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
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • 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
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
• • 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
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • 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
  • C09D11/50—Sympathetic, colour changing or similar inks
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
  • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
  • Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter

Definitions

• the present invention relates to the formulation of masterbatch concentrates for the manufacture of coating/ink compositions for laser imaging substrates, especially flexible substrates primarily used in the packaging industry.
• masterbatch concentrates can be simply mixed with different technical varnishes in order to obtain the final physical ink properties as required.
• US 8,105,506 describes coating compositions comprising an oxyanion of a multivalent metal, for example ammonium octamolybdate (AOM) , a binder which is typically polymeric, and a solvent such as water or ethanol, and a conductive polymer that absorbs IR radiation. Also listed is the addition of a color former and electron-donating dye precursor. Numerous separate individual formulations are listed.
• AOM ammonium octamolybdate
• US 8,101,545 describes coating compositions comprising a color former, an amine salt of an organic metal compound, a binder, a solvent and additional components. A comprehensive list is described together with individual examples.
• US 8,048,608 B2 describes the use of reduced Indium Tin Oxide (r-ITO) in AOM based ink formulations.
• the r-ITO is a non-stoichiometric compound; the ITO being reduced bestows NIR absorption properties.
• Individual ink formulations which are fiber laser reactive are listed.
• compositions are formulated to produce solvent coatings, which can be effectively imaged using a CO 2 laser.
• the main compound described is ammonium octamolybdate (AOM) .
• US 7,270,919 describes a process for forming an image on a substrate which comprises coating the substrate with an amine of molybdenum which changes color when subjected to a laser. Numerous individual ink formulations are described. [000010] Substrates produced on production lines, especially for the packaging industry of which paper, board, and polymeric films are examples, are usually marked with information such as logos, bar codes, expiry dates, and batch numbers.
• laser imaging aka “laser imaging”
• this method of marking is cheaper in terms of overall economics and also shows performance benefits such as high speed and contact-free marking.
• Different logos, dates and batch numbers can be easily and readily changed when required.
• the substrates to be marked typically have laser markable patches to be imaged. When clear polymeric filmic substrates are to be imaged, these patches can be imaged either from the top surface or from the bottom surface through the film.
• the present invention provides a laser masterbatch concentrate comprising
• said laser masterbatch concentrate can be combined with a technical varnish to form a laser reactive solvent- based finished ink.
• the present invention also provides a method of preparing a laser masterbatch concentrate comprising combining a. one or more laser reactive pigment systems;
• said laser masterbatch concentrate can be combined with a technical varnish to form a laser reactive solvent- based finished ink.
• the present invention also provides a method of preparing a laser reactive solvent-based finished ink comprising combining a masterbatch concentrate with a technical varnish to provide a finished solvent-based laser reactive ink.
• the present invention also provides a novel use of polyethylene glycols or polypropylene glycols, preferably with a molecular weight from about 200-8,000 g/mol, as dispersing aids. [000019]
• the present invention also provides a laser reactive solvent-based ink comprising combining a masterbatch concentrate and a technical varnish.
• the present invention also provides a printed article comprising a solvent-based laser reactive ink made from a masterbatch concentrate and a technical varnish.
• a laser masterbatch concentrate may be defined as a composition that contains a high wt% of laser reactive
• pigment (s) preferably at least 38 wt% laser reactive
• laser masterbatch concentrate would also be preferably at least 43 wt% laser reactive pigment (s), even more preferably at least 45 wt% laser reactive pigment (s), and most preferably at least 50 wt% laser reactive pigment (s).
• the laser masterbatch concentrate would also be preferably at least 43 wt% laser reactive pigment (s), even more preferably at least 45 wt% laser reactive pigment (s), and most preferably at least 50 wt% laser reactive pigment (s).
• the laser masterbatch concentrate would preferably be suitable for
• a technical varnish may be defined as a solution of a specific resin or blend of resins in solvents, with additives as needed, which is suitable for blending with a laser masterbatch concentrate to provide a laser reactive finished ink that meets end-use customer requirements.
• a laser reactive pigment system may be defined as a pigment system that changes color when irradiated with a laser. Various systems are described. Examples of preferred laser reactive pigments systems are those based on oxyanions, for example ammonium octamolybdate (AOM) , and those based on a color former/Leucodye and the salt of a carboxylic acid or other thermal acid generators. All these change color when subjected to the relevant lasers. More specific examples of laser reactive pigment systems, include but are not limited to:
• the maximum amount of oxyanion-type laser reactive pigment that would be found in a laser reactive finished ink is typically about 35-40 wt%. However, a more typical range would be 27-37 wt%.
