WO2011039081A1 - Uv curable inkjet compositions for high-density print heads - Google Patents
Uv curable inkjet compositions for high-density print heads Download PDFInfo
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- WO2011039081A1 WO2011039081A1 PCT/EP2010/063933 EP2010063933W WO2011039081A1 WO 2011039081 A1 WO2011039081 A1 WO 2011039081A1 EP 2010063933 W EP2010063933 W EP 2010063933W WO 2011039081 A1 WO2011039081 A1 WO 2011039081A1
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Classifications
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- 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
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J11/00—Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
- B41J11/0015—Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/435—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of radiation to a printing material or impression-transfer material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
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- 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
Definitions
- UV Curable Inkjet Compositions for High-Density Print heads are UV Curable Inkjet Compositions for High-Density Print heads
- the present invention relates to UV curable inkjet compositions, and more specifically to UV curable inkjet inks, which are suitable for jetting by high- density print heads having small outer nozzle diameters.
- tiny drops of fluid are projected directly onto an ink- receiver surface without physical contact between the printing device and the ink-receiver.
- the printing device stores the printing data electronically and controls a mechanism for ejecting the drops image-wise. Printing is accomplished by moving a print head across the ink-receiver or vice versa or both.
- the ink When jetting inkjet ink onto an ink-receiver, the ink typically includes a liquid vehicle and one or more solids, such as dyes or pigments and polymers.
- Ink compositions can be roughly divided in:
- UV-curable in which drying is replaced by polymerization.
- ink compositions are more suitable for an absorbing ink-receiver, whereas hot melt inks and UV- curable inks can also be printed on non-absorbing ink-receivers. Due to thermal requirements posed by hot melt inks on the substrates, especially UV curable inks have gained the interest of the industry in inkjet printing applications.
- the droplet volume is about 87 pL and leads to an ink layer thickness of 17.5 ml/m 2 .
- the droplet volume becomes 7.7 pL and the resulting ink layer thickness is only 9.7 mL/m 2 .
- a problem is that smaller ink droplets exhibit a smaller droplet velocity because of relatively higher friction losses in a nozzle.
- droplet velocity can be increased by addition of organic solvent or the use of monofunctional monomers.
- US 2009099277 discloses a radiation curable and jettable ink composition
- a radiation curable and jettable ink composition comprising an ethylenically unsaturated polyfunctional component and an ethylenically unsaturated monofunctional monomer, wherein the composition is substantially free of solvent.
- US 6310115 discloses radiation curable inkjet compositions for containing radiation curable polyfunctional monomers containing vinyl ether and acrylate functions.
- embodiments of the present invention provide a combination of an inkjet print head and a UV curable inkjet composition as defined by claim 1 producing thin layer images of high image quality at a high printing speed.
- Figure 1 to Figure 5 are photographs of straight lines of ink droplets jetted by a print head at different viscosities and/or outer nozzle diameters for evaluating the inkjet printing reliability.
- die as used in disclosing the present invention, means a colorant having a solubility of 10 mg/L or more in the medium in which it is applied and under the ambient conditions pertaining.
- pigment is defined in DIN 55943, herein incorporated by reference, as a colorant that is practically insoluble in the application medium under the pertaining ambient conditions, hence having a solubility of less than 10 mg/L therein.
- alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1 ,1-dimethyl-propyl, 2,2-dimethylpropyl and 2- methy!-butyl etc.
- the term "monofunctional monomer” means a monomer containing only one polymerizable group.
- polyfunctional monomer means a monomer containing two or more polymerizable groups.
- VEEA is used as an abbreviation for 2-(2- vinyloxyethoxy)ethyl acrylate.
- the inkjet print heads according to the present invention have a nozzle density of at least 600 dpi, more preferably 900 to 1200 dpi.
- the nozzles of the inkjet print head have an outer nozzle diameter D smaller than 25 pm, more preferably between 14 and 22 pm.
- the nozzles usually have a cone shape wherein the inner nozzle diameter in the nozzle plate on the inside of the print head is much larger than the outer nozzle diameter in the nozzle plate on the outside of the print head.
- the outer nozzle diameter is the smallest diameter of a nozzle.
- a preferred printing head for the inkjet printing system is a piezoelectric head. Piezoelectric inkjet printing is based on the movement of a piezoelectric ceramic transducer when a voltage is applied thereto. The application of a voltage changes the shape of the piezoelectric ceramic transducer in the printing head creating a void, which is then filled with ink. When the voltage is again removed, the ceramic expands to its original shape, ejecting a drop of ink from the print head.
- the inkjet printing method according to the present invention is not restricted to piezoelectric inkjet printing.
- Other inkjet printing heads can be used and include various types, such as a continuous type and thermal, electrostatic and acoustic drop on demand type.
- the nozzles on a nozzle plate of the print head can be drilled mechanically or can be made using a laser. Outer nozzle diameters above 5 pm can reproducible be made using a laser.
