition, marking method and marked substrate|

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US15/399,939| US10597546B2|2016-01-06|2017-01-06|Liquid composition, especially ink composition, for printing with a binary deflected continuous jet, with non-charged drops, use of said composition, marking method and marked substrate|

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CN201710011433.0A| CN106947323A|2016-01-06|2017-01-06|The substrate of fluid composition and its application, labeling method and mark|