WO2016039960A1 - Encres à base d'eau réactives au laser fabriquées à partir de concentrés de mélange-maître à base d'eau - Google Patents

Encres à base d'eau réactives au laser fabriquées à partir de concentrés de mélange-maître à base d'eau Download PDF

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Publication number
WO2016039960A1
WO2016039960A1 PCT/US2015/046001 US2015046001W WO2016039960A1 WO 2016039960 A1 WO2016039960 A1 WO 2016039960A1 US 2015046001 W US2015046001 W US 2015046001W WO 2016039960 A1 WO2016039960 A1 WO 2016039960A1
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WIPO (PCT)
Prior art keywords
concentrate
masterbatch
present
amount
masterbatch concentrate
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PCT/US2015/046001
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English (en)
Inventor
Brian CROMBIE
Peter SALTHOUSE
Nick PAGLIUCA
Robert DEIGHTON
Thierry Frinault
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Sun Chemical Corporation
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Publication of WO2016039960A1 publication Critical patent/WO2016039960A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts 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
    • C09D11/037—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
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3372—Macromolecular compounds
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids

Definitions

  • the present invention relates to the formulation of a water-based masterbatch concentrate for the manufacture of coating and ink compositions for laser imaging substrates, particularly substrates typically used in the packaging industry, including flexible substrates.
  • the masterbatch can be simply mixed with different water-based technical varnishes in order to obtain laser-reactive finished inks with the final physical properties as required.
  • Substrates produced on production lines are usually marked with information such as logos, bar codes, expiration dates, and batch numbers.
  • 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 through the film.
  • Laser markable patches can be formed by printing of an area with an ink or coating containing a pigment that changes color when exposed to a laser beam (color changing pigments).
  • Color changing pigments include dyes known as leuco dyes. These color changing pigments, particularly leuco dyes, are generally not stably dispersed in water-based systems, and can be included in the ink or coating composition only in low concentrations. Therefore, only finished ink or coating compositions, ready for printing, have generally been available. Thus, it has been necessary to buy and/or store separate compositions specific to each print job (i.e. for each type of printing method on different substrates).
  • WO 2013/192307 discloses solvent-based laser-reactive masterbatch
  • the laser-reactive masterbatch concentrate comprises one or more laser- reactive pigment systems; one or more solvents wherein at least one is a linear high chain alcohol with at least 3 carbon atoms; and one or more resins.
  • US 2012/0045624 describes laser-sensitive aqueous compositions comprising a color former, a developer, and a binder.
  • the color former generally comprises an electron donating leuco dye and an electron accepting developer.
  • Compositions may contain latent activator which can be either an acid derivative or a salt of an acid and an amine.
  • US 2011/0065576 discloses laser-sensitive coating compositions comprising titanium dioxide in the anatase form, or polymeric particles comprising a polymeric matrix comprising one or more water-insoluble polymers of titanium dioxide in the anatase form encapsulated in the polymeric matrix; and a polymeric binder.
  • Compositions may include additional components such as IR absorbers, catalysts, pigments, etc.
  • US 2010/0233447 discloses polymeric particles comprising a polymeric matrix comprising one or more water-insoluble polymers and a laser-sensitive system encapsulated in the polymeric matrix. Also described is the use of the polymeric particles in ink compositions.
  • 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 infrared (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
  • a binder which is typically polymeric
  • a solvent such as water or ethanol
  • a conductive polymer that absorbs infrared (IR) radiation.
  • IR infrared
  • thermosensitive marking material by laser marking.
  • a thermosensitive color forming layer is formed by printing with a printing ink containing a leuco dye as a color former, and an acidic substance as a color developer.
  • US 8, 101,544 describes coating compositions for making substrates comprising a color former, a metal salt of a carboxylic acid, a binder, and an organic solvent. Many individual binders are described as separate examples.
  • US 7,485,403 and US 8,048,605 disclose a laser markable coating composition
  • a binder and an oxyanion of a multivalent metal, such as ammonium octamolybdate (AOM). Coatings can be effectively imaged using a C0 2 laser, undergoing a color change upon exposure.
  • AOM ammonium octamolybdate
  • US 8,048,608 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 near-infrared (NIR) absorption properties.
  • NIR near-infrared
  • Individual ink formulations which are fiber laser reactive are listed.
  • US 7,270,919 discloses imageable coatings comprising an aqueous solution or dispersion, or a solution in an organic solvent, of amines of transition metal compounds, which change color when subjected to a laser.
  • the coatings also contain a thermoplastic polymer or a photopolymerizable monomer.
  • WO 2005/012442 describes a laser-markable composition comprising a pigment, a solvent, and a conductive polymer.
  • Amine molybdates are used as color developers, with color formers (e.g. color changing pigments).
