Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0029—Formation of a transparent pattern using a liquid marking fluid
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/0058—Digital printing on surfaces other than ordinary paper on metals and oxidised metal surfaces
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/007—Digital printing on surfaces other than ordinary paper on glass, ceramic, tiles, concrete, stones, etc.
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/0076—Digital printing on surfaces other than ordinary paper on wooden surfaces, leather, linoleum, skin, or flowers

Definitions

• the present invention relates to a radiation curable ink-jet printing process exhibiting consistent image quality on different ink-receivers.
• 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 jetting of the ink droplets can be performed in several different ways.
• a first type of process called continuous ink-jet printing
• the ink stream jetted from an orifice of the print head is broken up, by applying a pressure wave pattern to this orifice, into ink droplets of uniform size and spacing, which can be electrostatically charged or not as desired.
• the charged drops are deflected by an electric field into a gutter for recuperation, while the uncharged drops are undeflected and land on the ink-receiver to form an image.
• it is the charged droplets which land on the ink-receiver to form an image and it are the uncharged droplets, which are recuperated.
• the ink droplets can be created by a "drop on demand” method (DOD).
• DOD drop on demand
• a drop-on-demand device ejects ink droplets only when they are needed for imaging on the ink-receiver, thereby avoiding the complexity of drop charging, deflection hardware, and ink collection.
• the ink droplet can be formed by means of a pressure wave created by a mechanical motion of a piezoelectric transducer (so-called “piezo method”), or by means of discrete thermal pushes (so-called “bubble jet” method, or “thermal jet” method).
• 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 the 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 printhead 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, corona, flame treatment.
• Surface coatings can be either absorbing or non-absorbing.
• the surface treatment in EP 1199181 A (TOYO INK) consists of a corona treatment or a plasma treatment.
• EP 1199181 A discloses a method for ink-jet printing on a surface of a substrate of a synthetic resin, said method comprising the steps of:
• Corona discharge treatment is one of the most commonly used methods for activating a plastic surface prior to forming an adhesive bond. Corona discharges are produced from point sources, and as such produce localised energetic discharges, which are commonly known as streamers. The production of localised energetic discharges often result in a non-uniform treatment of the substrate and hence a non-uniform image quality. Corona treatment has the advantage of working well with newly manufactured substrates. However, recycled substrates may contain significant impurities or irregularities that may interfere with the treatment of the substrate.
• Plasma treatment infuses the treatment zone with an inert gas that is partially ionized by the energized electrodes. While plasma treatment may provide enhanced adhesion in certain applications, a special inert gas or gas mixture and a complex control mechanism are required to realize plasma treatment. This increases the cost, complexity and maintenance of the equipment used to process the substrates. Thus, it is desirable to avoid the plasma treatment process where possible.
• WO 03101747 discloses a method of selecting a coating to provide a surface to which inkjet ink adheres with a selectable and substantially consistent texture and gloss across the surface of a non-inkjet ready substrate comprising:
• the ink-jet ink must contain an organic solvent capable of at least partially dissolving the primed layer.
• the application is silent on radiation curable inks, which is also the case for the solvent-based inks jetted on a primed substrate of WO 03080356 (UCB) and WO 2004003093 (UCB) .
• US 20040126507 A discloses a substrate printed with a radiation cured inkjet printed image wherein the image is printed on a coating on the substrate and wherein the coating comprises a copolymer derived from a carboxylic acid containing vinylic unsaturation.
• the examples fail to teach how to achieve minimal differences in drop spread with the same coating on different substrates, e.g.DIGI-LYTE Film 65 (very little spread) and LABEL-LYTE Film 70 (excessive spread).
• an ink-jet printing process capable of producing approximately the same dotsize with the same radiation curable ink droplet volume on a wide variety of ink receivers provided with a surface layer of a fluid and wherein the thickness of the surface layer is not critical.
• the radiation curable inks should not be restricted to certain specific inks having enough organic solvent or monofunctional monomers present.
• a dot control fluid comprising film forming polymeric resin and inorganic filler in a certain ratio lead to a ink-jet printing process, wherein the differences in dotsize on different ink-receivers provided with a surface layer of this dot control fluid was minimalized to less than 30 ⁇ m.
• Objects of the present invention are realized by an ink-jet printing process comprising the steps of:
• 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
• DCF dot control fluid
• initiator means a Norrish type I initiator, a Norrish type II initiator or a photo-acid generator.
• Nevish Type I initiator as used in disclosing the present invention, means an initiator which cleaves after excitation, yielding the initiating radical immediately.
• Non-Reliable Type II initiator as used in disclosing the present invention, means an 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.
• photo-acid generator means an initiator which generates a photo-acid or hemi-acid upon exposure to actinic radiation.
• colorant means dyes and pigments.
• die as used in 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.
• filler means an inorganic material added to a layer on an ink-receiver to modify its properties, e.g. adhesion, opacity or tribo-electrical properties.
• 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 means saturated straight chain, branched chain and alicyclic hydrocarbon groups.
