Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/30—Ink jet printing

Definitions

• the present invention relates to an improved ink composition for direct sublimation printing, hereinafter also referred to as ink.
• the invention also relates to a method for producing the ink according to the invention, as well as a method for printing with the ink according to the invention, or the use of the ink according to the invention for direct sublimation printing.
• Sublimation printing which is also known as transfer printing, is a process known to the person skilled in the art from the 1960s in which the dye is evaporated (sublimed) into the carrier material, although - strictly speaking - no real sublimation takes place, but one upstream liquefaction of the dye ( dye ) takes place.
• the process is therefore sometimes referred to as dye diffusion .
• a transfer material is used, which can be, for example, a transfer paper or a transfer film.
• the motif to be printed is printed in reverse on this transfer material using special inks, and then in a second step by means of a thermal transfer press using the transfer printing process and when heated to temperatures in the range of usually 200 ° C to 220 ° C to the actual one Carrier material to be transferred.
• sublimation direct printing also has some disadvantages. So - especially when using textiles as a carrier material - a bleeding of the ink directly after printing is often observed, which leads to a blurred print image. Furthermore, a washing step of the printed carrier material is generally required in order to remove certain residues of the printed ink which remain after sublimation. These residues are usually polymers contained in the ink used in the printing process. If the washing step is omitted, an undesirable haze, e.g. a gray veil on the printed carrier material.
• the object of the present invention is therefore to provide an improved ink composition for direct sublimation printing.
• This object is achieved by the ink compositions according to the invention, which, inter alia, enable an improved print image, in particular on textiles.
• the improved printed image manifests itself in particular through a sharp printed image, ie a reduction in the run of the printed inks on the carrier material.
• textiles printed with the ink according to the invention have no — or at least a reduced — fog, even if the washing-out step after the heat treatment is omitted.
• the ink compositions of the present invention allow a high concentration of dye to be used without the dispersion becoming unstable. This advantageously makes a full one Coloring achieved.
• the ink compositions according to the invention not only enable an improved, since sharper and stronger, printed image, but also enable process improvements in direct sublimation printing, which are reflected, inter alia, in a significantly reduced expenditure of time.
• the ink composition according to the invention is further characterized in that it has a viscosity in the range of 6 6 and 9 9 mPa * s and a surface tension in the range of 25 25 and 50 50 mN / m. Adherence to these parameters surprisingly resulted in a sharp printed image on the printed carrier material. In particular, it was observed that the ink composition according to the invention printed on the carrier material was significantly less than conventional inks.
• the dye of the disperse dye can also be referred to as " dye ".
• the ink composition according to the invention contains water and can preferably also be referred to as a water-based ink composition.
• sublimation direct printing means that direct printing of a carrier material with understood the ink composition of the invention. This printing step is followed by a heat treatment of the printed carrier material, in which the dye contained in the ink composition essentially irreversibly binds to the carrier material.
• the sublimation direct printing is further preferably a direct sublimation printing on a textile.
• the carrier material is preferably a textile.
• the textile still more preferably has synthetic material, cotton material, wool material or mixtures thereof. Textiles with synthetic material and mixtures of cotton and / or wool textiles with synthetic textiles are particularly preferred. Most preferably, the textile is made of synthetic material.
• the synthetic material can be any material suitable for direct sublimation printing.
• the synthetic material is preferably selected from polyester, polyamide or mixtures thereof.
• the textile preferably has a synthetic material selected from the group consisting of polyester, polyamide or mixtures thereof. Polyester is particularly preferred as a synthetic material because the best printing results could be achieved with the ink according to the invention.
• the synthetic material is more preferably contained in mixtures of the synthetic material with cotton material and / or wool material with at least 50%.
• the synthetic material is very particularly preferably polyester.
• the synthetic material, the cotton material and / or the wool material of the textile is more preferably present as a fiber.
• An ink-jet printing method is preferably used for performing the sublimation direct printing.
• Inkjet printing is a method which is well known to the person skilled in the art for printing, for example, paper material.
