EP1652686B1 - Druck der strahlungshärtbaren Tinten in eine flüssige strahlungshärtbare Schicht - Google Patents

Druck der strahlungshärtbaren Tinten in eine flüssige strahlungshärtbare Schicht Download PDF

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Publication number
EP1652686B1
EP1652686B1 EP05107954A EP05107954A EP1652686B1 EP 1652686 B1 EP1652686 B1 EP 1652686B1 EP 05107954 A EP05107954 A EP 05107954A EP 05107954 A EP05107954 A EP 05107954A EP 1652686 B1 EP1652686 B1 EP 1652686B1
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Prior art keywords
ink
radiation curable
liquid layer
jet
radiation
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EP1652686A1 (de
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Roland Claes
Robert Janssens
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Agfa NV
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Agfa Graphics NV
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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

Definitions

  • the present invention relates to the printing of radiation curable inks into a radiation curable liquid layer, more specifically to high-speed ink-jet printing exhibiting high image quality.
  • tiny drops of ink 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 ink drops image-wise onto the ink-receiver. Printing can be accomplished by moving a print head across the ink-receiver or vice versa.
  • the ink fluids can be roughly divided into:
  • Hot melt and radiation curable inks are usually jetted on substantially non-absorbing ink-receivers. Hot melt inks are limited to thermally stable ink-receivers, while radiation curable inks can be jetted on a wide variety of ink-receivers.
  • the main problem of radiation curable inks is that the image quality tends to change with the selection of the ink-receiver.
  • the spreading of an ink droplet on the ink-receiver is highly dependent on the type of ink-receiver chosen.
  • One method to obtain a consistent image quality with a wide variety of ink-receivers would be to adapt the ink-jet ink set each time to the chosen ink-receiver.
  • changing inks in printer and print head is very time consuming and not really a viable solution for an industrial printing environment. Therefore, the general approach is to modify the surface chemistry either with a suitable surface layer coating or by pre-treatment, i.e. plasma or corona treatment.
  • Corona discharge treatment and plasma treatment increases the cost, complexity and maintenance of the equipment used to process the substrates.
  • Substrates may contain significant impurities or irregularities that may interfere with the treatment of the substrate. Thus, it is desirable to avoid the plasma treatment process where possible.
  • the other possibility for using the same ink-jet ink set on different ink-receivers is the application of a surface layer prior to jetting the radiation curable ink-jet ink.
  • radiation curable ink-jet ink is jetted onto a dry surface layer, or alternatively, radiation curable inks are all jetted on a liquid layer (i.e. without intermediate curing of the liquid layer), as for example in US 6720042 (3M).
  • a radiation curable ink droplet is deposited on a previously deposited, uncured radiation curable ink droplet or droplets which form a wet ink layer.
  • WO 03074619 A discloses a progressive dot printing ink-jet process comprising the steps of applying a first ink drop to a substrate and subsequently applying a second drop on to the first ink drop without intermediate solidification of the first ink drop, wherein the first and second ink drops have a different viscosity, surface tension or curing speed.
  • the spreading of the second ink drop on the first ink drop can be well controlled, as it is also the case for a possible third and fourth ink drop.
  • the spreading of the first ink drop on the substrate remains critical and is dependent on the surface properties of the substrate.
  • Using colourless ink for the first ink drop can reduce this image quality problem.
  • Suitable radiation curable inks, including a colourless ink, for wet-on-wet ink-jet printing are disclosed by US 6550905 (DOTRIX) .
  • the company AellorraTM Digital presented an ink-jet printing process with a high viscous white wet layer, produced by jetting a UV-curable white ink, instead of a colourless wet layer. A second radiation curable ink was jetted on top of the white wet layer and the UV-curing was performed.
  • Another problem associated with radiation curable ink-jet printing is that images exhibit a poor gloss compared to solvent or aqueous based inks on an absorbing substrate.
  • the amount of solids, i.e. the radiation curable compounds and colorants, deposited on an ink-receiver varies with the image information, resulting in a higher surface roughness and hence a reduced glossiness.
  • WO 0030856 discloses a method of ink-jet printing on a substrate, comprising the steps of forming a wet undercoat layer on the substrate; depositing onto the undercoat layer, whilst the undercoat layer remains wet, a pattern of wet ink droplets and subsequently transforming the undercoat layer and deposited ink droplets to a dry state.
  • WO 0030856 improves the print quality by varying the thickness of the undercoat inversely with the thickness of the ink, so that a flat print surface is achieved. Beside restrictions on the arrangements of print heads and the calculating power required to achieve the variation of thickness in accordance with the image to be printed, it is also difficult to avoid the spreading of undercoat layer from unprinted area's, i.e. full thickness of the undercoat layer, into the area's printed with 100% ink, i.e. zero thickness of undercoat layer, which results in less sharp images.