• unsaturated aliphatic group means straight chain, branched chain and alicyclic hydrocarbon groups which contain at least one double or triple bond.
• aromatic 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.
• substituted means that one or more of the carbon atoms and/or that a hydrogen atom of one or more of carbon atoms in an aliphatic group, an aromatic group or an alicyclic hydrocarbon group, are replaced by an oxygen atom, a nitrogen atom, a silicon atom, a sulphur atom, a phosphorous atom, selenium atom or a tellurium atom.
• substituents include hydroxyl groups, ether groups, carboxylic acid groups, ester groups, amide groups and amine groups.
• heteromatic group means an aromatic group wherein at least one of the cyclic conjugated carbon atoms is replaced a nitrogen atom or a phosphorous atom.
• heterocyclic group means an alicyclic hydrocarbon group wherein at least one of the cyclic conjugated carbon atoms is replaced by an oxygen atom, a nitrogen atom, a phosphorous atom, a silicon atom, a sulphur atom, a selenium atom or a tellurium atom.
• a dotsize control fluid suitable for the ink-jet printing process according to the present invention contains at least three components: (i) a film forming polymeric resin, (ii) an inorganic filler, and (iii) a solvent.
• the dotsize control fluid suitable for the ink-jet printing process according to the present invention has a P/F ratio greater than 3, with P the weight% of film forming polymeric resin and F the weight% of inorganic filler, both based on the total weight of the dotsize control fluid.
• the dotsize control fluid suitable for the ink-jet printing process according to the present invention may contain one or more dispersants.
• the dotsize control fluid suitable for the ink-jet printing process according to the present invention may contain one or more surfactants.
• the dotsize control fluid suitable for the ink-jet printing process according to the present invention may contain one or more biocides.
• the dotsize control fluid suitable for the ink-jet printing process according to the present invention may further contain one or more other additives required to optimize the coating quality of the surface layer or to improve the jetting quality of the dotsize control fluid.
• the dotsize control fluid suitable for the ink-jet printing process according to the present invention may be coated, sprayed or jetted onto an ink-receiver.
• the dotsize control fluid is preferably applied onto the ink-receiver by ink-jet technology and may by jetted only onto a portion of an ink-receiver intended to carry a radiation curable image.
• the inorganic particles should then be sufficiently small to permit free flow through the ink-jet printing device, especially at the ejecting nozzles which usually have a diameter ranging from 10 ⁇ m to 50 ⁇ m.
• the dotsize control fluid is applied onto the ink-receiver in an amount preferably between 0.1 and 10 g/m 2 and particular preferably between 0.1 and 5 g/m 2 .
• the dry thickness of the surface layer is preferably between 0.1 and 10 ⁇ m, and particularly preferably between 0.1 and 5 ⁇ m, most preferably between 0.1 and 1.5 ⁇ m.
• the dotsize control fluid is used in an ink-jet printing process comprising the steps of:
• the dotsize control fluid suitable for the ink-jet printing process according to the present invention comprises at least one film forming polymeric resin.
• two or more film forming polymeric resins may be used to further improve some properties of the surface layer, e.g. jettability, coating quality or adhesion.
• Suitable film forming polymeric resins include organic particles such as polystyrene and polymethyl methacrylate; silicones; melamine-formaldehyde condensation polymers; urea-formaldehyde condensation polymers; polyesters; polyurethanes; polyesterurethanes; polyamides; copolymers of vinylidene chloride such as vinylidene chloride /acrylonitrile /acrylic acid terpolymers or vinylidene chloride /methyl acrylate /itaconic acid terpolymers; homopolymers and copolymers of acrylates, methacrylates, vinylhalogenides, vinylacetate, styrene, acrylonitrile, olefines; cellulose and derivatives thereof; gelatin; polysaccharides; rubber like polymers based on butadienene and isoprene.
• Suitable film forming polymeric resins are producible with monomers selected from the group consisting of acrylates, methacrylates, vinyl esters, acrylic acid, methacrylic acid, itaconic acid, vinylidene chloride, polyisocyanates, aromatic polycarboxylic acids and polyols.
• the film forming polymeric resins preferably has an average particle size smaller than 1 ⁇ m, more preferably smaller than 300 nm, and particularly preferably smaller than 100 nm.
• the polymeric resin content in the dotsize control fluid is preferably controlled to give a viscosity of less than 50 mPa.s, preferably less than 30 mPa.s, and more preferably less than 10 mPa.s at a shear rate of 100s -1 .
• the dotsize control fluid suitable for the ink-jet printing process according to the present invention comprises at least one inorganic filler, which can be chosen from neutral, anionic and cationic filler types.
• Useful fillers include e.g. silica, talc, clay, hydrotalcite, kaolin, diatomaceous earth, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminosilicate, aluminum trihydroxide, aluminum oxide (alumina), titanium oxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulfide, satin white, alumina hydrate such as boehmite, zirconium oxide or mixed oxides.