• So-called drop-on-demand (DOD) printers are preferably used, which generate the print image by deliberately firing ink droplets from the print head. Examples of such DOD printers are the bubble jet printers, the piezo printers or the pressure valve printers.
• the ink composition according to the invention is particularly preferably suitable for use with an ink jet print head which is operated at a temperature of 30 30 ° C and 35 35 ° C, more preferably 31 31 ° C and 33 33 ° C and most preferably approximately 32 ° C , More preferably, the ink jet printhead is a printhead for printing a water based ink composition.
• the ink jet printhead prints at a frequency of up to 60 kHz, preferably up to 40 kHz, more preferably at about 30 kHz or about 40 kHz. As is known to the person skilled in the art, this means that each nozzle of the print head (for example at 40 kHz) prints up to 40,000 dots per second. More preferably, the ink jet print head prints at a resolution of up to 1200 dpi, more preferably in a range ⁇ 300 dpi and ⁇ 1200 dpi, most preferably at approximately 600 dpi.
• a particularly preferred inkjet printhead is the KJ4B from the manufacturer Kyocera.
• This print head has a frequency of up to 30 kHz and a resolution of 600 dpi.
• Printing is preferably carried out in a frequency range from 250 Hz to 30 kHz.
• the ink compositions of the invention surprisingly showed when used with this printhead very excellent printing results, especially with regard to the sharpness of the printed image.
• the surface tension of the ink composition according to the invention is in a range from 25 25 and 50 50 mN / m.
• the surface tension is preferably the static and / or the dynamic surface tension, the static surface tension being preferred.
• the static surface tension of the ink composition can be measured, for example, using the Wilhelmy plate method, the Du-Noüy ring method, a tensiometer or the hanging drop method.
• the dynamic surface tension can be determined using the bubble pressure method, for example.
• the surface tension can also be determined according to DIN EN 14370: 2004-11.
• the printed carrier material is uniformly wetted, without being restricted to a specific theory, which advantageously leads to the improved printed image.
• the viscosity of the ink composition according to the invention is in a range from 6 6 and 9 9 mPa * s, preferably in a range from 6,5 6.5 and 8 8.1 mPa * s.
• the viscosity is preferably the dynamic viscosity.
• the dynamic viscosity ( ⁇ ) can also be referred to as shear viscosity and can be determined using a viscometer or a rheometer.
• the viscosity can be determined according to ISO 2555: 1989.
• concentrations (in%) given in the description of the invention correspond to weight percent (% by weight) of the ink composition, unless stated otherwise.
• water content of the inks according to the invention is not always stated explicitly. This preferably corresponds to the 100% missing portion, whereby it must be taken into account that the weighed-in ingredients of the ink composition (for example commercially available disperse dyes) may already contain water, i.e. through which water is also introduced into the ink compositions according to the invention.
• the ink composition according to the invention has at least one disperse dye, which in turn has at least one dye and at least one polymer.
• the disperse dye is more preferably a sparingly soluble (1 to 10 g / l solvent), a very sparingly soluble (0.1 to 1 g / l solvent) or a temperature range from 15 ° C. to 25 ° C. practically (almost) insoluble ( ⁇ 0.1 g / l solvent) disperse dye, an at least very poorly soluble disperse dye being preferred.
• the dye of the disperse dye should be understood to mean any colorant which is suitable for direct sublimation printing. Such colorants are known to the person skilled in the art common.
• the disperse dye is preferably present in particle form in the ink composition.
• the dye is preferably an organic dye and / or a synthetically produced or non-synthetically produced organic dye.
• the organic dye is further preferably selected from the group consisting of anthracene, quinoline, quinacridone pigment, azo pigment, anthraquinone pigment and phythalocyanine pigment.
• the synthetic organic pigment is particularly preferably an azo pigment or an anthraquinone pigment, more preferably a monoazo or diazo dye.
• the disperse dye in the ink composition preferably has a particle size (D90) of 1 1 ⁇ m, more preferably 750 750 nm or 550 550 nm, more preferably 600 600 nm and most preferably ⁇ 200 nm.
