WO2019220107A1 - Encre d'impression - Google Patents

Encre d'impression Download PDF

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Publication number
WO2019220107A1
WO2019220107A1 PCT/GB2019/051328 GB2019051328W WO2019220107A1 WO 2019220107 A1 WO2019220107 A1 WO 2019220107A1 GB 2019051328 W GB2019051328 W GB 2019051328W WO 2019220107 A1 WO2019220107 A1 WO 2019220107A1
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WO
WIPO (PCT)
Prior art keywords
ink
alkyl
curable
led
radiation
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PCT/GB2019/051328
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English (en)
Inventor
Scott BIGGS
Shota Suzuki
Sean Slater
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Fujifilm Speciality Ink Systems Limited
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Publication of WO2019220107A1 publication Critical patent/WO2019220107A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the present invention relates to a printing ink and in particular, an LED-curable inkjet ink which has a desirable balance of properties.
  • the present invention also relates to a method of printing said ink.
  • inkjet printing minute droplets of black, white or coloured ink are ejected in a controlled manner from one or more reservoirs or printing heads through narrow nozzles on to a substrate which is moving relative to the reservoirs.
  • the ejected ink forms an image on the substrate.
  • the inks must flow rapidly from the printing heads, and, to ensure that this happens, they must have, in use, a low viscosity, typically below 100 mPas at 25°C (although in most applications the viscosity should be below 50 mPas, and often below 25 mPas).
  • the ink when ejected through the nozzles, the ink has a viscosity of less than 25 mPas, preferably 5-15 mPas and ideally 7-12 mPas at the jetting temperature, which is often elevated to about 40-50°C (the ink might have a much higher viscosity at ambient temperature).
  • the inks must also be resistant to drying or crusting in the reservoirs or nozzles. For these reasons, inkjet inks for application at or near ambient temperatures are commonly formulated to contain a large proportion of a mobile liquid vehicle or solvent.
  • this liquid is water - see for example the paper by Henry R. Kang in the Journal of Imaging Science, 35(3), pp. 179-188 (1991). In those systems, great effort must be made to ensure the inks do not dry in the head due to water evaporation.
  • the liquid is a low-boiling solvent or mixture of solvents - see, for example, EP 0 314 403 and EP 0 424 714.
  • inkjet inks that include a large proportion of water or solvent cannot be handled after printing until the inks have dried, either by evaporation of the solvent or its absorption into the substrate. This drying process is often slow and in many cases (for example, when printing on to a heat-sensitive substrate such as paper) cannot be accelerated.
  • inkjet ink contains radiation-curable material, such as radiation-curable monomers, which polymerise by irradiation with actinic radiation, commonly with ultraviolet light, in the presence of a photoinitiator.
  • radiation-curable material such as radiation-curable monomers, which polymerise by irradiation with actinic radiation, commonly with ultraviolet light, in the presence of a photoinitiator.
  • This type of ink has the advantage that it is not necessary to evaporate the liquid phase to dry the print; instead the print is exposed to radiation to cure or harden it, a process which is more rapid than evaporation of solvent at moderate temperatures.
  • UV sources include mercury discharge lamps, fluorescent tubes, light emitting diodes (LEDs), flash lamps and combinations thereof.
  • LED UV light sources are an attractive alternative.
  • LEDs offer significant cost reduction, longer maintenance intervals, higher energy efficiency and are an environmentally friendlier solution.
  • LEDs When LEDs are used, it is necessary to use an array of multiple LEDs in order to generate enough power to provide thorough curing of the ink. In fact, even with an array of multiple LEDs, inks which are cured by LEDs are prone to poor surface cure owing to the presence of oxygen in the atmosphere adjacent to the ink surface, and the spectral output of LEDs. Compared to conventional mercury lamp UV sources, LEDs have a narrow spectral output. The UV output of LED lamps is essentially monochromatic and most commercial devices operate at 385, 395 or 405 nm. LEDs emit radiation in the UVA region having a long wavelength over a narrow range of wavelengths, which although suitable for depth cure, provides a particular challenge for effective surface cure in normal atmospheric conditions.
  • Poor surface cure can be reduced in a number of ways. First, it can be overcome by blanketing the irradiated area with an inert gas such as nitrogen during the cure process but this adds considerably to the complexity and cost of the printer. Secondly, it can be overcome by working the LEDs at high power, providing more energy to react with the photoinitiators and oxygen, or the total amount of photoinitiators may be increased, thus allowing more radicals to be generated. However, working the LEDs at high power generates heat, which must be removed and both approaches add to the cost and complexity of the process - regard must be had to limitations on the media range, power consumption, ink viscosity and ink stability.
  • an inert gas such as nitrogen
  • a blend of photoinitiators may be used, including photoinitiators that function throughout the ink resulting in through cure and those that work at the surface of the ink, to obtain adequate surface cure.
  • a type II photoinitiator such as ITX (and hydrogen donating species such as amines) in conjunction with type I photoinitiators such as phosphine oxides may be used.
  • LED-curable inkjet inks suffer from colour shift postcure.
  • LED-curable inkjet inks often require a photoinitiator blend comprising ITX, which is a photoinitiator that works at the surface of the ink film during curing, and results in adequate surface cure.
  • ITX is a photoinitiator that works at the surface of the ink film during curing, and results in adequate surface cure.
  • ITX is a photoinitiator that works at the surface of the ink film during curing, and results in adequate surface cure.
  • ITX is a photoinitiator that works at the surface of the ink film during curing, and results in adequate surface cure.
  • ITX is a photoinitiator that works at the surface of the ink film during curing
  • Colour shift is a known phenomenon in the art. It is when the colour of the ink changes over a period of time, typically measured over 24 hours. The amount of colour change is represented in the art by a so-called delta E (or AE)-value on the CIELAB (L*a*b*) colour space system. As a guide, a delta E- value of 1.0 is the minimum colour change detectable by the human eye.
  • a delta E-value influenced by the shift on the b* axis (Ab*) in the yellow quadrant represents a change in the yellowness of the ink.
  • yellow shift occurs when the colour of the ink shifts towards positive or negative values on the b* axis in the yellow quadrant, and therefore becomes increasingly or decreasingly yellow respectively.
  • a shift towards more positive values on the b* axis in the yellow quadrant is associated with an increase in the yellowness of the ink whereas a shift towards more negative values in the yellow quadrant is associated with a decrease in the yellowness of the ink.
  • colour shift post-cure it is meant that colour shift of the ink is only assessed post-cure, i.e. the L*a*b* values are only recorded post-cure, using a spectrophotometer.
  • the L*a*b* values of the ink are also changing during and after printing.
  • the ink can be thought of as having initial L*a*b* values just before printing, which then change during and after printing, and during and after curing.
  • the first L*a*b* values (L T *, a and b ⁇ ) are recorded typically within one minute of curing.
  • the second L*a*b* values (l_ 2* , a 2* and b 2* ) are then recorded typically 24 hours later.
  • the formula for calculating delta E is as follows:
  • yellowing occurs immediately after curing and then fades away during the subsequent 24 hours - the colour of the cured ink images shifts towards negative values on the b* axis in the yellow quadrant.
  • the mechanism of yellow shift has not been confirmed, without wishing to be bound by theory, the inventors believe the photoinitiator breakdown products, which are generated during photocleaving, have a yellow chromophore, and then over a further period of time these unstable fragments further decompose to reduce the yellow coloration.
  • colour shift is also affected by storage temperature of the ink, concentrations of the photoinitiators and the choice of the binder or bulk material such as radiation-curable monomers.
  • concentrations of the photoinitiators and the choice of the binder or bulk material such as radiation-curable monomers.
  • an LED-curable inkjet ink comprising:
  • R>11 is hydrogen or C 1-3 alkyl
  • X 1 is oxygen or NR 15 , wherein R 15 is hydrogen or C 1-3 alkyl,
  • R 21 is hydrogen or C 1-3 alkyl
  • R 22 is hydrogen, hydroxy, C 1-12 alkyl, halogenated C M2 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl,
  • R 23 and R 24 are independently hydrogen, hydroxy, C M2 alkyl, halogenated C 1-12 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl, or R 23 and R 24 together represent oxo,
  • X 2 is oxygen or NR 25 , wherein R 25 is hydrogen or C 1-3 alkyl.
  • an LED-curable inkjet ink that comprises the specific polymeric thioxanthone-type photoinitiator and the amine-containing polymer as claimed has the desired balance of properties, namely a reduced colour shift post-cure, a high LED cure response and the necessary film-forming properties.