- the inks must be ejected readily from the printing heads, which puts a number of constraints on the physical properties of the ink, e.g. a low viscosity at the jetting temperature, a surface energy such that the printing head nozzle can form the necessary small droplets, a homogenous ink capable of rapid conversion to a dry printed area,- ⁇
- the inkjet printing head normally scans back and forth in a transversal direction across the moving ink-receiver surface. It is allowed that the inkjet print head does not print on the way back, but bi-directional printing is preferred for obtaining a high areal throughput.
- a more preferred printing method is by a "single pass printing process" , which can be performed by using page wide inkjet printing heads or multiple staggered inkjet printing heads which cover the entire width of the ink-receiver surface.
- the inkjet printing heads usually remain stationary and the ink-receiver surface is transported under the inkjet printing heads.
- A is defined by the Formula (I): 100 wt% - D x 3.0 wt%/Mim ⁇ A ⁇ 100 wt% - D x 1.0 wt%/pm
- the UV curable inkjet composition comprises:
- the present invention contains 0 to 10 wt% of one or more monofunctional monomers and at least A wt% of 2-(2-vinyloxyethoxy)ethyl acrylate, wherein both wt% are based on the total weight of the UV curable inkjet composition;
- the UV curable inkjet composition contains no more than 10 wt% of a monofunctional monomer. A higher amount has a negative effect on curing speed and latency. In a more preferred embodiment no monofunctional monomer is present in the UV curable inkjet composition.
- the UV curable inkjet composition may contain polyfunctional monomers, colorants, polymers, surfactants, photoinitiators, co-initiators, inhibitors and other additives.
- the polyfunctional monomers or oligomers preferably include at least two acrylate groups.
- the UV curable composition may contain a colorant, which is most
- UV curable inkjet ink preferably a pigment.
- the UV curable inkjet composition contains a colorant, it is usually referred to as an UV curable inkjet ink.
- inkjet printing according to the present
- an inkjet ink set including a plurality of UV curable inkjet inks.
- the UV curable compositions and inks are preferably part of an inkjet ink set, comprising at least one yellow curable ink (Y), at least one cyan curable ink (C) and at least one magenta curable ink (M) and preferably also at least one black curable ink (K).
- the curable CMYK- ink set may also be extended with extra inks such as red, green, blue, violet and/or orange to further enlarge the colour gamut of the image.
- the CMYK-ink set may also be extended by the combination of full density and light density inks of both colour inks and/or black inks to improve the image quality by lowered graininess.
- the UV curable inkjet ink set preferably contains also one or more white inkjet inks.
- the pigmented UV curable ink preferably contains a dispersant, more
- the pigmented curable ink may contain a dispersion synergist to improve the dispersion quality and stability of the ink.
- a dispersion synergist to improve the dispersion quality and stability of the ink.
- at least the magenta ink contains a dispersion synergist.
- a mixture of dispersion synergists may be used to further improve dispersion stability.
- the viscosity of the UV curable compositions and inks is preferably
- the surface tension of the UV curable composition and ink is preferably in the range of about 18 mN/m to about 70 mN/m at 25° C, more preferably in the range of about 20 mN/m to about 40 mN/m at 25° C.
- the UV curable composition or ink may further also contain at least one inhibitor for improving the thermal stability of composition or ink
- the UV curable composition or ink may further also contain at least one surfactant.
- acrylate used in the UV curable compositions and inks, especially for food packaging applications are preferably purified compounds having no or almost no impurities, more particularly no toxic or carcinogenic impurities.
- the impurities are usually derivative compounds obtained during synthesis of the polymerizable compound. Sometimes, however, some compounds may be added deliberately to pure polymerizable compounds in harmless amounts, for example, polymerization inhibitors or stabilizers.
- Any monomer or oligomer capable of free radical polymerization may be used as polymerizable compound.
- a combination of monomers, oligomers and/or prepolymers may also be used.
- the monomers, oligomers and/or prepolymers may possess different degrees of functionality, and a mixture including combinations of mono-, di-, tri-and higher functionality
- the viscosity of the UV curable compositions and inks can be adjusted by varying the ratio between the monomers and oligomers.
- Particularly preferred monomers and oligomers are those listed in [0106] to [0 15] in EP 1911814 A (AGFA GRAPHICS) incorporated herein as a specific reference.
- a preferred class of monomers and oligomers are vinyl ether acrylates such as those described in US 6310115 (AGFA) , incorporated herein by reference.
- photoinitiator or photoinitiator system such as, for example, one or more photoinitiators and one or more co-initiators.
- the photoinitiator or photoinitiator system absorbs light and is responsible for the production of initiating species, i.e. free radicals which induce the polymerization of monomers, oligomers and polymers and with
- polyfunctional monomers and oligomers thereby also induce cross-linking.
- Irradiation with actinic radiation may be realized in two steps by changing wavelength or intensity. In such cases it is preferred to use 2 types of photoinitiator together.
- Free radical photoinitiators can act as a Norrish type I or a Norrish type II initiator.