• the particle size of the disperse dye in the ink composition is more preferably in a range from 50 50 nm and 300 300 nm, more preferably 80 80 nm and 200 200 nm or 120 120 nm and 180 180 nm.
• Such particle sizes advantageously lead to a particularly homogeneous ink composition of which the disperse dyes are stably dispersed. A sharp print image is also achieved and blockage of the print head is prevented.
• the particle size can be determined, for example, by means of laser diffraction, in particular dynamic laser diffractometry.
• the specified diameter indicates the percentage of particles (90%) that are smaller than the specified value (eg D90 - 90% of the particles are smaller than 1 ⁇ m).
• the disperse dye further preferably has a median peak in the range of 50 50 nm and 200 200 nm, more preferably 80 80 nm and 180 180 nm and most preferably approximately 150 nm.
• the ink composition according to the invention preferably contains the dye in a concentration of 1,5 1.5% by weight and 9 9.0% by weight, more preferably 6 6.0% by weight and ⁇ 8.0% by weight and most preferably about 7.5% by weight.
• the stated% by weight here relate to the solids content of the dye in the ink composition according to the invention.
• the ink composition is an ink composition for the color black.
• the solids content of the dye in the ink composition is in a concentration range of von 5.0 and und 9.0% by weight, more preferably 6 6.0 and ⁇ 8 8.0% by weight and most preferably 7.5% by weight. -%.
• the dye for the color black is particularly preferably a mixture of dyes.
• the ink composition is an ink composition for the color magenta.
• the solids content of the pigment in the ink composition lies in a concentration range of ⁇ 5.0 and ⁇ 9.0% by weight, more preferably ⁇ 6.0 and ⁇ 8.0% by weight and most preferably 7.5% by weight. %.
• a particularly preferred dye for the magenta color is Disperse Red 60 (CAS 17418-58-5).
• the ink composition is an ink composition for the color cyan.
• the solids content of the pigment in the ink composition lies in a concentration range of ⁇ 4.5 and ⁇ 8.5% by weight, more preferably ⁇ 6.0 and ⁇ 8.0% by weight and most preferably 7.0% by weight. %.
• a particularly preferred dye for the cyan color is Disperse Blue 359 (CAS 62570-50-7).
• the ink composition is an ink composition for the color yellow.
• the solids content of the pigment in the ink composition lies in a concentration range of ⁇ 1.5 and ⁇ 5.0% by weight, more preferably ⁇ 2.5 and ⁇ 4.5% by weight and most preferably 4.0% by weight. %.
• a particularly preferred dye for the color yellow is Disperse Yellow 54 (CAS 12223-85-7).
• the present invention also encompasses ink cartridges containing the ink compositions according to the invention and sets / assemblies of the ink compositions or ink cartridges according to the invention which contain at least two, more preferably at least three, colored ink compositions.
• the colored ink composition is preferably selected from the group consisting of magenta, cyan and yellow. Even more preferably, such a set of ink compositions and / or ink cartridges comprises, in addition to the at least two colored ink compositions, at least one black ink composition and / or ink cartridge comprising a black ink composition.
• a very particularly preferred set comprises the three colored ink compositions magenta, cyan and yellow, the solids content of the dye of the magenta ink composition being in a concentration of 7.5% by weight, the solids content of the dye of the cyan ink composition being in a concentration of 7.0% by weight and wherein the solids content of the dye of the yellow ink composition is present in a concentration of 4.0% by weight.
• such a set can also have at least one black ink composition. In such a case - more preferably - the solid content of the dye of the black ink composition at 7.5% by weight.
• the polymer is preferably attached to the pigment and improves its dispersion.
• the polymer is more preferably a colorless polymer.
• Colorless should preferably be understood to mean “essentially transparent”.
• colorless is to be understood to mean that when irradiated with light in the UV region and / or in the region visible to humans (VIS), a coloring or a color cast is not visually perceptible to humans.
• VIS visible to humans
• a "colorless polymer” is to be understood as an essentially transparent polymer which is not perceptible to humans when irradiated with light in the UV and / or VIS range due to possible coloring.