• two or more inorganic fillers may be used to further improve some properties of the surface layer, e.g. coating quality and adhesion.
• the inorganic filler preferably has an average particle size smaller than 0.8 ⁇ m, more preferably smaller than 150 nm and most preferably smaller than 20 nm.
• the inorganic filler preferably has a specific surface greater than 50 m 2 /g, more preferably greater than 200 m 2 /g, and most preferably greater than 300 m 2 /g.
• the inorganic filler is a cationic type filler, it is preferably selected from alumina hydrates, aluminum oxides, aluminum hydroxides, aluminum silicates, and cationically modified silica's.
• a preferred type of alumina hydrate is crystalline boehmite, or ⁇ -AlO(OH).
• Useful types of boehmite include, in powder form, DISPERAL, DISPERAL HP14 and DISPERAL 40 from SASOL, MARTOXIN VPP2000-2 and GL-3 from MARTINSWERK GmbH.; liquid boehmite alumina systems, e.g. DISPAL 23N4-20, DISPAL 14N-25, DISPERAL AL25 from SASOL.
• Patents on alumina hydrate include EP 500021 A (ASAHI GLASS), EP 634286 A (ASAHI GLASS), US 5624428 (KIMBERLY CLARK), EP 742108 A (ASAHI GLASS), US 6238047 (ASAHI GLASS), EP 622244 A (CANON) and EP 810101 A (CANON) .
• Suitable cationic aluminum oxide (alumina) types for the dotsize control fluid for use in the ink-jet printing process according to the present invention include ⁇ -Al 2 O 3 types, such as NORTON E700, available from SAINT-GOBAIN CERAMICS & PLASTICS INC., and ⁇ -Al 2 O 3 types, such as ALUMINUM OXID C from DEGUSSA; other aluminum oxide grades, such as BAIKALOX CR15 and CR30 from BAIKOWSKI CHEMIE; DURALOX grades and MEDIALOX grades from BAIKOWSKI CHEMIE, BAIKALOX CR80, CR140, CR125, B105CR from BAIKOWSKI CHEMIE; CAB-O-SPERSE PG003TM available from CABOT, CATALOX GRADES and CATAPAL GRADES available from SASOL, such as PLURALOX HP14/150; colloidal Al 2 O 3 types, such as ALUMINASOLTM 100; ALUMINASOLTM 200, ALU
• cationic inorganic fillers include aluminum trihydroxides such as Bayerite, or ⁇ -Al(OH) 3 , such as PLURAL BT, available from SASOL, and Gibbsite, or ⁇ -Al(OH) 3 , such as MARTINALTM grades from MARTINSWERK GmbH, MARTIFINTM grades, such as MARTIFINTM OL104, MARTIFINTM OL 107 and MARTIFINTM OL111 from MARTINSWERK GmbH , MICRALTM grades, such as MICRALTM 1440, MICRALTM 1500; MICRALTM 632; MICRALTM 855; MICRALTM 916; MICRAL TM 932; MICRALTM 932CM; MICRALTM 9400 from JM HUBER COMPANY ; HIGILITETM grades, e.g. HIGILITETM H42 or HIGILITETM H43M from SHOWA DENKA K.K..
• Another suitable type of cationic filler for the dotsize control fluid according to the present invention is a zirconium oxide such as NALCOTM OOSS008 available from ONDEO NALCO, an acetate stabilized ZrO 2 such as ZR20/20, ZR50/20, ZR100/20 and ZRYS4 trademarks from NYACOL NANO TECHNOLOGIES.
• NALCOTM OOSS008 available from ONDEO NALCO
• ZrO 2 such as ZR20/20, ZR50/20, ZR100/20 and ZRYS4 trademarks from NYACOL NANO TECHNOLOGIES.
• Suitable mixed oxides for the dotsize control fluid according to the present invention according to the present invention include SIRAL grades from SSASOL, colloidal metal oxides from NALCO such as NALCOTM 1056, NALCOTM TX10496, NALCOTM TX11678.
• silica which can be used as such in its anionic form or after cationic surface modification.
• Silica is disclosed as a filler in numerous old and recent patents on ink-receiving elements, e.g. US 4892591 (MIZUSAWA INDUSTRIAL CHEM), US 4902568 (CANON), EP 373573 A (CIBA GEIGY), EP 423829 A (OJI PAPER), EP 487350 A (XEROX), EP 493100 A (SANYO KOKUSAKU PULP), EP 514633 A (SCHOELLER FELIX JUN PAPIER), etc.
• the silica can be chosen from different types, such as crystalline silica, colloidal silica, amorphous silica, precipitated silica, fumed silica, silica gel, and spherical and non-spherical silica.
• the silica may contain minor amounts of metal oxides from the group Al, Zr, Ti.