• masterbatch concentrates would preferably contain at least 40 wt% laser reactive pigment, more preferably at least 45 wt% laser reactive pigment, and most preferably at least 50 wt% laser reactive pigment. As listed in the examples, a typical range would be 30-80 wt%. Though AOM is preferred, other
• oyanions will also work, as it is the valency change in the octamolybdate which causes the color change, leaving the cation unchanged.
• ammonium octamolybdate the ammonium is the cation and the anion the octamolybdate.
• oxyanions includes molybdate, tungstate, or analogous
• transition metal compound Such compounds also include di, hepta, and octa - molybdates and also analogous tungstates.
• a non-limiting list of examples of cations includes ammonium, an alkali, or an alkali earth metal.
• the Carboxylic acid salt-type (or other thermal acid generators) / Leucodye-type masterbatch concentrate of the present invention would preferably contain at least 38 wt% laser reactive pigment, more preferably at least 43 wt% laser reactive pigment, most preferably at least 45 wt% laser reactive pigment, with a typical range being 35-55 wt%.
• the masterbatch examples 3 & 4 reflect these values.
• an infrared heat absorber e.g. r-ITO (reduced indium tin oxide), Iriotec 8800 & 8825 (from Merck), and others.
• the total amount of laser reactive pigment is at least 38 wt% laser reactive pigment, more preferably at least 43 wt% laser reactive pigment, most preferably at least 45 wt% laser reactive pigment .
• Oxyanion-type laser reactive pigment systems typically yield a white ink, which turns black with lasering.
• all of the laser reactive pigment system alternatives may be colored without any deterioration to the laser image.
• High chain alcohols may be defined as alcohols having 3 or more carbon atoms.
• linear high chain alcohols having 3 or more carbon atoms are especially preferred .
• Examples of the types of lasers that are typically used in the art of laser marking include but are not limited to CO 2 and fiber lasers.
• the present invention refers to the novel concept of the formulation of masterbatch concentrates for the manufacture of coating/ink compositions for laser imaging flexible
• masterbatch concentrates can simply be mixed with different technical varnishes in order to produce a finished ink with the final physical properties as required.
• the present application also describes the novel use of polyethylene glycols and polypropylene glycols as dispersants in these masterbatch concentrates, and the benefits obtained over conventional dispersants (e.g. Solsperse range obtained from Lubrizol) .
• the masterbatch concentrate can be combined with numerous technical varnishes to obtain finished coating/ink compositions for laser imaging onto various substrates and end- use applications.
• One of the main areas of application would be flexible substrates primarily used in the packaging industry, including polymeric types.
• a partial list of other substrates includes glass, paper, wood, metallics etc., or any other substrate that could be receptive to laser imaging inks.
• the ink formulation can be applied by printing techniques commonly used in the flexible packaging industry, for example flexographic and gravure printing. Conventional solvents used in the printing industry can be used in the formulation of finished inks.
• the inks made using the masterbatch concentrate concept of the present invention could also be applied using other printing processes (e.g. screen, litho, digital, etc.).
• a masterbatch concentrate can be prepared and subsequently inks with varying properties can easily be made.
• the masterbatch concentrate preparation is described in detail.
• hyperdispersants such as those supplied by Solsperse but not limited to these) can improve the dispersion by reducing the viscosity and improving the flow, which can reduce the milling time.
• These hyperdispersants are well known in printing inks, especially for flexible packaging, offering improved pigment dispersion in liquid organic media.
• polyethylene glycols with Mw ranging from 200-8,000 g/mol, more preferably between 200- 2,000 g/mol are selected as hyperdispersants as these exhibit good properties as dispersing aids in the manufacture of the masterbatch concentrate.
• the benefit of these hyperdispersants is that they are easier to disperse, there is a greater
• Polypropylene glycols of similar molecular weights as above may also be used.
• the resin system used in the masterbatch concentrate of the present invention preferably would have a low acid number
• the resin would also preferably have a glass transition temperature (Tg) between 80°-120°C. This helps enable good milling of the masterbatch concentrate.
• resins having these properties are Tego VariPlus SK® (Ketonic Polyol) ; Laropal® K80 & K1717 HMP (Polyketone) ; and Laropal® A81 (Aldehyde), but not limited to these.
