WO1999029788A1 - Compositions d'encre pour l'impression a jet d'encre sous cuisson electronique - Google Patents

Compositions d'encre pour l'impression a jet d'encre sous cuisson electronique Download PDF

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Publication number
WO1999029788A1
WO1999029788A1 PCT/GB1998/003628 GB9803628W WO9929788A1 WO 1999029788 A1 WO1999029788 A1 WO 1999029788A1 GB 9803628 W GB9803628 W GB 9803628W WO 9929788 A1 WO9929788 A1 WO 9929788A1
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WIPO (PCT)
Prior art keywords
ink
ink jet
weight
reactive
jet ink
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Application number
PCT/GB1998/003628
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English (en)
Inventor
Steve Johnson
Jill Woods
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Xaar Technology Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Xaar Technology Limited filed Critical Xaar Technology Limited
Priority to GB0013654A priority Critical patent/GB2346889B/en
Priority to AU13463/99A priority patent/AU1346399A/en
Publication of WO1999029788A1 publication Critical patent/WO1999029788A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • B41M5/0041—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
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers

Definitions

  • This invention relates to ink jet ink compositions and in particular to such compositions which are curable by ultraviolet radiation.
  • Radiation curable inks e.g. for screen printing and offset printing have been known for some time and more recently, there have been proposals for radiation-curable ink jet inks; see, for example, GB-A-2233928 , JP-A-63102936 , US-A- 4303924, EP-A-0540203, EP-A-0465039 and WO97/31071.
  • the formulations described in JP-A-63102936 and US-A-4303924 include some unreactive diluent, such as ethyl alcohol, methyl alcohol, methylethylketone, ethyl acetate, or the like; however, including such a diluent presents the operator with the problem of removal of the diluent. Where a volatile diluent is used, this presents problems with stability of the ink during storage or in the printer.
  • the amount of polyunsaturated component that can be employed is limited because of its viscosity, thereby providing a constraint on the level of crosslinking that can be achieved on curing and thus on the properties of the print.
  • the functionality that is the average number of unsaturated groups per molecule of the total of reactive components in the ink, is only about 1.22.
  • WO97/31071 proposes an ink jet ink composition for which a requirement is said to be that from 80 to 95%, based on the total weight of the composition, consists of alkoxylated and/or polyalkoxylated polyfunctional acrylate material .
  • compositions containing such levels of polyfunctional material even if it is all alkoxylated or polyalkoxylated acrylate, tend to be too viscous for use in many applications.
  • Inks according to the invention thus can be printed without difficulty from ink jet printers to give good quality print on a variety of substrates including such disparate materials as paper and non-adsorbent materials e.g. metal. They are of particular interest, however, in printing on plastics which are difficult to print on, e.g. polyolefins such as polyethylene and polypropylene.
  • a radiation curable ink jet ink comprising a colorant component, a diluent consisting essentially of reactive liquid material and, optionally, at least one photopolymerisation catalyst and wherein the reactive liquid material is formed of monofunctional material, difunctional material and tri- or higher functional material and wherein the total amount of tri- or higher functional material in the ink forms more than 10 but not more than 30% by weight of the total amount of reactive material in the ink, the total amount of monofunctional material in the ink is at least 20% by weight of the total amount of reactive material in the ink, and the total amount of difunctional material in the ink is at least 11%% by weight of the total amount of reactive material in the ink and is such that the total amount of di- or higher functional material is not less than 35% by weight, and the viscosity of the ink is not greater than 35 mPa.s at 30°C as measured using a Brookfield Viscometer fitted with a small sample adaptor having a No. 18
  • the diluent is free or substantially free of non- reactive components; that is to say, if any non-reactive liquid component is present in the diluent it forms no more than 1% by weight of the ink, preferably not more than 0.5%, by weight.
  • reactive material we mean material containing one or more unsaturated carbon-carbon bonds polymerisable by radiation.
  • the reactive material may comprise monomer or a mixture of monomer and oligomer. Oligomer is sometimes known as prepolymer.
  • monomers are acrylates, methacrylates and alkoxylated and polyalkoxylated derivatives thereof.
  • Non-limiting examples of oligomers (prepolymers) are polyester-, urethane- and epoxy-acrylates .
  • the ink includes at least one polyfunctional oligomer.
  • said at least one oligomer has an equivalent weight of at least 180.
  • Print obtained from inks containing such a component exhibits improved toughness, adhesion and/or scratch resistance as compared with print derived from the same ink composition but excluding the component .
  • the oligomer is liquid so as to maintain the desired low viscosity of the ink and preferably it has a functionality greater than 2. If it is not liquid, it should be soluble in the liquid components of the reactive material. In any event, the oligomer, if present, is deemed to form part of the reactive liquid material.
  • the ink composition includes a silicone derivative containing carbon-carbon unsaturation which is polymerisable by radiation, to adjust the surface tension of the ink.
  • This polymerisable silicone derivative if present, is also deemed to form part of the reactive liquid material.
  • compositions of the invention are preferably formulated to be curable by visible, or more preferably ultra violet, light, in which case they will usually include at least one photoinitiator.
  • compositions of the invention will now be described in greater detail .
  • the colorant is preferably thermally stable and water- insoluble. While the possibility of using colorants, such as dyes, which are soluble in the diluent, is not excluded, it is preferred to use those, such as pigments, which are insoluble, especially where light-fastness is important. In this case, it may be desirable to include a dispersant in the composition to stabilise the dispersion of insoluble colorant in the diluent.