• Suitable types of silica for the dotsize control fluid for use in the ink-jet printing process according to the present invention include AEROSILTM OX50 (BET surface area 50 ⁇ 15 m 2 /g, average primary particle size 40 nm, SiO 2 content > 99.8%, Al 2 O 3 content ⁇ 0.08%), AEROSILTM MOX170 (BET surface area 170 m 2 /g, average primary particle size 15 nm, SiO 2 content > 98.3%, Al 2 O 3 content 0.3-1.3%), AEROSILTM MOX80 (BET surface area 80 ⁇ 20 m 2 /g, average primary particle size 30 nm, SiO 2 content > 98.3%, Al 2 O 3 content 0.3-1.3%), or other hydrophilic AEROSILTM grades available from DEGUSSA-HÜLS AG, which may give aqueous dispersions with a small average particle size ( ⁇ 500 nm).
• AEROSILTM OX50 BET surface area 50 ⁇ 15
• KIESELSOLTM e.g. KIESELSOLTM 100, KIESELSOLTM 200 , KIESELSOLTM 300 and KIESELSOLTM 500, are also very suitable for the dotsize control fluid for use in the ink-jet printing process according to the present invention.
• colloidal silica grades include LudoxTM grades from GRACE GmbH; SytonTM 2XFS, SytonTM 240 and SytonTM D30 from MONSANTO; NalcoTM 1030 and NalcoTM 1034A from NALCO CHEMICAL; SnowtexTM Up and SnowtexTM OXS from NISSAN CHEMICAL INDUSTRIES; NyacolTM 5050 from NYACOL PRODUCT INC; KieselsaeureTM D17 and Kieselsaeure TM X197 from DEGUSSA; SylojetTM 4001 from GRACE GmbH; and Highlink NanoTM G502 31 liq from CLARIANT.
• the most preferred type of silica for the dotsize control fluid used in the ink-jet printing process according to the present invention is colloidal silica.
• the dotsize control fluid may further contain a dispersant, in order to obtain a stable dispersion of the inorganic filler(s) in the dotsize control fluid.
• 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).
• dispersants are incorporated at 2.5% to 200%, more preferably at 50% to 150% by weight of the inorganic filler.
• the dotsize control fluid may contain as a solvent, water and/or organic solvents, such as alcohols, fluorinated solvents and dipolar aprotic solvents.
• Water being the preferred solvent, is preferably present in a concentration between 10 and 80 wt%, particularly preferably between 20 and 50 wt%, each based on the total weight of the dotsize control fluid .
• 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.
• Surfactants may be incorporated in the dotsize control fluid suitable for the ink-jet printing process according to the present invention. They can be any of the cationic, anionic, amphoteric, and non-ionic ones as described in JP 62280068 A (CANON).
• Suitable surfactants for use in the dotsize control fluid suitable for the ink-jet printing process according to the present invention include N-alkylamino acid salts, alkylether carboxylic acid salts, acylated peptides, alkylsulfonic acid salts, alkylbenzene and alkylnaphthalene sulfonic acid salts, sulfosuccinic acid salts, ⁇ -olefin sulfonic acid salts, N-acylsulfonic acid salts, sulfonated oils, alkylsulfonic acid salts, alkylether sulfonic acid salts, alkylallylethersulfonic acid salts, alkylamidesulfonic acid salts, alkylphosphoric acid salts, alkylether-phosphoric acid salts, alkylallyletherphosphoric acid salts, alkyl and alkylallylpolyoxyethylene ethers, alkylallylform-aldehyde
• Suitable cationic surfactants for use in the dotsize control fluid suitable for the ink-jet printing process according to the present invention include N-alkyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, dodecyldimethyl-amine, tetradecyldimethylamine, ethoxylated alkyl guanidine-amine complex, oleamine hydroxypropyl bistrimonium chloride, oleyl imidazoline, stearyl imidazoline, cocamine acetate, palmitamine, dihydroxyethylcocamine, cocotrimonium chloride, alkyl polyglycolether ammonium sulphate, ethoxylated oleamine, lauryl pyridinium chloride, N-oleyl-1,3-diaminopropane, stearamidopropyl dimethylamine lactate, coconut fatty amide, oleyl hydroxyethyl imidazoline, isostearyl
• These surfactants are commercially available from DuPont and 3M.
• the concentration of the surfactant component in the surface layer is typically in the range of 0.1 to 2 %, and preferably in the range of 0.2 to 1.5 % by weight based on the total dry weight of the surface layer.
• Suitable biocides for the dotsize control fluid 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 dotsize control fluid is ProxelTM GXL and ProxelTM Ultra-5 available from AVECIA BIOCIDES.
• 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 dotsize control fluid .
• the dotsize control fluid may contain various inorganic salts, and acids or alkalis as pH adjusters.
• Stabilizers may also be added to the dotsize control fluid.
• the ink-receiver suitable for the ink-jet printing process according to the present invention is not restricted to any specific type, but substantially non-absorbing ink-receivers for aqueous solutions are preferred.
• standard paper is an absorbing ink-receiver.
• a resin-coated paper e.g. polyethylene-coated paper or polypropylene-coated paper, is substantially non-absorbing for an aqueous solution, and hence very suitable.
• the ink-receiver suitable for the ink-jet printing process according to the present invention can be transparent, translucent or opaque.