  • ink droplets The spreading of ink droplets on a substrate largely defines the resolution that can be obtained.
  • surface property modification by either coating or pre-treatment techniques has been widely employed, the exact nature of the ink-media interaction is not fully understood. Attempts are typically made to correlate the print quality to measurable surface parameters such as surface energy and surface roughness, but these parameters do not fully capture the behaviour of ink droplets on various media.
  • Objects of the present invention are realized by a printing process for ink-jet printing a radiation curable image on a substrate comprising the steps of:
  • Figure 1 is a schematic cross section through a substrate 14 printed in accordance with one aspect of the invention in 1 b and 1c.
  • a radiation curable inkjet ink droplet 10 is jetted in the jetting direction 11 onto a substrate 14 exhibiting a large spreading.
  • the radiation curable inkjet ink droplet 10 is jetted into a radiation curable liquid layer 12, exhibiting a reduced dotsize.
  • the thickness of the radiation curable liquid layer 12 is increased from 1b to 1c, which causes the dotsize of the radiation curable ink droplet 13 located in the liquid layer 12 to decrease further.
  • Figure 2 is a graph depicting the relation between the thickness of the liquid layer and the dot diameter of a radiation curable ink droplet jetted into the liquid layer.
  • actinic radiation means electromagnetic radiation capable of initiating photochemical reactions.
  • electromagnetic radiation means electromagnetic radiation in the wavelength range of 4 to 400 nanometers.
  • UV ultraviolet radiation
  • Nevish Type I initiator as used in disclosing the present invention, means a photo-initiator which cleaves after excitation, yielding the initiating radical immediately.
  • Nevish type II-initiator means a photo-initiator which is activated by actinic radiation and forms free radicals by hydrogen abstraction or electron extraction from a second compound that becomes the actual initiating free radical.
  • co-initiator means any molecule capable of transferring a hydrogen to the excited state of a Norrish type II-initiator and initiating the radical polymerization of a radiation curable composition.
  • colorant means dyes and pigments.
  • 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 an inorganic or organic, chromatic or achromatic colouring agent 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-methyl-butyl etc.
  • aliphatic group as used in disclosing the present invention means saturated straight chain, branched chain and alicyclic hydrocarbon groups.
  • aryl group as used in disclosing the present invention means an assemblage of cyclic conjugated carbon atoms, which are characterized by large resonance energies, e.g. benzene, naphthalene and anthracene.
  • alicyclic hydrocarbon group means an assemblage of cyclic conjugated carbon atoms, which do not form an aromatic group, e.g. cyclohexane.
  • the printing process according to the present invention is a radiation curable inkjet printing process.
  • the means for jetting may be one or more printing heads ejecting small droplets of ink in a controlled manner through nozzles towards an ink-receiver surface, which is moving relative to the printing head(s).
  • the ejected or jetted ink forms an image on the ink-receiver.
  • 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, which may vary from 25 to 110°C, a surface energy such that the printing head nozzle can form the necessary small droplets, and a homogenous liquid capable of rapid conversion to a dry printed area.
  • a preferred ink-jet printing head for the printing process according to the present invention is a piezoelectric head.
  • Piezoelectric ink-jet 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 ink-jet printing head is however not restricted to a piezoelectric ink-jet printing head.
  • Other ink-jet printing heads for ink ejection can be used and include various types, such as a continuous type and thermal, electrostatic and acoustic drop on demand type.
  • an ink-jet printing head normally scans back and forth in a transversal direction across the moving ink-receiver surface. Often the ink-jet print head does not print on the way back. Bi-directional printing is preferred for obtaining a high areal throughput. Particularly preferred, is printing in a "single pass printing process", which can be performed by using page wide ink-jet printing heads (e.g. a page wide printing head available from XAAR) or multiple staggered ink-jet printing heads which cover the entire width of the ink-receiver surface. In a single pass printing process the ink-jet printing heads usually remain stationary and the ink-receiver surface is transported under the ink-jet printing heads.
  • page wide ink-jet printing heads e.g. a page wide printing head available from XAAR
  • multiple staggered ink-jet printing heads which cover the entire width of the ink-receiver surface.
  • High areal throughput ink-jet printing means that images should be printed at more than 50m 2 /hour, preferably at more than 100m 2 /hour, even more preferably at more than 200m 2 /hour and most preferably at more than 300m 2 /hour.
  • the resolution should at least be 180 dpi, preferably at least 300 dpi.
  • the ink-receiver used in the high areal throughput ink-jet printing system according to this invention has preferably a width of at least 240 mm, then requiring a printing speed of at least 35 m/min. More preferably the width of the ink-receiver is at least 300 mm, and particularly preferably the width of the ink-receiver is at least 500 mm.