- Tertiary amines are today admixed to free radical polymerizable radiation curable formulations for two main reasons:
- ketones for example, of the benzophenone type, wherein the excited keto groups abstract a hydrogen from the amine, whereby radicals are formed promoting radical
- a suitable Norrish type l-photoinitiator is selected from the group
- a suitable Norrish type ll-initiator is selected from the group consisting of benzophenones, thioxanthones, 1,2-diketones and anthraquinones.
- photoinitiators suitable for the photoinitiating functional groups in preparing diffusion hindered photoinitiators are disclosed by CRIVELLO, J.V., et al.; Chemistry & technology of UV & EB Formulation for Coatings, Inks & Paints. Volume III: Photoinitiators for Free Radical, Cationic & Anionic Photopolymerisation, 2nd edition, John Wiley & Sons Ltd in association with SITA Technology Ltd, London, UK, 1998 edited by Dr. G. Bradley; ISBN 0471 978922, page 287 - 294.
- photo-initiators may include, but are not limited to, the following compounds or combinations thereof: benzophenone and substituted benzophenones, 1-hydroxycyclohexyl phenyl ketone, thioxanthones such as isopropylthioxanthone, 2-hydroxy-2-methyi-1- phenylpropan-1 -one, 2-benzyl-2-dimethylamino- (4-morphoiinophenyl) butan-1-one, benzil dimethylketal, bis (2,6- dimethylbenzoyi) -2,4, 4- trimethylpentylphosphine oxide, 2,4,6 trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6 ⁇ trimethylbenzoylphenylphosphinate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1 , 2- diphenylethan
- Suitable commercial photo-initiators include IrgacureTM 184, IrgacureTM
- IrgacureTM 907 IrgacureTM 369, IrgacureTM 379, IrgacureTM 1700, IrgacureTM 651 , IrgacureTM 819, IrgacureTM 907, IrgacureTM 1000,
- the UV curable inkjet composition according to the present invention preferably contains a so-called diffusion hindered photoinitiator.
- a diffusion hindered photoinitiator is a photoinitiator which exhibits a much lower mobility in a cured layer of the curable liquid or ink than a monofunctional photoinitiator, such as benzophenone.
- Several methods can be used to lower the mobility of the photoinitiator.
- One way is to increase the molecular weight of the photoinitiator so that the diffusion speed is reduced, e.g. difunctional photoinitiators or polymeric photoinitiators.
- Another way is to increase its reactivity so that it is built into the polymerizing network, e.g.
- the diffusion hindered photoinitiator is preferably selected from the group consisting of non-polymeric di- or multifunctional photoinitiators, oligomeric or polymeric photoinitiators and polymerizable photoinitiators.
- Non- polymeric di- or multifunctional photoinitiators are considered to have a molecular weight between 300 and 900 Dalton.
- Monofunctional photoinitiators with a molecular weight in that range are not diffusion hindered photoinitiators. Both type I and type II photoinitiators can be used in the present invention, alone or in combination.
- the UV curable inkjet composition contains one or more polymerizable
- the polymerizable photoinitiator contains an acrylate group as polymerizable group.
- a preferred amount of photoinitiator is 0.3 - 50 wt% of the total weight of the UV curable inkjet composition, and more preferably 1 - 5 wt% of the total weight of the UV curable inkjet composition.
- Suitable examples of co-initiators can be categorized in 3 groups:
- tertiary aliphatic amines such as methyldiethanolamine
- aromatic amines such as amylparadimethylaminobenzoate, 2-n- butoxyethyl-4-(dimethylamino) benzoate, 2-(dimethylamino)ethylbenzoate, ethyl-4-(dimethylamino)benzoate, and 2-ethylhexyl-4- (dimethylamino)benzoate; and
- (meth)acrylated amines such as dialkylamino alkyl(meth)acrylates (e.g., diethylaminoethylacrylate) or N-morpholinoalkyl-(meth)acrylates (e.g., N-morpholinoethyl-acrylate).
- dialkylamino alkyl(meth)acrylates e.g., diethylaminoethylacrylate
- N-morpholinoalkyl-(meth)acrylates e.g., N-morpholinoethyl-acrylate
- the preferred co-initiators are aminobenzoates, preferably polymerizable aminobenzoates.
- composition according to the present invention preferably these co- initiators are also diffusion hindered.
- a diffusion hindered co-initiator is preferably selected from the group
- the diffusion hindered co-initiator is selected from the group consisting of polymeric co-initiators and polymerizable co-initiators. Most preferably the diffusion hindered co-initiator is a polymerizable co-initiator.
- a preferred diffusion hindered co-initiator is a polymeric co-initiator having a dendritic polymeric architecture, more preferably a hyperbranched polymeric architecture.
- Preferred hyperbranched polymeric co-initiators are those disclosed in US 2006014848 (AGFA) incorporated herein as a specific reference.
- a more preferred diffusion hindered co-initiator is one or more
- polymerizable co-initiators comprises at least one (meth)acrylate group, most preferably at least one acrylate group.
