CN100537257C - Printing of radiation curable inks into a radiation curable liquid layer - Google Patents
Printing of radiation curable inks into a radiation curable liquid layer Download PDFInfo
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- CN100537257C CN100537257C CNB2005101184395A CN200510118439A CN100537257C CN 100537257 C CN100537257 C CN 100537257C CN B2005101184395 A CNB2005101184395 A CN B2005101184395A CN 200510118439 A CN200510118439 A CN 200510118439A CN 100537257 C CN100537257 C CN 100537257C
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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
Abstract
A printing process is disclosed for ink-jet printing a radiation curable image on a substrate ( 14 ). First a radiation curable liquid layer ( 12 ) is provided on at least a portion of the substrate ( 14 ). Radiation curable ink-jet ink droplets ( 10 ) are jetted into the radiation curable liquid layer ( 12 ) and the radiation curable liquid layer ( 12 ) containing the radiation curable ink-jet ink droplets ( 13 ) is then cured. The resolution of the radiation curable image is controlled by uniformly adjusting the thickness of the liquid layer ( 12 ) for the dotsize of the radiation curable ink-jet ink jetted onto the cured layer.
Description
Technical field
The present invention relates to the ink printing of the radiation-hardenable method in the liquid level of radiation-hardenable is related more specifically to show the high speed ink jet printing method of high image quality.
Background technology
The droplet of printing ink fluid is directly projected on the printing ink receiver surface and do not had a physics contact between printing equipment and printing ink receiver in ink jet printing.Printing equipment stores printed data in the electronics mode and control is ejected into mechanism on the printing ink receiver with imaging type with droplets of ink.Printing can move through that the printing ink receiver is finished or vice versa by making printhead.
The printing ink fluid can become in rough segmentation:
Water base, drying mechanism comprises absorption, infiltration and evaporation;
Oil base, drying mechanism comprises absorption and infiltration;
Solvent based, drying mechanism comprises infiltration but mainly is evaporation;
Hot melt or phase transformation, wherein printing ink is liquid under injection temperation but at room temperature is solid and wherein dry by solidifying replacement;
Radiation-hardenable, wherein drying is replaced by polymerization.
With water base, oil base with solvent based ink jet on the printing ink receiver, this printing ink receiver typically comprises one or more porous layers by the capillarity picks up ink, or one or more swelling is to absorb the polymeric layer of printing ink.Usually with the ink jet of hot melt and radiation-hardenable on non-absorbent substantially printing ink receiver.Hot melt printing ink is limited to heat-staple printing ink receiver, and the printing ink of radiation-hardenable can spray on a variety of printing ink receivers.
The subject matter of radiation curable ink is that picture quality tends to change with the selection of printing ink receiver.Especially, the type of droplets of ink sprawling on the printing ink receiver printing ink receiver that highly depends on selection.
A kind of method that adopts a variety of printing ink receivers to obtain the coherent image quality is to adjust the printing ink receiver of inkjet ink sets to be adapted to select at every turn.Yet it is very consuming time and in fact be not the spendable solution of industrial printing environment to change printing ink in printer and the printhead.Therefore, universal method is that the suitable superficial layer of employing applies or by preliminary treatment, promptly plasma or sided corona treatment are improved surface chemistry.
Corona discharge Treatment and plasma treatment increase are used for cost, complexity and the maintenance of the equipment of process substrate.Substrate can comprise the significant impurity or the irregularity that may disturb substrate processing.Wish to avoid plasma-treating technology when therefore, possible.
In other possibility of using identical inkjet ink sets on the different printing ink receivers is to apply superficial layer before the jetted ink of injection radiation-hardenable.Usually, the jetted ink of radiation-hardenable is ejected on the desiccated surface layer, perhaps, the printing ink of radiation-hardenable all is injected in (intermediate solidification that does not promptly have liquid level) on the liquid level, for example in US6720042 (3M).
US 6720042 (3M) discloses the goods that comprise following material:
A) contain the sheet material of the surface portion of priming; With
B) derived from the ink jet image of the radiation curing of ink composite, this ink composite comprises at least a monomer that is arranged in the radiation-hardenable on the described surface portion of priming of 25wt% at least.
In so-called " wet type chromatography ", the uncured radiation curable ink that the droplets of ink of radiation-hardenable is deposited on previous deposition drips and forms the wet ink layer.
WO 03074619A (DOTRIX ﹠amp; SERICOL) progressive point type ink jet printing method is disclosed, this method comprises that applying first printing ink drips to substrate and drip to the step that does not have the intermediate solidification of first droplets of ink on first droplets of ink with after-applied second, and wherein first and second droplets of ink have different viscosity, surface tension or curing rate.
By the wet type chromatography, can control second droplets of ink sprawling on first droplets of ink preferably, like this equally for the third and fourth possible droplets of ink situation.Yet first droplets of ink sprawling on substrate is surface property crucial and that depend on substrate.Use the colorless ink of first droplets of ink can reduce this image quality issues.Comprise colorless ink, the suitable radiation curable ink that is used for wet type ink-jet chromatography is open by US 6550905 (DOTRIX).
On the exhibition DRUPA2004 of Dusseldorf ,Germany, Aellorra
TMDigital company has showed the ink-jet printing process that uses the wet layer of high viscosity white, and the wet layer of this white replaces the colorless ink layer by spraying the white ink production of UV-curable.On the top of the wet layer of white, spray the printing ink of second kind of radiation-hardenable and carry out UV and solidify.
Another problem relevant with the ink jet printing of radiation-hardenable is to compare with solvent or moisture base oil China ink on the absorbability substrate, and image shows the gloss of difference.The solid that deposits on the printing ink receiver, promptly the quantity of the compound of radiation-hardenable and colouring agent changes with image information, the glossiness that causes higher surface roughness and therefore reduce.
WO0030856 (XAAR) discloses the method for ink jet printing on substrate, and this method comprises the steps: to form wet prime coat on substrate; The pattern of deposition wet ink drop also is transformed into drying regime with the droplet of ink of prime coat and deposition subsequently on prime coat when the prime coat maintenance is moistening.
WO 0030856 (XAAR) is by improving printing quality with the opposite thickness that changes priming paint of thickness of printing ink, so that obtain flat print surface.Except to the arrangement of printhead with require to reach according to the image calculation that will print the restriction of power of varied in thickness, also be difficult to avoid prime coat printing zone never, be that the full depth of prime coat spreads into the zone by 100% ink printing, be the zero thickness of prime coat, it causes more unsharp image.
Droplets of ink sprawling on substrate greatly limited the resolution ratio that can obtain.Although extensively adopted coating or preconditioning technique to carry out the surface property modification, still not exclusively understood the accurate essence of printing ink-medium interaction.Typically attempt with printing quality and measurable surface parameter as the surface can and surface roughness connect, but these parameters can not be obtained the behavior of droplets of ink on various media fully.
Therefore, need provide printing process, wherein can be on a variety of printing ink receivers accurately the control chart picture resolution ratio and thus image show high gloss.
Summary of the invention
An object of the present invention is to provide a kind of printing process, wherein the resolution ratio of printing image is precisely controlled on a variety of printing ink receivers.
Another object of the present invention provides a kind of printing process, and it transmits the image that shows high and even glossiness.
These and other objects of the present invention are high-visible by following explanation.
Be surprisingly found out that by the radiation-hardenable liquid level being provided to substrate and regulating the thickness of this liquid level equably, can on a variety of substrates, produce high-quality ink jet image.