  • the ink receiver suitable for the printing process according to the present invention is a substrate provided with a radiation curable liquid layer.
  • the substrate is provided with a radiation curable liquid layer on only a portion of its surface, i.e. that area intended to be imaged with radiation curable ink-jet ink. At least part of the radiation curable ink forming the image is jetted into the radiation curable liquid layer.
  • the radiation curable liquid layer may be applied to the substrate by any means known to one skilled in the art, e.g. spraying, jetting, screen-printing and coating.
  • the substrate may be chosen from the group consisting of paper, coated paper, polyolefin coated paper, cardboard, wood, composite boards, plastic, coated plastic, canvas, textile, metal, glasses, plant fibre products, leather, magnetic materials and ceramics.
  • the substrate for the ink-receiver is preferably substantially non-absorbing.
  • Suitable examples are a resin-coated paper, e.g. polyethylene-coated paper and polypropylene-coated paper, and polymeric substrates.
  • Suitable polymeric substrates include, for example, cellulose acetate propionate, cellulose acetate butyrate, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); oriented polystyrene (OPS); oriented nylon (ONy); polypropylene (PP), oriented polypropylene (OPP); polyvinyl chloride (PVC); and various polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), polyethers and polysulfonamides, opaque white polyesters and extrusion blends of polyethylene terephthalate and polypropylene. Acrylic resins, phenol resins, glass and metals may also be used as a substrate. Other suitable substrate materials can be found in . Modern Approaches to Wettability: Theory and Applications. Edited by SCHRADER Malcolm E.. New York 1992, ISBN 0306439859.
  • the substrate can be transparent, translucent or opaque.
  • the substrate may incorporate mineral particles as fillers, such as e.g. PET containing CaCO 3 , PET containing TiO 2 , a-PET and PET-g.
  • the substrate before printing may be coloured, e.g. a transparent PET containing a blue dye suitable for medical imaging may be used as an ink-receiver.
  • Polyester film substrates and especially polyethylene terephthalate are preferred for certain applications particularly types with excellent dimensional stability.
  • a subbing layer may be employed to improve the bonding of the jetted ink layer to the substrate, if it constitutes together with the unsubbed substrate a substantially non-absorbing ink-receiver.
  • Useful subbing layers for this purpose are well known in the photographic art and include, for example, polymers of vinylidene chloride such as vinylidene chloride /acrylonitrile /acrylic acid terpolymers or vinylidene chloride /methyl acrylate /itaconic acid terpolymers.
  • Uniformly adjusting the thickness of the radiation curable liquid layer allows to control the dot size of the ink droplets jetted into the radiation curable liquid layer and hence the resolution.
  • the jetted curable ink creates an uncured printed image.
  • the printed image is cured by exposing it to radiation or by electron beam curing.
  • a preferred means of radiation curing is ultraviolet light.
  • the curing means may be arranged in combination with the print head of the ink-jet printer, travelling therewith so that ink droplets are exposed to curing radiation very shortly after having been printed into the liquid layer.
  • a static fixed radiation source may be employed, e.g. a source of curing UV radiation, 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 curing radiation may be supplied from a fixed source to the radiation head by an arrangement of mirrors including a mirror upon the radiation head.
  • the source of radiation arranged not to move with the print head may also be an elongate 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.
  • each print head may have its own dedicated radiation source.
  • Any ultraviolet light source may be employed as 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 flashlight.
  • 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:
  • the first UV source can be selected to be rich in UV-C, in particular in the range of 240 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 ink-jet 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 can be maintained as low as 200 ppm, but are generally in the range of 2000 ppm to 20000 ppm.
  • the radiation curable liquid layer and/or radiation curable ink-jet ink are based on cationic polymerization, since this type of polymerization does not suffer from oxygen inhibition.
  • the radiation curable ink-jet ink is a cationic radiation curable ink-jet ink without an initiator, and the cationic initiator is contained in the radiation curable liquid layer
  • a radiation-curable liquid layer suitable for the printing process according to the present invention contains at least a radiation-curable compound.
  • the radiation-curable compound can be selected from monomers and/or oligomers that can be polymerized by a curing means of an inkjet printer.
  • the radiation-curable liquid layer may contain an initiator.
  • the radiation-curable liquid layer may further contain a colorant or a white pigment such as titanium oxide, although preferably the layer is a clear liquid layer.
  • the radiation-curable liquid layer may contain a polymerization inhibitor to restrain polymerization by heat or actinic radiation.
  • the radiation-curable liquid layer may further contain at least one resin in order to obtain a stable dispersion of the colorant in the inkjet ink.
  • the radiation-curable liquid layer preferably further contains at least one surfactant.
  • the radiation-curable liquid layer may further contain at least one solvent.
  • the radiation-curable liquid layer may further contain at least one biocide.