- a preferred polymerizable co-initiator is a co-initiator according to Formula (CO-I):
- R 1 and R 2 are independently selected from the group consisting of an alky! group, an alkenyl group, an alkynyl group, an aralkyl group, an alkaryl group, an aryl group and a heteroaryl group;
- R 3 to R 6 are independently selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, a thioalkyl group, an alkoxy group, a halogen, an aralkyl group, an alkaryl group, an aryl group and a heteroaryl group;
- R 7 is selected from the group consisting of hydrogen, an aldehyde group, a ketone group, an ester group, an amide group, an acyl group, a thioalkyl group, an alkoxy group, a halogen, a nitrile group, a sulphonate group, a sulphonamide group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an alkaryl group, an aryl group and a heteroaryl group; R 1 and R 2 , R 1 and R 3 , R 2 and R* R 3 and R 4 , R 4 and R 7 , R 5 and R , and R 6 and R 7 may represent the necessary atoms to form a 5- to 8-membered ring; and with the proviso that the aromatic amine has at least one Alfa hydrogen; and
- At least one of R 1 to R 7 comprises a poiymerizable ethylenically
- R 7 represents an electron withdrawing group selected from the group consisting of an aldehyde, a ketone, an ester and an amide, and more preferably R 3 , R 4 , R 6 and R 6 all represent hydrogen.
- alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, alkaryl groups, aryl groups and heteroaryl groups used for R 1 to R 7 can be substituted or unsubstituted groups, i.e. a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group and a substituted or
- unsubstituted (hetero)aryl group may be used.
- the UV curable inkjet composition preferably comprises the poiymerizable co-initiator in an amount of 0.1 to 50 wt%, more preferably in an amount of 0.5 to 25 wt%, most preferably in an amount of 1 to 10 wt% of the total weight of the UV curable inkjet composition.
- the UV curable compositions and inks may contain a polymerization
- Suitable polymerization inhibitors include phenol type
- antioxidants hindered amine light stabilizers, phosphor type antioxidants, hydroquinone monomethyl ether commonly used in (meth)acrylate monomers, and hydroquinone, t-butylcatechol, pyrogallol, 2,6-di-tert.butyl- 4-methylphenol may also be used.
- Suitable commercial inhibitors are, for example, SumilizerTM GA-80,
- SumilizerTM GM and SumilizerTM GS produced by Sumitomo Chemical Co. Ltd.; GenoradTM 16, GenoradTM 18 and GenoradTM 20 from Rahn AG;
- the inhibitor is preferably a polymerizable inhibitor.
- the amount capable of preventing polymerization is determined prior to blending.
- polymerization inhibitor is preferably lower than 5 wt%, more preferably lower than 3 wt% of the total ink or liquid.
- the UV curable compositions and inks may contain a surfactant.
- surfactant(s) can be anionic, cationic, non-ionic, or zwitter-ionic and are usually added in a total quantity less than 10 wt% based on the total weight of the UV curable compositions or ink and particularly in a total less than 5 wt% based on the total weight of the UV curable composition or ink.
- Suitable surfactants include those disclosed in paragraphs [0283] to [0291] of WO 2008/074548 (AGFA GRAPHICS) incorporated herein as a specific reference.
- Colorants used in the UV curable inks may be dyes, pigments or a
- Organic and/or inorganic pigments may be used.
- the colorant is preferably a pigment or a polymeric dye, most preferably a pigment.
- the pigments may be black, white, cyan, magenta, yellow, red, orange, violet, blue, green, brown, mixtures thereof, and the like.
- This colour pigment may be chosen from those disclosed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley - VCH , 2004. ISBN 3527305769.
- Suitable pigments are disclosed in paragraphs [0128] to [0138] of WO 2008/074548 (AGFA GRAPHICS) .
- Suitable pigments include mixed crystals of the above particular preferred pigments.
- Mixed crystals are also referred to as solid solutions.
- different quinacridones mix with each other to form solid solutions, which are quite different from both physical mixtures of the compounds and from the compounds themselves.
- the molecules of the components enter into the same crystal lattice, usually, but not always, that of one of the components.
- the x-ray diffraction pattern of the resulting crystalline solid is characteristic of that solid and can be clearly differentiated from the pattern of a physical mixture of the same components in the same proportion. In such physical mixtures, the x-ray pattern of each of the components can be
- Cinquasia Magenta RT-355-D from Ciba Specialty Chemicals.
- mixtures of pigments may be used in the UV curable inks.
- a neutral black inkjet ink is preferred and can be obtained, for example, by mixing a black pigment and a cyan pigment into the ink.
- the inkjet application may also require one or more spot colours, for example for packaging inkjet printing or textile inkjet printing. Silver and gold are often desired colours for inkjet poster printing and point-of-sales displays.
- Non-organic pigments may be used in the colour inkjet inks.
- Particular preferred pigments are C.I. Pigment Metal 1 , 2 and 3.
- Illustrative examples of the inorganic pigments include red iron oxide (III), cadmium red, ultramarine blue, prussian blue, chromium oxide green, cobalt green, amber, titanium black and synthetic iron black.