Purpose of the present invention by a kind of on substrate the printing process of ink jet printing radiation-hardenable image realize that this method comprises the steps:
A) at least a portion of described substrate, provide the liquid level of radiation-hardenable;
B) jetted ink with first radiation-hardenable drips the liquid level that sprays into described radiation-hardenable;
C) solidify the liquid level of the described radiation-hardenable that the jetted ink comprise described radiation-hardenable drips; And
It is characterized by on the described cured layer of step c) that the jetted ink that sprays second radiation-hardenable drips and the thickness of regulating described radiation-hardenable liquid level to control the resolution ratio of described radiation-hardenable image.
Further advantage of the present invention and embodiment are high-visible by following explanation.
Description of drawings
Fig. 1 is the schematic cross-section of printing by substrate 14 in 1b and 1c according to an aspect of the present invention.In the part 1a of Fig. 1, the jetted ink of radiation-hardenable is dripped 10 be ejected on the injection direction 11 on the substrate 14, show big sprawling.In the part 1b of Fig. 1, the jetted ink of radiation-hardenable is dripped 10 liquid levels 12 of spurting into radiation-hardenable, show the spot size that reduces.The thickness of the liquid level 12 of radiation-hardenable increases from 1b to 1c, and it causes that the spot size of the droplets of ink 13 of the radiation-hardenable that is arranged in liquid level 12 further reduces.
Fig. 2 shows liquid layer thickness and spurts into the figure that concerns between the radiation curable ink dropping point diameter of liquid level.
The specific embodiment
Definition
Be used for disclosing term of the present invention " actinic radiation " expression and can cause photochemically reactive electromagnetic radiation.
Being used for disclosing term of the present invention " ultra-violet radiation " expression wave-length coverage is the electromagnetic radiation of 4-400 nanometer.
Term " UV " is used for as the open the application of the abbreviation of ultra-violet radiation.
Be used for disclosing term of the present invention " Norrish I type initator " be illustrated in excite after division, obtain causing the light trigger of free radical immediately.
Be used for disclosing that term of the present invention " Norrish II type initator " expression is activated by actinic radiation and by taking hydrogen by force from second kind of compound or taking the light trigger that electronics forms free radical by force, this second kind of compound becomes actual initiation free radical.
Being used for disclosing term of the present invention " coinitiator " expression can be with hydrogen migration to the excitation state of NorrishII type initator and cause any molecule of the radical polymerization of radiation-hardenable composition.
Be used for disclosing term of the present invention " colouring agent " expression dyestuff and pigment.
Be used for disclosing term of the present invention " dyestuff " is illustrated in the medium that applies it and under relevant environmental condition solubility be 10mg/L or bigger colouring agent.
Be defined as among the DIN 55943 that term " pigment " is incorporated herein by reference herein that actual being insoluble to applies medium under relevant environmental condition, therefore wherein solubility less than inorganic or organic, colour or the leuco colorants of 10mg/L.
Term " alkyl " expression is for all possible variants of each carbon number in the alkyl, promptly for three carbon atoms: n-pro-pyl and isopropyl; For four carbon atom: normal-butyl, isobutyl group and the tert-butyl group; For five carbon atoms: n-pentyl, 1,1-dimethyl-propyl group, 2,2-dimethyl propyl and 2-methyl-butyl etc.
Be used for disclosing term of the present invention " acyl group " expression-(C=O)-aryl and-(C=O)-alkyl.
Be used for disclosing term of the present invention " aliphatic group " expression saturated straight chain, side chain and alicyclic alkyl.
Be used for disclosing the assembly of the cyclic conjugated carbon atom of term of the present invention " aryl " expression, it be characterized as big resonance energy, for example benzene, naphthalene and anthracene.
Be used for disclosing the assembly of the cyclic conjugated carbon atom of term of the present invention " alicyclic alkyl " expression, it does not form aromatic group, for example cyclohexane.
Printing process
Printing process according to the present invention is the ink jet printing method of radiation-hardenable.The device that is used to spray can be one or more printheads, this printhead in a controlled manner by nozzle to the little droplets of ink of printing ink receiver jet surface, move with respect to printhead on this surface.Ejection or the liquid that sprays form image on the printing ink receiver.Under high print speed, printing ink must spray from printhead easily, this is to the physical property of printing ink, can apply many restrictions as low viscosity, surface under injection temperation (can be 25-110 ℃), so that print-head nozzle can form necessary droplet and can change into the uniform liquid of dry printing zone fast.
The preferred ink jet-print head that is used for according to printing process of the present invention is a piezoelectric heads.Piezoelectric ink jet is printed the motion that is based on piezoelectric ceramics converter when it is applied voltage.Voltage application changes the shape of piezoelectric ceramics converter in the printhead, produces the space, and this space is filled by printing ink then.When removing voltage once more, pottery expand into its original shape, from printhead ejection droplets of ink.
Yet ink jet-print head is not limited to piezoelectric ink jet printing head.Can use to be used to spray other ink jet-print head of printing ink and comprise all kinds, fall type as required with heat, static harmony as continuous type.
For printing, ink jet-print head comes flyback retrace on the horizontal printing ink receiver surface of moving of crossing over usually.Usually ink jet-print head is not printed in backhaul.Bi-directional printing is preferred for obtaining high face output.Particularly preferably be the printing in " one way printing process ", it can be undertaken by the how staggered ink jet-print head that uses page width ink jet printhead (as derive from XAAR page width printing head) or cover the whole width in printing ink receiver surface.In the one way printing process, ink jet-print head keeps static usually and the printing ink receiver moves under ink jet-print head.
Represent should be greater than 50m in ink jet printing according to high face output of the present invention
2/ hour under, preferably greater than 100m
2/ hour under, even more preferably greater than 200m
2/ hour down and most preferably greater than 300m
2/ hour following printing image.Resolution ratio should be 180dpi at least, preferably is 300dpi at least.Be used for preferably having the width of 240mm at least, require the print speed of 35m/min at least thus according to the printing ink receiver of high face output ink-jet printing system of the present invention.More preferably the width of printing ink receiver is that the width of 300mm and preferred especially printing ink receiver at least is 500mm at least.
The printing ink receiver
The printing ink receiver that is suitable for printing process of the present invention is the substrate with radiation-hardenable liquid level.In preferred embodiments, substrate is only in the part on its surface, promptly intends having on the zone by the jetted ink imaging of radiation-hardenable the liquid level of radiation-hardenable.The ink jet that forms at least a portion radiation-hardenable of image is gone into the liquid level of radiation-hardenable.Can be by any method well known by persons skilled in the art, as spray, injection, serigraphy and coating the liquid level of radiation-hardenable is applied to substrate.
Substrate can be selected from plastics, canvas, textile, metal, glass, plant-fiber product, leather, magnetic material and the pottery of paper, art paper, polyolefin art paper, presspaper, timber, composite plate, plastics, coating.
The substrate that is used for the printing ink receiver preferably is non-absorbent substantially.Suitable example is the paper of resin-coating, as the paper of polyethylene coating and the paper and the polymer substrate of polypropylene coating.
The suitable polymers substrate comprises for example cellulose-acetate propionate, cellulose acetate-butyrate, polyester such as PETG (PET) and PEN (PEN); Oriented polystyrene (OPS); Oriented nylon (ONy); Polypropylene (PP), oriented polypropylene (OPP); Polyvinyl chloride (PVC); With various polyamide, Merlon, polyimides, polyolefin, poly-(vinyl acetal), polyethers and polysulfonamide, opaque white color polyester and PETG and the polyacrylic blend of extruding.Acrylic resin, phenol resin, glass and metal also can be used as substrate.The visible wetting modernism of other suitable backing material: theoretical and application (Modern Approaches to Wettability:Theory andApplications), SCHRADER, people such as Malcolm E. compile, and New York: Plenum Press, 1992.ISBN 0306439859.