  • US 8,083,973 discloses polychromic compounds that undergo a color change upon irradiation.
  • the polychromic compounds are derivatives of carboxylic acids.
  • Inks are described which contain the polychromic carboxylic acid derivatives and other substances capable of changing color.
  • US 8, 173,253 describes secondary package labeling applications.
  • One is a tape coated with a laser markable ink composition and a layer of adhesive.
  • Another is a laser- imageable composition being applied as a spray.
  • US 8, 178,277 describes electromagnetic radiation or thermally sensitive coating compositions for making substrates comprising a compound containing a carbonyl group, and a nucleophile compound; or a compound containing a free carbonyl group that is substituted with one or more nucleophilic groups.
  • Preferred carbonyl compounds are reducing carbohydrates, and preferred nucleophiles are amines.
  • EP1560715 discloses a process for the laser marking of thin, flexible plastic films.
  • a layer or layers of a laser-sensitive material and an ink are printed.
  • the laser-sensitive material and ink may be separate layers, or the laser-sensitive material and ink may be combined in a single layer.
  • the creation of a water-based laser-reactive masterbatch concentrate system would be advantageous to end users (i.e. printers, manufacturers, etc.) who can quickly and easily blend a technical varnish with a laser-reactive masterbatch concentrate to produce finished laser-reactive inks and coatings for many different applications.
  • the end user Using one masterbatch concentrate, the end user has the flexibility to choose from a number of different technical varnishes to impart the necessary performance properties (adhesion, resistance, printability, etc.) for a wide range of printing applications.
  • the present invention provides a masterbatch concentrate for laser reactive water-based inks comprising:
  • thermochromic leuco dye a thermochromic leuco dye
  • masterbatch concentrate can be combined with a technical varnish to form a laser reactive water-based ink.
  • the present invention also provides a masterbatch concentrate for laser reactive water-based inks comprising wherein the leuco dye is present in an amount of from about 10 wt% to about 30 wt%; the blocked/latent acid is present in an amount of from about 15 wt% to about 50 wt%; the alkali/amine is present in an amount of 1 wt% to about 10 wt%; and the water is present in an amount of about 15 wt% to about 50 wt%.
  • the present invention also provides a method of making a laser masterbatch concentrate comprising combining:
  • thermochromic leuco dye a thermochromic leuco dye
  • thermochromic leuco dye concentrate comprising:
  • the present invention also provides a blocked/latent acid concentrate comprising:
  • the present invention also provides a method of preparing a laser masterbatch concentrate by combining a thermochromic leuco dye concentrate and a blocked/latent acid concentrate.
  • the present invention also provides a laser reactive water-based ink comprising a masterbatch concentrate and a technical varnish.
  • the present invention also provides a method of making a laser reactive water- based ink comprising blending a masterbatch concentrate with a technical varnish, to form a finished water-based laser reactive ink.
  • the present invention also provides a method of making a laser reactive water- based ink, comprising:
  • the present invention also provides a printed article comprising a laser reactive water-based ink made from a masterbatch concentrate and a technical varnish.
  • the terms “comprises” and/or “comprising” specify the presence of the stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Furthermore, to the extent that the terms “includes,” “having,” “has,” “with,” “composed,” “comprised” or variants thereof are used in either the detailed description or the claims, such terms are intended to be inclusive in a manner similar to the term “comprising.”
  • ranges and amounts can be expressed as “about” a particular value or range. “About” is intended to also include the exact amount. Hence “about 5 percent” means “about 5 percent” and also “5 percent.” “About” means within typical experimental error for the application or purpose intended.
  • “technical varnish” refers to the vehicle used to let down (dilute) the masterbatch concentrate millbase to prepare the finished inks.
  • Technical varnishes generally comprise polymer resins, solvents, oils (such as drying oils), and other additives.
  • the present invention relates to the formulation of a water-based masterbatch concentrate for the manufacture of coating and ink compositions for laser imaging substrates, particularly substrates typically used in the packaging industry, including flexible substrates.
  • the masterbatch can be simply mixed with different water-based technical varnishes in order to obtain laser-reactive finished inks with the final physical properties as required.
  • the masterbatch concentrate can be combined with numerous technical varnishes to obtain 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.
  • Any suitable technical varnish can be used, and the choice will depend on the end use requirements of the finished laser-reactive ink or coating.
  • varnishes based on any suitable polymer resin can be used.
  • These polymer resins include, but are not limited to acrylic and methacrylic resins, and polyurethane resins.
  • Polymer resins suitable for use in the technical varnishes include, but are not limited to, Induprint 2622, Noncryl 90, Lucidene 605, Joncryl 535, Joncryl 1665, Neorez R650, and Joncryl 8050.