• the other components of the ink composition according to the invention - with the exception of the dye of the disperse dye - are furthermore colorless. This applies in particular to the surfactant and / or the organic solvent.
• the polymer is preferably selected from the group consisting of one Polyacrylate and / or a polyurethane.
• the polymer is preferably a dispersant.
• Polyacrylates are polymers made from esters of acrylic acid (acrylic acid esters). They are plastics and they can be produced by radical chain polymerization in aqueous solutions, preferably emulsions (emulsion polymerization) or by bulk polymerization with an end product as a powder.
• the polyacrylate is preferably an aqueous emulsion polymer or an aqueous dispersion polymer. This advantageously ensures a particularly stable ink composition.
• the polyacrylate is preferably those compounds whose molecular weight is 10.000 10,000 g / mol and more preferably in the range from 10.000 10,000 to 1.000 1,000,000 g / mol, even more preferably 10.000 10,000 to 200 200,000 g / mol. Polyacrylates with a molecular weight of 10.000 10,000 and 45 45,000 g / mol, preferably 25 25,000 and 35 35,000 g / mol, are particularly preferred.
• the polyacrylate is more preferably a polyacrylate copolymer, more preferably a block copolymer.
• the further monomer units of the polyacrylate copolymer are further preferably selected from the group consisting of methacrylic acid, methyl methacrylate, butyl acrylate, acrylamide, styrene, acrylonitrile, vinyl acetate, vinyl alcohol and urethane.
• the glass transition temperature (Tg) of the polyacrylate is preferably in the range of--50 ° C and 150 150 ° C, more preferably in the range of--40 ° C and 120 120 ° C, even more preferably in the range of--35 ° C and. 110 ° C, most preferably in the range of ⁇ -35 ° C and ⁇ 105 ° C.
• the polymer (and more preferably the polyacrylate) is preferably present in the ink composition according to the invention in a concentration in the range from 1,5 1.5 and 20 20% by weight.
• the polymer is more preferably present in the ink composition according to the invention in a concentration in the range of ⁇ 1.5 and 15 15% by weight or in the range of 1,5 1.5 and 10 10% by weight.
• the polymer is very particularly preferred in a concentration in the range from 1,5 1.5 and 8 8% by weight, in the range from 1,5 1.5 and 6 6% by weight or in the range from 1,8 1.8 and 4 4% by weight .-% contained in the ink composition of the invention.
• the weight percentages given relate to the solids content of the polymer in the ink composition according to the invention.
• Polyurethanes are polymers familiar to the person skilled in the art and can be prepared from the polyaddition reaction of dialcohols (diols) or polyols with polyisocyanates.
• the ink composition according to the invention has at least one organic solvent.
• the organic solvent can be any suitable organic solvent.
• the organic solvent is preferably a colorless organic solvent. More preferably, the organic solvent has at least two alcoholic hydroxy groups (-OH), i.e. it is a two, three, four or more alcohol.
• the organic solvent is further preferably selected from the group consisting of a dihydric alcohol, a trihydric alcohol, an alditol (sugar alcohol), a lactam, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-methyl-2-piperidone, ⁇ -butyrolactone, a sulfone, N-ethyl acetamide, N-methyl propionamide, N-acetylethanolamine , N-methylacetamide, formamide, tetramethyl sulfone, butadiene sulfone, ethylene carbonate, tetrahydrofurfuryl alcohol and glycereth-26 (26 mol ethoxylate of glycerol).
• the most preferred organic solvent is glycerin because surprisingly the best printing results have been observed here. Glycerin can be used as the sole organic solvent or together with one or more other organic solvents.
• Glycols are particularly preferred dihydric alcohols.
• the dihydric alcohol is more preferably selected from the group consisting of 1,2-propanediol, 3,3-thiodipropanol, 3-amino-1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, pantothenol, 1,4-cyclohexanedimethanol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol.
• Polyethylene glycol is very particularly preferred.