• the ink-receiver can be coloured or metallized.
• Suitable ink-receivers for the ink-jet printing process according to the present invention are polymeric substrates, 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.
• polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); oriented polystyrene (OPS); oriented nylon (ONy); polypropylene (PP), oriented polypropylene (OPP); polyvinyl
• Acrylic resins, phenol resins, glass and metals may also be used as an ink-receiver.
• Other suitable ink-receiver materials can be found in . Modern Approaches to Wettability: Theory and Applications. Edited by SCHRADER Malcolm E.. New York 1992, ISBN0306439859.
• a preferred type of ink receiver is an ink receiver provided with a self-adhesive backlayer.
• Suitable examples of self-adhesive PVC ink receivers include MPITM vinyls from AVERY-DENNISON, DigitalTM vinyls from METAMARK, Multi-fixTM digital white vinyls from MULTI-FIX and GrafiprintTM vinyls from GRAFITYP.
• the ink-receiver may also incorporate mineral particles as fillers, such as e.g. PET containing CaCO 3 , PET containing TiO 2 , a-PET and PET-g.
• mineral particles such as e.g. PET containing CaCO 3 , PET containing TiO 2 , a-PET and PET-g.
• Polyester film substrates and especially polyethylene terephthalate are preferred for certain applications particularly types with excellent dimensional stability.
• the ink-receiver may also be made from an inorganic material, such as a metal oxide or a metal (e.g. aluminium and steel).
• suitable ink-receivers may be selected from the group consisting of cardboard, wood, composite boards, coated plastic, canvas, textile, glasses, plant fibre products, leather, magnetic materials and ceramics.
• a radiation-curable ink-jet ink suitable for the ink-jet printing process according to the present invention contains at least two components: (i) a radiation-curable compound, and (ii) a photo-initiator.
• the radiation-curable compound can be selected from monomers and/or oligomers that can be polymerized by a curing means of an ink-jet printer.
• the radiation-curable ink-jet ink preferably further contains at least one colorant, i.e. pigment or dye.
• 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 ink-jet 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 ink-jet 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 humectant to prevent the clogging of the nozzle, due to its ability to slow down the evaporation rate of ink.
• a biocide may be added to the radiation curable ink-jet ink suitable for the ink-jet printing process according to the present invention to prevent unwanted microbial growth, which may occur in the ink-jet ink over time.
• the biocide may be used either singly or in combination.
• the radiation-curable ink-jet ink may contain additives such as buffering agents, anti-mold agents, pH adjustment agents, electric conductivity adjustment agents, chelating agents, anti-rusting agents, light stabilizers, anti-oxidants, thickeners, dendrimers, and the like. Such additives may be included in the ink-jet inks in any effective amount, as desired.
• pH controlling agents suitable for inks of the present invention include, but are not limited to, acids, and bases, including hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide. The amount included will depend, of course, on the specific component being included.
• An ink-jet printer generally uses a radiation-curable ink-jet ink set consisting of a plurality of radiation-curable ink-jet inks. Radiation curable compounds
• the radiation curable ink-jet ink contains monomers and/or oligomers, which are polymerized by the curing means of the ink-jet 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 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.
• the radiation-curable compound in the radiation curable ink-jet ink can be 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, tetrahydrofurfuryl acrylate, iso
• 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 JP 62280068 A (CANON), 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 ink-jet inks may also contain polymerizable oligomers.
• polymerizable oligomers include epoxy acrylates, aliphatic urethane acrylates, aromatic urethane acrylates, polyester acrylates, and straight-chained acrylic oligomers.
• the radiation curable ink-jet ink preferably contains less than 20 wt%, more preferably less than 15 wt% of a monofunctional monomer, each based on the total ink weight. Initiators
• An initiator is a catalyst, usually called a photo-initiator, for initiating the polymerization reaction.
• the photo-initiator requires less energy to activate than the monomers and oligomers to form the polymer.
• 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 Norrish type I initiator is an initiator which cleaves after excitation, yielding the initiating radical immediately.
• a preferred Norrish type I-initiator is selected from the group consisting of benzoinethers, benzil ketals, ⁇ , ⁇ -dialkoxyacetophenones, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, acylphosphine oxides, acylphosphine sulfides, ⁇ -haloketones, ⁇ -halosulfones and ⁇ -halophenylglyoxalates.
• a Norrish Type II initiator is an initiator which is activated by actinic radiation and forms free radicals by hydrogen abstraction or electron extraction from a second compound, the synergist, that becomes the actual initiating free radical.
• a preferred Norrish type II-initiator is selected from the group consisting of benzophenones, thioxanthones, 1,2-diketones and anthraquinones.
• Suitable Norrish type I and II-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.