- Pigment particles in inkjet inks should be sufficiently small to permit free flow of the ink through the inkjet-printing device, especially at the ejecting nozzles. It is also desirable to use small particles for maximum colour strength and to slow down sedimentation.
- the numeric average pigment particle size is preferably between 0.050 and 1 pm, more preferably between 0.070 and 0.300 pm and particularly preferably between 0.080 and 0.200 pm. Most preferably, the numeric average pigment particle size is no larger than 0.150 pm. An average particle size smaller than 0.050 pm is less desirable for decreased light- fastness, but mainly also because very small pigment particles or individual pigment molecules thereof may still be extracted in food packaging applications.
- the average particle size of pigment particles is determined with a Nicomp 30 Submicron Particle Analyzer based upon the principle of dynamic light scattering. The ink is diluted with ethyl acetate to a pigment concentration of 0.002 wt%.
- the numeric average particle diameter of the white pigment is preferably from 50 to 500 nm, more preferably from 150 to 400 nm, and most preferably from 200 to 350 nm. Sufficient hiding power cannot be obtained when the average diameter is less than 50 nm, and the storage ability and the jet-out suitability of the ink tend to be degraded when the average diameter exceeds 500 nm.
- the determination of the numeric average particle diameter is best performed by photon correlation spectroscopy at a wavelength of 633 nm with a 4mW HeNe laser on a diluted sample of the pigmented inkjet ink.
- a suitable particle size analyzer used was a Malvern nano-S available from Goffin-Meyvis.
- a sample can be, for example, be prepared by addition of one drop of ink to a cuvet containing 1.5 ml_ ethyl acetate and mixed until a homogenous sample was obtained.
- the measured particle size is the average value of 3 consecutive measurements consisting of 6 runs of 20 seconds.
- Suitable white pigments are given by Table 2 in [01 16] of WO
- the white pigment is preferably a pigment with a refractive index greater than .60.
- the white pigments may be employed singly or in combination.
- titanium dioxide is used as pigment with a refractive index greater than .60.
- Suitable titanium dioxide pigments are those disclosed in [01 17] and in [01 8] of WO
- the pigments are present in the range of 0.01 to 10 % by weight,
- the white pigment is preferably present in an amount of 3% to 30% by weight of the ink composition, and more preferably 5% to 25%. An amount of less than 3% by weight cannot achieve sufficient covering power and usually exhibits very poor storage stability and ejection property.
- pigments are stabilized in the dispersion medium by dispersing agents, such as polymeric dispersants.
- dispersing agents such as polymeric dispersants.
- the surface of the pigments can be modified to obtain so-called “self-dispersible” or “self-dispersing” pigments, i.e. pigments that are dispersible in the dispersion medium without dispersants.
- the dispersant is preferably a polymeric dispersant.
- Typical polymeric dispersants are copolymers of two monomers but may contain three, four, five or even more monomers.
- the properties of polymeric dispersants depend on both the nature of the monomers and their distribution in the polymer.
- Suitable copolymeric dispersants have the following polymer compositions:
- alternating polymerized monomers e.g. monomers A and B polymerized into ABABABAB
- block copolymers e.g. monomers A and B polymerized into AAAAABBBBBB wherein the block length of each of the blocks (2, 3, 4, 5 or even more) is important for the dispersion capability of the polymeric dispersant;
- graft copolymers consist of a polymeric backbone with polymeric side chains attached to the backbone; and mixed forms of these polymers, e.g. blocky gradient copolymers.
- EP 1911814 A (AGFA GRAPHICS) incorporated herein as a specific reference.
- the polymeric dispersant has preferably a number average molecular weight Mn between 500 and 30000, more preferably between 1500 and 10000.
- the polymeric dispersant has preferably a weight average molecular
- weight Mw smaller than 100000, more preferably smaller than 50000 and most preferably smaller than 30000.
- the polymeric dispersant has preferably a polydispersity PD smaller than 2, more preferably smaller than 1.75 and most preferably smaller than 1.5.
- polymeric dispersants are the following:
- Particularly preferred polymeric dispersants include SolsperseTM
- dispersants from NOVEON EfkaTM dispersants from CIBA SPECIALTY CHEMICALS INC and DisperbykTM dispersants from BYK CHEMIE GMBH.
- Particularly preferred dispersants are Solsperse' M 32000, 35000 and 39000 dispersants from NOVEON.
- the polymeric dispersant is preferably used in an amount of 2 to 600 wt%, more preferably 5 to 200 wt% based on the weight of the pigment.
- a dispersion synergist usually consists of an anionic part and a cationic part.
- the anionic part of the dispersion synergist exhibiting a certain molecular similarity with the colour pigment and the cationic part of the dispersion synergist consists of one or more protons and/or cations to compensate the charge of the anionic part of the dispersion synergist.
- the synergist is preferably added in a smaller amount than the polymeric dispersant(s).
- the ratio of polymeric dispersant/dispersion synergist depends upon the pigment and should be determined experimentally. Typically the ratio wt% polymeric dispersant/wt% dispersion synergist is selected between 2:1 to 100:1 , preferably between 2:1 and 20:1.