  • the use of the polymeric thioxanthone-type photoinitiator and the amine-containing polymer in an LED-curable inkjet ink reduces the level of colour shift in the cured ink image to an acceptable level over 24 hours and maintains LED cure response and film-forming properties. It is surprising that the LED-curable inkjet ink of the invention can achieve such advantages without recourse to ITX.
  • the polymeric thioxanthone-type photoinitiator allows the use of more thioxanthone photoinitiator in order to achieve the cure response and film-forming properties associated with a high amount of ITX but without the colour shift effects of ITX.
  • this specific photoinitiator in LED-curable inkjet inks reduces the colour shift in the cured ink image to an acceptable level (wherein DE is an absolute value from 0.0 to 5.0, preferably from 0.0 to 3.5 and more preferably from 0.0 to 2.0, over 24 hours) whilst maintaining LED cure response and film-forming properties.
  • An absolute value is the magnitude of a real number without regard to its sign.
  • the first L*a*b* values (L ! *, a ⁇ and b ⁇ ) are recorded within one minute of curing.
  • the second L*a*b* values (L 2 *, a 2 * and b 2 *) are then recorded 24 hours later.
  • Delta E is calculated using the formula hereinabove.
  • Delta E values vary with actinic radiation dose, so the delta E values quoted herein are determined at a total dose per unit area defined as the minimum dose per unit area required to achieve a fully cured film, i.e. a tack-free film.
  • a delta E of 5.0 is the largest acceptable delta E absolute value for any application of the present invention
  • a delta E of 3.5 is the largest acceptable delta E absolute value for moderately sensitive applications of the present invention
  • a delta E of 2.0 is the largest acceptable delta E absolute value for important sensitive graphic applications of the present invention. Therefore, the absolute value of delta E acceptable will depend on the ultimate application of the cured ink image of the present invention. This is in marked contrast to other known LED-curable inkjet inks which have a much higher colour shift, and in particular, much more than the acceptable delta E absolute value of the present invention over 24 hours when achieving acceptable surface cure.
  • colour shift is known in the art. It is when the colour of the ink changes over a period of time, typically measured over 24 hours.
  • the red/green opponent colours are represented along the a* axis, with green at negative a* values and red at positive a* values.
  • the yellow/blue opponent colours are represented along the b* axis, with blue at negative b* values and yellow at positive b* values.
  • the total shift along the b* axis is denoted as Ab* and is represented by delta E.
  • yellow shift occurs when the colour of the ink shifts towards positive or negative values on the b* axis in the yellow quadrant, and therefore becomes increasingly or decreasingly yellow respectively.
  • a colour shift occurs when the colour of the ink shifts over 24 hours.
  • the acceptable level of colour shift depends on the colour but a delta E on the CIELAB (L*a*b*) colour space system of at least 1 .0 is required to be visible to the human eye and a colour shift is generally acceptable wherein delta E is an absolute value from 0.0 to 5.0, preferably from 0.0 to 3.5 and more preferably from 0.0 to 2.0, over 24 hours, depending on the application of the present invention.
  • delta E is an absolute value from 0.0 to 5.0, preferably from 0.0 to 3.5 and more preferably from 0.0 to 2.0, over 24 hours, depending on the application of the present invention.
  • a yellow shift occurs when the yellow colour of the ink shifts over 24 hours towards positive or negative values on the b* axis in the yellow quadrant, and therefore becomes increasingly or decreasingly yellow respectively.
  • the inclusion of the amine-containing polymer surprisingly increases the cure speed of the ink of the present invention compared to an ink containing the amine-containing polymer alone or an ink containing the polymeric thioxanthone-type photoinitiator alone. Therefore, the amine-containing polymer and the polymeric thioxanthone-type photoinitiator of the present invention together ensure that the ink of the present invention has a high LED cure response. Without wishing to be bound by theory, it is believed that the polymeric thioxanthone-type photoinitiator and the amine-containing polymer undergo a Type II reaction. Both structural units of Formulas (1) and (2) contain a hindered hydrogen on the carbon alpha to nitrogen.
  • the polymeric thioxanthone-type photoinitiator is tetrafunctional in that it contains four thioxanthone structural units and it is believed that the tetrafunctional structure acts as a crosslinker between the radiation-curable material, further increasing cure speed.
  • the amine-containing polymer of the ink of the present invention also provides the ink with the necessary film-forming properties such as excellent hardness, adhesiveness and blocking resistance.
  • the present invention also provides a method of inkjet printing comprising inkjet printing the inkjet ink of the present invention onto a substrate and curing the ink by exposing the printed ink to a UV radiation source.
  • the LED-curable inkjet ink of the present invention comprises:
  • R is hydrogen or C ⁇ alkyl
  • R 12 , R 13 and R 14 are independently hydrogen, hydroxy, C 1-12 alkyl, halogenated C 1-12 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl,
  • R 21 is hydrogen or C 1-3 alkyl
  • R 22 is hydrogen, hydroxy, C 1-12 alkyl, halogenated C M2 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl,
  • R 23 and R 24 are independently hydrogen, hydroxy, C M2 alkyl, halogenated C 1-12 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl, or R 23 and R 24 together represent oxo,
  • X 2 is oxygen or NR 25 , wherein R 25 is hydrogen or C 1-3 alkyl.
  • the LED-curable inkjet ink comprises:
  • This photoinitiator which is utilised in the LED-curable inkjet ink of the present invention is available commercially as Speedcure 7010® sold by Lambson®.
  • the ink of the present invention comprises 0.5 to 15% by weight, preferably 1 to 10% by weight, more preferably 2 to 5% by weight of 1 ,3-di( ⁇ a-[1-chloro-9-oxo-9H- thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)] ⁇ oxy)-2,2-bis( ⁇ a-[1-chloro-9-oxo-9H- thioxanthen-4-yl)oxy]acetylpoly[oxy(1 -methylethylene)] ⁇ oxymethyl) propane, based on the total weight of the ink.
  • the LED-curable inkjet ink also comprises a polymer comprising a structural unit of Formula (1) and/or (2)
  • R 11 is hydrogen or C ⁇ alkyl
  • R 12 , R 13 and R 14 are independently hydrogen, hydroxy, C 1-12 alkyl, halogenated C 1-12 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl,
  • X 1 is oxygen or NR 15 , wherein R 15 is hydrogen or C 1-3 alkyl,
  • R 21 is hydrogen or C 1-3 alkyl
  • R 22 is hydrogen, hydroxy, C 1-12 alkyl, halogenated C M2 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl,
  • R 23 and R 24 are independently hydrogen, hydroxy, C M2 alkyl, halogenated C 1-12 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl, or R 23 and R 24 together represent oxo,
  • X 2 is oxygen or NR 25 , wherein R 25 is hydrogen or C 1-3 alkyl.
  • the structural unit of Formula (1) and/or (2) of the polymer of the ink of the present invention contains a number, b, of repeating units. These repeating units correspond to vinyl monomers, which have been polymerised to form the polymer of the ink of the present invention.
  • b is 20-80.
  • b is 30-70 and more preferably b is 40-60.
  • a high b value is advantageous in terms of performance.
  • amine units act as inhibitors in polymer synthesis and it can be difficult to synthesise a polymer with a high molecular weight.
  • R 11 is hydrogen or C 1-3 alkyl.
  • R 11 is preferably hydrogen, methyl or ethyl and more preferably hydrogen or methyl.
  • R 12 , R 13 and R 14 are independently hydrogen, hydroxy, C 1-12 alkyl, halogenated C 1-12 alkyl, C 2 -i 2 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl.
  • C 1-12 alkyl chloride is the preferred halogenated C 1-12 alkyl.
  • Phenyl, naphthyl and biphenyl are the preferred C 6-12 aryl.
  • Benzyl is the preferred C 7-12 aralkyl.
  • Phenoxyethyl is the preferred C 7-12 aryloxyalkyl.
  • R 12 is preferably hydrogen, C 1-12 alkyl or C 6-12 aryl, more preferably hydrogen, methyl or ethyl and most preferably, hydrogen or methyl.
  • R 13 and R 14 are independently preferably hydrogen, hydroxy, C 1-12 alkyl or C 6-12 aryl, more preferably hydrogen, hydroxy, C 1-8 alkyl or phenyl.
  • n in *(L a O) n is 1 to 3, more preferably 1 to 2 and most preferably 1.
  • X 1 is oxygen or NR 15 , wherein R 15 is hydrogen or C 1-3 alkyl.
  • R 15 is preferably hydrogen, methyl or ethyl and more preferably hydrogen or methyl.
  • R 21 is hydrogen or C 1-3 alkyl.
  • R 21 is preferably hydrogen, methyl or ethyl and more preferably hydrogen or methyl.
  • R 22 is hydrogen, hydroxy, C 1-12 alkyl, halogenated C 1-12 alkyl, C 2 -i 2 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl.