  • insoluble colorants include, in particular, carbon black and those colorants characterised as pigment dyes in The Colour Index.
  • suitable pigments include those within the ranges having the following Cl classifications:
  • pigments examples include IRGALITE BLUE GLNO , MONASTRAL BLUE FGX, IRGALITE BLUE GLSM, HELIOGEN BLUE L7101F, LUTETIA CYANINE ENJ, HELIOGEN BLUE L6700F, MONASTRAL GNXC, MONASTRAL GBX, MONASTRAL GLX, MONASTRAL 6Y, IRGAZIN DPP ORANGE RA, NOVAPERM ORANGE H5G70, NOVPERM ORANGE HL, MONOLITE ORANGE 2R, NOVAPERM RED HFG, HOSTAPERM ORANGE HGL, PALIOGEN ORANGE L2640, SICOFAST ORANGE 2953, IRGAZIN ORANGE 3GL, CHROMOPTHAL ORANGE GP, HOSTAPERM ORANGE GR, PV CARMINE HF4C, NOVAPERM RED F3RK 70, MONOLITE RED BR, I
  • Colorants may be employed, if desired, including mixtures of dyes, mixtures of pigments and mixtures of one or more dyes with one or more pigments .
  • the colorants are chosen to give the widest range of colours and tones in a hexachrome system.
  • the amount of colorant employed in the ink will depend on the choice of colorant and the depth of colour required in the print, and can be established by simple experiment. In general, for pigments it will fall within the range 0.01% to 50% by weight, the amount chosen being such that viscosity of the ink does not exceed 35 mPa . s . For organic pigments the amount will generally be in the range 0.01 to 10% weight, more preferably 0.05 to 6% most preferably 0.05 to 3%.
  • the colorant comprises a pigment which is to be dispersed in the diluent
  • it preferably has a particle size of not greater than l ⁇ m maximum dimension and more preferably not greater than 0.5 ⁇ m. Even more preferably, the particles have a narrow size range distribution.
  • the ink comprises a dispersion of pigment
  • a dispersant will normally be required to aid or stabilise the dispersion.
  • the choice of dispersant will depend upon the nature of the pigment and composition of the diluent. Examples of suitable materials may be found amongst dispersants sold under the trade names of Solsperse, EFKA and Byk. Mixtures of dispersants and mixtures of one or more dispersants with one or more dispersant synergists may be employed.
  • the amount of dispersant employed (or dispersant and synergist where used) will depend upon the choice and concentration of the pigment. For organic pigments, the amount will usually be in the range 15 to 100% by weight of the pigment, preferably 20 to 75% by weight. For inorganic pigments, lower concentrations may be acceptable, e.g. 5% or less.
  • the reactive liquid material of the ink composition comprises monofunctional, difunctional and tri- or higher functional material.
  • mono-, di-, tri- and higher functional material is meant compounds having, respectively, one, two, three or more unsaturated carbon- carbon groups which are polymerisable by radiation, especially but not exclusively ultra-violet light. Examples of some suitable compounds may be found in the publication U.V. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, edited by R. Holman and published by SITA-Technology, London, in 1984 and The Printing Ink Manual, Fourth Edition, published by VNR International, However, the choice of suitable compound is not limited to the compounds or classes of compounds disclosed in those publications.
  • the monofunctional material may comprise a single monomer or a mixture of monomers.
  • Straight chain acrylates of lower alcohols e.g. C,. 4 alcohols
  • Acrylates of branched chain alcohols e.g. isodecyl alcohol are less volatile but more preferred are acrylates of cyclic or polycyclic alkanols, e.g. tetrahydrofurfuryl acrylate and isobornyl acrylate.
  • Examples of the monofunctional acrylates that may be used include long chain aliphatic acrylates e.g.
  • the aliphatic group contains at least 8, preferably at least 10 carbon atoms, such as lauryl acrylate and stearyl acrylate, and acrylates of alkoxylated alcohols e.g. 2- (2-ethoxyethoxy) ethyl acrylate.
  • the monofunctional material need not necessarily be an acrylate; for example N-vinyl-2 -pyrrolidone may be used.
  • Further examples of monofunctional monomers are Sartomer CD 9050 (a monofunctional acid ester) and Sartomer CD 611 (an ethoxylated tetrahydrofuran acrylate) .
  • the overall viscosity of the monofunctional material of the diluent preferably is as low as possible, e.g. 20 mPa.s or less, more preferably 16 mPa.s or less, at 30°C.
  • the tri- or higher functional material may also comprise a single monomer or a mixture of monomers.
  • Alkoxylated acrylates such as those obtained by acrylating the products of ethoxylating or propoxylating an initiator containing three or more active hydrogen atoms are particularly preferred.
  • initiators having three or more active hydrogen atoms include glycerol , trimethylol propane, pentaerythritol and neopentyl alcohol.
  • alkoxylated acrylates examples include ethoxylated trimethylol propane triacrylates, propoxylated glyceryl triacrylates, Sartomer SR 9008 (an alkoxylated trifunctional acrylate ester) and propoxylated pentaerythritol tetraacrylates .
  • Other examples of tri- or higher functional monomers are tris (2 - hydroxyethyl) isocyanurate triacrylate, and Sartomer SR 9012 (a trifunctional acrylate ester) .
  • compounds having relatively low viscosities, e.g. 200 mPa.s or less at 30°C, are chosen so that amounts towards the upper end of the range of 10 to 30% by weight, may be employed in the diluent.