- Suitable dispersion synergists that are commercially available include
- Particular preferred pigments for the magenta ink used are a diketopyrrolo- pyrrole pigment or a quinacridone pigment.
- Suitable dispersion synergists include those disclosed in EP 1790698 A (AGFA GRAPHICS) , EP
- Cu-phthalocyanine dispersion synergist e.g. SolsperseTM 5000 from NOVEON is preferred.
- Suitable dispersion synergists for yellow inkjet inks include those disclosed in EP 1790697 A (AGFA GRAPHICS) .
- the inkjet printing system according to the present invention comprises the combination of the print head and the UV curable inkjet composition.
- the inkjet printing method according to the present invention comprises the steps of:
- an inkjet printer containing at least one inkjet print head having a nozzle density of at least 600 dpi and nozzles with a diameter D smaller than 25 pm;
- a UV curable inkjet composition containing 0 to 10 wt% of one or more monofunctional monomers and at least A wt% of 2-(2-vinyloxyethoxy)ethyl acrylate, wherein both wt% are based on the total weight of the UV curable inkjet composition;
- A is defined by the formula (I):
- the inkjet printer of the inkjet printing system and inkjet printing method contains a plurality of inkjet print heads having a nozzle density of at least 600 dpi and nozzles with a diameter D smaller than 25 pm.
- Printing is preferably performed in a single pass
- UV curable compositions and inks according to the present invention are cured by a curing means exposing them to UV radiation.
- the curing means may be arranged in combination with the print head of the inkjet printer, travelling therewith so that the curable liquid is exposed to curing radiation very shortly after been jetted.
- a static fixed radiation source may be employed, e.g. a source of curing UV-light, connected to the radiation source by means of flexible radiation conductive means such as a fibre optic bundle or an internally reflective flexible tube.
- the actinic radiation may be supplied from a fixed source to the print head by an arrangement of mirrors including a mirror upon the print head.
- the source of the curing means arranged not to move with the print head may also be an elongated radiation source extending transversely across the ink-receiver surface to be cured and adjacent the transverse path of the print head so that the subsequent rows of images formed by the print head are passed, stepwise or continually, beneath that radiation source.
- a radiation source such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser, and a flash light.
- the preferred source is one exhibiting a relatively long wavelength UV-contribution having a dominant wavelength of 300- 400 nm.
- a UV-A light source is preferred due to the reduced light scattering therewith resulting in more efficient interior curing.
- UV radiation is generally classed as UV-A, UV-B, and UV-C as follows:
- UV-A 400 nm to 320 nm
- UV-C 290 nm to 100 nm.
- the first UV-source can be selected to be rich in UV-C, in particular in the range of 260 nm-200 nm.
- the second UV-source can then be rich in UV-A, e.g. a gallium-doped lamp, or a different lamp high in both UV-A and UV-B.
- the use of two UV-sources has been found to have advantages e.g. a fast curing speed.
- the inkjet printer often includes one or more oxygen depletion units.
- the oxygen depletion units place a blanket of nitrogen or other relatively inert gas (e.g.CO 2 ), with adjustable position and adjustable inert gas concentration, in order to reduce the oxygen concentration in the curing environment. Residual oxygen levels are usually maintained as low as 200 ppm, but are generally in the range of 200 ppm to 1200 ppm. Preparation of curable inks
- the average particle size and distribution of a colour pigment is an
- the inkjet ink may be prepared by precipitating or milling the pigment in the dispersion medium in the presence of the dispersant.
- Mixing apparatuses may include a pressure kneader, an open kneader, a planetary mixer, a dissolver, and a Dalton Universal Mixer.
- Suitable milling and dispersion apparatuses are a ball mill, a pearl mill, a colloid mill, a high-speed disperser, double rollers, a bead mill, a paint conditioner, and triple rollers.
- the dispersions may also be prepared using ultrasonic energy.
- the grinding media can comprise particles, preferably substantially spherical in shape, e.g. beads consisting essentially of a polymeric resin or yttrium stabilized zirconium oxide beads.
- each process is performed with cooling to prevent build up of heat, and as much as possible under light conditions in which actinic radiation has been substantially excluded.
- the inkjet ink may contain more than one pigment, and may be prepared using separate dispersions for each pigment, or alternatively several pigments may be mixed and co-milled in preparing the dispersion.
- the dispersion process can be carried out in a continuous, batch or semi- batch mode.
- the preferred amounts and ratios of the ingredients of the mill grind will vary widely depending upon the specific materials and the intended applications.
- the contents of the milling mixture comprise the mill grind and the milling media.
- the mill grind comprises pigment, polymeric dispersant and a liquid carrier.
- the pigment is usually present in the mill grind at 1 to 50 wt%, excluding the milling media.
- the weight ratio of pigment over polymeric dispersant is 20:1 to 1 :2.
- the milling time can vary widely and depends upon the pigment
- pigment dispersions with an average particle size of less than 100 nm may be prepared.