  • C 1-12 alkyl chloride is the preferred halogenated C 1-12 alkyl.
  • Phenyl, naphthyl and biphenyl are the preferred C 6-12 aryl.
  • Benzyl is the preferred C 7-12 aralkyl.
  • Phenoxyethyl is the preferred C 7-12 aryloxyalkyl.
  • R 22 is preferably hydrogen, C 1-12 alkyl or C 6-12 aryl, more preferably hydrogen, methyl or ethyl and most preferably, hydrogen or methyl.
  • R 23 and R 24 are independently hydrogen, hydroxy, C M2 alkyl, halogenated C 1-12 alkyl, C 2-12 alkenyl, C 3-12 acyloxyalkyl, C 6-12 aryl, C 7-12 aralkyl or C 7-12 aryloxyalkyl, or R 23 and R 24 together represent oxo.
  • C 1-12 alkyl chloride is the preferred halogenated C 1-12 alkyl.
  • Phenyl, naphthyl and biphenyl are the preferred C 6-12 aryl.
  • Benzyl is the preferred C 7-12 aralkyl.
  • Phenoxyethyl is the preferred C 7-12 aryloxyalkyl.
  • n in *(L e O) n is 1 to 3, more preferably 1 to 2 and most preferably 1 .
  • X 2 is oxygen or NR 25 , wherein R 25 is hydrogen or C 1-3 alkyl.
  • R 25 is preferably hydrogen, methyl or ethyl and more preferably hydrogen or methyl.
  • Preferred structural units of Formula (2) are shown below.
  • the polymer comprises a structural unit of Formula (1).
  • a structural unit of Formula (1) is particularly advantageous in terms of the hardness and blocking resistance of the printed ink film.
  • the polymer comprises a structural unit of Formula (2).
  • the polymer comprises structural units of Formulas (1) and (2).
  • the polymer comprises a structural unit of Formula (1 -1), (1 -2), (1 -4) and/or (1 -8). This is particularly advantageous in terms of blocking resistance.
  • the polymer comprises a structural unit of Formula (1 -1), wherein b is 30-70 and more preferably 40-60.
  • the polymer of the ink of the present invention consists of a structural unit of Formula (1) and/or (2).
  • the polymer of the ink of the present invention contains additional structural units, for example structural units derived from a vinyl monomer.
  • the total amount of the structural unit of Formula (1 ) and/or (2) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight and most preferably 50 to 60% by weight, based on the total weight of the polymer.
  • the polymer of the inkjet ink of the present invention further comprises a structural unit of Formula (3), (4) and/or (5)
  • R 31 is hydrogen or C ⁇ alkyl
  • Cy 1 is phenyl, phenyl substituted with C W2 alkyl, naphthyl, biphenyl, cyclohexyl, cyclohexyl substituted with C 1-4 alkyl, norbornyl, norbornyl substituted with C 1-4 alkyl, dicyclopentanyl, dicyclopentenyl, adamantyl, furfuryl, tetrahydrofurfuryl, C 3 or C 4 cyclic acetal, C 3 or C 4 cyclic acetal substituted with C 1-4 alkyl, C 2.5 cyclic ether, C 2.5 cyclic ether substituted with C 1-4 alkyl, or C 3-6 lactone,
  • R 41 is hydrogen or C 1-3 alkyl
  • R 51 is hydrogen or C 1-3 alkyl
  • R 52 and R 53 are independently hydrogen, C 1-6 alkyl, or R 52 and R 53 together with nitrogen to which they are bonded form a ring with 5 to 7 members.
  • the structural unit of Formula (3), (4) and/or (5) contains a number of repeating units.
  • this number, c, is 1 -60.
  • c is 10-50 and more preferably c is 20-40.
  • this number, d is 1 -40.
  • d is 5-35 and more preferably d is 10-30.
  • this number, e is 1 -40.
  • e is 5-35 and more preferably e is 10-30.
  • the structural unit of Formula (3), (4) and/or (5) contributes to providing the ink with the necessary hardness and adhesiveness.
  • R 31 is hydrogen or C 1-3 alkyl.
  • R 31 is preferably hydrogen, methyl or ethyl and more preferably hydrogen or methyl.
  • n in *(LO) n is 1 to 3, more preferably 1 to 2 and most preferably 1 .
  • Cy 1 is phenyl, phenyl substituted with C 1-12 alkyl, naphthyl, biphenyl, cyclohexyl, cyclohexyl substituted with C 1-4 alkyl, norbornyl, norbornyl substituted with C 1-4 alkyl, dicyclopentanyl, dicyclopentenyl, adamantyl, furfuryl, tetrahydrofurfuryl, C 3 or C 4 cyclic acetal, C 3 or C 4 cyclic acetal substituted with C 1-4 alkyl, C 2.5 cyclic ether, C 2.5 cyclic ether substituted with C 1-4 alkyl, or C 3-6 lactone.
  • a polycyclic Cy 1 and particularly a polycyclic alicyclic Cy 1 is particularly advantageous in terms of blocking resistance and adhesiveness.
  • R 41 is hydrogen or C 1-3 alkyl.
  • R 41 is preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl and most preferably hydrogen.
  • R 41 is hydrogen, blocking resistance and adhesiveness are further improved.
  • Preferred rings with 5 to 7 members optionally including oxygen are pyrrolidine, piperidine, azepane and morpholine.
  • R 42 and R 43 are independently hydrogen, C 1-6 alkyl, or R 42 and R 43 together with nitrogen to which they are bonded form a ring with 5 to 7 members optionally including oxygen. More preferably, R 42 and R 43 are independently hydrogen, C 1-3 alkyl, or R 42 and R 43 together with nitrogen to which they are bonded form a ring with 5 to 7 members optionally including oxygen. Most preferably, R 42 and R 43 are independently C 1-3 alkyl, or R 42 and R 43 together with nitrogen to which they are bonded form a ring with 5 to 7 members optionally including oxygen; this is particularly advantageous in terms of hardness.
  • R 51 is hydrogen or C 1-3 alkyl.
  • R 51 is preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl and most preferably hydrogen.
  • R 52 and R 53 are independently hydrogen, C 1-6 alkyl, or R 52 and R 53 together with nitrogen to which they are bonded form a ring with 5 to 7 members.
  • Preferred rings with 5 to 7 members are y- butyrolactam and e-caprolactam.
  • R 52 and R 53 are independently hydrogen, C 1-3 alkyl, or R 52 and R 53 together with nitrogen to which they are bonded form a ring with 5 to 7 members. More preferably, R 52 and R 53 are independently C 1-6 alkyl, or R 52 and R 53 together with nitrogen to which they are bonded form a ring with 5 to 7 members; this is particularly advantageous in terms of hardness.
  • Preferred structural units of Formula (5) are shown below.
  • the polymer comprises a structural unit of Formula (3). In another embodiment, the polymer comprises a structural unit of Formula (4). In a further embodiment, the polymer comprises a structural unit of Formula (5).
  • the polymer may comprise structural units of Formulas (3) and (4). Alternatively, the polymer may comprise structural units of Formulas (4) and (5). In a preferred embodiment, the polymer comprises structural units of Formulas (3) and (5).
  • the polymer may also comprise structural units of Formulas (3), (4) and (5). Preferred structural units of Formula (3), (4) and/or (5) for reasons of blocking resistance and adhesiveness are shown below.
  • the polymer of the ink of the present invention comprises a structural unit of Formula (5-2):
  • the polymer of the ink of the present invention comprises a structural unit of Formula (5-2), wherein e is 5-35 and most preferably wherein e is 10-30.
  • the polymer of the ink of the present invention comprises a structural unit of Formula (3-5):
  • the polymer of the ink of the present invention comprises a structural unit of Formula (3-5), wherein c is 10-50 and most preferably wherein c is 20-40.
  • the polymer of the ink of the present invention comprises structural units of Formulas (5-2) and (3-5). More preferably, the polymer of the ink of the present invention comprises structural units of Formulas (5-2) and (3-5), wherein e is 5-35 and c is 10-50 and most preferably wherein e is 10-30 and c is 20-40.
  • the polymer of the ink of the present invention comprises structural units of Formulas (1- 1), (5-2) and (3-5). More preferably, the polymer of the ink of the present invention comprises structural units of Formulas (1-1), (5-2) and (3-5), wherein b is 30-70, e is 5-35 and c is 10-50 and most preferably wherein b is 40-60, e is 10-30 and c is 20-40.
  • the polymer of the ink of the present invention may contain additional structural units, for example structural units derived from a vinyl monomer.