  • Inks and coatings made from the masterbatch can be applied by printing techniques commonly used in the flexible packaging industry, for example flexographic and gravure printing.
  • the inks made using the masterbatch concept of the present invention could also be applied using other printing processes (e.g. screen, litho, digital, etc.).
  • Laser sensitive inks for C0 2 lasers (9400-10600nm), fiber lasers (1060- 1600nm) and YAG (neodymium-doped yttrium aluminum garnet) laser imaging can be produced using the masterbatch route.
  • This system can be used either by the ink manufacturer or by ink users (printers) who can mix the 'masterbatch' with the appropriate technical varnish as and when required.
  • good mixing, without additional milling, will suffice, as the materials that require milling will be pre-milled during the manufacture of the masterbatch.
  • the present invention refers specifically to the formulation of a water-based masterbatch concentrate for the manufacture of coating/ink compositions for laser imaging substrates primarily used in the packaging industry.
  • This masterbatch can be simply mixed with different technical water-based varnishes in order to obtain the final physical properties as required.
  • This masterbatch concentrate enables certain water-based inks to be used for both paper/board and filmic substrates.
  • the inks are based on leuco dye/blocked acid technology, for laser imaging.
  • the masterbatches can contain either of the combinations - leuco dye or blocked/latent acid alone, or a mixture/combination of leuco dye and blocked/latent acid.
  • a leuco dye concentrate masterbatch can be prepared, and a separate blocked/latent acid concentrate masterbatch can be prepared. Each of these separate masterbatches will be incorporated into the finished laser-reactive.
  • a single masterbatch, containing both the leuco dye and blocked/latent acid can be prepared. The single masterbatch would then be used to prepare the finished laser-reactive ink.
  • a white masterbatch can also be added to form a white laser imaging ink.
  • the milled masterbatch can be added, by simple mixing, to various technical varnishes either at the ink user (printer) or ink manufacturer.
  • prior laser-sensitive coatings/inks are generally based on individual specific formulations.
  • the systems described are based on a color former/leuco dye and the salt of a carboxylic acid. All these change color when subjected to the relevant lasers.
  • Typical pigments/sy stems used comprise a blocked/latent acid (e.g. carboxylic acid salt) or color developer, leuco dye, and, optionally, an infrared heat absorber (for any laser require an infrared absorbing component, e.g. fiber lasers, YAG lasers, etc.).
  • a blocked/latent acid e.g. carboxylic acid salt
  • leuco dye e.g. carboxylic acid salt
  • an infrared heat absorber for any laser require an infrared absorbing component, e.g. fiber lasers, YAG lasers, etc.
  • leucodye materials are described and listed in various publications, and can be incorporated herein to produce masterbatches. Such systems include those described in patents US 2012/0045624; US 8, 101,545; and US 8, 101,544, but are not only limited to these.
  • the color former can be any suitable color former, including, but not limited to, xanthene leuco dyes, thioxanthene leuco dyes, acridine leuco dyes, phenoxazine leuco dyes, phenazine leuco dyes, merocyanine leuco dyes, thiazine leuco dyes, oxazine leuco dyes, azine leuco dyes, methine leuco dyes, azo leuco dyes, pyrazoline leuco dyes, stilbene leuco dyes, coumarin leuco dyes, triarylmethane leuco dyes, spiropyran leuco dyes, phthalide leuco dyes, fluoran leuco dyes, acylleucoazine dyes, leucoauramine dyes, rhodaminelactam leuco dyes, chromene leuco dyes, chromene le
  • Suitable leuco dyes include, but are not limited to, 2-phenylamino-3-methyl-6- diethylaminofluorane (WinCon- 1 ), 3 -di- «-butylamino-6-methyl-7-phenylaminofluorane (WinCon-2), 2-(2 ' ,4 ' -dimethyl phenylamino-3 -methyl-6-diethylaminofluorane)
  • WinCon- 15 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluorane (WinCon-205), 2-di(phenylmethyl)amine-6'- diethylaminospiro(isobenzofuran)- 1-(3H), 9'-[9H] xanthen-3-one (WinCon-Green), 3-diethylaminobenzofluorane (WinCon-R3), 7- (4- (diethylamino)-2-ethoxyphenyl)-7-(l-ethyl-2-methyl-lH-indol-3-yl)furo(3,4- »)pyridin- 5(7H)-one (WinCon-Blue 63), and 3,3-bis(p-(dimethylamino)phenyl)-6- (dimethylamino)phthalide (Crystal Violet Lactone), all available from Connect
  • the leuco dye is present in the masterbatch concentrate in an amount of from about 10 wt% to about 30 wt%. In certain embodiments, the leuco dye is present in the masterbatch concentrate in an amount of from about 10 wt% to about 20 wt%; or 12 wt% to about 28 wt%; or from about 15 wt% to about 25 wt%; or from about 18 wt% to about 23 wt%; or from about 19 wt% to about 22 wt%.