Substrate can be transparent, translucent or opaque.Substrate can be introduced mineral particle as filler, as comprises CaCO
3PET, comprise TiO
2PET, a-PET and PET-g.
Substrate can be painted before printing, as the clear PET that comprises the blue dyes that is applicable to imaging of medical can be used as the printing ink receiver.
Polyester film substrate and particularly PETG are preferred for some and use, and particularly have the type of excellent in dimension stability.When such polyester when the substrate, glue-line can be used for improving bonding to substrate of ink jet layer, if it constitutes non-absorbent substantially printing ink receiver with the substrate of gummed not.The useful glue-line that is used for this purpose is that photography is known and comprise for example polymer such as the vinylidene chloride/acrylonitrile/acrylic ternary copolymer or the vinylidene chloride/methyl acrylate/itaconic acid terpolymer of vinylidene chloride.
The thickness of even regulation radiation-hardenable liquid level can be controlled the spot size and the control resolution thus of the droplets of ink of spurting into the radiation-hardenable liquid level.
The thickness of regulating the radiation-hardenable liquid level makes the spot size of spot size coupling droplets of ink of injection the solidified liquid layer after of drop in the liquid level.With respect to when equating the minimum dot size of dpd (dripping every point) when spraying down, when their diameter difference is not more than 10%, think that two spot sizes mate mutually.For example, because (40 μ m-30 μ m)/30 μ m * 100%=33%, two points of 30 μ m and 40 μ m do not match.On the other hand, because their diameter only differs 5%:(40 μ m-38 μ m)/38 μ m * 100%=5%, two some couplings of 38 μ m and 40 μ m.
Solidification equipment
In printing process according to the present invention, the curable ink of injection produces uncured printing image.By it being exposed to radiation or solidifying by the image of electronic beam curing with printing.The method for optimizing of radiation curing is a ultraviolet light.
Solidification equipment can combine layout with the printhead of ink-jet printer, therewith moves to make droplets of ink be exposed to curing radiation after being printed into liquid level very shortly.In such layout, may be difficult to provide the enough little radiation source that is connected to printhead and therewith moves.Therefore, can adopt the radiation source of stationary fixing, as be connected to the UV curing radiation source of radiation source by flexible radiation conduction device such as fibre bundle or internal reflection flexible pipe.
Perhaps, curing radiation can offer radiation head from stationary source by the mirror structure that comprises mirror on radiation head.
Arrange that the radiation source that does not move with printhead also can be an elongation radiation source of crossing over the transverse path of printing ink receiver surface horizontal expansion to be solidified and contiguous printhead, make the subsequent image row who forms by printhead progressively or continuously under this radiation source, pass through.
In the layout of reality, may need to provide a plurality of at the contiguous closely printhead of printing station, be used to adopt the ink printing of different colours to produce multicolor image.In this case, each can have it self special-purpose radiation source.
Any ultraviolet source can be used as radiation source, as high or low pressure mercury lamp, cold-cathode tube, black light, ultraviolet LED, ultraviolet laser and flash lamp.Wherein, optimized light source is the light source that shows the longer wavelength UV distribution with 300-400nm dominant wavelength.Particularly, preferred UV-A light source because adopt it to reduce light scattering, causes more effective inside solidification.
The UV radiation is categorized as UV-A usually, and UV-B and UV-C are as follows:
·UV-A：400nm-320nm
·UV-B：320nm-290nm
·UV-C：290nm-100nm
In addition, can use the image of two light source cured printed of different wave length or illumination.For example, first UV source can be chosen as is rich in UV-C, especially in the 240nm-200nm scope.UV-A can be rich in then in second UV source, as the lamp of doped gallium, or at all high different lamps of UV-A and UV-B.Find to use two UV sources to have advantage, as curing rate fast.
The absorption of inks UV radiation difference of known different colours, promptly they each at each UV-A, absorb different in UV-B and the UV-C scope.Curing fully with all colorants in two cure lamp assurance one way.
For promoting to solidify, ink-jet printer generally includes one or more oxygen consumption unit.Oxygen consumption unit placement nitrogen or other relative inertness gas are (as CO
2) cover layer, have adjustable position and adjustable inert gas concentration, to reduce the oxygen concentration in the curing environment.The residual oxygen level keeps being low to moderate 200ppm usually, but is generally 2000ppm-20000ppm.
In one embodiment, radiation-hardenable liquid level and/or radiation-hardenable jetted ink are based on cationic polymerization, because the oxygen inhibitory action is not experienced in such polymerization.
In another embodiment, the radiation-hardenable jetted ink is the cation radiation-hardenable jetted ink that does not contain initator, and cationic initiator is included in the liquid level of radiation-hardenable.
The liquid level of radiation-hardenable
The liquid level that is suitable for the radiation-hardenable of printing process of the present invention comprises the compound of radiation-hardenable at least.The compound of radiation-hardenable can be selected from can be by the monomer and/or the oligomer of the solidification equipment polymerization of ink-jet printer.
The liquid level of radiation-hardenable can comprise initator.
The liquid level of radiation-hardenable can further comprise colouring agent or Chinese white such as titanium dioxide, although preferably this layer is transparent liquid level.
The liquid level of radiation-hardenable can comprise polymerization inhibitor with the polymerization of restriction by heat or actinic radiation.
The liquid level of radiation-hardenable can further comprise at least a resin to obtain the stable dispersion of colouring agent in jetted ink.
The liquid level of radiation-hardenable preferably further comprises at least a surfactant.
The liquid level of radiation-hardenable can further comprise at least a solvent.
The liquid level of radiation-hardenable can further comprise at least a pesticide.
The thickness of the liquid level of radiation-hardenable can be about 0.1 μ m, if for example use the metal ink receiver, then preferred thickness is at least 1 μ m.
The jetted ink of radiation-hardenable
The jetted ink that is suitable for the radiation-hardenable of printing process of the present invention comprises at least two kinds of components: (i) compound of radiation-hardenable and (ii) colouring agent (being pigment or dyestuff).
The compound of radiation-hardenable can be selected from can be by the monomer and/or the oligomer of the solidification equipment polymerization of ink-jet printer.
The jetted ink of radiation-hardenable can comprise initator.
The jetted ink of radiation-hardenable can comprise polymerization inhibitor with the polymerization of restriction by heat or actinic radiation.Preferably during the preparation of jetted ink, add inhibitor.
The jetted ink of radiation-hardenable can further comprise at least a resin to obtain the stable dispersion of colouring agent in jetted ink.
The jetted ink of radiation-hardenable preferably further comprises at least a surfactant.
The jetted ink of radiation-hardenable preferably further comprises at least a solvent.
The jetted ink of radiation-hardenable preferably further comprises at least a pesticide.
Ink-jet printer uses the inkjet ink sets of the radiation-hardenable of being made up of multiple radiation-hardenable jetted ink usually.
