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WO2006129086A1 - Utilisation d'alginates dans l'imagerie laser - Google Patents

Utilisation d'alginates dans l'imagerie laser Download PDF

Info

Publication number
WO2006129086A1
WO2006129086A1 PCT/GB2006/001982 GB2006001982W WO2006129086A1 WO 2006129086 A1 WO2006129086 A1 WO 2006129086A1 GB 2006001982 W GB2006001982 W GB 2006001982W WO 2006129086 A1 WO2006129086 A1 WO 2006129086A1
Authority
WO
WIPO (PCT)
Prior art keywords
laser
alginate
coating
reaction
metal
Prior art date
Application number
PCT/GB2006/001982
Other languages
English (en)
Inventor
Joseph Gaunt
Original Assignee
Datalase Ltd.
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 Datalase Ltd. filed Critical Datalase Ltd.
Priority to EP06744043A priority Critical patent/EP1888348A1/fr
Priority to JP2008514188A priority patent/JP2008542077A/ja
Publication of WO2006129086A1 publication Critical patent/WO2006129086A1/fr

Links

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
    • B41M5/267—Marking of plastic artifacts, e.g. with laser
    • 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

Definitions

  • This invention relates to the use of alginates in laser imaging.
  • Background of the Invention WO02/068205 discloses a material that reacts with a separate metal compound on irradiation with a laser, such that a reaction product of contrasting colour to the reactants is formed. This reaction product is used to form an image on an object, e.g. an edible object.
  • a method for marking an object that comprises an alginate comprises directing a laser beam onto the areas of the object to be marked.
  • the product may be physiologically acceptable, or in other words edible.
  • the invention can be used in the marking of foodstuffs and pharmaceutical products such as tablets and pills. Description of the Invention
  • an object may comprise an alginate moiety and a metal ion.
  • this moiety On irradiation with a laser, this moiety may undergo an internal elimination reaction so as to form a reaction product in situ which is a colourant, dye or chromophore.
  • the elimination reaction is a dehydration reaction (i.e. elimination of water), and usually the elimination reaction results in charring of the functional group. In many instances, where appropriate starting materials are utilised, this process and its products are akin to caramelisation.
  • the object comprises a substrate and, coated thereon, a coating.
  • the moiety is preferably contained within the coating, as are any additional chemical additives.
  • the object or substrate upon which the image or mark is to be made can be a foodstuff, for example confectionary, eggs or fruit, or a pharmaceutical dosage unit such as a tablet or pill. If the object or substrate is intended for consumption or (if pharmaceutical) oral administration, then the moiety and reaction product are edible. Alternatively, the object or substrate can be paper, polymer film, card or board, plastic containers, or any other item capable of bearing a printed image.
  • the reaction product i.e. the colourant, dye or chromophore
  • the reaction product can be of greater colour intensity than the unreacted moiety, and preferably the unreacted moiety is substantially transparent or substantially colourless.
  • Alginates are known as flavouring agents and are approved as food ingredients. They can be readily marked, by means of the invention.
  • the metal ion in a metal alginate is preferably a mono-, di- or tri-valent metal cation.
  • preferred metal ions for use in the third embodiment include NH 4 + , Li + , Na + , K + , Ca 2+ , Mg 2+ , Sr 2+ and Al 3+ , where Na + is particularly preferred.
  • Cu 2+ is generally less preferred, since its salts may be highly coloured.
  • An exception is anhydrous CuSO 4 (which is colourless and non-toxic) which may be a desirable additive; its use may require anhydrous solvent and non-hygroscopic materials.
  • the metal ion may comprise a divalent transition metal cation, preferably from the first row of the Periodic Table.
  • metal ions examples include Mn 2+ , Co 2+ , Fe 2+ , Ni 2+ and Cu 2+ .
  • Mn 2+ and Co 2+ are most preferable as their salts are generally relatively pale in colour, and Fe 2+ is often least preferred since yellow aqueous ferrous ion solutions are sometimes readily darkened by atmospheric oxygen to ferric ion.
  • a preferred embodiment of the invention is based on the ability to improve the intensity of an image or mark by adding a substance comprising a second metal ion to either the object or the coating.
  • the second metal ion may react with functional groups on the moiety that do not undergo the internal elimination reaction, so as to give rise to a larger amount of product and hence a darker colour. It is believed that only some functional groups are capable of undergoing the internal reaction due to an excess of functional groups as opposed to metal ions in the original moiety. The extra metal ions provided by the additional substance therefore allow more functional groups to react.
  • Substances suitable for achieving this enhanced intensity effect include those containing a metal ion that may be the same as the metal ion present in the moiety. Such substances may be inorganic or organic in nature, and may also function as a binder. Methylcellulose salts of second metal ions are preferred. As an example, it has been shown that when sodium alginate is the moiety, sodium methylcellulose can be used to provide an enhanced intensity effect. Other preferred examples include sodium carbonate, sodium hydrogen carbonate and magnesium chloride.
  • objects or substrates to be marked may be pre-wrapped, provided that the wrapping is transparent to the applied energy; in other words, film-wrapped tablets, foodstuffs or other such products can be printed by means of the present invention.