  • the total amount of structural units of Formula (1), (2), (3), (4) and/or (5) is preferably 80% by weight or more, more preferably 90% by weight or more, even more preferably 95% by weight and most preferably 100% by weight, based on the total weight of the polymer.
  • the structural unit of Formula (1) and/or (2) may be present in any amount relative to the structural unit of Formula (3), (4) and/or (5).
  • the structural unit of Formula (1) and/or (2) is preferably present in 10 to 90% by weight, more preferably 20 to 80% by weight, and most preferably 30 to 70% by weight, based on the total weight of the structural unit of Formula (1), (2), (3), (4) and/or (5).
  • the structural unit of Formula (1) and/or (2) is present in 10% by weight or more, based on the total weight of the structural unit of Formula (1), (2), (3), (4) and/or (5), the adhesiveness and blocking resistance of the printed ink film are further improved.
  • the structural unit of Formula (1) and/or (2) is present in 90% by weight or less, based on the total weight of the structural unit of Formula (1), (2), (3), (4) and/or (5), the adhesiveness of the printed ink film is further improved.
  • the structural unit of Formula (1) and/or (2) is present in 10 to 90% by weight, more preferably 20 to 80% by weight, and most preferably 30 to 70% by weight, based on the total weight of the polymer.
  • the structural unit of Formula (1) and/or (2) is present in 10% by weight or more, based on the total weight of the polymer, the adhesiveness and blocking resistance of the printed ink film are further improved.
  • the structural unit of Formula (1) and/or (2) is present in 90% by weight or less, based on the total weight of the polymer, the adhesiveness of the printed ink film is further improved.
  • the weight average molecular weight (Mw) of the polymer of the ink of the present invention is not particularly limited and it may be in the range of 1 ,000 to 100,000 for example. However, in order to further improve hardness, the Mw is preferably 1 ,000 or more, more preferably 2,000 or more and most preferably 3,000 or more. In order to improve storage stability and ejection stability, the Mw is preferably 50,000 or less, more preferably 40,000 or less and most preferably 30,000 or less.
  • the weight average molecular weight (Mw) indicates a value measured by gel permeation chromatography (GPC).
  • the measurement with gel permeation chromatography is performed using HLC-8020 GPC (manufactured by TOSOH CORPORATION) as a measuring device; three of TSK gel Super Multipore HZ-H (4.6 mmID x 15 cm, manufactured by TOSOH CORPORATION) as a column; and tetrahydrofuran (THF) as an eluent.
  • the measurement is performed using an Rl detector under the conditions of a sample concentration of 0.45% by weight, a flow rate of 0.35 mL/min, a sample injection amount of 10 mI_, and a measurement temperature of 40°C.
  • the calibration curve is prepared from eight samples of “standard samples TSK standard, polystyrene” (manufactured by TOSOH CORPORATION):“F-40,”“F-20,”“F-4,”“F-1 ,”“A-5000,”“A- 2500,”“A-1000,” and“n-propylbenzene.”
  • the polymer is preferably present in the ink of the present invention in 0.5% to 10.0% by weight, based on the total weight of the ink.
  • the lower limit is 1.0% by weight, more preferably 1.5% by weight and most preferably 2.0% by weight, based on the total weight of the ink.
  • the upper limit is 9.0% by weight, more preferably 8.0% by weight and most preferably 7.0% by weight, based on the total weight of the ink.
  • the inkjet ink of the present invention is a LED-curable inkjet ink. It therefore comprises radiation curable-material.
  • the radiation-curable material is not particularly limited and the formulator is free to include any such radiation-curable material in the ink of the present invention to improve the properties or performance of the ink.
  • This radiation-curable material can include any radiation-curable material readily available and known in the art in inkjet inks.
  • radiation-curable is meant a material that polymerises and/or crosslinks when exposed to actinic radiation, in the presence of a photoinitiator.
  • LED-curable is meant that the actinic radiation source is an LED
  • the amount of radiation-curable material is not limited other than by the constraints imposed by the use in an inkjet ink, such as viscosity, stability, toxicity etc.
  • the ink of the present invention comprises 30 to 90% by weight more preferably 40 to 90% by weight and most preferably 50 to 90% by weight, of radiation-curable material, based on the total weight of the ink.
  • the LED-curable inkjet ink of the present invention comprises one or more radiation-curable monomers.
  • monomers may possess different degrees of functionality, which include mono, di, tri and higher functionality monomers.
  • the LED-curable inkjet ink of the present invention comprises one or more monofunctional monomers, such as a monofunctional (meth)acrylate monomer. In a particularly preferred embodiment, the inkjet ink of the present invention comprises at least two monofunctional monomers.
  • the ink of the present invention comprises 30 to 90% by weight, preferably 40 to 85% by weight and most preferably 50 to 80% by weight, of monofunctional monomers, based on the total weight of the ink.
  • a radiation-curable monofunctional monomer has one functional group, which takes part in the polymerisation reaction on curing.
  • the polymerisable groups can be any group that are capable of polymerising upon exposure to radiation and are preferably selected from a (meth)acrylate group and a vinyl ether group.
  • the substituents of the monofunctional monomers are not limited other than by the constraints imposed by the use in an inkjet ink, such as viscosity, stability, toxicity etc.
  • the substituents are typically alkyl, cycloalkyl, aryl and combinations thereof, any of which may be interrupted by heteroatoms.
  • Non-limiting examples of substituents commonly used in the art include C 1-18 alkyl, C 3-18 cycloalkyl, C 6-10 aryl and combinations thereof, such as C 6-10 aryl- or C 3-18 cycloalkyl-substituted CM S alkyl, any of which may be interrupted by 1 -10 heteroatoms, such as oxygen or nitrogen, with nitrogen further substituted by any of the above described substituents.
  • the substituents may together also form a cyclic structure.
  • the inkjet ink of the present invention comprises one or more monofunctional (meth)acrylate monomers, which are well known in the art and are preferably the esters of acrylic acid. A detailed description is therefore not required. Mixtures of (meth)acrylates may also be used.
  • Preferred examples include cyclic monofunctional (meth)acrylate monomers and acyclic-hydrocarbon monofunctional (meth)acrylate monomers.
  • 2-methyl-2-ethyl-1 ,3-dioxolane-4-yl)methyl acrylate (Medol-10), phenoxyethyl acrylate (PEA), cyclic TMP formal acrylate (CTFA), isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFA), 3,3,5-trimethylcyclohexyl acrylate (TMCHA), 2-(2- ethoxyethoxy)ethyl acrylate, octadecyl acrylate (ODA), tridecyl acrylate (TDA), isodecyl acrylate (IDA), lauryl acrylate and mixtures thereof.
  • the preferred examples of monofunctional (meth)acrylate monomers have the following chemical structures:
  • CFA Cyclic TMP formal acrylate
  • PDA Phenoxyethyl acrylate
  • IBOA Isobornyl acrylate
  • THFA Tetrahydrofurfuryl acrylate
  • ODA Octadecyl acrylate
  • TDA Tridecyl acrylate
  • the ink of the present invention comprises one or more monofunctional (meth)acrylate monomers selected from PEA, IBOA, CTFA and mixtures thereof.
  • the ink of the present invention comprises 30 to 90% by weight, preferably 40 to 85% by weight and most preferably 50 to 80% by weight, of monofunctional (meth)acrylate monomers, based on the total weight of the ink.
  • the inkjet ink of the present invention comprises an N-vinyl amide monomer, an N-acryloyl amine monomer and/or an N-vinyl carbamate monomer.
  • N-Vinyl amides are well-known monomers in the art and a detailed description is therefore not required.
  • N-vinyl amides have a vinyl group attached to the nitrogen atom of an amide which may be further substituted in an analogous manner to the (meth)acrylate monomers.
  • Preferred examples are N-vinyl caprolactam (NVC) and N-vinyl pyrrolidone (NVP).
  • N-acryloyl amines are also well-known in the art. N-acryloyl amines also have a vinyl group attached to an amide but via the carbonyl carbon atom and again may be further substituted in an analogous manner to the (meth)acrylate monomers. A preferred example is N-acryloylmorpholine (AC MO).
  • N-Vinyl carbamate monomers are defined by the following functionality:
  • N-vinyl carbamate monomers The synthesis of N-vinyl carbamate monomers is known in the art. For example, vinyl isocyanate, formed by the Curtius rearrangement of acryloyl azide, can be reacted with an alcohol to form N-vinyl carbamates (Phosgenations - A Handbook by L. Cotarca and H. Eckert, John Wiley & Sons, 2003, 4.3.2.8, pages 212-213).
  • a preferred N-vinyl carbamate monomer is NVMO.
  • NVMO is an N-vinyl oxazolidinone.