The compound of radiation-hardenable
The jetted ink of radiation-hardenable and the liquid level of radiation-hardenable comprise monomer and/or the oligomer by the solidification equipment polymerization of ink-jet printer.Monomer, oligomer or prepolymer can have degree of functionality in various degree, and can use and comprise list, two, three and the mixture of the combination of high functionality monomer more.These components are curable, and are photo curable typically, as UV-curable, and should be adhered to printing ink receiver surface after printing and be used to the colouring agent that bonds.The mixture of two or more monomers of same functionality preferably, preferred especially two kind of two functional monomer's mixture.
Can regulate the viscosity of the liquid level of the jetted ink of radiation-hardenable and radiation-hardenable by changing ratio between monomer and the oligomer.
Can adopt conventional radical polymerization, make the photocuring system of using up acid or light alkali propellant, or any method of photoinduction alternating copolymerization.Usually, preferably radical polymerization and cationic polymerization, and also can adopt and do not need the photoinduction of initator alternating copolymerization.In addition, the mixed system of these system combinations also is effective.
Because do not have because the polymerization of oxygen suppresses, cationic polymerization is renderd a service excellent, but it is slow and expensive.If the use cationic polymerization then preferably uses epoxide to increase rate of polymerization with oxetanes.Radical polymerization is preferred polymerization.
Can adopt any polymerizable compound well known in the art.What be preferably used as radiation curable compounds in the liquid level of the jetted ink of radiation-hardenable and radiation-hardenable especially is simple function and/or polyfunctional acrylic ester monomer, oligomer or prepolymer, as the acrylic acid isopentyl ester, the stearyl acrylate ester, lauryl acrylate, 2-ethyl hexyl acrylate, decyl acrylate, acrylic acid isoamyl benzene vinyl acetate, the different stearyl ester of acrylic acid, 2-ethylhexyl-glycol acrylate, acrylic acid 2-hydroxy butyl ester, 2-acryloxy ethyl hexahydrophthalic acid, acrylic acid butoxy ethyl ester, the ethoxydiglycol acrylate, methoxyl group diethylene glycol (DEG) acrylate, the methoxy poly (ethylene glycol) acrylate, the MPEG acrylate, the acrylic acid phenoxy ethyl, tetrahydrofurfuryl acrylate, isobornyl acrylate, acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, as the vinyl ethers acrylate of in US 4857630 (DU PONT), describing, 2-(ethyleneoxy) ethyl propylene acid esters, 2-acryloxy ethyl butanedioic acid, 2-acryloxy ethyl phthalic acid, 2-acryloxy ethyl-2-ethoxy-phthalic acid, interior ester modified flexible acrylic ester, with acrylic acid tert-butyl group cyclohexyl, the diacrylate triethyleneglycol ester, diacrylate tetraethylene glycol ester, the diacrylate macrogol ester, diacrylate dipropylene glycol ester, tripropylene glycol diacrylate, diacrylate polypropylene glycol ester, diacrylate 1,4 butanediol esters, diacrylate 1,6 hexylene glycol esters, diacrylate 1,9 nonanediol ester, diacrylic acid pentyl diol ester, dihydroxymethyl-tristane diacrylate, bisphenol-A EO (oxirane) adduct diacrylate, bisphenol-A PO (expoxy propane) adduct diacrylate, the hydroxy new pentane acid ester neopentylglycol diacrylate, ethoxylated neopentylglycol diacrylate, alkoxylate dihydroxymethyl cyclodecane diacrylate and polytetramethylene glycol diacrylate, trimethylolpropane triacrylate, the trimethylolpropane triacrylate of EO modification, three (propane diols) triacrylate, the trimethylolpropane triacrylate of caprolactone modification, pentaerythritol triacrylate, pentaerythritol tetracrylate, pentaerythrite ethyoxyl tetraacrylate, six acrylic acid dipentaerythritol ester, two-trimethylolpropane tetra-acrylate, glycerine propoxyl group triacrylate, six acrylic acid dipentaerythritol ester of caprolactam modification, N-vinylamide such as N-caprolactam or N-vinyl formamide; Or acrylamide or substituted acrylamide such as acryloyl morpholine; With polyether acrylate as the aminofunctional of description in US5196502 (KODAK).
In addition, the methacrylate corresponding to the aforesaid propylene acid esters can use with these acrylic acid.In methacrylate, since they than hypersensitivity and higher bonding to printing ink receiver surface, preferably vinyl ethers acrylate, hydroxyethyl methacrylate, methacrylic acid phenoxy ethyl, cyclohexyl methacrylate, dimethacrylate tetraethylene glycol ester and the dimethacrylate macrogol ester described in methoxy polyethylene glycol methacrylate-styrene polymer, methoxyl group triethylene glycol methacrylate, 4-(ethyleneoxy) butyl methyl acrylate, for example US5225522 (KODAK).
In addition, the liquid level of the jetted ink of radiation-hardenable and radiation-hardenable also can comprise polymerizable oligomer.The example of these polymerizable oligomerses comprises epoxy acrylate, aliphatic urethane acrylates, aromatic urethanes acrylate, polyester acrylate and straight acrylics oligomer.
Colouring agent
Colouring agent can be a dyestuff, but preferably pigment or its combination.Can use organic and/or inorganic pigment.
Pigment particles should be enough little to allow printing ink to flow freely by ink jet printing device, particularly by typically having a diameter from the jetting nozzle of 10 μ m-50 μ m.Granularity also influences the pigment dispersion stabilization.Also need to use small-particle to be used for maximum color intensity.The granularity of the pigment particles that disperses in jetted ink should be less than 10 μ m, preferably less than 3 μ m with most preferably less than 1 μ m.The particle mean size of pigment particles is preferably 0.05-0.5 μ m.The very thin dispersion of pigment and their preparation method are disclosed in for example EP 776952A (KODAK), US5538548 (BROTHER), US 5443628 (VIDEOJET SYSTEMS), EP259130A (OLIVETTI), US 5285064 (EXTREL), EP 429828A (CANON) and EP 526198 A (XEROX).
Suitable pigment comprises the following pigment as redness or magenta pigment: 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; Following pigment as blueness or green pigment: pigment blue 1,15,15:1,15:2,15:3,15:4,15:6,16,17-1,22,27,28,29,36 and 60; Following pigment as viridine green: pigment Green 7,26,36 and 50; Following pigment as yellow uitramarine: pigment yellow 1,3,12,13,14,17,34,35,37,55,74,81,83,93,94,95,97,108,109,110,128,137,138,139,153,154,155,157,166,167,168,177,180,185 and 193; Following pigment as Chinese white: Pigment white 6,18 and 21.
In addition, pigment can be selected from by HERBST, people such as W, and industrial organic pigment is produced, performance, use (Industrial Organic Pigments, Production, Properties, Application), and the 2nd edition, VCH, those disclosed in 1997.
Most preferred pigment is 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 purple 9.
Carbon black is usually as the coloured material in the black ink.Suitable mineral black material comprises that carbon black such as pigment black 7 (as derive from the carbon black of MITSUBISHI CHEMICAL
), derive from the Regal of CABOT Co.
TM400R, Mogul
TML, Elftex
TM320, or derive from the carbon black FW18 of DEGUSSA, special black 250, special black 350, special black 550, Printex
TM25, Printex
TM35, Printex
TM55, Printex
TM90, Printex
TM150T.The other example of suitable pigments is disclosed in US 525522 (KODAK).
The scope that exists of pigment is 0.1-10wt%, and preferred 1-5wt% is based on the gross weight of the jetted ink of radiation-hardenable.
The dyestuff that is applicable to the jetted ink of radiation-hardenable comprises direct dyes, acid dyes, basic-dyeable fibre and chemically-reactive dyes.