  • While compounds having a functionality higher than 3 may also be used, they should be included at most in only small amounts, the maximum tolerable amount being less as the functionality of the compound increases. This is because as the functionality increases, so does the crosslink density in the cured product unless the molecular weight of the compound is increased but increase in molecular weight tends to lead to an increase in the viscosity of the compound .
  • the difunctional material which may comprise a single monomer or mixture of monomers, makes up the balance of the reactive material. It is preferred that the viscosity of the difunctional material is not greater than 30mPa.s, and preferably not greater than 20 mPa.s, at 30°C.
  • Preferred components are diacrylates of glycols and polyglycols, especially propylene glycol and polypropylene glycols e.g. di-, tri- and higher propylene glycols. Di- acrylates of tri- or higher hydric alcohols may also be used.
  • diacrylates having a viscosity at 30°C of not greater than 20 mPa.s are the diacrylates of 1,4- butanediol , neopentylglycol , propoxylated neopentyl glycol , diethylene glycol, hexanediol, dipropylene glycol, tripropylene glycol, triethylene glycol and polyethylene glycols.
  • the reactive liquid material also includes at least one polyfunctional oligomer, so as to provide print of improved toughness, adhesion and/or scratch resistance.
  • This oligomer may comprise any suitable compound or mixture of compounds containing at least two, and preferably more than two, unsaturated carbon-carbon bonds polymerisable by radiation and an equivalent weight which is preferably at least 180, more preferably at least 200 or 220.
  • equivalent weight is preferably at least 180, more preferably at least 200 or 220.
  • increase in equivalent weight is accompanied by increase in viscosity, thus restricting the amount of the oligomer that may be included in the composition.
  • the equivalent weight does not exceed 750 and more preferably does not exceed 500.
  • oligomers which are polyacrylates are preferred because of their relatively low viscosity compared with other oligomeric polyfunctional materials.
  • examples include the polyfunctional products Of acrylating hydroxy-terminated polyesters, known as polyester acrylates, the polyfunctional products of acrylating urethane oligomers, known simply as urethane acrylates, and epoxy acrylates. Alkoxylated acrylates are not regarded as oligomers.
  • oligomeric material there is an optimum concentration for the oligomeric material beyond which the improvement in properties is marginal. Since increasing the concentration tends to increase viscosity, it is generally not desirable to employ more than this optimum amount which will vary according to the choice of the oligomeric material and of the other components of the reactive liquid material. In general, this optimum will not exceed 30% of the reactive liquid material and will generally be not more than 25% e.g. 10 to 22%, more generally 15 to 20%, by weight of the total amount of reactive liquid material in the ink.
  • the amount of oligomeric material employed is to be included in the calculation of the overall amount of di- or tri- (or higher) functional material in the reactive liquid material, according to its functionality. Thus, if it is trifunctional, the total amount of oligomeric material and other tri- or higher functional material must be greater than 10% but not more than 30% by weight of the total amount of reactive liquid material in the ink.
  • the reactive liquid material should be essentially of low volatility and preferably substantially non-volatile at ambient temperatures and preferably also at the printhead temperature if above ambient .
  • a silicone derivative containing at least one radiation- polymerisable carbon-carbon unsaturation is a preferred component of the ink composition for reducing its surface tension, especially when the ink is intended for printing on plastics with low surface tension surfaces e.g. polyolefins and ABS.
  • it is employed in amount to give a surface tension below 35 dynes/cm and generally in the range 25 to 35 dynes/cm.
  • the silicone derivative will be used in amounts of 0.05-015 to 1-3% by weight, depending on the molecular weight of the derivative, and more preferably 0.1 to 0.6% by weight of the ink. The inclusion of the silicone derivative in such quantities also reduces the tendency to blocking of sheets printed with the ink and improves dot definition.
  • silicone acrylates e.g. acrylates of organo modified silicones, for example organo modified polysiloxanes e.g. comprising repeating units of
  • R the structure - Si - 0 - where each R is a monovalent
  • R hydrocarbyl group e.g. methyl or phenyl , and at least one
  • X above and X contains an acrylate (CH 2 -CH.C00-) group.
  • the acrylate group is connected to the silicon atom via an alkoxy or polyalkoxy group.
  • the chosen silicone derivative will have one or two radiation-polymerisable unsaturated carbon-carbon bonds. While the silicone component is deemed to be part of the reactive liquid material of the composition, as the amount of the silicone derivative used in the composition is relatively small, it may be ignored when calculating relative the amounts of mono-, di- and/or tri- or higher functional material in the reactive liquid material.
  • the ink should form at least 20%, e.g. from 20 to 60% by weight, preferably from 20 to 50% by weight, and more preferably from 40 to 50% by weight of the total reactive material in the ink. If less than about 20% is employed, the viscosity of the ink will tend to be too high. If, on the other hand, the amount significantly exceeds 60%, the properties of the print, and in particular abrasion resistance and hardness may suffer, and also the rate and/or degree of cure of the ink may be reduced.
  • the total amount of tri- or higher functional material in the ink is greater than 10 but not more than 30% by weight of the total amount of reactive material in the ink. Preferably it is present in an amount of at least 15% by weight and more preferably from 20 to 30% by weight. If used in an amount of less than 10% by weight, the properties of the print obtained from the ink, and in particular hardness and scratch resistance, tend to suffer. On the other hand, if used in amounts of more than about 30% by weight, the viscosity of the ink tends to be too high and the print may become unacceptably brittle and inflexible .