  • the radiation-curable liquid layer may have a thickness of about 0.1 ⁇ m, for example, if metal ink-receivers are used, but preferably a thickness of at least 1 ⁇ m is preferred.
  • a radiation-curable ink-jet ink suitable for the printing process according to the present invention contains at least two components: (i) a radiation-curable compound and (ii) a colorant (i.e. pigment or dye).
  • the radiation-curable compound can be selected from monomers and/or oligomers that can be polymerized by a curing means of an inkjet printer.
  • the radiation-curable ink-jet ink may contain an initiator.
  • the radiation-curable ink-jet ink may contain a polymerization inhibitor to restrain polymerization by heat or actinic radiation. It is preferred to add an inhibitor during preparation of the inkjet ink.
  • the radiation-curable ink-jet ink may further contain at least one resin in order to obtain a stable dispersion of the colorant in the inkjet ink.
  • the radiation-curable ink-jet ink preferably further contains at least one surfactant.
  • the radiation-curable ink-jet ink preferably further contains at least one solvent.
  • the radiation-curable ink-jet ink preferably further contains at least one biocide.
  • An inkjet printer generally uses a radiation-curable ink-jet ink set consisting of a plurality of radiation-curable inkjet inks.
  • the radiation curable ink-jet ink and the radiation curable liquid layer contain monomers and/or oligomers, which are polymerized by the curing means of the inkjet printer.
  • Monomers, oligomers or prepolymers may possess different degrees of functionality, and a mixture including combinations of mono-, di-, tri-and higher functionality monomers, oligomers and/or prepolymers may be used.
  • These components are curable, typically photo-curable, e.g. UV curable, and should adhere to the ink-receiver surface after printing and serve to bind the colorant.
  • a mixture of two or more monomers of the same functionality is preferred, with particularly preferred a mixture of two di-functional monomers.
  • the viscosity of the radiation curable ink-jet ink and the radiation curable liquid layer can be adjusted by varying the ratio between the monomers and oligomers.
  • radical polymerization Any method of conventional radical polymerization, photo-curing system using photo acid or photo base generator, or photo induction alternating copolymerization may be employed.
  • radical polymerization and cationic polymerization are preferred, and photo induction alternating copolymerization needing no initiator may also be employed.
  • a hybrid system of combinations of these systems is also effective.
  • Cationic polymerization is superior in effectiveness due to lack of inhibition of the polymerization by oxygen, however it is slow and expensive. If cationic polymerization is used, it is preferred to use an epoxy compound together with an oxetane compound to increase the rate of polymerization. Radical polymerization is the preferred polymerization process.
  • any polymerizable compound commonly known in the art may be employed.
  • Particularly preferred for use as a radiation-curable compound in the radiation curable ink-jet ink and the radiation curable liquid layer are monofunctional and/or polyfunctional acrylate monomers, oligomers or prepolymers, such as isoamyl acrylate, stearyl acrylate, lauryl acrylate, octyl acrylate, decyl acrylate, isoamylstyl acrylate, isostearyl acrylate, 2-ethylhexyl-diglycol acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethylhexahydrophthalic acid, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxypropylene glycol acrylate, phenoxyethyl acrylate,
  • methacrylates corresponding to the above-mentioned acrylates may be used with these acrylates.
  • methacrylates methoxypolyethylene glycol methacrylate, methoxytriethylene glycol methacrylate, 4-(vinyloxy)butylmethacrylate, vinyl ether acrylates such as described in US 5225522 (KODAK), hydroxyethyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate are preferred due to their relatively high sensitivity and higher adhesion to an ink-receiver surface.
  • the radiation curable ink-jet ink and the radiation curable liquid layer may also contain polymerizable oligomers.
  • polymerizable oligomers include epoxy acrylates, aliphatic urethane acrylates, aromatic urethane acrylates, polyester acrylates, and straight-chained acrylic oligomers.
  • Colorants may be dyes, but are preferably pigments or a combination thereof.
  • Organic and/or inorganic pigments may be used.
  • the pigment particles should be sufficiently small to permit free flow of the ink through the inkjet printing device, especially at the ejecting nozzles which usually have a diameter ranging from 10 ⁇ m to 50 ⁇ m.
  • the particle size influences also the pigment dispersion stability. It is also desirable to use small particles for maximum colour strength.
  • the particles of the pigment dispersed in the ink-jet ink should have a particle size of less than 10 ⁇ m, preferably less than 3 ⁇ m, and most preferably less than 1 ⁇ m.
  • the average particle size of pigment particles is preferably 0.05 to 0.5 ⁇ m. Very fine dispersions of pigments and methods for their preparation are disclosed in e.g.
  • EP 776952 A (KODAK) , US 5538548 (BROTHER) , US 5443628 (VIDEOJET SYSTEMS), EP 259130 A (OLIVETTI), US 5285064 (EXTREL) , EP 429828 A (CANON) and EP 526198 A (XEROX).