The suitable direct dyes that is used for the jetted ink of radiation-hardenable comprises:
C.I. direct yellow 1,4,8,11,12,24,16,27,28,33,39,44,50,58,85,86,100,110,120,132,142 and 144
C.I. directly red 1,2,4,9,11,134,17,20,23,24,28,31,33,37,39,44,47,48,51,62,63,75,79,80,81,83,89,90,94,95,99,220,224,227 and 343
C.I. direct blue 1,2,6,8,15,22,25,71,76,78,80,86,87,90,98,106,108,120,123,163,165,192,193,194,195,196,199,200,201,202,203,207,236 and 237
C.I. directly deceive 2,3,7,17,19,22,32,38,51,56,62,71,74,75,77,105,108,112,117 and 154
The suitable acid dyes that is used for the jetted ink of radiation-hardenable comprises:
C.I. Indian yellow 2,3, and 7,17,19,23,25,20,38,42,49,59,61,72 and 99
C.I. acid orange 56 and 64
C.I. azogeramine, 8,14,18,26,32,37,42,52,57,72,74,80,87,115,119,131,133,134,143,154,186,249,254 and 256
C.I. acid violet 11,34 and 75
C.I. Blue VRS, 7,9,29,87,126,138,171,175,183,234,236 and 249
C.I. acid green 9,12, and 19,27 and 41
C.I. acid black 1,2,7,24,26,48,52,58,60,94,107,109,110,119,131 and 155
The suitable reactivity dyestuff that is used for the jetted ink of radiation-hardenable comprises:
C.I. reactive yellow 1,2,3,14,15,17,37,42,76,95,168 and 175
C.I. reactive red 2,6,11,21,22,23,24,33,45,111,112,114,180,218,226,228 and 235
C.I. reactive blue 7,14, and 15,18,19,21,25,38,49,72,77,176,203,220,230 and 235
C.I. reactive orange 5,12,13,35 and 95
C.I. reactive palm fibre 7,11,33,37 and 46
C.I. reactive green 8 and 19
C.I. reactive purple 2,4,6,8,21,22 and 25
C.I. reactive black 5,8,31 and 39
The suitable basic-dyeable fibre that is used for the jetted ink of radiation-hardenable comprises:
C.I. basic yellow 11,14, and 21 and 32
C.I. alkali red 1:1,2,9,12 and 13
C.I. alkaline purple 3,7 and 14
C.I. alkali blue 3,9,24 and 25
Dyestuff only can show desirable color in proper pH range.Therefore, the jetted ink of radiation-hardenable preferably further comprises the pH buffer, as potassium hydroxide (KOH).
Light trigger
The catalyst that is called light trigger is initiated polymerization typically.Light trigger requires less energy to form polymer with activated monomer and oligomer.The light trigger that is applicable to the liquid level of the jetted ink of radiation-hardenable and radiation-hardenable can be Norrish I type initator, Norrish II type initator or light acid propellant.
Light trigger absorbs light and works free radical or the cationic effect of producing.Free radical or cation be induce monomer, oligomer and polymer and with the polymerization of polyfunctional monomer and oligomer, therefore also induce crosslinked anakinetomer.
Preferred Norrish I type initator is selected from benzoin ether, benzil ketals α, α-dialkoxy acetophenone, alpha-hydroxyalkyl benzophenone, alpha-aminoalkyl benzophenone, acylphosphine oxide, acyl group phosphine sulfide, α-Lu Daitong, alpha-halogen sulfone and alpha-halogen phenyl glyoxylic acid ester.
Preferred Norrish II type initator is selected from benzophenone, thioxanthones, 1,2-diketone and anthraquinone.Preferred coinitiator is selected from aliphatic amine, aromatic amine and mercaptan.Tertiary amine, heterocyclic thiol and 4-dialkyl amido-benzoic acid are especially preferably as coinitiator.
Suitable light trigger is disclosed in CRIVELLO, people such as J.V., and the III volume is used for the photopolymerisable light trigger of radical cation and anion (Photoinitiators for FreeRadical Cationic ﹠amp; Anionic Photopolymerization), the 2nd edition, BRADLEY, G. compiles, London, UK:John Wiley and Sons Ltd., 1998.287-294 page or leaf.
The object lesson of light trigger includes but not limited to following compound or its combination: benzophenone and substituted diphenylamine ketone; the 1-hydroxycyclohexylphenylketone; thioxanthones such as isopropyl thioxanthone; 2-hydroxy-2-methyl-1-phenyl third-1-ketone; 2-benzyl-2-dimethylamino-(4-morpholino phenyl) fourth-1-ketone; the benzil dimethyl ketal; two (2; the 6-dimethylbenzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino third-1-ketone; 2; 2-dimethoxy-1; 2-diphenyl second-1-ketone or 5,7-two iodo-3-butoxy-6-fluorones; diphenyl fluorine iodine and hexafluorophosphoric acid triphenylsulfonium.
Suitable commercial light trigger comprises the Irgacure that derives from CIBA SPECIALTY CHEMICALS
TM184, Irgacure
TM500, Irgacure
TM907, Irgacure
TM369, Irgacure
TM1700, Irgacure
TM651, Irgacure
TM819, Irgacure
TM1000, Irgacure
TM1300, Irgacure
TM1870, Darocur
TM1173, Darocur
TM4265 and Darocur
TMITX derives from the Lucerin TPO of BASF AG, derives from the Esacure of LAMBERTI
TMKT046, Esacure
TMKIP150, Esacure
TMKT37 and Esacure
TMEDB derives from SPECTRA GROUP Ltd., H-Nu
TM470 and H-Nu
TM470X.
The preferred amount of initator is the 0.3-50wt% of total ink by weight or total liquid level weight, and is more preferably the 1-25wt% of total ink by weight or total liquid level weight.
Can in two steps, realize impinge actinic radiation by changing wavelength or intensity.Preferably use 2 types initator under these circumstances together.
Polymerization inhibitor
Suitable polymerization inhibitor comprises phenol type antioxidant, hindered amine as light stabilizer, phosphorescence build antioxidant, the Hydroquinone monomethylether that is generally used for (methyl) acrylate monomer, and also can use quinhydrones, tert-butyl catechol, pyrogallol.Wherein, particularly preferably be the phenolic compounds of the two keys that in molecule, contain derived from propylene acid, even because it also has the effect of limit polymerization when heating in airtight oxygen-free environment.Suitable polymerization inhibitor is for example by Sumitomo Chemical Co., the Sumilizer that Ltd produces
TMGA-80, Sumilizer
TMGM and Sumilizer
TMGS, and derive from Rahn, Zurich, the Genorad of Switzerland
TM16, Genorad
TM18.
Because the excessive of these polymerization inhibitors adds the sensitiveness of affiliation reduction printing ink to solidifying, so the preferred quantity of determining to prevent polymerization before blend.The quantity of polymerization inhibitor is generally the 200-20 of total ink by weight or total liquid level weight, 000ppm.
Resin
The jetted ink of radiation-hardenable and the liquid level of radiation-hardenable can further comprise resin, are also referred to as to be used for obtaining pigment stabiliser or the dispersant of pigment in the jetted ink stable dispersion.
Pigment can be joined in the jetted ink of radiation-hardenable as the dispersion that comprises dispersant.
