WO2014188209A1 - Encre d'impression - Google Patents

Encre d'impression Download PDF

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Publication number
WO2014188209A1
WO2014188209A1 PCT/GB2014/051588 GB2014051588W WO2014188209A1 WO 2014188209 A1 WO2014188209 A1 WO 2014188209A1 GB 2014051588 W GB2014051588 W GB 2014051588W WO 2014188209 A1 WO2014188209 A1 WO 2014188209A1
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WO
WIPO (PCT)
Prior art keywords
ink
weight
radiation
curable
total weight
Prior art date
Application number
PCT/GB2014/051588
Other languages
English (en)
Inventor
Jeremy Ward
Nigel Gould
James Turner
Original Assignee
Sericol 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.)
Filing date
Publication date
Application filed by Sericol Limited filed Critical Sericol Limited
Priority to GB1522801.8A priority Critical patent/GB2531188A/en
Publication of WO2014188209A1 publication Critical patent/WO2014188209A1/fr

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Classifications

    • 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
    • C09D11/30—Inkjet printing inks
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks

Definitions

  • the present invention relates to a printing ink, and particularly to an ink for printing onto PET containers, such as PET bottles.
  • Inkjet printing is an attractive technique for printing onto a wide-range of substrates on account of its flexibility and ease of use.
  • PET containers represent a particular challenge.
  • the principle of printing an ink directly onto such a container is superficially attractive as it would streamline the process, but adhesion of the ink to the containers represents a serious challenge.
  • the present invention provides a hybrid inkjet ink comprising: (i) at least 30% by weight of an organic solvent based on the total weight of the ink; (ii) a radiation-curable oligomer and/or a radiation-curable multifunctional monomer; (iii) a photoinitiator; (iv) optionally a colorant; and (v) 8-25% by weight, based on the total weight of the ink, of a passive thermoplastic resin having a weight-average molecular weight of 1 ,500 to 70,000.
  • the ink of the present invention comprises a modified ink binder system.
  • the presence of a radiation-curable material, a passive thermoplastic resin and a photoinitiator in the ink means that crosslinked polymers can be formed in the dried ink film, leading to improved adhesion to PET containers and improved resistance to solvents.
  • the presence of at least 30% by weight of organic solvent means that the advantageous properties of solvent-based inkjet inks are maintained.
  • radiation-curable is meant a material that polymerises or crosslinks when exposed to actinic radiation, commonly ultraviolet light, in the presence of a photoinitiator.
  • the radiation-curable material includes one or more radiation-curable oligomers and/or one or more radiation-curable multifunctional monomers.
  • the monomers/oligomers may possess different degrees of functionality.
  • Radiation-curable oligomers suitable for use in the present invention comprise a backbone, for example a polyester, urethane, epoxy or polyether backbone, and one or more radiation polymerisable groups.
  • the oligomer preferably comprises a urethane backbone.
  • the polymerisable group can be any group that is capable of polymerising upon exposure to radiation.
  • the oligomers are multifunctional, more preferably have a functionality of 2-6.
  • the oligomers are (meth)acrylate oligomers.
  • Particularly preferred radiation-curable materials are urethane acrylate oligomers as these have excellent adhesion and elongation properties. Most preferred are tri-, tetra-, penta- or hexa-functional urethane acrylates, particularly hexafunctional urethane acrylates as these yield films with good solvent resistance.
  • radiation-curable oligomers include epoxy based materials such as bisphenol A epoxy acrylates and epoxy novolac acrylates, which have fast cure speeds and provide cured films with good solvent resistance.
  • Preferred oligomers have a molecular weight of 600 to 4,000. Molecular weights (number average) can be calculated if the structure of the oligomer is known or molecular weights can be measured using gel permeation chromatography using polystyrene standards. In a preferred embodiment the radiation-curable oligomer polymerises by free-radical polymerisation.
  • the radiation-curable oligomer used in the ink of the invention cures upon exposure to radiation in the presence of a photoinitiator to form a crosslinked, solid film.
  • the resulting film has good adhesion to substrates and good solvent resistance.
  • Any radiation-curable oligomer that is compatible with the remaining ink components and that is capable of curing to form a crosslinked, solid film is suitable for use in the ink of the present invention.
  • the ink formulator is able to select from a wide range of suitable oligomers.
  • the oligomer can be a low molecular weight material that is in liquid form at 25°C. This is beneficial when aiming to produce a low viscosity ink.