- the milling media is separated from the milled particulate product (in either a dry or liquid dispersion form) using conventional separation techniques, such as by filtration, sieving through a mesh screen, and the like. Often the sieve is built into the mill, e.g. for a bead mill.
- the milled pigment concentrate is preferably separated from the milling media by filtration.
- the inkjet ink is adjusted to the desired viscosity, surface tension, colour, hue, saturation density, and print area coverage for the particular application.
- VEEA is mer available from NIP
- PB15:4 is an abbreviation used for Hostaperm I Blue P-BFS, a C.I.
- PB7 is an abbreviation used for Special BlackTM 550, which is a carbon black available from EVONIK DEGUSSA.
- S35000 is an abbreviation used for SOLSPERSETM 35000, a
- polyethyleneimine-polyester hyperdispersant from NOVEON polyethyleneimine-polyester hyperdispersant from NOVEON.
- S35000-sol is an abbreviation used for a 40wt% solution of
- DPGDA is dipropyleneglycoldiacrylate from SARTOMER.
- M600 is dipentaerythntol hexaacrylate and an abbreviation for MiramerTM
- SR256 is 2-(2-ethoxy ethoxy)ethyl acrylate and an abbreviation for
- SR285 is SartomerTM 285, a tetrahydrofurfuryl acrylate monomer available from SARTOMER.
- SR395 is SartomerTM 395, an isodecyl acrylate monomer available from SARTOMER.
- CD420 is SartomerTM CD420, an isophoryl acrylate monomer available from SARTOMER.
- SR9003 is an abbreviation for SartomerTM SR9003, a propoxylated
- neopentyl glycol diacrylate monomer available from SARTOMER.
- ITX is DarocurTM ITX is an isomeric mixture of 2- and 4- isopropylthioxanthone from CIBA SPECIALTY CHEMICALS.
- IrgacureTM 819 is a photoinitiator available from CIBA SPECIALTY having
- IrgacureTM 379 is a ph Y having
- IrgacureTM 907 is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan- 1-one, a photoinitiator available from CIBA SPECIALTY CHEMICALS.
- EPD is ethyl 4-dimethylaminobenzoate, available under the trade name of GenocureTM EPD from RAHN AG.
- TPO is an abbreviation used for GenocureTM TPO is 2,4,6- trimethylbenzoyl-diphenyl-phosphineoxide from RAHN AG.
- BYKTM UV3510 is a polyether modified polydimethylsiloxane wetting agent available from BYK CHEMIE GMBH.
- GenoradTM 16 is a polymerization inhibitor from RAHN AG.
- the curing speed of the radiation curable compositions was evaluated using a Fusion DRSE-120 conveyer, equipped with a Fusion VPS/I600 lamp (D-bulb), which transported the samples under the UV-lamp on a conveyer belt at a speed of 20 m/min.
- the curing speed was defined as the percentage of the maximum output of the lamp needed to fully cure the samples. The lower the number the higher curing speed. A sample was considered as fully cured at the moment scratching with a Q-tip caused no visual damage.
- the viscosity of the formulations was measured using a Brookfield DV-II+ viscometer at 25° C at 3 rotations per minute (RPM) using a CPE 40 spindle.
- the weight loss was measured after keeping an UV curable ink in an open container for 200h at 40° C. The weight loss is expressed as a wt% based on the original weight of the UV curable ink.
- the weight loss is indicative for latency according to Table 1 below.
- Submicron Particle Analyzer available from Particle Sizing Systems and is based upon the principle of dynamic light scattering.
- the ink or dispersion was diluted with ethyl acetate to a pigment concentration of 0.002 wt%.
- This example illustrates the relation between the outer nozzle diameter in a high nozzle density print head and the amount of 2-(2- vinyloxyethoxy)ethyl acrylate in a radiation curable inkjet ink.
- a concentrated pigment dispersion D-1 was prepared by mixing for 30 minutes the components according to Table 2 using a DISPERLUXTM Dissolver (from DISPERLUX S.A.R.L., Germany) and subsequently milling this mixture in a Eiger Lab Bead mill (from EIGER TORRANCE Ltd.) having a bead filling of 42% with 0.4 mm yttrium stabilized zirconium oxide beads ( "high wear resistant zirconia grinding media" from TOSOH Co.) and milling for 100 minutes. After milling the dispersion was separated from the beads using a filter cloth.
- the average particle size of the concentrated dispersion D-1 was 109 nm measured with a Nicomp 30 Submicron Particle Analyzer .
- the UV curable inkjet inks lnk-1 to lnk-7 were prepared by adding to the cyan pigment dispersion D-1 , the components according to Table 3. The weight% (wt%) of the components are based on the total weight of the UV curable inkjet ink. Only lnk-6 and lnk-7 contain 2-(2-vinyloxyethoxy)ethyl acrylate.
- UV curable inkjet inks lnk-1 , lnk-6 and lnk-7 have a good curing speed and latency.