• Other resins that can be used include but are not limited to fumaric/rosin adducts, maleic modified rosins, maleic/rosin esters. Trade names for these are Pentalyn®, Unirez®, etc.
• the lower chain alcohols are kept at a maximum of 10 wt%, more preferably at a maximum of 5 wt%, and most preferably eliminated completely from the masterbatch concentrate formulation.
• the masterbatch concentrate approach can be used to provide inks that are sensitive to all lasers, particularly CO 2 and fiber lasers.
• the method of using the masterbatch concentrate of the present invention to make laser reactive finished inks can be used either by ink manufacturers or by ink users (printers) who can mix the masterbatch concentrate with the appropriate
• masterbatch concentrate method of producing finished inks good mixing will preferably suffice as the materials that require milling will preferably be pre-milled during the manufacture of the masterbatch concentrate. This gives the user greater ease of use and versatility when printing onto a variety of substrates, e.g. paper/board and various polymeric films. When printing on polymeric films, a recommended adhesion promoter system is described . [000050]
• the masterbatch concentrates of the present invention or finished inks made from the masterbatch concentrates may be tinted by incorporating traditional colorants. These colorants may be incorporated as color concentrates, flushes, liquid dyes, powders, etc.
• Suitable colorants include, but are not limited to organic or inorganic pigments and dyes.
• the dyes include but are not limited to azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, combinations thereof and the like.
• Organic pigments may be one pigment or a combination of pigments, such as for instance Pigment Yellow Numbers 12, 13, 14, 17, 74, 83, 114, 126, 127, 174, 188; Pigment Red Numbers 2, 22, 23, 48:1, 48:2, 52, 52:1, 53, 57:1, 112, 122, 166, 170, 184, 202, 266, 269;
• Inorganic pigments may be one of the following non-limiting pigments: iron oxides, titanium dioxides, chromium oxides, ferric ammonium ferrocyanides , ferric oxide blacks, Pigment Black Number 7 and/or Pigment White Numbers 6 and 7.
• Other organic and inorganic pigments and dyes can also be employed, as well as combinations that achieve the colors desired. If used, it is preferred that traditional colorants be incorporated in relatively small amounts (e.g. less than 10 wt%, more preferably less than 5 wt%) .
• Adhesion promoters may be used in either the
• masterbatch concentrate examples include waxes, ammonia, defoamers, dispersants, stabilizers, silicones, rheological modifiers, plasticizers and the like.
• an infrared heat absorber may be incorporated into the formulation.
• the examples list reduced indium tin oxide (r-ITO) , but the IR absorber is not limited to this; many are listed in the prior art.
• Other IR absorbers are Iriotec 8800 & 8825 (from Merck) , and Baytron P
• masterbatch concentrates can also be imaged using a CO 2 laser.
• the laser CO 2 optimum settings in these cases may be different to the settings used in laser reactive pigment systems without an IR heat absorber.
• films include but are not limited to polymeric packaging films (e.g. OPP - orientated polypropylene, polyethylene, PET, polyester, etc.) and coated and/or treated polymeric packaging films (e.g. those coated or treated with acrylic, PVDC, aluminum (Alox) , silicone oxide
• adhesion promoter is preferably added when the masterbatch concentrate is blended with the technical varnish to form a finished ink, but adhesion promoter could also be incorporated directly into the masterbatch concentrate. When the finished ink is to be printed on paper/board, adhesion promoter may not be required.
• adhesion promoters are those based on zirconium propionate, as these materials can help reduce or eliminate undesirable color changes in wet inks based on certain laser reactive pigment systems.
• adhesion promoters are those based on titanium complexes with and without stabilizers.
• titanium-based adhesion promoters include but are not limited to Tyzor® range from DuPont, Vertec® range from Johnson Matthey, Tytan® range from Borica.
• the preferable amount of adhesion promoter added ranges from 0.5 wt% to 25 wt%.
• the masterbatch concentrates of the present invention may also contain thermochromic pigments, preferably irreversible thermochromic pigments.
• the solvents to be used are determined by the particular thermochromic pigment properties.
• a range of thermochromic pigments suitable for solvent-based ink systems are obtainable, for example, from Lawrence Industries Ltd (UK) .
• concentrate examples were dispersed using specific equipment, but it is understood that other typical dispersing equipment could be used (e.g. 3-roll mill, bead mill, high shear mixers, etc.) .