• a preferred amount of initiator is 1-50 wt% of the total ink weight, and more preferably 1 to 25 wt% of the total ink 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 photo-initiators include IrgacureTM 184, IrgacureTM 500, IrgacureTM 907, IrgacureTM 369, IrgacureTM 1700, IrgacureTM 651, IrgacureTM 819, IrgacureTM 1000, lrgacure TM1300, IrgacureTM 1870, DarocurTM 1173, DarocurTM 4265 and DarocurTM ITX available from CIBA SPECIALTY CHEMICALS, Lucerin TPO available from BASF AG, EsacureTM KT046, EsacureTM KIP150, EsacureTM KT37 and EsacureTM EDB available from LAMBERTI, H-NuTM 470 and H-NuTM 470X available from SPECTRA GROUP Ltd.. Synergists
• a synergist or co-initiator known in the prior art can be used.
• 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 derivatives are particularly preferred.
• Inhibitors are particularly preferred.
• 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; GenoradTM 16 avaliable from RAHN.
• 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.
• 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 ink-jet 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) .
• the pigment particles should be sufficiently small to permit free flow of the ink through the ink-jet 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 average particle diameter of the pigment should be between 0.005 ⁇ m and 15 ⁇ m.
• the average pigment particle size is between 0.005 and 5 ⁇ m, more preferably between 0.005 and 1 ⁇ m, and particularly preferably between 0.005 and 0.3 ⁇ m. Larger pigment particle sizes may be used as long as the objectives of the present invention are achieved.
• the pigment can be black, cyan, magenta, yellow, red, orange, violet, blue, green, brown, mixtures thereof, and the like.
• Suitable pigments for the radiation curable ink-jet ink include those described in The Colour Index, Vols. 1-8, Society of Dyers and Colourists, Yorkshire, England having the designations: C. I. Pigment Yellow 17, C. I. Pigment Blue 27, C. I. Pigment Red 49:2, C. I. Pigment Red 81:1, C. I. Pigment Red 81:3, C. I. Pigment Red 81 :x, C. I. Pigment Yellow 83, C. I. Pigment Red 57:1, C. I. Pigment Red 49:1, C. I. Pigment Violet 23, C. I. Pigment Green 7, C. I. Pigment Blue 61, C. I. Pigment Red 48:1, C. I. Pigment Red 52:1, C. I.
• Pigment Yellow 93 C.I. Pigment Yellow 74, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 154, C. I. Pigment Yellow 185, C.I. Pigment Yellow 180, C.I. Pigment Red 122, C.I. Pigment Red 184, bridged aluminium phthalocyanine pigments and solid solutions of pigments.
• suitable pigment materials include carbon blacks such as Regal 400R, Mogul L, Elftex 320 from Cabot Co., or Carbon Black FW18, Special Black 250, Special Black 350, Special Black 550, Printex 25, Printex 35, Printex 55, Printex 150T from DEGUSSA Co., and C.I. Pigment Black 7 and C.I. Pigment Black 11. Additional examples of suitable pigments are disclosed in US 5389133 (XEROX) .
• 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, 10, 12, 13, 14, 17, 65, 73, 74, 75, 83, 93, 109, 120, 128, 138, 139, 150, 151, 154, 155, 180, 185; Pigment Red 17, 22, 23, 57:1, 122, 144, 146,170, 176, 184, 185, 188, 202, 206, 207, 210; Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, and Pigment Blue 16. Resins
• the radiation curable ink-jet ink may further contain a resin, also called a pigment stabilizer or dispersant, in order to obtain a stable dispersion of the pigment(s) in the ink-jet ink.
• a resin also called a pigment stabilizer or dispersant
• 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.
• Surfactants are incorporated at 2.5% to 200%, more preferably at 50% to 150% by weight of the pigment.
• the radiation curable ink-jet ink 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 20 wt% based on the total ink weight and particularly in a total below 10 wt% based on the total ink weight.
• a fluorinated or silicone compound may be used as a surfactant, however, a potential drawback is extraction by food from ink-jet 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 may contain as solvent, water and/or organic solvents, such as alcohols, fluorinated solvents and dipolar aprotic solvents.
• the solvent is preferably present in a concentration between 10 and 80 wt%, particularly preferably between 20 and 50 wt%, each based on the total weight of the radiation curable ink-jet ink.
• 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 0.1-5.0 wt%, and particularly preferably 0.1-3.0 wt%, 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 humectants include triacetin, N-methyl-2-pyrrolidone, glycerol, urea, thiourea, ethylene urea, alkyl urea, alkyl thiourea, dialkyl urea and dialkyl thiourea, diols, including ethanediols, propanediols, propanetriols, butanediols, pentanediols, and hexanediols; glycols, including propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, diethylene glycol, tetraethylene glycol, and mixtures and derivatives thereof.
• a preferred humectant is polyethylene glycerol and added to the ink-jet ink formulation in an amount of 0.1 to 30 wt% of the formulation, more preferably 0.1 to 10 wt% of the formulation, and most preferably approximately 4.0 to 7.0 wt%.
• Suitable biocides for the radiation curable ink-jet ink 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 is ProxelTM GXL available from AVECIA BIOCIDES.
• 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 radiation curable ink-jet ink.