- a concentrated pigment dispersion D-2 was prepared by mixing for 30 minutes the components according to Table 5 using a DISPERLUXTM Dissolver (from DISPERLUX S.A.R.L., Luxembourg) and subsequently milling this mixture in a DYNOMILL ECM POLY mill (from BACHOFEN GmbH) having a bead filling of 42% with 0.4 mm yttrium stabilized zirconium oxide beads ( "high wear resistant zirconia grinding media" from TOSOH Co.) and milling for 140 minutes at a rotation speed of 14.7 m/s. After milling the dispersion was separated from the beads using a filter cloth.
- the average particle size of the concentrated dispersion D-2 was 106 nm measured with a Nicomp 30 Submicron Particle Analyzer .
- the UV curable inkjet inks lnk-8 to lnk-11 were prepared by adding to the black pigment dispersion D-2, the components according to Table 6.
- the weight% (wt%) of the components are based on the total weight of the UV curable inkjet ink. Table 6
- the inks lnk-8 to lnk-1 1 were jetted on an ink-receiver using a Kyocera KJ4B print head with a driving voltage of 24 V to produce images at 600 x 300 dpi resolution with 1 dpd drops.
- the nozzle diameter was 20 pm.
- the wt% A of VEEA should be between 40 wt% and 80 wt% based on the total weight of the ink.
- the inkjet ink lnk-8 does not comply with this criterion as it contains only 35 w ⁇ % of the difunctional monomer VEEA.
- the inkjet inks lnk-9 to lnk- 1do not contain a monofunctional monomer.
- the concentrated pigment dispersions D-3 and D-4 were prepared by mixing for 30 minutes the components according to Table 8 using a DISPERLUXTM Dissolver (from DISPERLUX S.A.R.L., Germany) and subsequently milling this mixture in a DYNOMILL ECM PRO mill (from BACHOFEN GmbH ) having a bead filling of 42% with 0.4 mm yttrium stabilized zirconium oxide beads ( "high wear resistant zirconia grinding media" from TOSOH Co.) and milling for 13 hours. After milling the dispersions were separated from the beads using a filter cloth.
- Dispersion D-3 Dispersion D-4
- UV curable inkjet inks lnk-12 to lnk-14 were prepared by mixing the components according to Table 10.
Abstract
Description
Claims
Priority Applications (7)
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JP2012531326A JP5799017B2 (en) | 2009-10-02 | 2010-09-22 | UV curable ink jet composition for high-density printheads |
KR1020127008128A KR101486391B1 (en) | 2009-10-02 | 2010-09-22 | UV curable inkjet compositions for high-density print heads |
US13/394,552 US8807734B2 (en) | 2009-10-02 | 2010-09-22 | UV curable inkjet compositions for high-density print heads |
BR112012007541A BR112012007541A2 (en) | 2009-10-02 | 2010-09-22 | UV curable inkjet compositions for high density printheads |
CA2769166A CA2769166C (en) | 2009-10-02 | 2010-09-22 | Uv curable inkjet compositions for high-density print heads |
CN201080045016.4A CN102575122B (en) | 2009-10-02 | 2010-09-22 | UV curable inkjet compositions for high-density print heads |
AU2010300145A AU2010300145B2 (en) | 2009-10-02 | 2010-09-22 | UV curable inkjet compositions for high-density print heads |
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EP09172025.0 | 2009-10-02 | ||
EP09172025A EP2305762B1 (en) | 2009-10-02 | 2009-10-02 | UV curable inkjet compositions for high-density print heads |
US25002209P | 2009-10-09 | 2009-10-09 | |
US61/250,022 | 2009-10-09 |
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US (1) | US8807734B2 (en) |
EP (1) | EP2305762B1 (en) |
JP (1) | JP5799017B2 (en) |
KR (1) | KR101486391B1 (en) |
CN (1) | CN102575122B (en) |
AU (1) | AU2010300145B2 (en) |
BR (1) | BR112012007541A2 (en) |
CA (1) | CA2769166C (en) |
ES (1) | ES2386104T3 (en) |
PL (1) | PL2305762T3 (en) |
WO (1) | WO2011039081A1 (en) |
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Also Published As
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US8807734B2 (en) | 2014-08-19 |
AU2010300145B2 (en) | 2013-10-17 |
AU2010300145A1 (en) | 2012-02-09 |
PL2305762T3 (en) | 2012-11-30 |
BR112012007541A2 (en) | 2016-12-06 |
EP2305762A1 (en) | 2011-04-06 |
CA2769166A1 (en) | 2011-04-07 |
KR20120073258A (en) | 2012-07-04 |
JP2013506573A (en) | 2013-02-28 |
CN102575122B (en) | 2014-10-29 |
JP5799017B2 (en) | 2015-10-21 |
ES2386104T3 (en) | 2012-08-09 |
CA2769166C (en) | 2014-01-21 |
EP2305762B1 (en) | 2012-06-27 |
CN102575122A (en) | 2012-07-11 |
US20120194616A1 (en) | 2012-08-02 |
KR101486391B1 (en) | 2015-01-26 |
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