Appropriate resin: oil type resin (as styrene type, acrylic type, polyester, polyurethane-type, phenol type, butyral type, cellulose type and rosin); And thermoplastic resin (as vinyl chloride, vinylacetate type).The object lesson of these resins comprises the polyvinyl alcohol and the vinyl acetate co-polymer of acrylate copolymer, copolymer in cinnamic acrylic ester, acetylation and not exclusively saponification.Commercial resin is known to trade name Solsperse
TM32000 and Solsperse
TM39000 derive from AVECIA, with EFKA
TM4046 derive from EFKA CHEMICALSBV, with Disperbyk
TM168 derive from BYK CHEMIE GmbH.
The detailed list of non-polymeric and some polymeric dispersants is by MC CUTCHEON. functional material (Functional Materials), the North America version, Glen Rock, N.J.:ManufacturingConfectioner Publishing Co., the 1990.110-129 page or leaf is open.
Suitable pigment stabiliser is also at DE 19636382 (BAYER), US 5720802 (XEROX), and US 5713993 (DU PONT), PCT/GB95/02501, open among US5085689 (BASF) and the US2303376 (FUJITSU ISOTEC).
Typically, more preferably introduce resin with 50wt%-150wt% with the 2.5wt%-200wt% of pigment.
Surfactant
The jetted ink of radiation-hardenable and the liquid level of radiation-hardenable can comprise at least a surfactant.Surfactant can be anion, cation, nonionic or zwitterionic and common with the total amount adding less than 20wt%, respectively based on total ink by weight, total liquid level weight, and add with the total amount less than 10wt% especially, respectively based on total ink by weight, total liquid level weight.
Fluoridize or silicone compounds can be used as surfactant, but potential shortcoming is that food is from the extraction of ink-jet packaging material for food because this surfactant is not crosslinked.Therefore the preferred copolymerisable monomer with surface-active effect that uses is as silicone-modified acrylate, silicone-modified methacrylate, fluorinated acrylic ester and fluorinated methyl acrylate.
Solvent
The jetted ink of radiation-hardenable and the liquid level of radiation-hardenable can comprise as the water of solvent and/or organic solvent as alcohol, fluorated solvent and dipolar aprotic solvent, the concentration that solvent exists is preferably 10-80wt%, be preferably 20-50wt% especially, each is respectively based on the gross weight of the liquid level of the gross weight of the jetted ink of radiation-hardenable, radiation-hardenable.
Yet, but the jetted ink of radiation-hardenable does not preferably comprise evaporated components, but sometimes can be advantageously in this printing ink, introduce a spot of especially organic solvent to improve after UV solidifies bonding to printing ink receiver surface.In the case, the solvent of adding can be for not causing any amount of solvent resistance and VOC problem, and be preferably 0.1-5.0wt%, and be preferably 0.1-3.0wt% especially, and each is based on the gross weight of the jetted ink of radiation-hardenable.
Appropriate organic solvent comprises alcohol, aromatic hydrocarbons, ketone, ester, aliphatic hydrocarbon, higher fatty acids, carbitol, cellosolve, high-grade aliphatic ester.Suitable alcohol comprises methyl alcohol, ethanol, propyl alcohol and 1-butanols, 1-amylalcohol, 2-butanols, the tert-butyl alcohol.Suitable aromatic hydrocarbons comprises toluene and dimethylbenzene.Suitable ketone comprises MEK, methyl iso-butyl ketone (MIBK), 2,4-pentanedione and Hexafluoro acetone.Also can use glycol, glycol ethers, N-methyl pyrrolidone, N, N-dimethylacetylamide, N, dinethylformamide.
Pesticide
The suitable pesticide that is used for the liquid level of the jetted ink of radiation-hardenable and radiation-hardenable comprises dehydro sodium acetate, 2-phenoxetol, Sodium Benzoate, pyridine thion-1-sodium oxide molybdena, ethyl-para-hydroxybenzoate and 1,2-benzisothiazole-3-ketone and salt thereof.The preferred pesticide that is used for radiation-hardenable jetted ink and radiation-hardenable liquid level is the Proxel that derives from ZENECACOLOURS
TMGXL.
Preferably with 0.001-3wt%, more preferably the quantity of 0.01-1.00wt% adds pesticide, and each is based on the gross weight of the liquid level of the jetted ink of radiation-hardenable or radiation-hardenable.
The preparation of the jetted ink of radiation-hardenable
Be used for mixing that the colorant dispersion of the jetted ink of radiation-hardenable can be by colouring agent and resin, mill and disperse preparation.Mixing apparatus can comprise pressure kneader, open kneader, planet mixer, dissolvers and dalton's universal mixer.Suitable mill and dispersing apparatus is ball mill, pearly-lustre mill, colloid mill, high speed dispersion device, two roller, ball mill, paint adjuster and three rollers.Also can use ultrasonic energy to prepare dispersion.
Many dissimilar materials can be as milling medium, as glass, pottery, metal and plastics.In preferred embodiments, abrasive media can comprise particle, and the particle of preferred substantially spherical is as bead or the stable zirconium bead of being made up of fluoropolymer resin substantially of yttrium.
In the technology of mixing, milling and disperseing, each process using cooling is carried out preventing the accumulation of heat, and carries out under the basic optical condition of getting rid of UV light as much as possible.
If the jetted ink of radiation-hardenable comprises more than one pigment, then can use the independent dispersion of every kind of pigment to prepare colored ink, perhaps can when the preparation dispersion, mix and several pigment of milling altogether.
Dispersing technology can adopt continuously, intermittently or semi-batch mode carry out.
The preferred amount of grinding mill abrasive components and ratio depend on the application of concrete material and hope and change at wide region.The inclusion of mill admixture comprises the grinding mill abrasive material and the medium of milling.
Grinding time can and depend on pigment, mechanical device and the stop condition of selection, initial and required final size etc. in the wide region variation.Can prepare the pigment dispersion of particle mean size in the present invention less than 100nm.
Finish mill after, use conventional isolation technics, as by filtering, grading by mesh screen the medium of milling is separated from the partical (with drying or liquid dispersion form) of milling.Usually sieve is embedded grinding mill, for example be used for ball mill.Preferably from the medium of milling, separate the condensed pigment of milling by filtering.
Usually need prepare colored ink with the form that concentrates the grinding mill abrasive material, this grinding mill abrasive material is diluted to the debita spissitudo that is used for ink-jet printing system subsequently.This technology allows from the bigger quantity coloring printing ink of this equipment preparation.The preferred pigment dispersion that uses monomer and/or oligomer dilution to be used to prepare the jetted ink of radiation-hardenable.By dilution, printing ink is adjusted to required viscosity, color, tone, saturated density and the printed article area coverage that is used for application-specific.
Embodiment
Describe the present invention in detail by following examples now.
Measuring method
1. spot size
Spot size adopts the Videomet system measurement that derives from KASPAR WALTER GmbH, and the precision of this system is 1 μ m.
2. gloss
Gloss adopts the REFO 60 that derives from Dr.Lange to measure under 60 ° angle.
3. coalescent
The printing ink receiver must be wetting easily, so that there be not " puddling ", promptly being flocked on of adjacent droplets of ink forms big dripping on the printing ink receptor surface.Estimate according to following standard then.
Standard:
1=does not have coalescent
Limited coalescent of 2=
3=is coalescent
4=is coalescent widely
5=is coalescent fully
Material
Unless otherwise indicated, all material that is used for following examples derives from AldrichChemical Co. (Belgium) easily." water " that is used for embodiment is deionized water.Use following material:
Pigment
Hostaperm
TMRed E5B02 is the magenta pigment (pigment violet 1 9) that derives from CLARIANT
Sunfast
TMBlue 249-1284 is the green pigment (pigment purplish blue 15:3) that derives from SUN CHEMICAL
The radiosusceptibility compound
DPGDA
TMBe the two functional acrylate's monomers that derive from UCB.