  • Suitable pigments include as red or magenta pigments: Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53: 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; as blue or cyan pigments: Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36, and 60; as green pigments: Pigment green 7, 26, 36, and 50; as yellow pigments: Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94
  • the pigment may be chosen from those disclosed by HERBST, W, et al. Industrial Organic Pigments, Production, Properties, Applications. 2nd edition. 1997 , .
  • Pigment Yellow 1 3, 128, 109, 93, 17, 14, 10, 12, 13, 83, 65, 75, 74, 73, 138, 139, 154, 151, 180, 185; Pigment Red 122, 22, 23, 17, 210, 170, 188, 185, 146, 144, 176, 57:1, 184, 202, 206, 207; Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16 and Pigment Violet 19.
  • Carbon black is usually used as the colouring material in black ink.
  • Suitable black pigment materials include carbon blacks such as Pigment Black 7 (e.g. Carbon Black MA8TM from MITSUBISHI CHEMICAL), RegalTM 400R, MogulTM L, ElftexTM 320 from CABOT Co., or Carbon Black FW18, Special Black 250, Special Black 350, Special Black 550, PrintexTM 25, PrintexTM 35, PrintexTM 55, PrintexTM 90, PrintexTM 150T from DEGUSSA. Additional examples of suitable pigments are disclosed in US 5225522 ( KODAK) .
  • the pigment is present in the range of 0.1 to 10wt%, preferably in the range 1 to 5wt% based on the total weight of the radiation curable inkjet ink.
  • Dyes suitable for the radiation curable ink-jet ink include direct dyes, acidic dyes, basic dyes and reactive dyes.
  • Suitable direct dyes for the radiation curable ink-jet ink include:
  • Suitable acidic dyes for the radiation curable ink-jet ink include:
  • Suitable reactive dyes for the radiation curable ink-jet ink include:
  • Suitable basic dyes for the radiation curable ink-jet ink include:
  • the radiation curable ink-jet ink preferably further comprises a pH buffer, such as potassium hydroxide (KOH).
  • KOH potassium hydroxide
  • a catalyst called a photo-initiator typically initiates the polymerization reaction.
  • the photo-initiator requires less energy to activate than the monomers and oligomers to form the polymer.
  • the photo-initiator suitable for use in the radiation curable ink-jet ink and the radiation curable liquid layer may be a Norrish type I initiator, a Norrish type II initiator or a photo-acid generator.
  • the photo-initiator absorbs light and is responsible for the production of free radicals or cations.
  • Free radicals or cations are high-energy species that induce polymerization of monomers, oligomers and polymers and with polyfunctional monomers and oligomers thereby also inducing cross-linking.
  • a preferred Norrish type I-initiator is selected from the group consisting of benzoinethers, benzil ketals, ⁇ , ⁇ -dialkoxyacetophenones, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, acylphosphine oxides, acylphosphine sulphides, ⁇ -haloketones, ⁇ -halosulfones and ⁇ -halophenylglyoxalates.
  • a preferred Norrish type II-initiator is selected from the group consisting of benzophenones, thioxanthones, 1,2-diketones and anthraquinones.
  • a preferred co-initiator is selected from the group consisting of an aliphatic amine, an aromatic amine and a thiol. Tertiary amines, heterocyclic thiols and 4-dialkylamino-benzoic acid are particularly preferred as co-initiator.
  • Suitable photo-initiators are disclosed in CRIVELLO, J.V., et al VOLUME III: Photoinitiators for Free Radical Cationic & Anionic Photopolymerization. 2nd edition. Edited by BRADLEY G.. London,UK 1998, p. 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-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino- (4-morpholinophenyl) butan-1-one, benzil dimethylketal, bis (2,6- dimethylbenzoyl) -2,4, 4-trimethylpentylphosphine oxide, 2,4,6trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4-(methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1, 2-diphenylethan-1-one or 5,7-diiodo-3- butoxy-6-fluorone, diphenyliodonium fluoride and trip
  • Suitable commercial photo-initiators include IrgacureTM 184, IrgacureTM 500, IrgacureTM 907, IrgacureTM 369, IrgacureTM 1700, IrgacureTM 651, IrgacureTM 819, IrgacureTM 1000, IrgacureTM 1300, IrgacureTM 1870, DarocurTM 1173, DarocurTM 4265 and DarocurTM ITX available from CIBA SPECIALTY CHEMICALS, Lucerin TPO available from BASF AG, Esacure TM KT046, EsacureTM KIP150, EsacureTM KT37 and EsacureTM EDB available from LAMBERTI, H-NuTM 470 and H-NuTM 470X available from SPECTRA GROUP Ltd..