  • the total amount of difunctional material (including difunctional oligomer, if present) is required to form at least 173 ⁇ % by weight of the total amount of reactive material in the ink and to be such that the viscosity of the ink is not greater than 35 mPa.s at 30°C and the di- and higher functional material in the ink forms at least 35% of the total of reactive material in the ink.
  • the difunctional material is present in an amount in the range 17 to 35% by weight of the total amount of reactive material in the ink, more preferably 20 to 30% by weight.
  • a feature that is relevant to the control of the properties of the print derived from the ink, and in particular its physical properties such as hardness, abrasion resistance, modulus, flexibility and elasticity, is the overall functionality of the reactive material in the ink; i.e. the average number of radiation polymerisable unsaturated carbon-carbon bonds per molecule. If this value is too low, the print will be too soft but if it is too high, the print will tend to be brittle and to craze or crack when the substrate on which it has been printed is non- absorbent, e.g. as in a plastic substrate, and is flexed.
  • the amounts of mono-, di- and tri- and higher functional components of the ink are selected such that this value will be in the range 1.25 to 2, more preferably 1.25 to 1.85, most preferably 1.3 to 1.7..
  • inks according to the invention may be formulated for curing by any suitable form of electromagnetic radiation, visible light or, more preferably, ultra-violet light is preferred and for this purpose the ink will also preferably include at least one photoinitiator.
  • photoinitiators may be employed and the choice will depend upon the choice of colorant and the wave length of the radiation. Examples of suitable photoinitiators are:
  • a mixture of photoinitiators is preferably used whose peak energy absorbtion levels are at different wave lengths within the range of the selected radiation.
  • preferential absorption of incident UN radiation by the pigments leads to depletion of the available energy for the photoinitiator (s) .
  • This can place considerable constraints on the cure speed and level of conversion achievable especially with black pigmented ink formulations.
  • photoinitiator blends which are sensitive to the wavelengths not absorbed, or only partially affected, by the pigments. Typically this "absorption window" is between 350-400nm.
  • the initiators will generally be used in amounts of from about 3 to about 15% more usually about 5 to about 10% by weight of the ink.
  • Activators e.g. co-initiators or amine synergists, for the photoinitiators may also be included, if desired. Examples include ethyl -4- (dimethylamino) benzoate, 2-ethylhexyl dimethylaminobenzoate, and dimethylaminoethyl methacrylate.
  • the ink is ejected from an ink jet printer and exposed to the selected radiation during its flight from the printhead to the substrate to be printed or, more preferably after deposition on the substrate.
  • the smaller the throw distance that is the distance from the printhead to the substrate, the better the print quality.
  • it is preferably no less than 0.5 mm and even at distances of 1.5 mm or 2 mm or even higher, acceptable results may be obtained.
  • the preferred throw distance will be in the range 0.5 to 0.75 mm.
  • Curing of the ink is aided by the absence of oxygen and thus it is preferred to provide an inert gas atmosphere, e.g. nitrogen over the substrate in the zone where the ink is exposed to the radiation. Curing is preferably effected using radiation in the UVA and near- visible frequencies.
  • Inks according to the invention may be formulated for use in any of the available kinds of continuous and drop-on- demand ink jet printers although in general they may not be suitable for use in apparatus which employs thermal means of droplet generation.
  • a continuous ink jet printer for example, former kind, for example, ink droplets which are produced continuously may be passed through a charging area where individual droplets receive an electrical charge in response to a signal and are directed towards a substrate to be printed. The droplets then pass through an electrical field causing them to be deflected by an amount which is dependent on the intensity of the charge and the field. Droplets not required to form print on the substrate may be directed to a by-pass gutter.
  • Drop-on-demand ink jet printers may be of the kind using an electrostatically accelerated ink jet or droplet sequences ejected by pressure impulse actuation, e.g. when each droplet is individually ejected from a nozzle by means of pressure pulses induced e.g. by means of a piezoelectric actuator acting on the ink in the channel supplying the nozzle .
  • the diluent, colorant (s) , dispersant (s) (where present), dispersant synergist (s) (where present), photoinitiator (s) including activator (s) therefor (where present), and conducting additive (where present) will normally form at least 99% of the composition and preferably substantially the entire composition. As indicated above, preferably at least 99.5% by weight of the diluent is reactive liquid material .
  • the inks may be employed for printing on to a wide variety of substrates, both absorbent and non-absorbent including paper, glass, plastic and metal, e.g. steel, copper and aluminium, but are particularly suitable for printing on to plastics to provide a strongly bonded print of good definition and optical density, especially if the surface to be printed is pre-treated e.g. by flame, plasma etch or corona treatment to raise the surface energy.
  • the surface energy should be at least about 36 dynes/cm and more preferably from 42 to 48 dynes/cm.
  • plastics on which the inks of the present invention have been successfully printed are polyolefins such as polyethylene (including high density polyethylene) , and polypropylene, vinyl chloride polymers, ABS and foamed plastics such as expanded polystyrene.
  • Example 1 The compositions set out in Table 1 below were formulated into inks in the manner now described.
  • the pigment was ground, with the appropriate amount of hyperdispersant to ensure minimum millbase viscosity, using conventional bead milling techniques.
  • the millbase so formed was processed until a fine particle dispersion was obtained.
  • the particle grind was assessed by visual microscopy and a filterability test.
  • the finished millbase was removed from the grinding media using an appropriately sized mesh either by pressure or gravity.
