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

Abstract

A liquid composition, including a solvent, for printing with a binary deflected continuous jet printing technique, wherein upon printing the liquid composition form drops that are each: not charged by an electric field, have a zero electric charge, form a dipole under the effect of an electric field, and are then deflected by the electric field. The liquid composition has all the following characteristics: a conductivity at 20° C. from 5 to 500 μS/cm, still preferably a conductivity at 20° C. from 5 to 500 μS/cm, the value of 500 μS/cm being excluded, better a conductivity at 20° C. from 5 to 400 μS/cm, still better a conductivity at 20° C. from 30 to 400 μS/cm, for example from 30 to 200 μS/cm; a dynamic viscosity at 20° C. from 1 to 25 cPs, preferably from 6 to 25 cPs; and a density from 0.8 to 2.5 g/cm3, preferably from 1.2 to 2.5 g/cm3.

Claims

1. A liquid composition comprising a solvent, said liquid composition being an aqueous liquid composition specifically for printing with a binary deflected 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 has all the following characteristics a), b) and c): a) a conductivity at 20° C. from 5 to 500 μS/cm; b) a dynamic viscosity at 20° C. from 1 to 25 cPs; and c) a density from 0.8 to 2.5 g/cm.sup.3; wherein the solvent comprises water or a combination of water and one or more organic solvent compound(s); and wherein the solvent comprises a majority amount by weight of water based on the total weight of the solvent.

2. The liquid composition according to claim 1, wherein the organic solvent compound is selected from among alcohols; ketones; ethers of alkylene glycols; esters of alkylene glycols; esters of alkylene glycol ethers; dimethyl formamide; N-methyl pyrrolidone; acetals; esters; linear or cyclic ethers; aliphatic, cyclic or linear hydrocarbons; aromatic hydrocarbons; and carbonates; and mixtures thereof.

3. The liquid composition according to claim 1, wherein the solvent represents at least 20% by weight of the total weight of the liquid composition.

4. The liquid composition according to claim 1, which comprises less than 10% by weight of the organic solvent compound based on the total weight of the composition of the liquid.

5. The liquid composition according to claim 1, wherein the solvent consists of one or more organic solvent compound(s) and water.

6. The liquid composition according to claim 5, wherein said organic solvent compound comprises a volatile organic solvent compound and a non-volatile organic solvent compound.

7. The liquid composition according to claim 5, wherein the solvent comprises one or several solvent compound(s) selected from ketones with 3 to 10 carbon atoms.

8. The liquid composition according to claim 7, wherein, the solvent comprises a majority amount by weight based on the total weight of the ketones with 3 to 10 carbon atoms, of MEK.

9. The liquid composition according to claim 7, wherein the solvent further comprises another solvent compound, other than the ketone, preferably selected from esters, ethers of ethyleneglycol or of propyleneglycol, and acetals.

10. The liquid composition according to claim 1, which further comprises one or several dyes and/or pigments.

11. The liquid composition according to claim 10, wherein said dye(s) and/or pigment(s) is (are) selected from dyes and pigments known under the name of “C.I. Solvent Dyes” and “C.I. Pigments”, and from among the solid particles not referenced in the “Color Index” (C.I.).

12. The liquid composition according to claim 11, wherein said <<Solvent Dye(s)>> is(are) selected from among the C.I. Solvent Black 3, 7, 27, 28, 29, 35, 48, 49, the C.I. Solvent Blue 38, 44, 45, 70, 79, 98, 100, 129, the C.I. Solvent Red 8, 49, 68, 89, 124, 160, 164, the C.I. Solvent Yellow 83:1, 126, 146, 162, the C.I. Solvent Green 5, the C.I. Solvent Orange 97, the C.I. Solvent Brown 20, 52, and the C.I. Solvent Violet 9.

13. The liquid composition according to claim 11, wherein said <<C.I. Pigment(s)>> is(are) selected from among 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, of Pigment Yellow 17, 83, 93, 139, 151, 155, 180, 191, of Pigment Brown 23, 25, 41, or of Pigment White 6.

14. The liquid composition according to claim 10, comprising all in all from 0.05 to 25% by weight of dye(s) and/or pigment(s) based on the total weight of the liquid composition.

15. The liquid composition according to claim 1, which further comprises a binder consisting of one or several binding polymer(s).

16. The liquid composition according to claim 15, wherein the binding polymer(s) is(are) selected from among (meth)acrylic, vinylic, ketonic, hydroxyaromatic, cellulosic, styrenic, epoxy polymers, polyurethanes, styrene-acrylates, alkoxysilanes, and combinations of two or more thereof.

17. The liquid composition according to claim 15, wherein the binder represents from 1% to 45% by weight of the total weight of the liquid composition.

18. The liquid composition according to claim 1, further comprising, one or several plasticizers in an amount of at least 0.05% by weight of the total weight of the liquid composition.

19. The liquid composition according to claim 1, further comprising at least one conductivity salt in an amount from 0.01 to 10% by weight of the total weight of the liquid composition.

20. The liquid composition according to claim 19, wherein said conductivity salt is selected from salts of alkaline metals such as lithium, sodium, potassium, salts of earth-alkaline metals 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 and sulfonates.

21. The liquid composition according to claim 1, further comprising one or several additives selected from anti-foam agents; chemical stabilizers; UV stabilizers; surfactants; agents inhibiting corrosion by salts; bactericides, fungicides and biocides; and pH regulating buffers.