• the dot size was determined with a ImageXpertTM set-up available from IMAGEXPERT using Image-Pro image analysis software available from MEDIA CYBERNETICS. Dot size measurement was performed by measuring the diameter of a single dot ignoring any satellites, a satellite being an overlapping dot produced by another ink-jet ink droplet or produced by a part of the same ink-jet ink droplet. The dotsize was determined as the average of about 100 dots measured.
• the MDD is an abbreviation for the Maximum Difference in Dotsize. It is the absolute value of the largest difference in dotsize between a first and a second ink receiver for a given set of ink-receivers, either having the same surface layer or having no surface layer.
• the initiator solution was added to the pre-emulsion and stirred for 15 minutes.
• 0.66 g sodium metabisulfite was added to the reactor at 70°C and 0.47 L of the pre-emulsion containing the initiator solution.
• the heating of the reactor was stopped and the rest of the pre-emulsion and the reductor solution were added via separate flows over 1 hour.
• the temperature increased to 95°C and was kept at 95°C during the rest of the reaction. After adding these two flows, the pre-emulsion reactor was rinsed with 0.57 kg demineralized water and the reductor recipient was rinsed with 0.11 kg demineralized water.
• This rinsing water was then pumped to the reactor. After adding the rinsing water, the reaction mixture was stirred for one hour at 95°C. Demonomerization was performed under vacuum until 0.57 L of liquid was condensed. The reaction mixture was cooled and adjusted with demineralized water to have 27% by weight of solids and then filtered.
• LATEX-2 is NEOCRYL A639 available from ZENECA RESINS BV, which contains 45% solids.
• LATEX-3 was prepared according to the following procedure:
• the reaction was cooled to room temperature and filtered through a nylon tissue with a pore size of 50 ⁇ .
• the end dispersion had a solid content of about 20 wt%. This dispersion was de-alcoholized by decanting after settling down of the particles (several weeks), and by replacing the decanted solution by demineralized water.
• LATEX-4 is a 30% aqueous solution of a film forming polymeric resin based on a copolymer (CAS 29757-50-4) of 88wt% vinylidene chloride, 10wt% methylacrylate and 2wt% itaconic acid and containing 2.5wt% of Hostapon T based on the weight of the copolymer.
• KIESELSOLTM 100 and KIESELSOLTM 500 are colloidal silica's available from BAYER AG, whereby the number indicates the surface area in m 2 per gram.
• SIL-500 is a 15% aqueous dispersion of KIESELSOLTM 500.
• SIL-100 is a 36% aqueous dispersion of KIESELSOLTM 100.
• NaOH-sol is a 8% solution of sodium hydroxide in water.
• MERSOL is a 4.85% aqueous solution of MersolatTM H.
• ArkopalTM N060 a nonylphenol ethoxylate type surfactant from CLARIANT.
• TSC 033TM is cyan colorant (CAS 152876-71-6) available from AGFA.
• Carbon Black MA8TM is a carbon black available from MITSUBISHI CHEMICAL.
• SunfastTM Blue 249-1284 is a cyan pigment (Pigment Blue 15:3) available from SUN CHEMICAL.
• HostapermTM Red E5B02 is a magenta pigment (Pigment Violet 19) available from CLARIANT.
• DPGDATM is a difunctional acrylate monomer available from UCB.
• CraynorTM CN 501 is a monomer available from CRAY VALLEY.
• SartomerTM SR9003 is a difunctional acrylate monomer available from SARTOMER.
• SartomerTM SR339 is 2-phenoxyethyl acrylate available from SARTOMER.
• CraynorTM CN 386 is an amine modified acrylate synergist available from CRAY VALLEY.
• DarocurTM ITX is a photo-initiator available from CIBA SPECIALTY CHEMICALS.
• SolsperseTM 32000 is a resin available from AVECIA.
• SolsperseTM 5000 is a resin available from AVECIA.
• BykTM-333 is a surfactant available from BYK CHEMIE GmbH.
• ProxelTM Ultra-5 is a biocide available from AVECIA BIOCIDES, UK.
• NMP is N-methyl pyrrolidone.
• SURF-sol is an aqueous solution of 323 mL of NMP, 30 mL of ProxelTM Ultra-5 and 90 g of ArkopalTM N060 in 557 mL of water.
• CUNO filters are available from CUNO Belux
• the dotsize control fluids DCF-1 to DCF-9 were prepared by the mixing of the components LATEX-1, LATEX-2, LATEX-3, NaOH-sol, SURF-sol and SIL-500 according to Table 1 and Table 2. The fluids were then diluted with water to 4 L and filtered over a 5 micron CUNO filter.
• the dotsize control fluid DCF-10 was prepared according to Table 3 by the mixing of 246mL of LATEX-4, 48 mL of SIL-100 and 10 ml of MERSOL. This solution was then diluted with water to 1 L and filtered over a 5micron CUNO filter. Table 3 Component DCF-10 (in mL) Water 696 LATEX-4 246 SIL-100 48 MERSOL 10
• the dotsize control fluid DCF-11 was prepared by the mixing of the components LATEX-1, LATEX-2, LATEX-3, NaOH-sol, SURF-sol and SIL-500 according to Table 4.