  • the ink composition so formed was filtered using a proprietary cartridge filter rated at 1 micron absolute filter rating. Following bottling a retained sample was analysed for viscosity, visual appearance, cure rate, surface tension and ageing at elevated temperature (60°C) .
  • the viscosities of the ink compositions were all in the range 15-20cps measured using a Brookfield Viscometer at 30°C and their values for surface tension were all in the range of 26-28 dynes/cm.
  • the inks were used to form coloured print on moulded ABS cards using a 128 channel greyscale drop-on-demand printhead of the kind described for example in EP-A-0.277.703 and EP-A-0.278.590 with a nozzle diameter of 25 ⁇ m and a distance of 2mm between the printhead and the card.
  • Curing was by means of a Fusion F300s UV Lamp with a 152mm (6 inch) long "D bulb" at 11.8 w/mm (300w/inch) using cure energies in the range l-3J/cm 2 . Curing was complete within one second.
  • the print was well defined with acceptable colour density.
  • the cyan, magenta and black inks all exhibited colour densities greater than 1.5 and were typically about 1.8.
  • the colour density of the yellow ink was greater than 1, typically 1.1.
  • the print exhibited good adhesion to the card and good scratch resistance. Scratching with a fingernail did not remove the print and on further testing of adhesion by scoring and crosslinking the print with a scalpel and attempting to remove it by applying Sellotape to the scored surface and then peeling off the Sellotape, no detectable removal of ink was observed.
  • the hardness of the print was assessed in conventional manner using pencils of different hardnesses . The hardness is determined as the lowest hardness value to form a scratch on the print .
  • Print formed from the inks of the present invention generally exhibited hardnesses of 6H-7H.
  • Solsperse 5000/22000/24000 - hyperdispersants (ex Zeneca) Regal 250R - carbon black, C.I. pigment black 7 (ex Cabot) Irgalite Blue GLVO - copper phthalocyanine, C.I, pigment blue 15:4 - (ex Ciba Geigy)
  • Irgacure 907 2-methyl-l- (4 -methylthio) phenyl-2- morpholino-propan-1-one (ex Ciba Geigy)
  • Lucirin TPO - 2 , 4 6-trimethylbenzoyl-diphenyl-phosphine oxide (ex BASF) .
  • Example 2 In the same manner as Example 1, a further series of ink jet ink formulations were prepared having the compositions set out in Table 2 below. Coloured print was formed from the inks in the manner described in Example 1 and similar results were obtained. TABLE 2
  • Example 4 In the same manner as described in Example 1, a further series of ink jet ink formulations were prepared having the compositions set out in Table 3. '
  • Example 5 A white ink was prepared having the following formulation:
  • Actilane 422 18.55% Actilane 251 15% N-vinyl pyrrolidone 20% Solsperse 24000 1.05% Tegorad 2200 0.4% Irgacure 907 10% White pigment 35% Actilane 422 is dipropylene glycol diacrylate (ex Akcros) . The white pigment is Tioxide TR92.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne une encre pour l'impression à jet d'encre sous cuisson électronique, qui comprend un colorant, un diluant essentiellement constitué de matière liquide réactive et, éventuellement, au moins un catalyseur de photopolymérisation. La matière liquide réactive renferme les matériaux suivants : matériau monofonctionnel, matériau difonctionnel et matériau trifonctionnel ou à fonctionnalité plus élevée. La quantité totale de ce dernier matériau dans l'encre représente plus de 10 % mais pas plus de 30 %, en poids, de la quantité totale de matière réactive dans l'encre. La quantité totale de matériau monofonctionnel dans l'encre représente au moins 20 %, en poids, de la quantité totale de matière réactive dans l'encre. Enfin, la quantité totale de matériau difonctionnel dans l'encre représente au moins 17,5 %, en poids, de la quantité totale de matière réactive dans l'encre, sachant que la quantité totale de matériau difonctionnel ou à fonctionnalité plus élevée n'est pas inférieure à 35 %, en poids. La viscosité de l'encre n'excède pas 35 mPa.s à 30° C.