  • N-Vinyl oxazolidinones have the following structure:
  • R 1 to R 4 are not limited other than by the constraints imposed by the use in an ink-jet ink, such as viscosity, stability, toxicity etc.
  • the substituents are typically hydrogen, alkyl, cycloalkyl, aryl and combinations thereof, any of which may be interrupted by heteroatoms.
  • substituents commonly used in the art include C 1-18 alkyl, C 3-18 cycloalkyl, C 6-10 aryl and combinations thereof, such as C 6-10 aryl- or C 3-18 cycloalkyl-substituted CM S alkyl, any of which may be interrupted by 1 -10 heteroatoms, such as oxygen or nitrogen, with nitrogen further substituted by any of the above described substituents.
  • R 1 to R 4 are independently selected from hydrogen or CH 0 alkyl. Further details may be found in WO 2015/022228 and US 4,831 ,153.
  • NVMO is available from BASF and has the following structure:
  • NVMO has the IUPAC name 5-methyl-3-vinyl-1 ,3-oxazolidin-2-one and CAS number 3395-98-0. NVMO includes the racemate and both enantiomers. In one embodiment, NVMO is a racemate. In another embodiment, NVMO is (R)-5-methyl-3-vinyl-1 ,3-oxazolidin-2-one. Alternatively, NVMO is (S)- 5-methyl-3-vinyl-1 ,3-oxazolidin-2-one.
  • the inkjet ink of the present invention comprises 10-30% by weight of an N-vinyl amide monomer, an N-(meth)acryloyl amine monomer and/or an N-vinyl carbamate monomer, based on the total weight of the ink.
  • the LED-curable inkjet ink of the present invention comprises one or more di- and/or multifunctional radiation-curable monomers. The one or more di- and/or multifunctional radiation-curable monomers further provide the ink with good film-forming properties.
  • Di- and/or multifunctional radiation-curable monomer has its standard meaning, i.e. di or higher, that is two or more groups, respectively, which take part in the polymerisation reaction on curing.
  • the di- and/or multifunctional radiation-curable monomer is a di-, tri-, tetra- , penta- or hexa- functional monomer, i.e. the radiation curable monomer has two, three, four, five or six functional groups.
  • the inkjet ink of the present invention comprises a difunctional monomer.
  • the functional group of the di- and/or multifunctional radiation-curable monomer, which is utilised in the ink of the present invention may be the same or different but must take part in the polymerisation reaction on curing.
  • Examples of such functional groups include any groups that are capable of polymerising upon exposure to radiation and are preferably selected from a (meth)acrylate group and a vinyl ether group.
  • the di- and/or multifunctional radiation-curable monomer may possess different degrees of functionality, and a mixture including combinations of di, tri and higher functionality monomers may be used.
  • the substituents of the di- and/or multifunctional radiation-curable monomer are not limited other than by the constraints imposed by the use in an ink-jet ink, such as viscosity, stability, toxicity etc.
  • the substituents are typically alkyl, cycloalkyl, aryl and combinations thereof, any of which may be interrupted by heteroatoms.
  • Non-limiting examples of substituents commonly used in the art include C 1-18 alkyl, C 3-18 cycloalkyl, C 6-10 aryl and combinations thereof, such as C 6-10 aryl- or C 3.18 cycloalkyl- substituted CMS alkyl, any of which may be interrupted by 1 -10 heteroatoms, such as oxygen or nitrogen, with nitrogen further substituted by any of the above described substituents.
  • the substituents may together also form a cyclic structure. (The same groups may also be used for difunctional monomers.)
  • the ink of the present invention comprises 5 to 35% by weight of di- and/or multifunctional radiation-curable monomers, based on the total weight of the ink.
  • di- and/or multifunctional radiation-curable monomer examples include difunctional (meth)acrylate monomers, multifunctional (meth)acrylate monomers, divinyl ether monomers and vinyl ether (meth)acrylate monomers. Mixtures of di- and/or multifunctional radiation-curable monomer may also be used. Difunctional (meth)acrylate monomers are well known in the art and a detailed description is therefore not required.
  • Preferred examples include decanediol diacrylate, hexanediol diacrylate (HDDA), tricyclodecanedimethanol diacrylate (TCDDMDA), polyethyleneglycol diacrylate (for example tetraethyleneglycol diacrylate), dipropyleneglycol diacrylate, neopentylglycol diacrylate, 3-methyl pentanediol diacrylate, and the acrylate esters of ethoxylated or propoxylated glycols and polyols, for example, propoxylated neopentyl glycol diacrylate, and mixtures thereof.
  • HDDA hexanediol diacrylate
  • TCDDMDA tricyclodecanedimethanol diacrylate
  • polyethyleneglycol diacrylate for example tetraethyleneglycol diacrylate
  • dipropyleneglycol diacrylate dipropyleneglycol diacrylate
  • suitable difunctional methacrylate monomers also include esters of methacrylic acid (i.e. methacrylates), such as decanediol dimethacrylate, hexanediol dimethacrylate, triethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, ethyleneglycol dimethacrylate, 1 ,4-butanediol dimethacrylate and mixtures thereof.
  • methacrylates esters of methacrylic acid
  • decanediol dimethacrylate i.e. hexanediol dimethacrylate
  • triethyleneglycol dimethacrylate diethyleneglycol dimethacrylate
  • ethyleneglycol dimethacrylate ethyleneglycol dimethacrylate
  • 1 ,4-butanediol dimethacrylate 1,4-butanediol dimethacrylate
  • the difunctional (meth)acrylate monomer is selected from decanediol diacrylate, hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, dipropylene glycol diacrylate, and mixtures thereof.
  • the one or more difunctional (meth)acrylate monomers comprises 1 ,10-decanediol diacrylate (DDDA).
  • the ink of the present invention comprises 5 to 25% by weight of a difunctional (meth)acrylate monomer, based on the total weight of the ink.
  • the amount present may be higher and in such a preferred embodiment, the ink of the present invention comprises 10 to 80% by weight of a difunctional (meth)acrylate monomer, based on the total weight of the ink.
  • the ink of the present invention comprises one or more monofunctional monomers and one or more di- and/or multifunctional radiation-curable monomers. In a particularly preferred embodiment, the ink of the present invention comprises two or more monofunctional monomers and one or more difunctional monomers.
  • Multifunctional (which do not include difunctional) are well known in the art and a detailed description is therefore not required. Multifunctional has its standard meaning, i.e. tri or higher, that is three or more groups, respectively, which take part in the polymerisation reaction on curing.
  • Suitable multifunctional (meth)acrylate monomers include tri-, tetra-, penta-, hexa-, hepta- and octa-functional monomers.
  • multifunctional acrylate monomers examples include trimethylolpropane triacrylate, dipentaerythritol triacrylate, tri(propylene glycol) triacrylate, bis(pentaerythritol) hexaacrylate, and the acrylate esters of ethoxylated or propoxylated glycols and polyols, for example, ethoxylated trimethylolpropane triacrylate, and mixtures thereof.
  • Suitable multifunctional (meth)acrylate monomers also include esters of methacrylic acid (i.e. methacrylates), such as trimethylolpropane trimethacrylate. Mixtures of (meth)acrylates may also be used.
  • a particularly preferred multifunctional (meth)acrylate monomer is dipentaerythritol penta-/hexa-acrylate (DPHA).
  • the ink of the present invention comprises 1 to 25% by weight, more preferably 1 to 10% by weight, of a multifunctional (meth)acrylate monomer, based on the total weight of the ink.
  • the amount present may be higher and in such a preferred embodiment, the ink of the present invention comprises 10 to 80% by weight of a multifunctional (meth)acrylate monomer, based on the total weight of the ink.
  • the di- and/or multifunctional radiation-curable monomer may have at least one vinyl ether functional group.
  • vinyl ethers such as triethylene glycol divinyl ether, diethylene glycol divinyl ether, 1 ,4- cyclohexanedimethanol divinyl ether and 2-(2-vinyloxyethoxy)ethyl acrylate, bis[4-(vinyloxy)butyl] 1 ,6- hexanediylbiscarbamate, bis[4-(vinyloxy)butyl] isophthalate, bis[4-(vinyloxy)butyl] (methylenedi-4,1- phenylene), bis[4-(vinyloxy)butyl] succinate, bis[4-(vinyloxy)butyl]terephthalate, bis[4- (vinyloxymethyl)cyclohexylmethyl] glutarate, 1 ,4-
  • (Meth)acrylate is intended herein to have its standard meaning, i.e. acrylate and/or methacrylate.