  • the leuco dye may be present in an amount of from 10 wt5 to about 20 wt%; or from about 10 wt% to about 15 wt%; or from about 15 wt% to about 30 wt%; or from about 20 wt% to about 30 wt%.
  • Blocked/latent acids that can be used in the masterbatch concentrate include, but are not limited to, a carboxylic acid salt, a sulfonic acid salt, a phosphonic acid salt, and mixtures thereof.
  • the blocked/latent acid is a carboxylic acid salt.
  • Suitable carboxylic acid salts include, but are not limited to, tri-n- butylammonium borodisalicylate (this component may be formed in situ from an acid and a suitably basic blocking agent as described in US 5,413,629), phenylacetic acid, /?- tolylacetic acid, mandelic acid, sorbic acid, succinic acid, lactic acid, 4-biphenylacetic acid, and trans-styrylacetic acid.
  • Blocked/latent acids are present in the masterbatch in an amount from about 15 wt% to about 50 wt%.
  • the blocked/latent acid may be present in the masterbatch in an amount from about 18 wt% to about 45 wt%; or from about 20 wt% to about 40 wt%; or from about 25 wt% to about 35 wt%; or from about 20 wt% to about 30 wt%.
  • the blocked/latent acid may be present in an amount of from about 15 wt% to about 30 wt%; from about 20 wt% to about 40 wt%; or from about 40 wt% to about 50 wt%.
  • Suitable infrared radiation/heat (IR) absorbers include, but are not limited to, r- ITO (reduced indium tin oxide); Iriotec 8800 (potassium aluminum silicate) and Iriotec 8825 (mica coated with antimony-doped tin oxide (from Merck); antimony-doped tin oxide pigment (Mark-it available from BASF); mica based metal-oxide layer-substrate pigments (Laserflair pigments available from BASF); copper (II) hydroxyl phosphate (Fabulase 322 available from Budenheim); 3,4-polyethylenedioxythiophene- polystyrenesulfonate; carbon blacks; and a conductive polymer (Baytron P available from HC Starck).
  • r- ITO reduced indium tin oxide
  • Iriotec 8800 potassium aluminum silicate
  • Iriotec 8825 mica coated with antimony-doped tin
  • IR absorbers are present in the masterbatch in an amount of from about lwt% to about 15 wt%. In certain embodiments, the IR absorbers are present in the masterbatch in an amount from about 2 wt% to about 12 wt%; or from about 3 wt% to about 10 wt%; or from about 5 wt% to about 8 wt%.
  • the masterbatch concentrates of the invention contain an
  • alkali/amine compound Suitable alkali/amine compounds include, but are not limited to, monoethanolamine, ammonia, sodium hydroxide, potassium hydroxide, triethanolamine, amine propyl alcohol, and mixtures thereof.
  • the alkali/amine is present in the masterbatch in an amount of from about 1 wt% to about 10 wt%.
  • the alkali/amine may be present in an amount of from about 2 wt% to about 8 wt%; or from about 3 wt% to about 6 wt%; or from about 4 wt% to about 5 wt%.
  • the alkali/amine may be present in an amount of from about 1 wt% to about 4 wt%; from about 2 wt% to about 6 wt%; or from about 5 wt% to about 10 wt%.
  • the systems are considered to be 'transparent'. However the inks may be colored without any deterioration to the laser image.
  • 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
  • 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 colorants be incorporated in relatively small amounts (e.g. ⁇ 10%, more preferably ⁇ 5%).
  • Optical brighteners can also be added to the masterbatch concentrate. This is useful to show where a transparent laser-reactive finished ink has been printed. Suitable optical brighteners include, but are not limited to, Tinopal NFW, Tinopal SFP, and Uvitex OB (all from BASF); and combinations thereof.
  • a dispersing aid to this system can greatly improve the dispersion by reducing the viscosity and improving the flow significantly, which can reduce the milling time. These dispersants and surfactants are well known in printing inks, especially for flexible packaging, offering improved pigment dispersion in liquid organic media.
  • Suitable dispersing aids include, but are not limited to, Disperbyk 190, 199 and 2010 (from Byk); TegoDispers 760W, 755W, and 757W (from Evonik); Orotan 850 and 731 (from Dow); Silcosperse HLD-11 (from Siltech); Edaplan 492 (from Munzing); and combinations thereof. Dispersing aids are typically present in the masterbatch concentrate in an amount of from about 0 wt% to about 5 wt%.
  • the dispersing aid may be present in an amount of from about 1 wt% to about 5 wt%; or from about 1 wt% to about 3 wt%; or from about 1 wt% to about 4 wt%; or from about 2 wt% to about 4 wt%; or from about 3 wt% to about 5 wt%.