  • the use of a low molecular weight, liquid oligomer is advantageous when formulating the ink because low molecular weight liquid oligomers are likely to be miscible in a wide range of solvents.
  • Radiation-curable multifunctional monomers suitable for use in the present invention typically have a molecular weight of less than 600. They preferably have a functionality of 3-6, e.g. tri- and tetra-, penta- and hexafunctional monomers.
  • multifunctional (meth)acrylate monomers examples include hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate (for example tetraethylene glycol diacrylate), dipropylene glycol diacrylate, tri(propylene glycol) triacrylate, neopentyl glycol diacrylate, bis(pentaerythritol) hexaacrylate, and the acrylate esters of ethoxylated or propoxylated glycols and polyols, for example, propoxylated neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate (DPHA), ethoxylated pen
  • DPHA dipentaerythritol pentaacrylate
  • Suitable multifunctional (meth)acrylate monomers also include esters of methacrylic acid (i.e. methacrylates), such as hexanediol dimethacrylate, trimethylolpropane trimethacrylate, triethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, ethyleneglycol dimethacrylate, 1 ,4-butanediol dimethacrylate. Mixtures of (meth)acrylates may also be used.
  • methacrylates esters of methacrylic acid
  • methacrylates such as hexanediol dimethacrylate, trimethylolpropane trimethacrylate, triethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, ethyleneglycol dimethacrylate, 1 ,4-butanediol dimethacrylate.
  • the total amount of the radiation-curable oligomer and radiation-curable multifunctional monomer present in the ink is preferably 5 to 30% by weight based on the total weight of the ink, more preferably 5 to 20% by weight, and most preferably 5 to 15% by weight.
  • the ink of the present invention is typically used for packaging food and drink. Therefore, it is beneficial for the ink to be substantially free of migrateable monofunctional monomers, including (meth)acrylates, ⁇ , ⁇ -unsaturated ethers and vinyl amides. Accordingly, the present invention preferably contains less than 5% by weight of monofunctional monomers, more preferably less than 2% by weight and most preferably less than 1 % by weight, based on the total weight of the ink
  • Typical monofunctional (meth)acrylate monomers to be excluded are phenoxyethyl acrylate (PEA), cyclic TMP formal acrylate (CTFA), isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFA), 2-(2-ethoxyethoxy)ethyl acrylate, octadecyl acrylate (ODA), tridecyl acrylate (TDA), isodecyl acrylate (IDA) and lauryl acrylate.
  • PEA phenoxyethyl acrylate
  • CFA cyclic TMP formal acrylate
  • IBOA isobornyl acrylate
  • THFA tetrahydrofurfuryl acrylate
  • 2-(2-ethoxyethoxy)ethyl acrylate 2-(2-ethoxyethoxy)ethyl acrylate
  • ODA octadecyl acrylate
  • TDA tri
  • NVC N-vinyl caprolactam
  • NVP N-vinyl pyrrolidone
  • ACMO N-acryloylmorpholine
  • (Meth)acrylate is intended herein to have its standard meaning, i.e. acrylate and/or methacrylate.
  • Mono and multifunctional are also intended to have their standard meanings, i.e. one and two or more groups, respectively, which take part in the polymerisation reaction on curing.
  • the radiation-curable material is capable of polymerising by cationic polymerisation.
  • Suitable materials include, oxetanes, cycloaliphatic epoxides, bisphenol A epoxides, epoxy novolacs and the like.
  • the radiation-curable material according to this embodiment may comprise a mixture of cationically curable monomer and oligomer.
  • the radiation-curable material may comprise a mixture of an epoxide oligomer and an oxetane monomer.
  • the radiation-curable material can also comprise a combination of free-radical polymerisable and cationically polymerisable materials.
  • the ink of the invention includes one or more photoinitiators.
  • the photoinitiator system includes a free-radical photoinitiator and when the inks include a cationic polymerisable material the photoinitiator system includes a cationic photoinitiator.
  • the inks comprise a combination of free- radical polymerisable and cationically polymerisable materials both a free-radical and cationic initiator are required.
  • the ink is preferably free-radical polymerisable.
  • the free-radical photoinitiator can be selected from any of those known in the art.
  • benzophenone 1 -hydroxycyclohexyl phenyl ketone, 1 -[4-(2-hydroxyethoxy)-phenyl]- 2-hydroxy-2-methyl-1 -propane-1 -one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan- 1 -one, isopropyl thioxanthone, benzil dimethylketal, bis(2,6-dimethylbenzoyl)-2,4,4- trimethylpentylphosphine oxide or mixtures thereof.
  • photoinitiators are known and commercially available such as, for example, under the trade names Irgacure and Darocur (from Ciba) and Lucerin (from BASF).
  • the ink of the present invention may be formulated to comply with regulations for printing onto secondary food packaging.