  • Monomers typically have a molecular weight of less than 600, preferably more than 200 and less than 450. Monomers are typically added to inkjet inks to reduce the viscosity of the inkjet ink. They therefore preferably have a viscosity of less than 150 mPas at 25°C, more preferably less than l OOmPas at 25°C and most preferably less than 20 mPas at 25°C. Monomer viscosities can be measured using an ARG2 rheometer manufactured by T.A. Instruments, which uses a 40 mm oblique / 2° steel cone at 25°C with a shear rate of 25 s 1 .
  • the ink of the present invention may further comprise a radiation-curable (i.e. polymerisable) oligomer, such as a (meth)acrylate oligomer.
  • a radiation-curable (i.e. polymerisable) oligomer such as a (meth)acrylate oligomer.
  • curable oligomer has its standard meaning in the art, namely that the component is partially reacted to form a pre-polymer having a plurality of repeating monomer units, which is capable of further polymerisation.
  • the oligomer preferably has a molecular weight of at least 450 and preferably at least 600 (whereas monomers typically have a molecular weight below these values).
  • the molecular weight is preferably 4,000 or less.
  • Molecular weights (number average) can be calculated if the structure of the oligomer is known or molecular weights can be measured using gel permeation chromatography using polystyrene standards.
  • the degree of functionality of the oligomer determines the degree of crosslinking and hence the properties of the cured ink.
  • the oligomer is preferably multifunctional meaning that it contains on average more than one reactive functional group per molecule.
  • the average degree of functionality is preferably from 2 to 6.
  • Oligomers are typically added to inkjet inks to increase the viscosity of the inkjet ink or to provide filmforming properties such as hardness or cure speed. They therefore preferably have a viscosity of 150 mPas or above at 25°C. Preferred oligomers for inclusion in the ink of the invention have a viscosity of 0.5 to 10 Pas at 50°C. Oligomer viscosities can be measured using an ARG2 rheometer manufactured by T.A. Instruments, which uses a 40 mm oblique / 2° steel cone at 60°C with a shear rate of 25 s 1 .
  • Radiation-curable oligomers comprise a backbone, for example a polyester, urethane, epoxy or polyether backbone, and one or more radiation-curable groups.
  • the oligomer preferably comprises a polyester backbone.
  • the polymerisable group can be any group that is capable of polymerising upon exposure to radiation.
  • the oligomers are (meth)acrylate oligomers.
  • Particularly preferred radiation-curable oligomers are polyester acrylate oligomers as these have excellent adhesion and elongation properties. Most preferred are di-, tri-, tetra-, penta- or hexa- functional polyester acrylates, as these yield films with good solvent resistance.
  • the radiation-curable oligomer is an amine-modified polyester acrylate oligomer.
  • Such a radiation-curable oligomer is commercially available as Ebecryl 80.
  • radiation-curable oligomers include epoxy based materials such as bisphenol A epoxy acrylates and epoxy novolac acrylates, which have fast cure speeds and provide cured films with good solvent resistance.
  • the radiation-curable oligomer polymerises by free-radical polymerisation.
  • the radiation-curable oligomer cures upon exposure to radiation in the presence of a photoinitiator to form a crosslinked, solid film.
  • the total amount of the oligomer is preferably from 1-15% by weight, based on the total weight of the ink.
  • Preferably the oligomer is present from 2-5% by weight, based on the total weight of the ink.
  • the ink of the present invention may further comprise an a,b-unsaturated ether monomer, which can polymerise by free-radical polymerisation and may be useful for reducing the viscosity of the ink when used in combination with one or more (meth)acrylate monomers.
  • a,b-unsaturated ether monomer which can polymerise by free-radical polymerisation and may be useful for reducing the viscosity of the ink when used in combination with one or more (meth)acrylate monomers.
  • vinyl ethers such as triethylene glycol divinyl ether, diethylene glycol divinyl ether, 1 ,4- cyclohexanedimethanol divinyl ether and ethylene glycol monovinyl ether. Mixtures of a,b- unsaturated ether monomers may be used.
  • the ink of the present invention may also include radiation-curable material, which is capable of polymerising by cationic polymerisation. Suitable materials include, oxetanes, cycloaliphatic epoxides, bisphenol A epoxides, epoxy novolacs and the like.
  • the radiation-curable material according to this embodiment may comprise a mixture of cationically curable monomer and oligomer.
  • the radiation-curable material may comprise a mixture of an epoxide oligomer and an oxetane monomer.
  • the ink comprises radiation-curable material, which polymerises by cationic polymerisation
  • the ink must also comprise a cationic photoinitiator.
  • any suitable cationic initiator can be used, for example sulfonium or iodonium based systems.
  • Non limiting examples include: Rhodorsil PI 2074 from Rhodia; MC AA, MC BB, MC CC, MC CC PF, MC SD from Siber Hegner; UV9380C from Alfa Chemicals; Uvacure 1590 from UCB Chemicals; and Esacure 1064 from Lamberti spa.
  • the ink of the present invention cures by free radical polymerisation only and hence the ink is substantially free of radiation-curable material, which polymerises by cationic polymerisation.
  • the inkjet ink of the present invention is LED-curable and comprises one or more photoinitiators and in particular, the specific polymeric thioxanthone type photoinitiator as claimed, namely 1 ,3-di( ⁇ a-[1- chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)] ⁇ oxy)-2,2-bis( ⁇ a-[1-chloro-9- oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)] ⁇ oxymethyl) propane.
  • the inkjet ink of the present invention comprises one or more additional photoinitiators.
  • the inkjet ink of the present invention comprises 1 ,3-di( ⁇ a-[1-chloro-9-oxo-9H- thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)] ⁇ oxy)-2,2-bis( ⁇ a-[1-chloro-9-oxo-9H- thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)] ⁇ oxymethyl) propane and one or more further photoinitiators.
  • the ink of the present invention preferably comprises one or more additional free radical photoinitiators.
  • Free radical photoinitiators can be selected from any of those known in the art. For example, benzophenone, 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2- hydroxy-2-methyl-1 -propane-1 -one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, benzil dimethylketal, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- phenylphosphine oxide and bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide.
  • the additional one or more photoinitiators present in the ink of the present invention is tailored for UV LED light.
  • tailored for UV LED light it is meant that the photoinitiators absorb the radiation which is emitted by the UV LED light source.
  • the one or more additional photoinitiators present in the ink of the present invention absorbs radiation in a region of from 360 nm to 410 nm and absorbs sufficient radiation to cure the ink within a 50 nm or less, preferably 30 nm or less, most preferably 15 nm or less bandwidth.
  • the one or more additional photoinitiators comprises a phosphine oxide photoinitiator, such as TPO and BAPO.
  • the one or more additional photoinitiators comprises bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide.
  • the ink of the present invention comprises a photoinitiator package consisting of 1 ,3- di( ⁇ a-[1 -chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1 -methylethylene)] ⁇ oxy)-2,2-bis( ⁇ a-[1 - chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1 -methylethylene)] ⁇ oxymethyl) propane and bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide.
  • the inkjet ink of the present invention is substantially free of isopropyl thioxanthone.
  • the inkjet ink comprises less than 2% by weight of isopropyl thioxanthone, preferably less than 1 % by weight of isopropyl thioxanthone, based on the total weight of the ink.
  • isopropyl thioxanthone helps to achieve improved surface cure but results in an increased yellow shift.
  • Replacing isopropyl thioxanthone with the claimed photoinitiator has surprisingly been found to maintain surface cure whilst reducing yellow shift.
  • the amount of one or more phosphine oxide photoinitiator present in the ink is 1 to 20% by weight, based on the total weight of the ink.
  • the inkjet ink comprises two or more additional photoinitiators.
  • the total amount of photoinitiator including the polymeric thioxanthone type photoinitiator, namely 1 ,3-di( ⁇ a-[1 -chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1 -methylethylene)] ⁇ oxy)-2,2- bis( ⁇ a-[1 -chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1 -methylethylene)] ⁇ oxymethyl) propane, present in the ink of the present invention is 1 -20% by weight, based on the total weight of the ink.
  • the inkjet ink of the present invention further comprises a colouring agent, which may be either dissolved or dispersed in the liquid medium of the ink.
  • the colouring agent can be any of a wide range of suitable colouring agents that would be known to the person skilled in the art.
  • the colouring agent is a dispersible pigment, of the types known in the art and commercially available such as, for example, under the trade-names Paliotol (available from BASF pic), Cinquasia, Irgalite (both available from Ciba Speciality Chemicals) and Hostaperm (available from Clariant UK).
  • the pigment may be of any desired colour such as, for example, Pigment Yellow 13, Pigment Yellow 83, Pigment Yellow 120, Pigment Red 9, Pigment Red 184, Pigment Blue 15:3, Pigment Green 7, Pigment Violet 19, Pigment Black 7. Especially useful are black and the colours required for trichromatic process printing. Mixtures of pigments may be used.