  • polyethylene glycols with M w ranging from 200 to 8,000, more preferably between 200 to 2,000 are selected, as these exhibit good properties as dispersing aids in the manufacture of the masterbatch concentrate.
  • M w ranging from 200 to 8,000, more preferably between 200 to 2,000
  • the benefit of these is that they are easier to disperse, there is a greater availability, lower cost, and they are approved by regulatory agencies.
  • Binders such as acrylic resins and polyurethane resins, are typically included in the masterbatch concentrates. Suitable binders include, but are not limited to, Joncryl 671, 674, 678, 682, and 694; Induprint SR10; and NeoRez R650. When present, binders are generally present in an amount of from about 5 wt% to about 30 wt%. In certain embodiments, the binders may be present in the masterbatch in an amount of from about 8 wt% to about 25 wt%; or from about 10 wt% to about 20 wt%; or from about 15 wt% to about 18 wt%. For example, binders may be present in an amount of from about 5 wt% to about 20 wt%; or from about 5 wt% to about 15 wt%; or from about 10 wt% to about 30 wt%.
  • binders are typically included in the masterbatch concentrate, a masterbatch can also be made without a binder. In this case, the dispersing aid/surfactant would be used as the milling medium.
  • a masterbatch concentrate without binder resin typically contains from about 10 wt% to about 30 wt% leuco dye; from about 0 wt% to about 3 wt% defoamer; about 35 wt% to about 70 wt% blocked/latent acid; about 30 wt% to about 50 wt% water; and about 5 wt% to about 20 wt% dispersing aid/surfactant.
  • Adhesion promoters may be used in either the masterbatch or finished inks made from the masterbatch. Suitable adhesion promoters include, but are not limited to: organic titanates, such as Tyzor LA (from Dorf Ketal); chlorinated polyolefins, such as CP310W, 347W, and 349W, all from Eastman; silanes, such as Addid 900 and 906 from Evonik; zinc oxides; and zirconium proponiates; and combinations thereof. When present, adhesion promoters are present in an amount of from about 0 wt% to about 3 wt%, for example from about 1 wt% to about 2 wt%.
  • defoamers include, but are not limited to, Byk 017, Byk 1740, B 094, (from Byk); Fluxair 85 SGR (from
  • Tego Foamex 3062 and Tego Foamex 1488 (from Evonik); and combinations thereof.
  • Defoamers are typically present in an amount of from about 0 wt% to about 3 wt%, for example from about 1 wt% to about 2 wt%.
  • Water is typically present in the masterbatch concentrate in an amount of from about 15 wt% to about 50 wt%.
  • the water may be present in the masterbatch in an amount of from about 18 wt% to about 45 wt%; or from about 20 wt% to about 40 wt%; or from about 25 wt% to about 35 wt%; or from about 20 wt% to about 30 wt%.
  • water may be present in an amount of from about 15 wt% to about 30 wt%; from about 20 wt% to about 40 wt%; or from about 40 wt% to about 50 wt%.
  • the masterbatch concentrate can be prepared with the leuco dye and the blocked/latent acid in a single composition, which can then be mixed with the relevant technical varnish.
  • separate individual masterbatch concentrates are required of the leuco dye and blocked acid, once these are prepared, they can either be added together before mixing with the relevant technical varnish or added separately. That is, separate leuco dye and blocked/acid concentrates can be prepared, these concentrates mixed to produce a final masterbatch concentrate, and the final masterbatch concentrate blended into an ink or technical varnish, with or without colorant.
  • leuco dye concentrate and the blocked/latent acid concentrate can be blended individually into the ink or technical varnish, with or without colorant.
  • a masterbatch concentrate could be created by first forming the blocked acid solution component and subsequently adding and mixing in the leuco dye component and the other materials. Conversely, the leuco dye solution component could be formed and subsequently the blocked acid component and other materials could be added and mixed together to form a finished masterbatch concentrate.
  • a leuco dye masterbatch concentrate typically contains leuco dye, a binder, an alkali/amine, water, a dispersing aid/surfactant, and a defoamer. Typical amounts of each are given below.
  • the leuco dye is generally present in the leuco dye concentrate in an amount of from about 40 wt% to about 70 wt%.
  • the leuco dye may present in an amount of from about 35 wt% to about 65 wt%; or from about 30 wt% to about 60 wt%; or from about 40 wt% to about 50 wt%.
  • the leuco dye may be present in an amount of from about 40 wt% to about 60 wt%; or from about 45 wt% to about 70 wt%; or from about 50 wt% to about 65 wt%.