PCT/GB1998/003628 1997-12-05 1998-12-04 Compositions d'encre pour l'impression a jet d'encre sous cuisson electronique WO1999029788A1 (fr)

Priority Applications (2)

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GB0013654A GB2346889B (en) 1997-12-05 1998-12-04 Radiation curable ink jet ink compositions
AU13463/99A AU1346399A (en) 1997-12-05 1998-12-04 Radiation curable ink jet ink compositions

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GBGB9725928.7A GB9725928D0 (en) 1997-12-05 1997-12-05 Radiation curable ink jet ink compositions
GB9725928.7 1997-12-05

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WO1999029788A1 true WO1999029788A1 (fr) 1999-06-17

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EP1199181A2 (fr) * 2000-10-10 2002-04-24 Toyo Ink Manufacturing Co. Ltd. Impression à jet d'encre dans un substrate en matière synthétique
WO2002053382A2 (fr) 2001-01-02 2002-07-11 3M Innovative Properties Company Procedes et dispositifs pour la selection de parametres d'impression a jet d'encre
WO2002053384A1 (fr) 2001-01-02 2002-07-11 3M Innovative Properties Company Dispositif d'impression a jet d'encre a tambour rotatif pour encre durcissable par rayonnement
WO2002085638A1 (fr) 2001-04-18 2002-10-31 3M Innovative Properties Company Substrats amorces comprenant des images a jet d'encre sechees par rayonnement
FR2828203A1 (fr) * 2001-08-01 2003-02-07 Armor Encre pigmentaire liquide sans solvant, pour impression par jet d'encre
US6534128B1 (en) 2000-11-09 2003-03-18 3M Innovative Properties Company Inks and other compositions incorporating low viscosity, radiation curable, polyester urethane oligomer
US6543890B1 (en) 2001-12-19 2003-04-08 3M Innovative Properties Company Method and apparatus for radiation curing of ink used in inkjet printing
US6550906B2 (en) 2001-01-02 2003-04-22 3M Innovative Properties Company Method and apparatus for inkjet printing using UV radiation curable ink
WO2003044106A1 (fr) * 2001-11-19 2003-05-30 Agfa-Gevaert Encre pour imprimante a jet d'encre relativement depourvue de photo-initiateur, procede et appareil de polymerisation de l'encre
WO2003099947A1 (fr) * 2002-05-24 2003-12-04 Huntsman Advanced Materials (Switzerland) Gmbh Compositions se pretant a la formation de jets
WO2004026978A1 (fr) * 2002-09-20 2004-04-01 Avecia Limited Compositions d'encres sechant sous l'effet de rayonnements utilisees pour l'impression a jet d'encre
WO2004106444A1 (fr) * 2003-06-03 2004-12-09 Ciba Specialty Chemicals Holding Inc. Procede de preparation de concentres de pigment a utiliser dans des revetements sechables par rayonnement
US6846075B2 (en) 2001-06-29 2005-01-25 3M Innovative Properties Company Imaged articles comprising a substrate having a primed surface
WO2005026270A1 (fr) * 2003-09-16 2005-03-24 Sun Chemical B.V. Encre par jet apte au sechage par rayonnement
US6881458B2 (en) 2002-06-03 2005-04-19 3M Innovative Properties Company Ink jet receptive coating
US6896937B2 (en) 2002-11-15 2005-05-24 Markem Corporation Radiation-curable inks
WO2005061634A1 (fr) * 2003-12-20 2005-07-07 Fujifilm Imaging Colorants Limited Encres pour jet d'encre durcissables par faisceau de particules
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US7140711B2 (en) 2003-07-21 2006-11-28 3M Innovative Properties Company Method and apparatus for inkjet printing using radiation curable ink
WO2007067466A2 (fr) * 2005-12-06 2007-06-14 General Electric Company Impression numerique avec encres ultraviolettes
EP1829680A1 (fr) * 2006-02-27 2007-09-05 FUJIFILM Corporation Composition d'encre, procédé d'enregistrement de jet d'encre, matériau d'impression, et procédé de production de plaque d'impression lithographique
EP1840176A1 (fr) * 2006-03-28 2007-10-03 FUJIFILM Corporation composition d'encre, procédé de jet d'encre, matériau imprimé et procédé pour produire une planche lithoghraphique à imprimer
US7342076B2 (en) 1998-10-08 2008-03-11 Kaneka Corporation Polymers and curable compositions
US7423072B2 (en) * 2000-11-09 2008-09-09 3M Innovative Properties Company Weather resistant, ink jettable, radiation curable, fluid compositions particularly suitable for outdoor applications
US7427360B2 (en) 2002-09-20 2008-09-23 Fujifilm Imaging Colorants Limited Process and ink for making electronic devices
WO2008117092A1 (fr) * 2007-03-27 2008-10-02 Sericol Limited Encre d'imprimerie
EP2053104A1 (fr) * 2007-10-26 2009-04-29 Agfa Graphics N.V. Procédés d'impression par jet d'encre durcissable par radiation
EP2088177A3 (fr) * 2008-02-06 2009-09-16 FUJIFILM Corporation Composition d'encre, procédé d'enregistrement à jet d'encre, et matériau imprimé
CN1852954B (zh) * 2003-09-16 2010-12-08 太阳化学有限公司 辐射可固化的喷墨油墨
US8053169B2 (en) * 2006-07-28 2011-11-08 Fujifilm Corporation Ink composition, inkjet recording method, printed material, and process for producing lithographic printing plate
US8585814B2 (en) * 2005-04-14 2013-11-19 Konica Minolta Medical & Graphic, Inc. Active ray curable ink-jet ink, image forming method and ink-jet recording apparatus using the same