22. The liquid composition according to claim 1, which, when it comprises at least one polymer, is characterized in that said polymer has a weight average molecular mass of more than 70,000 Daltons.

23. The liquid composition according to claim 1, which, when it further comprises solid particles, is characterized in that the maximum size of the solid particles is from 2 to 10 μm.

24. The use of the liquid composition according to claim 1, in a printer or printing head applying a printing technique with a binary deflected continuous jet, 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.

25. A method for marking or treating substrates, supports or other objects by spraying a liquid composition with a printing technique with a binary deflected continuous jet, 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 is the liquid composition according to claim 1.

26. A substrate, support or object characterized in that it is provided with a marking obtained by drying and/or absorption of the liquid composition according to claim 1.

27. The substrate, support or object according to claim 26, characterized in that the substrate is made of metal; made of glass; made of ceramic; made of a material containing cellulose; made of an organic polymer; made of poly (methyl methacrylate) PMMA (<<Plexiglas>>); made of a fabric; made of a textile; made of natural or synthetic rubber; or made of any other non-porous or porous substance; or made of a composite of several of the aforementioned materials.

28. The liquid composition of claim 1, the solvent comprising 100% water.

Description

DETAILED DISCUSSION OF PARTICULAR EMBODIMENTS

(1) The invention will be better understood upon reading the following description of embodiments of the invention, given as illustrative and non-limiting examples.

Examples 1 to 6

(2) In all these examples, ink compositions according to the invention are prepared.

(3) These ink compositions comprise the ingredients mentioned in Table I, in the proportions mentioned in Table I.

(4) These compositions are generally prepared by simply mixing the ingredients.

(5) In Table I, according to the ink compositions, and when these parameters apply, the average particle size <<Z.sub.ave>> (in μm), the conductivity (in μS/cm), the viscosity (in cPs=mPa.Math.s) are also indicated, and finally it is specified whether the inks were suitable or not for printing with the deflected continuous jet technique or with the so-called <<SPI>> technique.

(6) TABLE-US-00001 TABLE I INK COMPOSITIONS Constituents Exam- Exam- Exam- Exam- (percentages by mass) ple 1 ple 2 ple 3 ple 4 Methyl-Ethyl-Ketone 1.6 Ethanol 67.26 Dioxolanne 87.3 Ethyl Acetate 87.4 60% Ag—Cu dispersed in an or- 98 ganic solvent (Cima-Nanotech ® Israel) 75% TiO.sub.2 chips dispersed in 25.6 Neocryl ® B813 Microlith ® Blue A3R-K 5 Valifast ® Black 3808 5 Neocryl ® B817 7.04 Vinnol ® E15-45M 5.7 7.6 Triethyleneglycoldimethylether 1.5 Tetrabutylammonium 0.4 hexafluorophosphate Sodium Thiocyanate 0.1 Potassium 0.5 hexafluorophosphate Average particle size Z.sub.ave (μm) 0.3 μm <0.1 μm 0.1 μm N.A. Conductivity (μS/cm) 188 13 74.9 117 Viscosity at 20° C. (cPs = mPa .Math. s) 12.3 13.6 12.9 6.4 Density (g/cm.sup.3) 1.004 1.89 1.098 0.948 Printing by   CIJ  No No No No Printing by   SPI  Yes Yes Yes Yes 60% Ag—Cu from the Cima-Nanotech ® company, Israel, is a concentrated dispersion of silver and copper submicron particles in an organic solvent, its density, specific gravity, is very large as compared with what may be projected with a CIJ ink jet. Microlith ® Blue A3R-K is a blue pigment of the C.I. Pigment blue 60 type from BASF ®. Neocryl ® B813 and B817 are acrylic resins from DSM ®. Vinnol ® E15-45M is a vinylic resin from Wacker ®. Valifast ® Black 3808 is a C.I. Solvent black 29. The indication   No   indicates that the ink is not suitable for printing with the targeted technique such as   CIJ   . The   Yes   indication indicates that the ink is suitable for printing with the targeted technique such as   SPI   .

(7) The ink composition according to the invention, of Example 1, is a white ink composition with a very high white pigment concentration and a high viscosity.

(8) The ink composition according to the invention, of Example 2, is an ink composition with a high density, specific gravity, a very low conductivity and a high viscosity.

(9) The ink composition according to the invention, of Example 3, is an ink composition in a solvent not promoting conductivity and having a high viscosity.

(10) The ink composition according to the invention, of Example 4, is an ink composition with low viscosity.

(11) The compositions of Examples 1 to 4 used each in a printer 9040 or 9040 Contrast head G from Markem Imaje®, which is a printer which applies a standard <<CIJ>> technique, were not able to give satisfactory markings:

(12) For the composition of Example 1, the drops are poorly placed, in a very random way.

(13) For the composition of Example 2, the viscosity is too high, and the conductivity too low, so that both the pressure required for obtaining the nominal jet velocity, and the suitable charge of the drops, cannot be obtained.

(14) For the composition of Example 3, no printing was able to be obtained because of a too high density, specific gravity, and viscosity. The pressure required for obtaining the nominal jet velocity, was not able to be obtained.

(15) For the composition of Example 4, the conductivity is too low, so that the suitable charge of the drops cannot be obtained, a fault occurs, a so-called <<phase detection>> fault.

(16) On the other hand, the compositions of Examples 1 to 4 gave suitable printings in a prototype printer applying the so called “SPI” technique having a nozzle diameter of 40 μm.