  • the binder is generally present in the leuco dye concentrate in an amount of from about 5 wt% to about 30 wt%. In certain embodiments, the binder is present in an amount of from about 8 wt% to about 25 wt%; or from about 10 wt% to about 20 wt%; or from about 15 wt% to about 18 wt%. For example, the binder may be present in an amount of from about 5 wt% to about 25 wt%; or from about 5 wt% to about 20 wt%; or from about 5 wt% to about 15 wt%; or from about 10 wt% to about 20 wt%.
  • the alkali/amine is generally present in the leuco dye concentrate in an amount of from about 1 wt% to about 10 wt%. In certain embodiments, the alkali/amine is present in an amount of from about 2 wt% to about 8 wt%; or from about 3 wt% to about 6 wt%; or from about 4 wt% to about 5 wt%. For example, the alkali/amine may be present in an amount of from about 1 wt% to about 8 wt%; or from about 2 wt% to about 10 wt%; or from about 3 wt% to about 6 wt%.
  • the water is generally present in the leuco dye concentrate in an amount of from about 15 wt% to about 40 wt%. In certain embodiments, the water is present in an amount of from about 20 wt% to about 35 wt%; or from about 25 wt% to about 30 wt%; or from about 20 wt% to about 25 wt%. For example, the water may be present in an amount of from about 15 wt% to about 30 wt%; or from about 20 wt% to about 40 wt%; or from about 15 wt% to about 25 wt%.
  • the dispersing aid/ surfactant is generally present in the leuco dye concentrate in an amount of from about 0 wt% to about 5 wt%. In certain embodiments, the dispersing aid/surfactant may be present in an amount of from about 1 wt% to about 4 wt%; or from about 2 wt% to about 3 wt%. For example, the dispersing aid may be present in an amount of from about 1 wt% to about 5 wt%; or from about 2 wt% to about 5 wt%; or from about 2 wt% to about 4 wt%; or from about 3 wt% to about 5 wt%.
  • the defoamer is generally present in the leuco dye concentrate in an amount of from about 0 wt% to about 3 wt%.
  • the defoamer may be present in an amount of from about 1 wt% to about 3 wt%; or from about 1.5 wt% to about 3 wt%; or from about 0.5 wt% to about 2 wt%.
  • a blocked/latent acid concentrate typically contains a blocked/latent acid, a binder, an alkali/amine, water, a dispersing aid/ surfactant, and a defoamer. Typical amounts are given below.
  • the blocked/latent acid is generally present in the blocked/latent acid concentrate in an amount of from about 40 wt% to about 70 wt%. In certain
  • the blocked/latent acid is present in an amount of from about 35 wt% to about 65 wt%; or from about 30 wt% to about 60 wt%; or from about 40 wt% to about 50 wt%.
  • the blocked/latent acid may be present in an amount of from about 40 wt% to about 60 wt%; or from about 45 wt% to about 70 wt%; or from about 50 wt% to about 65 wt%.
  • the binder is generally present in the blocked/latent acid concentrate in an amount of from about 5 wt% to about 30 wt%.
  • the binder may be present in an amount of from about 8 wt% to about 25 wt%; or from about 10 wt% to about 20 wt%; or from about 15 wt% to about 18 wt%.
  • the binder may be present in an amount of from about 5 wt% to about 25 wt%; or from about 5 wt% to about 20 wt%; or from about 5 wt% to about 15 wt%; or from about 10 wt% to about 20 wt%.
  • the alkali/amine is generally present in the blocked/latent acid concentrate in an amount of from about 1 wt% to about 10 wt%.
  • the alkali/amine may be present in an amount of from about 2 wt% to about 8 wt%; or from about 3 wt% to about 6 wt%; or from about 4 wt% to about 5 wt%.
  • the alkali/amine may be present in an amount of from about 1 wt% to about 8 wt%; or from about 2 wt% to about 10 wt%; or from about 3 wt% to about 6 wt%.
  • the water is generally present in the blocked/latent acid concentrate in an amount of from about 15 wt% to about 40 wt%. In certain embodiments, the water is present in an amount of from about 20 wt% to about 35 wt%; or from about 25 wt% to about 30 wt%; or from about 20 wt% to about 25 wt%. For example, the water may be present in an amount of from about 15 wt% to about 30 wt%; or from about 20 wt% to about 40 wt%; or from about 15 wt% to about 25 wt%.
  • the dispersing aid/ surfactant is typically present in the blocked/latent acid concentrate in an amount of from about 0 wt% to about 5 wt%.
  • the dispersing aid/surfactant may be present in an amount of from about 1 wt% to about 4 wt%; or from about 2 wt% to about 3 wt%.
  • the dispersing aid may be present in an amount of from about 1 wt% to about 5 wt%; or from about 2 wt% to about 5 wt%; or from about 2 wt% to about 4 wt%; or from about 3 wt% to about 5 wt%.