  • a preferred amount of initiator is 0.3 - 50 weight% of the total ink weight or of the total liquid layer weight, and more preferably 1 - 25 weight% of the total ink weight or of the total liquid layer weight.
  • 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 initiator together.
  • 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 may also be used.
  • a phenol compound having a double bond in molecules derived from acrylic acid is particularly preferred due to its having a polymerization-restraining effect even when heated in a closed, oxygen-free environment.
  • Suitable inhibitors are, for example, SumilizerTM GA-80, SumilizerTM GM and SumilizerTM GS produced by Sumitomo Chemical Co., Ltd, and GenoradTM 16, GenoradTM 18 available from Rahn of Zurich, Switzerland.
  • the amount capable of preventing polymerization be determined prior to blending.
  • the amount of a polymerization inhibitor is generally between 200 and 20,000 ppm of the total ink weight or the total liquid layer weight.
  • the radiation curable ink-jet ink and the radiation curable liquid layer may further contain a resin, also called a pigment stabilizer or dispersant used to obtain a stable dispersion of the pigment(s) in the inkjet ink.
  • a resin also called a pigment stabilizer or dispersant used to obtain a stable dispersion of the pigment(s) in the inkjet ink.
  • the pigments may be added to the radiation curable ink-jet ink as a dispersion comprising a dispersant.
  • Suitable resins petroleum type resins (e.g., styrene type, acryl type, polyester, polyurethane type, phenol type, butyral type, cellulose type, and rosin); and thermoplastic resins (e.g., vinyl chloride, vinylacetate type). Concrete examples of these resins include acrylate copolymers, styrene-acrylate copolymers, acetalized and incompletely saponified polyvinyl alcohol, and vinylacetate copolymers.
  • petroleum type resins e.g., styrene type, acryl type, polyester, polyurethane type, phenol type, butyral type, cellulose type, and rosin
  • thermoplastic resins e.g., vinyl chloride, vinylacetate type. Concrete examples of these resins include acrylate copolymers, styrene-acrylate copolymers, acetalized and incompletely saponified polyvinyl alcohol, and vinylacetate copolymers.
  • Suitable pigment stabilizers are also disclosed in DE 19636382 (BAYER), US 5720802 (XEROX), US 5713993 (DU PONT), PCT/GB95/02501 , US 5085689 (BASF) and US 2303376 (FUJITSU ISOTEC).
  • resins are incorporated at 2.5% to 200%, more preferably at 50% to 150% by weight of the pigment.
  • the radiation curable ink-jet ink and the radiation curable liquid layer may contain at least one surfactant.
  • the surfactant(s) can be anionic, cationic, non-ionic, or zwitter-ionic and are usually added in a total quantity below 20wt% based on the total ink weight, respectively the total liquid layer weight, and particularly in a total below 10wt% based on the total ink weight, respectively the total liquid layer weight.
  • a fluorinated or silicone compound may be used as a surfactant, however, a potential drawback is extraction by food from inkjet food packaging material because the surfactant does not cross-link. It is therefore preferred to use a copolymerizable monomer having surface-active effects, for example, silicone-modified acrylates, silicone modified methacrylates, fluorinated acrylates, and fluorinated methacrylates.
  • the radiation curable ink-jet ink and the radiation curable liquid layer may contain as a solvent, water and/or organic solvents, such as alcohols, fluorinated solvents and dipolar aprotic solvents, the solvent preferably being present in a concentration between 10 and 80wt%, particularly preferably between 20 and 50wt%, each based on the total weight of the radiation curable inkjet ink, respectively the total weight of the radiation curable liquid layer.
  • solvent water and/or organic solvents, such as alcohols, fluorinated solvents and dipolar aprotic solvents
  • the radiation curable ink-jet ink preferably does not contain an evaporable component, but sometimes, it can be advantageous to incorporate an extremely small amount of an organic solvent in such inks to improve adhesion to the ink-receiver surface after UV curing.
  • the added solvent can be any amount in the range which does not cause problems of solvent resistance and VOC, and preferably 0.1-5.0wt%, and particularly preferably 0.1-3.0wt%, each based on the total weight of the radiation curable ink-jet ink
  • Suitable organic solvents include alcohol, aromatic hydrocarbons, ketones, esters, aliphatic hydrocarbons, higher fatty acids, carbitols, cellosolves, higher fatty acid esters.
  • Suitable alcohols include, methanol, ethanol, propanol and 1-butanol, 1-pentanol, 2-butanol, t.-butanol.
  • Suitable aromatic hydrocarbons include toluene, and xylene.
  • Suitable ketones include methyl ethyl ketone, methyl isobutyl ketone, 2,4-pentanedione and hexafluoroacetone.
  • glycol, glycolethers, N-methylpyrrolidone, N,N-dimethylacetamid, N, N-dimethylformamid may be used.