• the polyethylene glycol more preferably has an average molecular weight in the range from 200 200 and 2000 2000.
• the polyethylene glycol has an average molecular weight of approximately 200, 300, 400, 600, 900, 1000, 1500 or 2000.
• the average molecular weight is in the range of ⁇ 200 and ⁇ 1000.
• the polyethylene glycol has an average molecular weight of approximately 200, 300, 400, 600, 900 or 1000.
• Preferred trihydric alcohols are glycerol, 1,2,6-hexanetriol, 1,2,4-butenetriol, trimethylolpropane. Glycerin and 1,2,6-hexanetriol are very particularly preferred.
• a particularly preferred alditol is sorbitol.
• the organic solvents according to the invention are very particularly preferably selected from the group consisting of an ethylene glycol, preferably a polyethylene glycol or a diethylene glycol, glycerol, a diol and mixtures thereof. All three have in common that they advantageously have good solubility in water, that they are hygroscopic and can therefore serve as humectants which prevent the print head from drying out, and that they are not dangerous to the environment, preferably non-toxic.
• the organic solvents according to the invention are even more preferably selected from the group consisting of polyethylene glycol, diethylene glycol and glycerol and mixtures thereof.
• the ink composition according to the invention further preferably contains the organic solvent in a concentration of 25 25 and 60 60% by weight, more preferably in a concentration range of 30 30 and 60 60% by weight.
• concentration ranges the viscosity required for the ink composition according to the invention could be adjusted / achieved particularly well.
• the required surface tension of the ink composition according to the invention can advantageously be regulated by means of the surfactant. Furthermore, the combination according to the invention of the surfactant contained in the ink composition with the organic solvent surprisingly led to a stabilization of the ink composition according to the invention.
• the surfactant is preferably a colorless surfactant.
• the polysiloxanes have proven to be particularly suitable and therefore preferred surfactants.
• the polysiloxane is particularly preferably a polyether-modified polysiloxane, more preferably a polyether-modified polydimethylsiloxane.
• the BYK-333 (Byk), BYK-348 and / or BYK-346 surfactants turned out to be very particularly preferred in this class, which surprisingly led to a very clean printed image and a significantly reduced bleeding of the ink composition according to the invention on the carrier material.
• the ink composition particularly preferably has a concentration of 0,0 0.01 and 0,4 0.4% by weight, more preferably 0,0 0.02 and 0,3 0.3% by weight of the surfactant.
• concentration of the surfactant in the ink composition according to the invention is most preferably in a concentration range of 0,0 0.05 and 0,2 0.2% by weight.
• the pH of the ink composition is preferably in a slightly basic range. As is known to the person skilled in the art, this means a pH of just above 7.
• the pH of the ink composition is particularly preferably in a range from 7,5 7.5 and 9 9, more preferably in a range from 8 8.1 and ⁇ 8.6.
• the present invention also includes an ink cartridge containing one of the ink compositions described above.
• the ink cartridge can preferably be an ink cartridge with or without a print head act a printhead, an ink cartridge without a printhead is particularly preferred.
• the ink compositions and / or ink cartridges of the present invention can also be assembled into sets.
• Such a set preferably contains at least two of the ink compositions and / or ink cartridges according to the invention. Even more preferably, these at least two ink compositions and / or at least two ink cartridges are ink compositions and / or ink cartridges for color printing.
• the ink compositions are colored ink compositions, i. H. not black ink compositions. More preferably, such a set can additionally have at least one black ink composition and / or ink cartridge comprising a black ink composition.
• a very particularly preferred set of ink compositions and / or ink cartridges according to the invention has at least ink compositions of the three colors magenta, cyan and yellow. More preferably, it additionally has at least one ink composition of the color black.
• Another aspect of the present invention relates to a method for producing the ink composition according to the invention.
• the method has the following steps: a) providing a mixture comprising an organic solvent according to the present invention and a surfactant according to the present invention and b) mixing the mixture of a) with a disperse dye comprising at least one dye and at least one polymer according to the present invention.