  • the defoamer is typically present in the blocked/latent acid concentrate in an amount of from about 0 wt% to about 3 wt%.
  • the defoamer may be present in an amount of from about 1 wt% to about 3 wt%; or from about 1.5 wt% to about 3 wt%; or from about 0.5 wt% to about 2 wt%.
  • leuco dye concentrate and blocked/latent acid concentrates are typically mixed in a ratio of leuco dye: blocked/latent acid of 1 :99 to 99: 1. The ratio is dependent on the end use requirements.
  • the raw materials in the masterbatch concentrate formulation are mixed using a high shear mixer (for example a Silverson).
  • a high shear mixer for example a Silverson
  • the acrylic resin is first mixed with water and the alkali/amine.
  • the other constituents are then added and milled until the particle size is preferably less than 5mm as tested on a Hegman grind gauge.
  • optical brightener UV tracer
  • Optical brightener is added in order to see where and how much ink has been printed, as the ink is primarily clear. This is particularly useful when printing on white paper/board, and clear and white films.
  • a white ink is required, a white masterbatch can be accommodated in the final ink. Certain customers require a white patch in their design. This is typical for a date or batch number which is sometimes situated in a printed box.
  • a typical formulation for a finished white ink may be 50 wt% masterbatch concentrate, 25 wt% technical varnish, and 25 wt% white concentrate. However, it is to be understood that the amounts may be varied according to the required end use.
  • a white concentrate generally contains white pigment, binder, an alkali/amine, water, dispersing aid, and defoamer. The white concentrate may also contain a UV additive.
  • the white pigment is present in an amount of from about 30 wt% to about 50 wt%. In certain embodiments, the white pigment may be present in an amount of from about 35 wt% to about 45 wt%; or from about 30 wt% to about 40 wt%. For example, the white pigment may be present in an amount of from about 30 wt% to about 40 wt%; or from about 35 wt% to about 50 wt%; or from about 40 wt% to about 50 wt%.
  • the binder is generally present in the white concentrate in an amount of from about 10 wt% to about 30 wt%. In certain embodiments, the binder is present in an amount of from about 12 to about 28 wt%; or from about 15 wt% to about 25 wt%; or from about 18 wt % to about 23 wt%; or from about 19 wt% to about 22 wt%. For example, the binder may be present in amount of from about 10 wt% to about 25 wt%; or from about 15 wt% to about 30 wt%; or from about 15 wt% to about 25 wt%.
  • the alkali/amine is generally present in the white concentrate in an amount of from about 0.5 wt% to about 10 wt%. In certain embodiments, the alkali/amine is present in an amount of from about 1 wt% to about 10 wt%; or from about 2 wt% to about 8 wt%; or from about 3 wt% to about 6 wt%; or from about 4 wt% to about 5 wt%.
  • the alkali/amine may be present in an amount of from about 0.5 wt% to about 5 wt%; or from about 1 wt% to about 10 wt%; or from about 1 wt% to about 5 wt%; or from about 0.5 wt% to about 3 wt%; or from about 0.5 wt% to about 1 wt%.
  • the water is generally present in the white concentrate in an amount of from about 30 wt% to about 50 wt%.
  • the water may be present in an amount of from about 35 wt% to about 45 wt%; or from about 30 wt% to about 40 wt%.
  • the water may be present in an amount of from about 30 wt% to about 45 wt%; or from about 30 wt% to about 40 wt%; or from 35 wt% to about to about 50 wt%; or from about 40 wt% to about 50 wt%.
  • the dispersing aid is generally present in the white concentrate in an amount of from about 0 wt% to about 5 wt%.
  • the dispersing aid/surfactant may be present in an amount of from about 1 wt% to about 4 wt%; or from about 2 wt% to about 3 wt%.
  • the dispersing aid may be present in an amount of from about 1 wt% to about 5 wt%; or from about 2 wt% to about 5 wt%; or from about 2 wt% to about 4 wt%; or from about 3 wt% to about 5 wt%.
  • the defoamer is generally present in the white concentrate in an amount of from about 0 wt% to about 3 wt%.
  • the defoamer may be present in an amount of from about 1 wt% to about 3 wt%; or from about 1.5 wt% to about 3 wt%; or from about 0.5 wt% to about 2 wt%.
  • a UV additive is typically present in the white concentrate in an amount of approximately 5 wt%.
  • the UV additive may be present in an amount of from about 1 wt% to about 5 wt%; or from about 1 wt% to about 3 wt%; or from about 2 wt% to about 4 wt%.
  • an IR absorber is preferably added.
  • Reduced indium tin oxide would preferably be added to the formulation when imaging with a fibre laser is used.