  • Many commonly available wrapping films have been found to be transparent to IR laser energy, including PE, PP, PET, PVC, cellulose and cellulose acetate.
  • the space allocated on an object or substrate, or its wrapping, for the batch code, sell-by date, etc. is usually a small patch printed in a light colour to give good contrast to the (normally) black print.
  • this may be a white or lightly-coloured coating, which is printed with a laser-sensitive ink. On exposure to a threshold dose of laser energy, the ink changes colour to give the image.
  • the object to be marked may be formulated with the additional components that allow marking.
  • these components are formulated and used to coat a substrate.
  • the material or materials used in this invention may be formulated in an aqueous or non-aqueous system, as a solution or dispersion achieved by, for example, ball milling.
  • the materials are formulated in an aqueous system comprising ethanol or a water/ethanol mix.
  • the materials are formulated to include a binder, for example polyvinyl alcohol or polyacrylic acid or cellulosic binder(s).
  • the formulation also includes IR absorbers, which enhance the sensitivity of the coating to the wavelength of light emitted by a particular laser.
  • coating may be done more than once, if desired.
  • a protective layer of for example carnauba wax can be applied by a conventional coating process, provided the coatings are laser-markable through the protective layer, as is the case for carnauba wax.
  • a coating composition may comprise 0.1 to 20% w/v of each component.
  • an image can be formed by the application of heat.
  • heat is applied locally, on irradiation with a laser.
  • Suitable lasers include those emitting at high energy, including Nd-YAG lasers and CO 2 lasers, the latter typically at a wavelength of 10,600 nm.
  • a low-energy laser such as diode laser, typically emitting light at a wavelength in the range of 800-1500 nm.
  • this energy input may be insufficient to cause the desired reaction, and the composition to be irradiated then preferably comprises a suitable absorbent material.
  • IR-absorbent materials many of which are known.
  • any suitable such material may be incorporated, for the purposes of this invention, and can be chosen by one of ordinary skill in the art.
  • the laser can operate in either the dot matrix mode or continuous- wave, scribing mode. In this latter mode, improved quality of print can be obtained. Because of the low output of the laser, highly reliable, approaching maintenance-free, operation is offered.
  • the system can operate in a scribe mode, and coding onto moving lines at up to 200 m/min is possible. For higher speeds than this, dot matrix printing is suitable.
  • the system can be used for coding through packing film, or coding into film laminates.
  • a low-power laser ensures that puncturing does not occur.
  • Example 2 When a solid sample of sodium alginate was irradiated using a Videojet Focus S10 CO 2 laser, the material was marked black.
  • Example 2 92 g ethanol was used to dissolve 8 g hydroxypropylcellulose; 25 g sodium alginate was added and the resulting suspension was ground for 48 hours. When this composition was applied to a lemon, orange, apple, egg or pharmaceutical tablet, a white coating was obtained. Irradiation using a Videojet Focus S10 CO 2 laser resulted in legible dark brown/black markings.
  • Example 3
  • Example 5 A mixture of 67.5 g ethanol, 6 g hydroxypropylcellulose, 1.5 g aerosil 200 (fumed silica), 5 g sodium carbonate and 20 g sodium alginate (Manugel DJX) was prepared. When this composition was applied to a lemon, orange, apple, egg or pharmaceutical tablet, an opaque coating was obtained. Irradiation using a Videojet Focus S10 CO 2 laser resulted in legible, dark brown/black markings at applied fluence less than examples without additional sodium carbonate (e.g. Example 2).
  • Example 5 A mixture of 67.5 g ethanol, 6 g hydroxypropylcellulose, 1.5 g aerosil 200 (fumed silica), 5 g sodium carbonate and 20 g sodium alginate (Manugel DJX) was prepared. When this composition was applied to a lemon, orange, apple, egg or pharmaceutical tablet, an opaque coating was obtained. Irradiation using a Videojet Focus S10 CO 2 laser resulted in legible, dark brown/black markings at applied fluence
  • a mixture of 67.5 g ethanol, 6 g hydroxypropylcellulose, 1.5 g aerosil 200 (fumed silica), 5 g sodium hydrogen carbonate and 20 g of sodium alginate (Manugel DJX) was prepared.
  • this composition was applied to a lemon, orange, apple, egg or pharmaceutical tablet, an opaque coating was obtained.
  • Irradiation using a Videojet Focus S10 CO 2 laser resulted in legible, dark brown/black markings at applied fluence less than examples without additional sodium hydrogen carbonate (e.g. Example 2).
  • Example 6 A mixture of 83.95 g deionised water, 5 g glycerol, 0.05 g sodium dodecyl sulphate, 1 g sodium carbonate and 1O g of sodium alginate (Manucol LB) was prepared. When this composition was applied to a lemon, orange, apple, egg or pharmaceutical tablet, a clear coating was obtained. Irradiation using a Videojet Focus S10 CO 2 laser resulted in legible, dark brown/black markings.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne un procédé pour marquer un objet en dirigeant un rayon laser sur les zones de l'objet à marquer. Ces zones comprennent au moins un alginate.
PCT/GB2006/001982 2005-05-31 2006-05-31 Utilisation d'alginates dans l'imagerie laser WO2006129086A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP06744043A EP1888348A1 (fr) 2005-05-31 2006-05-31 Utilisation d'alginates dans l'imagerie laser
JP2008514188A JP2008542077A (ja) 2005-05-31 2006-05-31 アルギン酸塩を使用したレーザーイメージング方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0511096A GB0511096D0 (en) 2005-05-31 2005-05-31 Laser imaging
GB0511096.0 2005-05-31