• step a) all of the constituents of the ink composition according to the invention, with the exception of the disperse dye, are preferably mixed. It was surprisingly found that such The ink compositions according to the invention could be produced particularly easily and in a time-saving manner and led to stable compositions.
• step b) the mixture from step a) is further preferably added slowly to the disperse dye.
• This can be understood in particular as a continuous addition.
• This addition is very particularly preferably carried out by pumping the mixture from step a) into the disperse dye.
• the mixture from step a) is mixed with the disperse dye using a dispersing unit.
• the dispersing unit is preferably operated at a speed in the range from 2500 to 20,000 revolutions per minute (rpm), more preferably from 2500 to 10,000 rpm. It surprisingly turned out that particularly stable ink compositions according to the invention could be produced here.
• the method for printing textiles with the ink composition according to the invention preferably has a method step in which the ink compositions are printed directly onto the textile.
• the process for printing textiles is a direct printing process.
• the printing of the textile with the ink composition according to the invention is further preferably carried out by means of an inkjet printer.
• the step of printing the ink according to the invention onto the textile is followed by a heat treatment step. During this heat treatment step, the dye of the ink composition according to the invention is evaporated into the carrier material and essentially irreversibly binds to it.
• the method for Printing on textiles preferably by a sublimation direct printing process.
• the heat treatment is carried out at a temperature in the range of 140 140 degrees Celsius and 240 240 ° C, more preferably in a range of ⁇ 200 degrees Celsius and 220 220 ° C.
• Another aspect of the present invention relates to the use of the ink composition according to the invention for the sublimation direct printing process.
• the dye and the polymer were introduced into the ink composition according to the invention via the dye sublimation dispersion (DSD).
• This dye sublimation dispersion contained 16% by weight solids content of the dye Disperse Blue 359, 8 % By weight of the polymer polyacrylate (Joncryl 4468) and the rest water. Accordingly, the ink composition of Formulation 1 contained 6.4% by weight of the dye and 3.2% by weight of the polymer.
• the ink composition of formulation 1 had a viscosity of 7.38 mPa * s at 60 rpm.
• the static or dynamic surface tension (5 Hz) was 32.47 and 34.50 mN / m.
• the dye and the polymer were introduced into the ink composition according to the invention via the same dye-sublimation dispersion of formulation 1. Accordingly, the ink composition of the formulation contained 2 4% by weight of the dye and 2% by weight of the polymer.
• the ink composition of formulation 2 had a viscosity of 7.52 mPa * s at 60 rpm.
• the static or dynamic surface tension (5 Hz) was 32.86 and 35.90 mN / m.
• the dye and the polymer were introduced into the ink composition according to the invention via the same dye-sublimation dispersion of formulation 1. Accordingly, the ink composition of Recipe 3 contained 5.6% by weight of the dye and 2.8% by weight of the polymer.
• the ink composition of formulation 3 had a viscosity of 6.10 mPa * s at 60 rpm.
• the static or dynamic surface tension (5 Hz) was 32.64 and 35.10 mN / m.
• the dye and the polymer were introduced into the ink composition according to the invention via the same dye-sublimation dispersion of formulation 1. Accordingly, the ink composition of Formulation 4 contained 4.96% by weight of the dye and 2.48% by weight of the polymer.
• the ink composition of formulation 4 had a viscosity of 7.14 mPa * s at 60 rpm.
• the static or dynamic surface tension (5 Hz) was 32.99 and 35.50 mN / m.
• the dye and the polymer were introduced into the ink composition according to the invention via the same dye sublimation dispersion (DSD) of formulation 1. Accordingly, the ink composition of the formulation 5 contained 6.4% by weight of the dye and 3.2% by weight of the polymer.
• DSD dye sublimation dispersion
• the ink composition of formulation 5 had a viscosity of 7.31 mPa * s at 60 rpm.
• the static or dynamic surface tension (5 Hz) was 33.81 and 36.60 mN / m.

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• 2018
  • 2018-07-19 EP EP18184564.5A patent/EP3597818A1/fr not_active Withdrawn

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