  • the masterbatch can be used for all substrates, for specific substrates different masterbatch formulations are recommended. The difference is in the
  • Finished ink formulations can be made by mixing masterbatch concentrate, technical varnish, and water. When a finished colored ink is required, this can be achieved by mixing masterbatch concentrate, technical varnish, colorant, and water. Typical amounts are shown in Tables A to C.
  • Colorants and/or white pigment can be 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. But it would also be possible to incorporate colorants that require milling by adding them and then subjecting the ink to further milling.
  • All inks produced using the masterbatch concentrates of the present invention can be printed using flexographic or gravure printing.
  • the inks can be printed either as a surface print or as a reverse print.
  • the performance properties of the inks are comparable among all of the print processes, and the data shown in the examples can be extrapolated to each of these print processes.
  • Adhesive strength of the printed finished laser-reactive inks to film substrates was tested using a tape adhesion test.
  • Adhesive Tape (Scapa tape - ref: 1112) was stuck on top of a proof print of the ink and was then pulled off. The level of ink removal was evaluated.
  • a laser-reactive masterbatch concentrate was made according to the formulation in Table 1.
  • a leuco dye masterbatch concentrate was prepared according to the formulation in Table 2A below.
  • a blocked/latent acid masterbatch concentrate was prepared according to the formulation in Table 2B below.
  • the concentrates of 2A and 2B were blended to produce the masterbatch concentrate (MB2) according to the formulation given in Table 2C below.
  • Table 2C Blending of 2A and 2B to produce a masterbatch concentrate 2 (MB2)
  • the surfactant was used as the milling medium.
  • a finished white ink was made according to the formulation in Table 4.
  • Table 7 Formulations for technical varnishes 5 to 8 (V5 to V8) Example 6. Performance of finished laser-reactive inks prepared with MBl
  • Substrate film (FS), paper (PS).
  • the finished laser-reactive inks prepared from masterbatch concentrates of the present invention are suitable for flexographic and gravure printing, and can either be printed as a surface print or a reverse print. Suitable print processes are shown below, in Table 10.
  • Substrate film (FS), paper (PS).
  • Print Process flexographic printing (FP), gravure printing (GP), surface printing (SP), and reverse printing (RP).
  • FP flexographic printing
  • GP gravure printing
  • SP surface printing
  • RP reverse printing

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention se rapporte à la formulation d'un concentré de mélange-maître à base d'eau pour la fabrication de compositions de revêtement et d'encre pour substrats d'imagerie laser, en particulier des substrats normalement utilisés dans l'industrie de l'emballage, notamment des substrats souples. Le mélange-maître peut être simplement mélangé avec différents vernis techniques à base d'eau finies réactives au laser avec les propriétés physiques finales telles que requises.
PCT/US2015/046001 2014-09-08 2015-08-20 Encres à base d'eau réactives au laser fabriquées à partir de concentrés de mélange-maître à base d'eau WO2016039960A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3626471A1 (fr) 2018-09-24 2020-03-25 Agfa Nv Compositions pouvant être marquées au laser
EP3626472A1 (fr) 2018-09-24 2020-03-25 Agfa Nv Compositions pouvant être marquées au laser
CN116814091A (zh) * 2023-03-06 2023-09-29 中国民航大学 一种提高染料激光输出的隐色染料溶液及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5611818A (en) * 1991-05-23 1997-03-18 Sandoz Ltd. Dry leuco sulphur dyes in particulate form
US20120045624A1 (en) * 2008-10-27 2012-02-23 Basf Se Aqueous laser-sensitive composition for marking substrates
WO2013192307A1 (fr) * 2012-06-21 2013-12-27 Sun Chemical Corporation Encres à base de solvant réagissant au laser fabriquées à partir de concentrés de mélanges maîtres

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5611818A (en) * 1991-05-23 1997-03-18 Sandoz Ltd. Dry leuco sulphur dyes in particulate form
US20120045624A1 (en) * 2008-10-27 2012-02-23 Basf Se Aqueous laser-sensitive composition for marking substrates
WO2013192307A1 (fr) * 2012-06-21 2013-12-27 Sun Chemical Corporation Encres à base de solvant réagissant au laser fabriquées à partir de concentrés de mélanges maîtres

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3626471A1 (fr) 2018-09-24 2020-03-25 Agfa Nv Compositions pouvant être marquées au laser
EP3626472A1 (fr) 2018-09-24 2020-03-25 Agfa Nv Compositions pouvant être marquées au laser
WO2020064633A1 (fr) 2018-09-24 2020-04-02 Agfa Nv Compositions marquables au laser
WO2020064427A1 (fr) 2018-09-24 2020-04-02 Agfa Nv Compositions marquables au laser
CN116814091A (zh) * 2023-03-06 2023-09-29 中国民航大学 一种提高染料激光输出的隐色染料溶液及其制备方法

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