• Each example was dispersed to a preferred grind
• Example 1 Masterbatch Concentrate for Laser Reactive Pigment System 1 - CO 2 Laser Image
• Hyperdispersant / PEG 1500 0.6 0.1-5.0
• Ketone Varnish (Tego VariPlus SK) 25.0 10-40
• Table 1 shows an example of a masterbatch concentrate which could be blended with a technical varnish to provide a laser reactive finished ink preferably for use with a CO 2 laser.
• the far right column under the heading "Typical wt% Range” is meant to exemplify general ranges for the materials that could be used to provide variations on Example 1.
• the laser reactive pigment system can be dispersed using a high shear mixer (e.g. Silverson) or by other typical milling
• Hyperdispersant / PEG 1500 0.6 0.1-5.0
• Ketone Varnish (Tego VariPlus SK) 22.2 8-40
• Table 2 shows an example of a masterbatch concentrate which could be blended with a technical varnish to provide a laser reactive finished ink preferably for use with a fiber laser.
• the far right column under the heading "Typical wt% Range” is meant to exemplify general ranges for the materials that could be used to provide variations on Example 2.
• the laser reactive pigment system can be dispersed using a high shear mixer (e.g. Silverson) or by other typical milling equipment.
• Table 3 shows an example of a masterbatch concentrate which could be blended with a technical varnish to provide a laser reactive finished ink preferably for use with CO 2 lasers.
• the far right column under the heading "Typical wt% Range” is meant to exemplify general ranges for the materials that could be used to provide variations on Example 3.
• Example 3 would preferably be made by milling using an Eiger-Torrance 50 ml capacity bead-mill. Other milling equipment could also be used.
• Table 4 shows an example of a masterbatch concentrate which could be blended with a technical varnish to provide a laser reactive finished ink preferably for use with a fiber laser.
• Range is meant to exemplify general ranges for the materials that could be used to provide variations on Example 4.
• Example 4 would preferably be made by milling using an Eiger-Torrance 50 ml capacity bead-mill. Other milling equipment could also be used .
• Table 5 shows an example of a laser reactive finished ink that was made by blending a masterbatch concentrate of the present invention with a technical varnish.
• the far right column under the heading "Typical wt% Range” is meant to exemplify general ranges for the materials that could be used to provide variations on Example 5.
• Table 6 shows an example of a laser reactive finished ink that was made by blending a masterbatch concentrate of the present invention with a technical varnish.
• the far right column under the heading "Typical wt% Range” is meant to exemplify general ranges for the materials that could be used to provide variations on Example 6.
• colorant/white pigment was added by the addition of a concentrate to obtain the desired color.
• Colorants and/or white pigment would preferably be incorporated as either a pre-dispersed concentrate or in a form that can be dispersed into the finished ink by means of mixing, without the need for milling. However, it would also be possible to incorporate colorants that require milling by adding them and them subjecting the ink to further milling.
• Table 7 shows Examples 7-16 which were made to show a partial list of the types of laser reactive finished inks that can be made by blending the masterbatch concentrates of the present invention with various technical varnishes. But this list is by no means exhaustive. Any varnish that is compatible with the masterbatch concentrate could be utilized and depends on the intended end-use application of the ink or coating.
• PA/Acrylic 13 75/15/10 5 5 5 3 4 4
• Adhesion promoter is preferred in formulations for printing on some films to produce optimum adhesion.
• Resistance properties test results are expressed as a score from 0 (worst) 5 (best) , 0 being 100% ink removal, 5 being no 0% ink removal or print surface damage.
• Inks in Table 7 were printed using 2 hits of a 140# Anilox roller / blue rubber roller onto typical substrates used in the packaging industry.
• Tape Adhesion - Adhesive Tape (Scapa tape - ref: 1112) is stuck on top of a proof print of the ink and is then pulled off. Evaluate level of ink removal. Only tested on films.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2013
  • 2013-06-19 JP JP2015518547A patent/JP6148335B2/ja not_active Expired - Fee Related
  • 2013-06-19 EP EP13807229.3A patent/EP2852642A4/en not_active Withdrawn
  • 2013-06-19 US US14/406,808 patent/US20150152272A1/en not_active Abandoned
  • 2013-06-19 WO PCT/US2013/046575 patent/WO2013192307A1/en not_active Ceased

Patent Citations (8)

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