CN103666082A (zh) * 2013-12-23 2014-03-26 深圳市深赛尔股份有限公司 一种应用于马口铁的防伪uv印铁油墨及其制备方法
CN109135412A (zh) * 2018-06-12 2019-01-04 苏州中亚油墨有限公司 环保水性柔印uv油墨
CN109535998A (zh) * 2018-09-30 2019-03-29 广州申威新材料科技有限公司 一种高拉伸率的紫外光固化涂料及涂层

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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JP4561031B2 (ja) 2002-11-27 2010-10-13 コニカミノルタホールディングス株式会社 活性光線硬化型インクジェット無溶剤インク及び画像形成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0465039A1 (fr) * 1990-06-27 1992-01-08 Domino Printing Sciences Plc Composition d'encre
EP0540203A1 (fr) * 1991-10-30 1993-05-05 Domino Printing Sciences Plc Encre non-conductrice
EP0555069A1 (fr) * 1992-02-07 1993-08-11 Sericol Limited Compositions durcissables par radiations
WO1997031071A1 (fr) * 1996-02-21 1997-08-28 Coates Brothers Plc Composition d'encre durcissant sous l'effet de radiations

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0465039A1 (fr) * 1990-06-27 1992-01-08 Domino Printing Sciences Plc Composition d'encre
EP0540203A1 (fr) * 1991-10-30 1993-05-05 Domino Printing Sciences Plc Encre non-conductrice
EP0555069A1 (fr) * 1992-02-07 1993-08-11 Sericol Limited Compositions durcissables par radiations
WO1997031071A1 (fr) * 1996-02-21 1997-08-28 Coates Brothers Plc Composition d'encre durcissant sous l'effet de radiations

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US7342076B2 (en) 1998-10-08 2008-03-11 Kaneka Corporation Polymers and curable compositions
EP1199181A3 (fr) * 2000-10-10 2002-09-04 Toyo Ink Manufacturing Co. Ltd. Impression à jet d'encre dans un substrate en matière synthétique
EP1199181A2 (fr) * 2000-10-10 2002-04-24 Toyo Ink Manufacturing Co. Ltd. Impression à jet d'encre dans un substrate en matière synthétique
US7423072B2 (en) * 2000-11-09 2008-09-09 3M Innovative Properties Company Weather resistant, ink jettable, radiation curable, fluid compositions particularly suitable for outdoor applications
US7943681B2 (en) 2000-11-09 2011-05-17 3M Innovative Properties Company Weather resistant, ink jettable, radiation curable, fluid compositions particularly suitable for outdoor applications
US6534128B1 (en) 2000-11-09 2003-03-18 3M Innovative Properties Company Inks and other compositions incorporating low viscosity, radiation curable, polyester urethane oligomer
US6595615B2 (en) 2001-01-02 2003-07-22 3M Innovative Properties Company Method and apparatus for selection of inkjet printing parameters
WO2002053382A2 (fr) 2001-01-02 2002-07-11 3M Innovative Properties Company Procedes et dispositifs pour la selection de parametres d'impression a jet d'encre
WO2002053384A1 (fr) 2001-01-02 2002-07-11 3M Innovative Properties Company Dispositif d'impression a jet d'encre a tambour rotatif pour encre durcissable par rayonnement
US6550906B2 (en) 2001-01-02 2003-04-22 3M Innovative Properties Company Method and apparatus for inkjet printing using UV radiation curable ink
US6554414B2 (en) 2001-01-02 2003-04-29 3M Innovative Properties Company Rotatable drum inkjet printing apparatus for radiation curable ink
US6720042B2 (en) 2001-04-18 2004-04-13 3M Innovative Properties Company Primed substrates comprising radiation cured ink jetted images
AU2002247025B2 (en) * 2001-04-18 2006-08-24 3M Innovative Properties Company Primed substrates comprising radiation cured ink jetted images
WO2002085638A1 (fr) 2001-04-18 2002-10-31 3M Innovative Properties Company Substrats amorces comprenant des images a jet d'encre sechees par rayonnement
US6896944B2 (en) 2001-06-29 2005-05-24 3M Innovative Properties Company Imaged articles comprising a substrate having a primed surface
US7025453B2 (en) 2001-06-29 2006-04-11 3M Innovative Properties Company Imaged articles comprising a substrate having a primed surface
US6846075B2 (en) 2001-06-29 2005-01-25 3M Innovative Properties Company Imaged articles comprising a substrate having a primed surface
WO2003011989A1 (fr) * 2001-08-01 2003-02-13 Armor Encre pigmentaire liquide sans solvant, pour impression par jet d'encre
FR2828203A1 (fr) * 2001-08-01 2003-02-07 Armor Encre pigmentaire liquide sans solvant, pour impression par jet d'encre
WO2003044106A1 (fr) * 2001-11-19 2003-05-30 Agfa-Gevaert Encre pour imprimante a jet d'encre relativement depourvue de photo-initiateur, procede et appareil de polymerisation de l'encre
EP1473341A1 (fr) * 2001-11-19 2004-11-03 Agfa-Gevaert Encre pour imprimante à jet d'encre avec une faible teneur en photoinitiateur et méthode et appareil de durcissement de celle-ci.
CN100543093C (zh) * 2001-11-19 2009-09-23 爱克发印艺公司 相对不含光敏引发剂的喷墨墨水及使其固化的方法和设备
US6543890B1 (en) 2001-12-19 2003-04-08 3M Innovative Properties Company Method and apparatus for radiation curing of ink used in inkjet printing
US7871556B2 (en) 2002-05-24 2011-01-18 Huntsman Advanced Materials Americas Llc Jettable compositions
US8569398B2 (en) 2002-05-24 2013-10-29 3D Systems, Inc. Jettable compositions
CN1304501C (zh) * 2002-05-24 2007-03-14 亨斯迈先进材料（瑞士）有限公司 可喷射组合物