Craynor
TMCN501 is the monomer that derives from CRAY VALLEY.
SartomerT
MSR9003 is the two functional acrylate's monomers that derive from SARTOMER.
Craynor
TMCN386 is the amine modified propylene ester synergist that derives from CRAY VALLEY.
Craynor
TMCN501 is the amine modified polyether propylene ester oligomer that derives from CRAY VALLEY.
Irgacure
TMThe 500th, derive from the light trigger of CIBA SPECIALTY CHEMICALS.
Irgacure
TMThe 907th, derive from the light trigger of CIBA SPECIALTY CHEMICALS.
Irgacure
TMThe 1870th, derive from the light trigger of CIBA SPECIALTY CHEMICALS.
Darocur
TMITX is the light trigger that derives from CIBA SPECIALTY CHEMICALS.
Surfactant and dispersant
Solsperse
TMThe 32000th, derive from the resin of AVECIA.
Solsperse
TMThe 5000th, derive from the resin of AVECIA.
Byk
TMThe-333rd, derive from the surfactant of BYK CHEMIE GmbH.
Substrate
PE-paper is the not gummed RC-paper that derives from poly-(ethene) coating of FRANTSCHACH BELCOAT (Belgium).
PET is the thick PETG substrate of not gummed 175 μ m that derives from AGFA.
How this embodiment illustrates the spot size by the THICKNESS CONTROL droplets of ink.
The preparation of the liquid level of radiation-hardenable
According to table 1 by mixing each composition and stirring the liquid layer composition printing ink-L that prepared colourless radiation-hardenable in a hour with all components that guarantees to distribute well.Weight % (wt%) is based on the gross weight of radiation-hardenable liquid layer composition.
Table 1
| The wt% of following material | Printing 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 |
Adopt the conventional configurations ink-jet printer of assembling, the liquid layer composition printing ink-L of radiation-hardenable be injected on the PET from the UPH printhead of AGFA, with manufacture of ink receiver IR-2 to IR-7.Adopt resolution printing numerous dpd (dripping every point) as shown in table 2 of 360 * 360dpi, wherein 1dpd equals the droplet size of 3pL.
Table 2
| The printing ink recipient | The #dpd of liquid level |
| IR-1 | 0 |
| IR-2 | 2 |
| IR-3 | 4 |
| IR-4 | 5 |
| IR-5 | 6 |
| IR-6 | 8 |
| IR-7 | 15 |
The preparation of the jetted ink of radiation-hardenable
The jetted ink of the radiation-hardenable among this embodiment is made up of 100% solid, does not use solvent or water during the preparation of ink composite.Ink composite printing ink-M (magenta ink) and printing ink-C (cyan ink) according to table 3 preparation radiation-hardenable.Weight % (wt%) is based on total ink by weight.
Table 3
| The wt% of following material | Printing ink-M | Printing ink-C |
| Hostaperm TMRed E5B02 | 5.00 | --- |
| Sunfast TMBlue 249-1284 | --- | 2.00 |
| DPGDA TM | 34.97 | 40.47 |
| Sartomer TM?SR?9003 | 40.00 | 40.00 |
| Darocur TM?ITX | 5.00 | 5.00 |
| Craynor TM?CN?386 | 10.00 | 10.00 |
| Byk TM-333 | 0.03 | 0.03 |
| Solsperse TM?32000 | 5.00 | 2.00 |
| SOlsperse TM?5000 | --- | 0.50 |
At first by adopting dissolvers hybrid pigment, polymeric dispersant Solsperse
TM32000 and monomer DPGDA
TMAnd adopt the Eiger ball mill to handle the concentrated dispersion that this mixture prepares color pigment.For preparation printing ink-C, with dispersant synergist Solsperse
TM5000 and Solsperse
TM32000 are used in combination.In the following order under agitation with the second monomer Sartomer
TMSR9003, synergist Craynor
TMCN386, surfactant B yk
TM-333 and light trigger Darocur
TMITX joins in the concentrated pigment dispersion.Stir and continue one hour to guarantee to distribute well all components.Obtain uniform ink composite.
Performance evaluation
To IR-7, spray the jetted ink printing ink-M and the printing ink-C of 1dpd radiation-hardenable at printing ink recipient IR-1 by the conventional configurations ink-jet printer that uses the 2nd UPH printhead with the resolution ratio of 360 * 360dpi.Use the Fusion DRSE-120 conveyer cured printing ink recipient of assembling Fusion VPS/1600 lamp (D-lamp), this conveyer under the UV lamp on conveyer belt with the speed transportation sample of 20m/min.Measure the spot size of each solidified sample.
Table 4
| The printing ink recipient | Spot diameter (μ m) printing ink-M | Spot diameter (μ m) printing ink-C |
| IR-1 | 82 | 80 |
| IR-2 | 64 | 68 |
| IR-3 | 50 | 52 |
| IR-4 | 44 | 44 |
| IR-5 | 40 | 44 |
| IR-6 | 30 | 30 |
| IR-7 | 30 | 30 |
Clearly visible from table 4, the spot diameter of the printing ink-M of injection increases and reduces gradually to the thickness that IR-6 goes up liquid level with printing ink recipient IR-1.Under the thickness of 8dpd or thicker (at 15dpd on the IR-7), spot diameter is held constant at 30 μ m.The result is also presented by Fig. 2 with diagram form.
Replace to spray, the liquid layer composition printing ink-L of radiation-hardenable is used excellent applicator and the coating of wrapping wire rod with the wet thickness of 5 μ m on PE-paper.Spray the jetted ink printing ink-M and the printing ink-C of 1dpd radiation-hardenable then by the ink-jet printer of conventional configurations with the resolution ratio of 360 * 360dpi.Use the sample of the FusionDRSE-120 conveyer cured printed of assembling Fusion VPS/1600 lamp (D-lamp), the sample that this conveyer prints with the speed transportation of 20m/min on conveyer belt under the UV lamp.The spot size of measuring two jetted inks is 30 μ m.
In this embodiment, estimate the spot size of jetted ink after solidifying of spraying on the liquid level.
Adopt the mode identical with the printing ink recipient IR-7 of embodiment 1 to prepare printing ink recipient IR-8, difference is to use the jetted ink printing ink-M of radiation-hardenable to replace printing ink-L.At first use the Fusion DRSE-120 conveyer of assembling Fusion VPS/1600 lamp (D-lamp) to solidify printing ink recipient IR-5 and the printing ink recipient IR-8 of embodiment 1, this conveyer under the UV lamp on conveyer belt with the speed transportation printing ink receiver of 20m/min.
On printing ink recipient IR-5 that solidifies and IR-8, spray the jetted ink printing ink-M and the printing ink-C of 1dpd radiation-hardenable by the ink-jet printer of conventional configurations with the resolution ratio of 360 * 360dpi.Sample by the process cured printed identical with being used for cured printing ink recipient IR-5 and IR-8.Because vision is distinguished difficulty, on printing ink recipient IR-8, do not spray the printing ink printing ink-M of radiation-hardenable.