  • regulations for printing onto secondary food packaging For compositions designed specifically for use on food packaging it is essential that they meet regulations regarding migrateable materials.
  • photoinitiators allowed by legislation and guidance (e.g. EuPIA Inventory List 2012, Nestle Guidance Notes).
  • Non limiting examples of allowed photoinitiators include 2-dimethylamino-2-(4-methyl-benzyl)- 1 -(4-morpholin-4-yl-phenyl)butan-1 -one (Irgacure 379), bis(2,4,6-trimethylbenzoyl)- phenylphosphineoxide (Irgacure 819), 2-hydroxy-1 -[4-(2-hydroxyethoxy)phenyl]-2-methyl-1 - propanone (Irgacure 2959) and polymeric photoinitiators such as polymeric ITX or polymeric benzophenone for example Speedcure 7010 (polymeric ITX from Lambsons) and Genopol BP-2 (polymeric benzophenone from Rahn).
  • Polymeric ITX or polymeric benzophenone for example Speedcure 7010 (polymeric ITX from Lambsons) and Genopol BP-2 (polymeric benzophenone from Rahn).
  • any suitable cationic initiator can be used, for example sulfonium or iodonium based systems.
  • Non limiting examples include Esacure 1064 and Esacure 1 187 from Lamberti, Irgacure 250, Irgacure 270 and Irgacure 290 from BASF, Uvacure 1600 from Cytec and, Speedcure 992 and Speedcure 976 from Lambsons.
  • the photoinitiator is present in an amount of 1 to 20% by weight, preferably 3 to 10% by weight, based on the total weight of the ink.
  • the ink also contains a passive (or “inert") thermoplastic resin.
  • Passive resins are resins which do not enter into the curing process, i.e. the resin is free of functional groups which polymerise under the curing conditions to which the ink is exposed. In other words, resin is not a radiation-curable material.
  • the resin may be selected from epoxy, polyester, vinyl, ketone, nitrocellulose, phenoxy or acrylate resins, or a mixture thereof and is preferably a polyester resin.
  • the passive thermoplastic resin has a weight-average molecular weight (Mw) of 1 ,500 to 70,000.
  • Mw weight-average molecular weight
  • the molecular weight is 2,000 or more, more preferably 3,000 or more, more preferably 4,000 or more and most preferably 5,000 or more; and 30,000 or less, more preferably 20,000 or less, more preferably 15,000 or less and most preferably 10,000 or less.
  • the Mw may be measured by known techniques in the art, such a gel permeation chromatography (GPC).
  • a suitable GPC apparatus for measuring Mw is an LC instrument having the following parameters - Column set: MiniMix E or MiniMix D (depending on molecular weight), Eluent: THF, Detector: UV/vis and/or ELS, Calibration: conventional vs polystyrene. This approach is applicable to polymers having a Mw of 400-400,000.
  • the resin also preferably has a melting point range falling within the range of 30 to 150°C.
  • a particularly preferred resin is LTH resin from Evonik. This resin has a viscosity of 600- 1 ,500 mPas at 23°C in 60% xylene, a Mn of 2,766, a Mw of 5,717 and a melting point of 90- 102°C.
  • the resin is present at 8-25% by weight, preferably 10-20% by weight, based on the total weight of the ink.
  • the combination of the oligomer and/or multifunctional monomer and the passive thermoplastic resin provide the necessary binding properties to the substrate after the ink has cured/dried to a solid film, whilst providing an appropriate viscosity for jetting and providing the required printed film properties and necessary stability to the ink suspension on storage, i.e. prior to jetting.
  • the ink of the invention contains an organic solvent.
  • the organic solvent is in the form of a liquid at ambient temperatures and is capable of acting as a carrier for the remaining components of the ink.
  • the organic solvent component of the ink may be a single solvent or a mixture of two or more solvents.
  • the organic solvent used in the ink of the present invention is required to evaporate from the printed ink, typically on heating, in order to allow the ink to dry.
  • the solvent can be selected from any solvent commonly used in the printing industry, such as glycol ethers, glycol ether esters, alcohols, ketones, esters, organic carbonates, lactones and pyrrolidones.
  • the organic solvent is present in an amount of at least 30% by weight, preferably at least 50% by weight, and most preferably at least 60% by weight based on the total weight of the ink.
  • the upper limit is typically 85% or 75% by weight based on the total weight of the ink.
  • the organic solvent is a low toxicity and/or a low odour solvent. Solvents that have been given VOC exempt status by the United States Environmental Protection Agency or European Council are also preferred. The most preferred solvents are selected from alcohols, glycol ethers, glycol ether acetates, lactones and mixtures thereof.
  • dibasic esters and/or bio-solvents may be used.
  • Dibasic esters are known solvents in the art. They can be described as di(C -C 4 alkyl) esters of a saturated aliphatic dicarboxylic acid having 3 to 8 carbon atoms having following general formula:
  • A represents (CH 2 )i- 6