  • the inks may be in the form of a multi-chromatic inkjet ink set, which typically comprises a cyan ink, a magenta ink, a yellow ink and a black ink (a so-called trichromatic set).
  • the inks in a trichromatic set can be used to produce a wide range of colours and tones.
  • the total proportion of pigment present is preferably from 0.5 to 15% by weight, more preferably from 1 to 10% by weight, based on the total weight of the ink.
  • the ink of the present invention comprises a cyan colouring agent, and preferably a cyan pigment.
  • the cyan pigment is dispersed in the liquid medium of the ink and is typically in the form of a powdered cyan pigment.
  • a preferred blue pigment is Heliogen Blue 7110 F available from BASF.
  • the ink comprises 1-10% by weight of the cyan pigment, based on the total weight of the ink.
  • yellow shift is particularly problematic for cyan inks, as cyan is at the opposite end of the colour spectrum to yellow. Yellow shift is however a problem for all colours of inks, including black inks and other colours of the trichromatic process printing, including magenta and yellow. In yellow inks, yellow shift changes the yellow hue of the ink.
  • the inkjet ink of the present invention dries primarily by curing, i.e. by the polymerisation of the monomers present, as discussed hereinabove, and hence is a curable ink.
  • the ink does not, therefore, require the presence of water or a volatile organic solvent to effect drying of the ink.
  • the absence of water and volatile organic solvents means that the ink does not need to be dried to remove the water/solvent.
  • water and volatile organic solvents have a significant viscositylowering effect making formulation of the ink in the absence of such components significantly more challenging.
  • the inkjet ink of the present invention is preferably substantially free of water and volatile organic solvents.
  • the inkjet ink comprises less than 5% by weight of water and volatile organic solvent combined, preferably less than 3% by weight combined, more preferably, less than 2% by weight combined and most preferably less than 1 % by weight combined, based on the total weight of the ink.
  • Some water will typically be absorbed by the ink from the air and solvents may be present as impurities in the components of the inks, but such low levels are tolerated.
  • the inks of the present invention may comprise a passive (or“inert”) thermoplastic resin.
  • Passive resins are resins which do not enter into the curing process, i.e. the resin is free of functional groups which polymerise under the curing conditions to which the ink is exposed. In other words, resin is not a radiation-curable material.
  • the resin may be selected from epoxy, polyester, vinyl, ketone, nitrocellulose, phenoxy or acrylate resins, or a mixture thereof and is preferably a poly(methyl (meth)acrylate) resin.
  • the resin has a weight-average molecular weight of 70-200 KDa and preferably 100-150 KDa, as determined by GPC with polystyrene standards. Particularly preferred resins are Paraloid® A11 from Rohm and Haas and BR-113 from Dianal Resins.
  • the resin is preferably present at 1 -5% by weight, based on the total weight of the ink.
  • the ink of the present invention may be present in the ink of the present invention to improve the properties or performance.
  • these components may be, for example, additional surfactants, defoamers, dispersants, stabilisers against deterioration by heat or light, reodorants, flow or slip aids, biocides and identifying tracers.
  • photosensitisers are added to the ink, which are selected to absorb strongly in the desired wavelength band of UV LED radiation source and are able to transfer energy to the photoinitiators of the ink.
  • the inkjet ink of the present invention further comprises a dispersant.
  • the dispersant is not particularly limited and the formulator is free to include any dispersant in the ink of the present invention to improve the properties or performance of the ink.
  • This dispersant can include any dispersant readily available and known in the art in inkjet inks.
  • a particularly preferred dispersant is Solsperse® 32000 from Lubrizol Limited.
  • the inkjet ink of the present invention further comprises a stabiliser.
  • the stabiliser is not particularly limited and the formulator is free to include any stabiliser in the ink of the present invention to improve the properties or performance of the ink.
  • This stabiliser can include any stabiliser readily available and known in the art in inkjet inks.
  • a particularly preferred stabiliser is Florstab UV-12 from Kromachem Limited.
  • the inkjet ink of the present invention further comprises a surfactant.
  • the surfactant is not particularly limited and the formulator is free to include any surfactant in the ink of the present invention to improve the properties or performance of the ink.
  • This surfactant can include any surfactant readily available and known in the art in inkjet inks.
  • a particularly preferred surfactant is BYK-307 from BYK-Chemie GmbH.
  • the amounts by weight provided herein are based on the total weight of the ink.
  • the inkjet ink of the present invention exhibits a desirable low viscosity (200 mPas or less, preferably 100 mPas or less and more preferably 30 mPas or less at 25 °C). In a preferred embodiment, the viscosity of the inkjet ink is 10 mPas to 30 mPas at 25 °C.
  • the inkjet ink is jetted at drop sizes below 90 picolitres, preferably below 35 picolitres and most preferably below 10 picolitres.
  • a viscosity of 30 mPas or less at 25°C is preferred, for example, 10 to 12 mPas, 18 to 20 mPas, or 24 to 26 mPas.
  • Ink viscosity may be measured using a Brookfield viscometer fitted with a thermostatically controlled cup and spindle arrangement, such as a DV1 low-viscosity viscometer running at 20 rpm at 25°C with spindle 00.
  • Print heads account for a significant portion of the cost of an entry level printer and it is therefore desirable to keep the number of print heads (and therefore the number of inks in the ink set) low. Reducing the number of print heads can reduce print quality and productivity. It is therefore desirable to balance the number of print heads in order to minimise cost without compromising print quality and productivity.
  • the inkjet ink may be prepared by known methods such as stirring with a high-speed water-cooled stirrer, or milling on a horizontal bead-mill.
  • the present invention also provides a method of inkjet printing the inkjet ink of the present invention.
  • the present invention provides a method of inkjet printing comprising inkjet printing the inkjet ink of the present invention onto a substrate and curing the ink by exposing the printed ink to a UV radiation source, which is preferably a UV LED radiation source.
  • a UV radiation source which is preferably a UV LED radiation source.
  • the inventors have surprisingly found that the ink of the present invention is particularly suitable as an ink which can be cured using a UV LED light source, whilst minimising colour shift and maintaining surface cure.
  • the inkjet ink is printed onto a substrate.
  • Printing is performed by inkjet printing, e.g. on a single-pass inkjet printer, for example for printing (directly) onto a substrate, on a roll-to-roll printer or a flat-bed printer.
  • inkjet printing is well known in the art and a detailed description is not required.
  • the ink is jetted from one or more reservoirs or printing heads through narrow nozzles on to a substrate to form a printed image.
  • the substrate is not limited. Examples of substrates include those composed of PVC, polyester, polyethylene terephthalate (PET), PETG, polyethylene, polypropylene, and all cellulosic materials or their mixtures/blends with the aforementioned synthetic materials.
  • the printed image is then exposed to a UV radiation source, preferably UV LED light, to cure the inkjet ink.
  • a UV radiation source preferably UV LED light
  • Any suitable radiation source may be used.
  • Suitable UV sources include mercury discharge lamps, fluorescent tubes, light emitting diodes (LEDs), flash lamps and combinations thereof.
  • a UV LED light source is used to cure the ink.
  • UV LED light is emitted from a UV LED light source.
  • UV LED light sources comprise one or more LEDs and are well known in the art. Thus, a detailed description is not required.
  • UV LED light sources emit radiation having a spread of wavelengths.
  • the emission of UV LED light sources is identified by the wavelength which corresponds to the peak in the wavelength distribution.
  • UV LED light sources emit UV radiation over a narrow range of wavelengths on the wavelength distribution.
  • the width of the range of wavelengths on the wavelength distribution is called a wavelength band. LEDs therefore have a narrow wavelength output when compared to other sources of UV radiation.
  • a narrow wavelength band it is meant that at least 90%, preferably at least 95%, of the radiation emitted from the UV LED light source has a wavelength within a wavelength band having a width of 50 nm or less, preferably, 30 nm or less, most preferably 15 nm or less.
  • At least 90%, preferably at least 95%, of the radiation emitted from the UV LED light source has a wavelength in a band having a width of 50 nm or less, preferably 30 nm or less, most preferably 15 nm or less.
  • the wavelength of the UV LED source substantially matches the absorption profile of the ink.
  • the wavelength distribution of the UV LED light peaks at a wavelength of from 360 nm to 410 nm.
  • the wavelength distribution of the UV LED light peaks at a wavelength of around 365 nm, 395 nm, 400 nm or 405 nm.
  • the ink of the present invention is preferably formulated to respond to the emission of the UV LED source.