WO2003099947A1 (fr) * 2002-05-24 2003-12-04 Huntsman Advanced Materials (Switzerland) Gmbh Compositions se pretant a la formation de jets
US6881458B2 (en) 2002-06-03 2005-04-19 3M Innovative Properties Company Ink jet receptive coating
US7427360B2 (en) 2002-09-20 2008-09-23 Fujifilm Imaging Colorants Limited Process and ink for making electronic devices
GB2406858A (en) * 2002-09-20 2005-04-13 Avecia Ltd Radiation curable inkjet inks compositions
GB2406858B (en) * 2002-09-20 2006-04-05 Avecia Ltd Radiation curable inkjet inks compositions
WO2004026978A1 (fr) * 2002-09-20 2004-04-01 Avecia Limited Compositions d'encres sechant sous l'effet de rayonnements utilisees pour l'impression a jet d'encre
US6896937B2 (en) 2002-11-15 2005-05-24 Markem Corporation Radiation-curable inks
US7121661B2 (en) 2003-01-21 2006-10-17 Konica Minolta Holdings, Inc. Ink jet recording method employing inks with specific surface tensions
EP1630213A1 (fr) 2003-05-14 2006-03-01 Konica Minolta Medical & Graphic, Inc. Assortiment d'encres pour imprimantes à jet d'encre et méthode d'enregistrement l'utilisant
WO2004106444A1 (fr) * 2003-06-03 2004-12-09 Ciba Specialty Chemicals Holding Inc. Procede de preparation de concentres de pigment a utiliser dans des revetements sechables par rayonnement
US7140711B2 (en) 2003-07-21 2006-11-28 3M Innovative Properties Company Method and apparatus for inkjet printing using radiation curable ink
GB2422612B (en) * 2003-09-16 2007-04-11 Sun Chemical Bv A jet ink
WO2005026270A1 (fr) * 2003-09-16 2005-03-24 Sun Chemical B.V. Encre par jet apte au sechage par rayonnement
CN1852954B (zh) * 2003-09-16 2010-12-08 太阳化学有限公司 辐射可固化的喷墨油墨
GB2422612A (en) * 2003-09-16 2006-08-02 Sun Chemical Bv A radiation curable jet ink
GB2423304A (en) * 2003-12-20 2006-08-23 Fujifilm Imaging Colorants Ltd Particle beam curable ink jet inks
WO2005061634A1 (fr) * 2003-12-20 2005-07-07 Fujifilm Imaging Colorants Limited Encres pour jet d'encre durcissables par faisceau de particules
GB2423304B (en) * 2003-12-20 2008-06-18 Fujifilm Imaging Colorants Ltd Particle beam curable ink jet inks
US7700263B2 (en) 2003-12-20 2010-04-20 Fujifilm Imaging Colorants Limited Substantially solvent-free and photoinitiator-free curable ink
EP1586459A1 (fr) * 2004-02-20 2005-10-19 Agfa-Gevaert Assemblage et procédé pour l'impression par jet d'encre
JP2005254521A (ja) * 2004-03-10 2005-09-22 Fuji Photo Film Co Ltd 三次元造形物及び三次元造形物の製造方法
US8585814B2 (en) * 2005-04-14 2013-11-19 Konica Minolta Medical & Graphic, Inc. Active ray curable ink-jet ink, image forming method and ink-jet recording apparatus using the same
WO2007067466A2 (fr) * 2005-12-06 2007-06-14 General Electric Company Impression numerique avec encres ultraviolettes
WO2007067466A3 (fr) * 2005-12-06 2007-08-09 Gen Electric Impression numerique avec encres ultraviolettes
EP1829680A1 (fr) * 2006-02-27 2007-09-05 FUJIFILM Corporation Composition d'encre, procédé d'enregistrement de jet d'encre, matériau d'impression, et procédé de production de plaque d'impression lithographique
EP1840176A1 (fr) * 2006-03-28 2007-10-03 FUJIFILM Corporation composition d'encre, procédé de jet d'encre, matériau imprimé et procédé pour produire une planche lithoghraphique à imprimer
US8053169B2 (en) * 2006-07-28 2011-11-08 Fujifilm Corporation Ink composition, inkjet recording method, printed material, and process for producing lithographic printing plate
WO2008117092A1 (fr) * 2007-03-27 2008-10-02 Sericol Limited Encre d'imprimerie
US8377516B2 (en) 2007-03-27 2013-02-19 Sericol Limited Printing ink
WO2009053311A3 (fr) * 2007-10-26 2009-06-18 Agfa Graphics Nv Procédés d'impression à jet d'encre à séchage par rayonnement
EP2053104A1 (fr) * 2007-10-26 2009-04-29 Agfa Graphics N.V. Procédés d'impression par jet d'encre durcissable par radiation
WO2009053311A2 (fr) * 2007-10-26 2009-04-30 Agfa Graphics Nv Procédés d'impression à jet d'encre à séchage par rayonnement
US8371688B2 (en) 2007-10-26 2013-02-12 Agfa Graphics Nv Single pass radiation curable inkjet printing methods for producing printed flexible foils and plastic bags
US8684515B2 (en) * 2007-10-26 2014-04-01 Agfa Graphics Nv Single pass radiation curable inkjet printing methods for producing printed flexible foils and plastic bags
US8168695B2 (en) 2008-02-06 2012-05-01 Fujifilm Corporation Ink composition, inkjet recording method, and printed material
EP2088177A3 (fr) * 2008-02-06 2009-09-16 FUJIFILM Corporation Composition d'encre, procédé d'enregistrement à jet d'encre, et matériau imprimé
CN103666082A (zh) * 2013-12-23 2014-03-26 深圳市深赛尔股份有限公司 一种应用于马口铁的防伪uv印铁油墨及其制备方法
CN109135412A (zh) * 2018-06-12 2019-01-04 苏州中亚油墨有限公司 环保水性柔印uv油墨
CN109535998A (zh) * 2018-09-30 2019-03-29 广州申威新材料科技有限公司 一种高拉伸率的紫外光固化涂料及涂层
CN109535998B (zh) * 2018-09-30 2021-05-18 广州申威新材料科技有限公司 一种高拉伸率的紫外光固化涂料及涂层

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GB2346889B (en) 2001-06-27
AU1346399A (en) 1999-06-28
GB2346889A (en) 2000-08-23
GB0013654D0 (en) 2000-07-26
GB9725928D0 (en) 1998-02-04

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