  • R and R 2 may be the same or different and represent C C 4 alkyl which may be a linear or branched alkyl radical having 1 to 4 carbon atoms, preferably methyl or ethyl, and most preferably methyl.
  • Mixtures of dibasic esters can be used.
  • Bio-solvents, or solvent replacements from biological sources have the potential to reduce dramatically the amount of environmentally-polluting VOCs released in to the atmosphere and have the further advantage that they are sustainable. Moreover, new methods of production of bio-solvents derived from biological feedstocks are being discovered, which allow bio- solvent production at lower cost and higher purity.
  • bio-solvents include soy methyl ester, lactate esters, polyhydroxyalkanoates, terpenes and non-linear alcohols, and D-limonene.
  • Soy methyl ester is prepared from soy.
  • the fatty acid ester is produced by esterification of soy oil with methanol.
  • Lactate esters preferably use fermentation-derived lactic acid which is reacted with methanol and/or ethanol to produce the ester.
  • An example is ethyl lactate which is derived from corn (a renewable source) and is approved by the FDA for use as a food additive.
  • Polyhydroxyalkanoates are linear polyesters which are derived from fermentation of sugars or lipids.
  • Terpenes and nonlinear alcohols may be derived from corn cobs/rice hulls.
  • An example is D-limonene which may be extracted from citrus rinds.
  • the organic solvent component may be included in the organic solvent component.
  • a particularly common source of other solvents is derived from the way in which the colouring agent is introduced into the inkjet ink formulation.
  • the colouring agent may be prepared in the form of a pigment dispersion in a solvent, e.g. 2-ethylhexyl acetate.
  • the solvent tends to be around 40 to 50% by weight of the pigment dispersion based on the total weight of the pigment dispersion and the pigment dispersion typically makes up around 5 to 15% by weight of the ink and sometimes more.
  • the ink is preferably substantially free of water, although some water will typically be absorbed by the ink from the air or be present as impurities in the components of the inks, and such levels are tolerated.
  • the ink may comprise less than 5% by weight of water, more preferably less than 2% by weight of water and most preferably less than 1 % by weight of water, based on the total weight of the ink.
  • the ink of the present invention may be a coloured or a colourless ink.
  • colourless is meant that the ink is free of colorant such that no colour can be detected by the naked eye. Minor amounts of colorant that do not produce colour that can be detected by the eye can be tolerated, however.
  • the amount of colorant present will be less than 0.3% by weight based on the total weight of the ink, preferably less than 0.1 %, more preferably less than 0.03%.
  • Colourless inks may also be described as “clear” or “water white”. Colourless inks may also be used as a varnish, where it is applied over a coloured ink. For the avoidance of doubt, coloured inks include white inks.
  • the coloured inks comprise at least one colouring agent.
  • the colouring agent may be either dissolved or dispersed in the liquid medium of the ink.
  • the colouring agent is a dispersible pigment, of the types known in the art and commercially available such as under the trade-names Paliotol (available from BASF pic), Cinquasia, Irgalite (both available from Ciba Speciality Chemicals) and Hostaperm (available from Clariant UK).
  • the pigment may be of any desired colour such as, for example, Pigment Yellow 13, Pigment Yellow 83, Pigment Red 9, Pigment Red 184, Pigment Blue 15:3, Pigment Green 7, Pigment Violet 19, Pigment Black 7.
  • black and the colours required for trichromatic process printing are black and the colours required for trichromatic process printing.
  • pigments may be used. In one aspect the following pigments are preferred. Cyan: phthalocyanine pigments such as Phthalocyanine blue 15.4. Yellow: azo pigments such as Pigment yellow 120, Pigment yellow 151 and Pigment yellow 155. Magenta: quinacridone pigments, such as Pigment violet 19 or mixed crystal quinacridones such as Cromophtal Jet magenta 2BC and Cinquasia RT-355D. Black: carbon black pigments such as Pigment black 7.
  • Cyan phthalocyanine pigments such as Phthalocyanine blue 15.4.
  • Yellow azo pigments such as Pigment yellow 120, Pigment yellow 151 and Pigment yellow 155.
  • Magenta quinacridone pigments, such as Pigment violet 19 or mixed crystal quinacridones such as Cromophtal Jet magenta 2BC and Cinquasia RT-355D. Black: carbon black pigments such as Pigment black 7.
  • Pigment particles dispersed in the ink should be sufficiently small to allow the ink to pass through an inkjet nozzle, typically having a particle size less than 8 ⁇ , preferably less than 5 ⁇ , more preferably less than 1 ⁇ and particularly preferably less than 0.5 ⁇ .
  • the colorant is preferably present in an amount of 20 weight% or less, preferably 10 weight% or less, more preferably 8 weight% or less and most preferably 2 to 5% by weight, based on the total weight of the ink.