  • the wavelength distribution of the UV LED light peaks at a wavelength of from 360 nm to 410 nm, and at least 90%, preferably at least 95%, of the radiation has a wavelength in a band having a width of 50 nm or less, preferably 30 nm or less, most preferably 15 nm or less.
  • the wavelength distribution of the UV LED light peaks at a wavelength of around 365 nm, 395 nm, 400 nm or 405 nm, and at least 90%, preferably at least 95%, of the radiation has a wavelength in a band having a width of 50 nm or less, preferably 30 nm or less, most preferably 15 nm or less.
  • LEDs have a longer lifetime and exhibit no change in the power/wavelength output over time. LEDs also have the advantage of switching on instantaneously with no thermal stabilisation time and their use results in minimal heating of the substrate.
  • the ink Upon exposure to a radiation source, the ink cures to form a relatively thin polymerised film.
  • the ink of the present invention typically produces a printed film having a thickness of 1 to 20 pm, preferably 1 to 10 pm, for example 2 to 5 pm. Film thicknesses can be measured using a confocal laser scanning microscope.
  • the exposure to UV LED light may be performed in an inert atmosphere, e.g. using a gas such as nitrogen, in order to assist curing of the ink, although this is not required to achieve full cure, including surface cure owing to the components present in the ink of the present invention.
  • curing the ink by exposing the printed ink to a UV radiation source preferably a UV LED radiation source, is performed in the absence of an oxygen-deficient atmosphere.
  • the exposure to UV light preferably UV LED light, is performed in air.
  • the method of the present invention minimises the complexity and cost of the printer required when using LEDs, whilst achieving a cured ink image with reduced colour shift, a high LED cure response and the necessary film-forming properties.
  • the present invention also provides a cartridge containing the inkjet ink as defined herein. It also provides a printed substrate having the ink as defined herein printed thereon.
  • Inkjet inks were prepared according to the formulations set out in Table 1 .
  • the inkjet ink formulations were prepared by mixing the components in the given amounts. Amounts are given as weight percentages based on the total weight of the ink. Table 1
  • PEA, IBOA and CTFA are monofunctional monomers.
  • DDDA is a difunctional monomer.
  • DPHA is a multifunctional monomer.
  • UV 12 is a stabiliser.
  • Speedcure 7010 and Irgacure 819 are photoinitiators.
  • Polymer 1 contains the following structural units:
  • Polymer 1 has a weight average molecular weight of 11 ,000.
  • the cyan pigment dispersion of the inks of Table 1 comprises 59% PEA, 1 % stabiliser, 10% dispersant and 30% blue pigment.
  • the dispersion was prepared by mixing the components in the given amounts and passing the mixture through a bead mill until the dispersion had a particle size of less than 0.3 microns. Amounts are given as weight percentages based on the total weight of the dispersion.
  • Ink 1 and comparative inks 1 and 2 were drawn down onto SAV using a 12 pm K-bar.
  • the inks were cured using a Phoseon 20W LED lamp set at 50%, with a belt speed of 50 m/min.
  • the number of passes required to fully cure each ink is set out in Table 2. Full cure is achieved when the film is tack- free. Table 2
  • Comparative inks 3-6 were prepared according to the formulations set out in Table 3.
  • the inkjet ink formulations were prepared by using comparative ink 2 as a base formulation and mixing the components in the given amounts. Amounts are given as weight percentages based on the total weight of the ink.
  • Genopol TX-2 is a photoinitiator available from Rahn, with a molecular weight of 980 g/mol.
  • Omnipol TX is a photoinitiator available from IGM, with a molecular weight of 790 g/mol.
  • Genopol TX-2 and Omnipol TX have the following general structure:
  • ITX is isopropylthioxanthone, a photoinitiator with a molecular weight of 254.3 g/mol. It is typically commercially available as a mixture of 2-isopropylthioxanthone and 4-isopropylisothioxanthone.
  • Speedcure 7010 has a molecularweight of 1839 g/mol. Taking into account the molecular weights of ITX and Speedcure 7010, and that Speedcure 7010 has four thioxanthone structural units, Speedcure 7010 can be thought of as being equivalent to 55.3% ITX ([4 x 254.3J/1839 x 100). Therefore, 4 parts Speedcure 7010 can be thought of as being equivalent to 2.2 parts ITX. Therefore, ink 1 and comparative ink 5 can be thought of as containing an equivalent number of thioxanthone structural units.
  • Genopol TX-2 can be thought of as being equivalent to 51.9% ITX ([2 x 254.3J/980 x 100). Therefore, 4 parts Genopol TX-2 can be thought of as being equivalent to 2.1 parts ITX. Therefore, comparative inks 3 and 5 can be thought of as containing an equivalent number of thioxanthone structural units.
  • Omnipol TX can be thought of as being equivalent to 64.4% ITX ([2 x 254.3J/790 x 100). Therefore, 4 parts Omnipol TX can be thought of as being equivalent to 2.6 parts ITX. Therefore, comparative inks 4 and 5 can be thought of as containing an equivalent number of thioxanthone structural units.
  • Ink 1 and comparative inks 3-6 were drawn down onto SAV using a 12 pm K-bar.
  • the inks were cured using a Jenton LED lamp set at 50%, with a belt speed of 50 m/min, and four passes. Colour shift was then measured on a photospectrometer for L*, a* and b* values over a period of 48 hours and the Ab* and delta E values found. The results of the colour shift of the inks are set out in Table 4.
  • the target delta E absolute value for an acceptable colour shift is from 0.0 to 5.0 after 24 hours, preferably from 0.0 to 3.5 and more preferably from 0.0 to 2.0, depending on the application of the present invention. It can be seen that only ink 1 has an acceptable colour shift after 24 hours. This is in marked contrast to comparative inks 3-6, which have a colour shift higher than the target after 24 hours.
  • Example 4 Ink 1 and comparative inks 1 and 2 were printed and cured as in Example 4. Colour shift was then measured as in Example 4 and the results of the colour shift of the inks are set out in Table 5.
  • ink 1 has the fastest cure speed as can be seen in Example 2 above. Only the ink of the invention has the correct balance of fast cure speed and acceptable colour shift.
  • Example 6 Comparative inks 7 and 8 were prepared according to the formulations set out in Table 6.
  • the inkjet ink formulations were prepared by mixing the components in the given amounts. Amounts are given as weight percentages based on the total weight of the ink. Table 6
  • Genomer 5275 is an acrylated amine that can be used as an amine co-initiator in combination with a type II photoinitiator.
  • Omnipol ASA is a polymeric amine synergist that can also be used in combination with a type II photoinitiator.
  • the cyan pigment dispersion was the same as used in Example 1.
  • Example 7 Ink 1 and comparative inks 1 and 2 were printed and cured as in Example 2. The number of passes required to fully cure each ink is set out in Table 7.
  • ink 1 has the most acceptable colour shift after 24 hours. Further, ink 1 has the fastest cure speed as can be seen in Example 7 above. Only the ink of the invention has the correct balance of fast cure speed and acceptable colour shift.

Abstract

La présente invention concerne une encre d'impression et plus spécifiquement une encre pour jet d'encre durcissable par DEL. L'encre pour jet d'encre durcissable par DEL comprend un photoinitiateur de type thioxanthone polymère spécifique et un polymère contenant une amine renfermant une unité structurale de formule (1) et/ou (2). La présente invention concerne également un procédé d'impression à jet d'encre comprenant l'impression de ladite encre sur un Substrat et l'encre de durcissement par exposition de l'encre imprimée à une source de rayonnement UV.
PCT/GB2019/051328 2018-05-16 2019-05-15 Encre d'impression WO2019220107A1 (fr)

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US4831153A (en) 1983-06-27 1989-05-16 The Dow Chemical Company Preparation of N-vinyl-2-oxazolidinone
EP0424714A2 (fr) 1989-10-27 1991-05-02 Lexmark International, Inc. Compositions non aqueuses d'encre au jet thermique
WO2015022228A1 (fr) 2013-08-12 2015-02-19 Basf Se Encre d'impression par jet d'encre contenant de la n-vinyloxazolidinone
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EP0314403A1 (fr) 1987-10-27 1989-05-03 Videojet Systems International, Inc. Encre d'impression par jet pour le marquage de substrats vinyliques
EP0424714A2 (fr) 1989-10-27 1991-05-02 Lexmark International, Inc. Compositions non aqueuses d'encre au jet thermique
WO2015022228A1 (fr) 2013-08-12 2015-02-19 Basf Se Encre d'impression par jet d'encre contenant de la n-vinyloxazolidinone
US20160333201A1 (en) * 2014-02-13 2016-11-17 Fujifilm Corporation Radiation curable type ink jet ink set and ink jet recording method
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