Table 5
| The printing ink recipient | Spot diameter (μ m) printing ink-M | Spot diameter (μ m) printing ink-C |
| IR-5 | 46 | 44 |
| IR-8 | --- | 42 |
Table 5 shows by the jetted ink printing ink-M of printing 1dpd radiation-hardenable on printing ink recipient IR-5 that solidifies and IR-8 and the spot size that printing ink-C obtains 42-46 μ m.In the structure ink-jet printing system, need cause with the radiation curable ink that 1dpd spurts into uncured liquid layer with 1dpd about identical spot size after the printing ink that sprays on the liquid level is solidifying.From table 3 and Fig. 2, should be understood that in the case the preferably selection for the radiation-hardenable liquid level is 5dpd, i.e. printing ink recipient IR-4.
Estimate coalescent and gloss in this embodiment.
The preparation of the liquid level of radiation-hardenable
According to table 6 by mixing each composition and stirring the liquid layer composition printing ink-L2 that prepared colourless radiation-hardenable in five minutes.Weight % (wt%) is based on the gross weight of radiation-hardenable liquid layer composition.
Table 6
| The wt% of following material | Printing ink-L2 |
| Craynor TM?CN501 | 70.0 |
| Irgacure TM?500 | 16.7 |
| Craynor TM?CN386 | 8.3 |
| Irgacure TM?1870 | 3.3 |
| Byk TM-333 | 1.7 |
The evaluation of performance
Adopt the conventional configurations printer of assembling, the liquid layer composition printing ink-L2 of radiation-hardenable is injected on half PET film surface with 8dpd and 360 * 360dpi from the UPH printhead of AGFA.In comparative sample COMP-1, the jetted ink printing ink-M of radiation-hardenable is ejected on the PET film, and in sample INV-1 of the present invention, the jetted ink printing ink-M of radiation-hardenable is spurted in the liquid level of PET film on second half.After UV-solidifies (Fusion VPS/1600 lamp (D-lamp)) two samples, estimate coalescent and measurement gloss.The results are shown in Table 7.
Table 7
Clearly visible from table 7, do not take place coalescently for sample INV-1 of the present invention, COMP-1 is opposite with comparative sample.Be not only for sample INV-1 of the present invention, the gloss of droplets of ink of spurting into liquid level is more much higher than the gloss that is directly injected to the droplets of ink (comparative sample COMP-1) on the PET, but also is comparable to the gloss of liquid level in the printing zone not.This causes printing and the very good homogeneous of gloss in the printing zone not.
After describing the preferred embodiments of the invention in detail,, can carry out many improvement and do not deviate from the scope of the present invention that following claim limits now to it will be apparent to one skilled in the art that.
Claims (10)
1. the printing process of an ink jet printing radiation-hardenable image on substrate comprises the steps:
A) at least a portion of described substrate, provide the liquid level of radiation-hardenable;
B) jetted ink with first radiation-hardenable drips the liquid level of spurting into described radiation-hardenable;
C) solidify the liquid level of the described radiation-hardenable that the jetted ink comprise described radiation-hardenable drips;
It is characterized by jetted ink with second radiation-hardenable and drip the liquid layer thickness that is ejected on the cured layer that step c) obtains and regulates described radiation-hardenable to control the resolution ratio of described radiation-hardenable image.
2. according to the printing process of claim 1, wherein with respect to the minimum dot size when the dpd that equates (dripping every point) sprays down, the diameter difference of the spot size of the jetted ink of described first and second radiation-hardenables is not more than 10%.
3. according to the printing process of claim 1 or 2, wherein in step a), at least a portion of described substrate, provide the liquid level of described radiation-hardenable by ink jet printing.
4. according to the printing process of claim 1 or 2, the thickness of the liquid level of wherein said radiation-hardenable is at least 1 μ m.
5. according to the printing process of claim 1 or 2, wherein to be higher than 50m
2Print speed printing speed printing image hourly.
6. according to the printing process of claim 1 or 2, the liquid level of wherein said radiation-hardenable is the transparency liquid layer.
7. according to the printing process of claim 1 or 2, the liquid level of wherein said radiation-hardenable is the white liquid layer.
8. according to the printing process of claim 1 or 2, the jetted ink of the liquid level of wherein said radiation-hardenable and/or described first radiation-hardenable is based on cationic polymerization.
9. printing process according to Claim 8, the jetted ink of wherein said first radiation-hardenable are the jetted inks that does not have the cation radiation-hardenable of cationic initiator.
10. printing process according to Claim 8, wherein cationic initiator exists in the liquid level of described radiation-hardenable.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04105394.3 | 2004-10-29 | ||
| EP04105394 | 2004-10-29 |
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| CN100537257C true CN100537257C (en) | 2009-09-09 |
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| CNB2005101184395A Expired - Fee Related CN100537257C (en) | 2004-10-29 | 2005-10-28 | Printing of radiation curable inks into a radiation curable liquid layer |
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| EP (1) | EP1652686B1 (en) |
| JP (1) | JP2006137185A (en) |
| CN (1) | CN100537257C (en) |
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| JP2007007949A (en) * | 2005-06-29 | 2007-01-18 | Fujifilm Holdings Corp | Active energy curing ink jet recorder and its recording method |
| JP5300175B2 (en) | 2006-03-02 | 2013-09-25 | 富士フイルム株式会社 | Ink set for inkjet recording and inkjet recording method |
| JP4903618B2 (en) | 2006-09-25 | 2012-03-28 | 富士フイルム株式会社 | Inkjet recording method and inkjet recording apparatus |
| FR2906185B1 (en) * | 2006-09-27 | 2009-08-28 | Tattoo Fleurs | EQUIPMENT AND METHOD FOR CUSTOMIZING FLOWERS BY PRINTING ON AN ORGANIC PART |
| JP4907414B2 (en) † | 2006-09-29 | 2012-03-28 | 富士フイルム株式会社 | Inkjet recording method and inkjet recording apparatus |
| JP4907413B2 (en) | 2006-09-29 | 2012-03-28 | 富士フイルム株式会社 | Inkjet recording method and inkjet recording apparatus |
| IN2009CN03597A (en) * | 2006-12-21 | 2015-09-11 | Agfa Graphics Nv | |
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| US4857630A (en) | 1987-12-07 | 1989-08-15 | E. I. Du Pont De Nemours And Company | Hyperbranched polyarylene |
| US5196502A (en) | 1991-11-05 | 1993-03-23 | Eastman Kodak Company | Method for the preparation of multiply-branched aromatic polyesters |
| US5225522A (en) | 1992-07-13 | 1993-07-06 | Eastman Kodak Company | Multiply-branched aliphatic-aromatic polyesters and method for preparing multiply-branched aliphatic-aromatic polyesters |
| US5679138A (en) | 1995-11-30 | 1997-10-21 | Eastman Kodak Company | Ink jet inks containing nanoparticles of organic pigments |
| GB9825359D0 (en) | 1998-11-20 | 1999-01-13 | Xaar Technology Ltd | Methods of inkjet printing |
| US6720042B2 (en) | 2001-04-18 | 2004-04-13 | 3M Innovative Properties Company | Primed substrates comprising radiation cured ink jetted images |
| US6550905B1 (en) | 2001-11-19 | 2003-04-22 | Dotrix N.V. | Radiation curable inkjet ink relatively free of photoinitiator and method and apparatus of curing the ink |
| GB0205151D0 (en) | 2002-03-05 | 2002-04-17 | Sericol Ltd | An ink-jet ink printing process and ink-jet inks used therein |
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- 2005-08-31 DE DE602005007675T patent/DE602005007675D1/en active Active
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| JP2006137185A (en) | 2006-06-01 |
| EP1652686A1 (en) | 2006-05-03 |
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