  • a higher concentration of pigment may be required for white inks, however, for example up to and including 30 weight%, or 25 weight% based on the total weight of the ink.
  • the inks may be in the form of an ink set comprising a cyan ink, a magenta ink, a yellow ink and a black ink (a so-called trichromatic set).
  • the inks in a trichromatic set can be used to produce a wide range of colours and tones.
  • the inkjet ink exhibits a desirable low viscosity (200 mPas or less, preferably 100 mPas or less, more preferably 25 mPas or less and most preferably 15 mPas or less.
  • a small jetted drop size is desirable.
  • small droplets have a higher surface area to volume ratio when compared to larger drop sizes, which facilitates evaporation of solvent from the jetted ink. Small drop sizes therefore offer advantages in drying speed.
  • the inkjet ink of the invention is jetted at drop sizes below 50 picolitres, preferably below 30 picolitres and most preferably below 10 picolitres.
  • Ink viscosity may be measured using a Brookfield viscometer fitted with a thermostatically controlled cup and spindle arrangement, such as a DV1 low-viscosity viscometer running at 20 rpm at 25 °C with spindle 00.
  • the surface tension of the ink is controlled by the addition of one or more surface active materials such as commercially available surfactants. Adjustment of the surface tension of the inks allows control of the surface wetting of the inks on various substrates, for example, plastic substrates. Too high a surface tension can lead to ink pooling and/or a mottled appearance in high coverage areas of the print. Too low a surface tension can lead to excessive ink bleed between different coloured inks.
  • the surface tension is preferably in the range of 20-32 mNm " and more preferably 21 -27 mNm " .
  • the ink may be prepared by known methods such as stirring with a high-speed water-cooled stirrer, or milling on a horizontal bead-mill.
  • the ink of the present invention is formulated for printing onto polyethylene terephthalate (PET) containers, and particularly PET bottles.
  • PET polyethylene terephthalate
  • the present invention also provides a substrate having the ink as defined herein printed thereon, and particularly where the substrate is a PET container
  • the printing is preferably all performed by inkjet printing, e.g. on a single-pass inkjet printer, for example for printing (directly) onto packaging, such as food packaging or bottles.
  • Evaporation of the solvent can occur simply by exposure of the inks to the atmosphere, but the inks may also be heated to accelerate evaporation.
  • the inks are exposed to actinic radiation to cure the ink.
  • the present invention further provides a method of inkjet printing comprising the following steps: inkjet printing the ink as defined herein onto a substrate and, in either order, evaporating the solvent and exposing the ink to actinic radiation to cure the radiation-curable oligomer and, if present, the radiation-curable monomer.
  • the ink may be partially cured (i.e. "pinning" by exposure to actinic radiation, typically UV, e.g. by LED.
  • the substrate for the method is preferably a PET container.
  • drying and “cure” are often used interchangeably in the art when referring to radiation-curable inkjet inks to mean the conversion of the inkjet ink from a liquid to solid by polymerisation and/or crosslinking of the radiation-curable material.
  • drying is meant the removal of the solvent by evaporation
  • curing is meant the polymerisation and/or crosslinking of the radiation-curable material.
  • An inkjet ink was prepared according to the formulation set out in Table 1 .
  • the inkjet ink formulation was prepared by mixing the components in the given amounts. Amounts are given as weight percentages based on the total weight of the ink. Table 1
  • the viscosity of the ink was measured using a Brookfield viscometer fitted with a thermostatically controlled cup and spindle arrangement, such as a DV1 low-viscosity viscometer running at 20 rpm at 25°C with spindle 00. The viscosity was measured as 8.3 mPas.
  • the ink was then printed onto a PET substrate, using a 12 micron K-bar onto a corona discharge-treated proprietary PET substrate and dried for 3 minutes at 60°C then UV cured at 25 m/min using a 1 x 120 W/cm 2 medium-pressure mercury lamp.
  • the solvent resistance was measured using an IPA ink rub test.
  • the double rub test is well known in the art.
  • the ink is applied to the substrate by any suitable means. It is then dried and cured. One then takes a lint-free (cotton) cloth saturated in the solvent. One then carries out a double rub, each rub being 10 cm. The number of rubs is counted until the substrate is visible under the ink.
  • a coloured solvent-based ink preferably having one rub solvent resistance, may be printed under the ink to be tested so that the colour is easily visible. The substrate will then become visible when the colour is removed.
  • the ink of Example 1 showed a very high solvent resistance of 70-80 double rubs.