• Table 4 Component DCF-11 (in mL) Water 1761 LATEX-1 12 NaOH-sol 4 SURF-sol 60 LATEX-2 100 SIL-500 60 LATEX-3 3 Ink receivers
• REC-1 is a 175 ⁇ m unsubbed PET substrate with on the backside an antiblocking layer with antistatic properties available from AGFA-GEVAERT as P175C PLAIN/ABAS.
• REC-2 is an unsubbed, untreated PE-paper of 140 g/m 2 having 20 g/m 2 of polyethylene on both sides, available from FRANTSCHACH BELCOAT.
• REC-3 is Filmolux 136, an unsubbed, untreated opaque, glossy, 60 ⁇ m polymeric Vinyl support with self-adhesive back, available from NESCHEN AG.
• REC-4 is obtained by air knife coating of DCF-1 0 to a uniaxially oriented PET (140m 2 /l), then dried at 150°C air temperature and stretched in a transversal direction (factor 3.6).
• the other ink-receivers were obtained by selecting one of the above ink-receivers REC-1 to REC-4, and applying one of the dotsize control fluids DCF-1 to DCF-9 and DCF-11 to these ink-receivers. All dotsize control fluids are coated on the ink-receiver in the same manner as exemplified for DCF-1 coated onto REC-1.
• the dotsize control fluid DCF-1 is filtered over a 5micron CUNO filter and coated at 12 m/min and 42°C with a slot coating at a wet thickness of 33.3 ⁇ m onto the ink-receiver REC-1 having a temperature of 50°C.
• the coated layer is dried at a temperature of 60°C for 2 minutes
• the radiation curable ink-jet inks were prepared to consist of 100% solids; no solvents or water are used during the preparation of the ink composition.
• the ink compositions Ink-1 to Ink-5 were prepared according to Table 5. The weight% (wt%) was based on the total ink weight.
• a concentrated dispersion was prepared of the pigments by mixing the pigment(s), the polymeric dispersant SolsperseTM 32000 and SolsperseTM 5000 and the monomers SartomerTM SR 9003, DPGDATM, SartomerTM SR339 and/or CraynorTM CN501 with a dissolver and treating this mixture with an Eiger bead mill.
• the other compounds were added in the order of Table 5 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.
• the ratio P/F represents the ratio of P, the weight% of film forming polymeric resin, over F, the weight% of inorganic filler, both weight% are based on the total weight of the dotsize control fluid.
• Three different ink-receivers REC-1 to REC-3 were selected and were used as reference samples REF-1 TO REF-3 not provided with a dot control fluid.
• the comparative samples COMP-1 to COMP-3 were coated with a dot control fluid DCF-3 having a P/F ratio smaller than 3.0, while the inventive samples INV-1 to INV-6 were coated with a dot size control fluid having a P/F ratio greater than 3.0.
• the radiation curable inkjet ink-1 was jetted with a droplet volume of 45 pL on all the samples of Table 6 using a custom built ink-jet printer equipped with a UPH print head available from AGFA. About 2 seconds after jetting, the samples 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 results are shown in Table 7.
• ink-receivers REC-1 to REC-4 were used as reference samples REF-4 to REF-7 not provided with any dot control fluid DCF.
• the comparative samples COMP-4 to COMP-15 were coated on the ink-receivers REC-1 to REC-4 with a dot control fluid having a P/F ratio smaller than 3.0.
• the inventive samples INV-7 to INV-30 were coated on the ink-receivers REC-1 to REC-4 with a dot size control fluid having a P/F ratio greater than 3.0.
• the thickness of the coated surface layer was varied according to Table 8 from about 550 to about 2160 mg/m 2 .
• the radiation curable inkjet ink-1 was jetted with a droplet volume of 45 pL on all the samples of Table 8 using a custom built ink-jet printer equipped with a UPH print head available from AGFA. About 2 seconds after jetting, the samples 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 results are also shown in Table 8.
• Table 9 The results in Table 9 , Table 10 and Table 11 demonstrate that only the inventive samples INV-7 tot INV-30 exhibited differences in dotsize smaller than 30 ⁇ m and this for every set for of a first and a second ink-receiver and for every thickness of the coated surface layer.
• Table 10 For the reference samples REF-4 to REF-7 and also for the comparative samples COMP-4 to COMP-15, at least one set of a first and a second ink-receiver was found exhibiting a difference in dotsize of at least 50 ⁇ m.
• This example demonstrates that different radiation curable inkjet inks can be used when a surface layer was applied onto an ink-receiver using the dotsize control fluids according to the invention.
• the samples 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 and is shown in Table 12.
• Table 13 the results of the radiation curable inkjet inks INK-1 to INK-5, are compared for each set of a first and a second ink receiver either without or with a surface layer with a ratio P/F of 4.9.

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