  • Suitable biocides for the radiation curable ink-jet ink and the radiation curable liquid layer include sodium dehydroacetate, 2-phenoxyethanol, sodium benzoate, sodium pyridinethion-1-oxide, ethyl p-hydroxybenzoate and 1,2-benzisothiazolin-3-one and salts thereof.
  • a preferred biocide for the radiation curable ink-jet ink and the radiation curable liquid layer is ProxelTM GXL available from ZENECA COLOURS.
  • a biocide is preferably added in an amount of 0.001 to 3 wt%, more preferably 0.01 to 1.00 wt. %, each based on the total weight of the radiation curable ink-jet ink or the radiation curable liquid layer.
  • a dispersion of colorant for use in the radiation curable ink-jet ink may be prepared by mixing, milling and dispersion of colorant and resin.
  • 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 beads.
  • each process is performed with cooling to prevent build up of heat, and also as much as possible under light conditions in which UV-light has been substantially excluded.
  • the colour ink 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 milling time can vary widely and depends upon the pigment, mechanical means and residence conditions selected, the initial and desired final particle size, etc.
  • 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 colour ink in the form of a concentrated mill grind, which is subsequently diluted to the appropriate concentration for use in the ink-jet printing system.
  • This technique permits preparation of a greater quantity of pigmented ink from the equipment.
  • the pigment dispersion for preparing a radiation curable ink-jet ink is preferably diluted using monomers and/or oligomers. By dilution, the ink is adjusted to the desired viscosity, color, hue, saturation density, and print area coverage for the particular application.
  • the dot size was determined with a Videomet system available from KASPAR WALTER GmbH, which has an accuracy of 1 ⁇ m.
  • the gloss was measured at an angle of 60° with a REFO 60 available from Dr. Lange.
  • the ink receiver must be readily wetted so that there is no "puddling", i.e. coalescence of adjacent ink-droplets to form large drops on the surface of the ink receiver. An evaluation was then made in accordance with a criterion described below. Criterion:
  • This example which is not an embodiment of the invention but is useful for understanding the invention, illustrates how the dotsize of an ink droplet is controlled by the thickness.
  • a colourless radiation curable liquid layer composition Ink-L was prepared according to Table 1 by mixing the ingredients and stirring for one hour to ensure that all components were well distributed. The weight% (wt%) was based on the total weight of the radiation curable liquid layer composition. Table 1 wt% of: Ink-L DPGDA TM 66.5 Irgacure TM 907 2.5 Darocur TM ITX 5.0 Craynor TM CN 501 25.0 Byk TM -333 1.0
  • the radiation curable liquid layer composition INK-L was jetted on PET with a custom built ink-jet printer equipped with a UPH print head from AGFA to produce the ink receivers IR-2 to IR-7.
  • a resolution of 360x360dpi was used to print in a number of dpd (droplets per dot) as indicated by Table 2 , wherein 1 dpd is equal to a droplet volume of 3 pL.
  • Table 2 Ink receiver # dpd of Liquid layer IR-1 0 IR-2 2 IR-3 4 IR-4 5 IR-5 6 IR-6 8 IR-7 15
  • the radiation curable ink-jet inks in this example consist of 100% solids, no solvents or water are used during the preparation of the ink composition.
  • the radiation curable ink compositions Ink-M (Magenta ink) and Ink-C (Cyan ink) were prepared according to Table 3. The weight% (wt%) was based on the total ink weight.
  • a concentrated dispersion was prepared of the colour pigments by mixing the pigment, the polymeric dispersant SolsperseTM 32000 and the monomer DPGDATM with a dissolver and treating this mixture with an Eiger bead mill.
  • a dispersant synergist SoisperseTM 5000 was used in combination with SolsperseTM 32000.
  • the second monomer SartomerTM SR9003 , the synergist CraynorTM CN 386, the surfactant BykTM TM -333 and the photo-initiator Darocur ITX were added in this order under stirring to the concentrated pigment dispersion. Stirring was continued for one hour to ensure that all components were well distributed. A homogeneous ink composition was obtained.
  • a 1 dpd of the radiation curable ink-jet inks INK-M and INK-C were jetted at a resolution of 360x360dpi with the custom built ink-jet printer using a second UPH print head.
  • the ink receivers were cured 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 dotsize was determined for each cured sample..
  • the radiation curable liquid layer composition INK-L was coated at a wet thickness of 5 ⁇ m on PE-paper using a bar coater and a wired bar. Then a 1 dpd of the radiation curable ink-jet inks INK-M and INK-C were jetted at a resolution of 360x360dpi with the custom built ink-jet printer.
  • the printed samples were cured using a Fusion DRSE-120 conveyer, equipped with a Fusion VPS/I600 lamp (D-bulb), which transported the printed samples under the UV lamp on a conveyer belt at a speed of 20 m/min. The dotsize was determined to be 30 ⁇ m for both ink-jet inks.