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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)

Abstract

La présente invention concerne une encre pour jet d'encre hybride comprenant : (i) au moins 30% en poids d'un solvant organique sur la base du poids total de l'encre; (ii) un oligomère durcissable par rayonnement et/ou un monomère multifonctionnel durcissable par rayonnement; (iii) un photoinitiateur; (iv) éventuellement un colorant; et (v) 8 à 25 % en poids, sur la base du poids total de l'encre, d'une résine thermoplastique passive ayant un poids moléculaire moyen de 1500 à 70000.
PCT/GB2014/051588 2013-05-24 2014-05-23 Encre d'impression WO2014188209A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB1522801.8A GB2531188A (en) 2013-05-24 2014-05-23 Printing ink

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1309432.1A GB201309432D0 (en) 2013-05-24 2013-05-24 Printing ink
GB1309432.1 2013-05-24

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WO2014188209A1 true WO2014188209A1 (fr) 2014-11-27

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016181162A1 (fr) * 2015-05-13 2016-11-17 Fujifilm Speciality Ink Systems Limited Procédé d'impression
US10435577B2 (en) 2016-03-31 2019-10-08 Fujifilm Corporation Ink set and image forming method
WO2019226645A1 (fr) * 2018-05-25 2019-11-28 Corning Incorporated Encres hybrides comprenant des monomères uv, des oligomères, et des résines
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US10844234B2 (en) 2015-05-13 2020-11-24 Fujifilm Speciality Ink Systems Limited Method of printing
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