  • An ink receiver IR-8 was prepared in the same manner as the ink receiver IR-7 of Example 1, except that the radiation curable ink-jet ink INK-M was used instead of INK-L.
  • the ink receiver IR-5 of Example 1and the ink receiver IR-8 were first cured using a Fusion DRSE-120 conveyer, equipped with a Fusion VPS/1600 lamp (D-bulb), which transported the ink receivers under the UV lamp on a conveyer belt at a speed of 20 m/min.
  • Table 5 shows that in a dotsize between 42 and 46 ⁇ m is obtained by printing 1 dpd of the radiation curable ink-jet inks INK-M and INK-C on the cured ink receivers IR-5 and IR-8.
  • a radiation curable ink jetted into the uncured liquid layer at 1 dpd would result in approximately the same dotsize as inks jetted at 1 dpd on the liquid layer after curing. From Table 3 and Figure 2 , it should be clear that the best choice in this case for the thickness of the radiation curable liquid layer is 5 dpd, i.e. ink receiver IR-4.
  • a colourless radiation curable liquid layer composition Ink-L2 was prepared according to Table 6 by mixing the ingredients and stirring for five minutes. The weight% (wt%) was based on the total weight of the radiation curable liquid layer composition. Table 6 Wt% of: INK-L2 Craynor TM CN501 70.0 Irgacure TM 500 16.7 Craynor TM CN 386 8.3 Irgacure TM 1870 3.3 Byk TM -333 1.7

Claims (10)

  1. Ein Druckverfahren zum Drucken eines strahlungshärtbaren Bildes auf ein Substrat gemäß der Tintenstrahldrucktechnik, gekennzeichnet durch die Schritte:
    (a) Auftrag einer strahlungshärtbaren Flüssigkeitsschicht auf zumindest einen Teil des Substrats,
    (b) Einspritzen eines ersten strahlungshärtbaren Tintenstrahltintentröpfchens in die strahlungshärtbare Flüssigkeitsschicht,
    (c) Härtung der das strahlungshärtbare Tintenstrahltintentröpfchen enthaltenden strahlungshärtbaren Flüssigkeitsschicht und
    dadurch gekennzeichnet, dass durch Aufspritzen eines zweiten strahlungshärtbaren Tintenstrahltintentröpfchens auf die gehärtete Schicht von Schritt (c) und durch Einstellung der Stärke der strahlungshärtbaren Flüssigkeitsschicht erreicht wird, dass die Punktgröße des ersten Tintentröpfchens in der Flüssigkeitsschicht der Punktgröße des auf die gehärtete Flüssigkeitsschicht aufgespritzten zweiten Tintentröpfchens entspricht und so die Auflösung des strahlungshärtbaren Bildes gesteuert wird.
  2. Druckverfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Punktgrößen der ersten und der zweiten strahlungshärtbaren Tintenstrahltinte beim Aufspritzen bei gleich bleibendem TpP (Tröpfchen pro Punkt) um nicht mehr als 10% in Durchmesser von der kleinsten Punktgröße abweichen.
  3. Druckverfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass in Schritt (a) die strahlungshärtbare Flüssigkeitsschicht durch Tintenstrahldruck auf zumindest einen Teil des Substrats angebracht wird.
  4. Druckverfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Stärke der strahlungshärtbaren Flüssigkeitsschicht zumindest 1 µm beträgt.
  5. Druckverfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass Bilder bei einer Druckgeschwindigkeit von mehr als 50 m2/Stunde gedruckt werden.
  6. Druckverfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die strahlungshärtbare Flüssigkeitsschicht eine klare Flüssigkeitsschicht ist.
  7. Druckverfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die strahlungshärtbare Flüssigkeitsschicht eine weiße Flüssigkeitsschicht ist.
  8. Druckverfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die strahlungshärtbare Flüssigkeitsschicht und/oder die erste strahlungshärtbare Tintenstrahltinte kationisch polymerisierbar ist.
  9. Druckverfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die erste strahlungshärtbare Tintenstrahltinte eine kationische strahlungshärtbare Tintenstrahltinte ohne kationischen Initiator ist.
  10. Druckverfahren nach Anspruch 9, dadurch gekennzeichnet, dass die strahlungshärtbare Flüssigkeitsschicht einen kationischen Initiator enthält.
EP05107954A 2004-10-29 2005-08-31 Druck der strahlungshärtbaren Tinten in eine flüssige strahlungshärtbare Schicht Not-in-force EP1652686B1 (de)

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CN100537257C (zh) 2009-09-09
CN1765636A (zh) 2006-05-03
JP2006137185A (ja) 2006-06-01
DE602005007675D1 (de) 2008-08-07
ATE399094T1 (de) 2008-07-15

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