Publications (1)

Publication Number Publication Date
WO2006129086A1 true WO2006129086A1 (fr) 2006-12-07

Family

ID=34834918

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/GB2006/001969 WO2006129078A1 (fr) 2005-05-31 2006-05-31 Utilisation de malonates ou d'aldonates dans l'imagerie laser
PCT/GB2006/001982 WO2006129086A1 (fr) 2005-05-31 2006-05-31 Utilisation d'alginates dans l'imagerie laser

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/GB2006/001969 WO2006129078A1 (fr) 2005-05-31 2006-05-31 Utilisation de malonates ou d'aldonates dans l'imagerie laser

Country Status (4)

Country Link
EP (2) EP1888347A1 (fr)
JP (2) JP4827920B2 (fr)
GB (1) GB0511096D0 (fr)
WO (2) WO2006129078A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010026408A3 (fr) * 2008-09-03 2010-04-29 Datalase Ltd. Papier de transfert d'image par laser
WO2010112940A1 (fr) 2009-04-02 2010-10-07 Datalase Ltd. Imagerie laser
WO2011121265A1 (fr) 2010-04-01 2011-10-06 Datalase Ltd. Coloration de plastiques
WO2012114121A2 (fr) 2011-02-24 2012-08-30 Datalase Ltd. Diacétylènes activables de façon réversible et leur utilisation à titre de chromogènes
US8865620B2 (en) 2007-03-15 2014-10-21 Datalase, Ltd. Heat-sensitive coating compositions based on resorcinyl triazine derivatives
US8900414B2 (en) 2007-11-07 2014-12-02 Datalase, Ltd. Fiber products
US9045619B2 (en) 2007-08-22 2015-06-02 Datalase Ltd. Laser-sensitive coating composition
US9047542B2 (en) 2007-11-21 2015-06-02 Quad/Graphics, Inc. System and method for adding data to a printed publication
US9663675B2 (en) 2013-07-30 2017-05-30 Datalase Ltd. Ink for laser imaging
US9982157B2 (en) 2008-10-27 2018-05-29 Datalase Ltd. Aqueous laser-sensitive composition for marking substrates
US10798949B2 (en) 2014-06-27 2020-10-13 Conopco, Inc. Apparatus and method for the decoration of foodstuffs

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0521513D0 (en) 2005-10-21 2005-11-30 Sherwood Technology Ltd Laser marking on substrates
GB0524673D0 (en) * 2005-12-02 2006-01-11 Sherwood Technology Ltd Laser-imageable marking composition
JP5581208B2 (ja) 2007-07-18 2014-08-27 データレース リミテッド レーザー感受性被覆配合物
SE0802123A2 (sv) * 2008-10-09 2010-07-20 Tetra Laval Holdings & Finance Metod, anordning och system för informationsregis trering och informationsomvandling
KR101691898B1 (ko) 2008-10-23 2017-01-02 데이터레이즈 리미티드 열 흡수 첨가제
WO2010049282A1 (fr) 2008-10-27 2010-05-06 Basf Se Composition de revêtement pour le marquage de substrats
ES2356013B2 (es) * 2010-10-28 2011-11-15 Laser Food 2007, S.L. Procedimiento de marcado de frutos.
WO2013023672A1 (fr) 2011-08-12 2013-02-21 Tetra Laval Holdings & Finance S.A. Formulation d'encre innovante
CN103619970A (zh) 2011-08-12 2014-03-05 利乐拉瓦尔集团及财务有限公司 新型标记化合物
JP2014233898A (ja) * 2013-05-31 2014-12-15 京セラドキュメントソリューションズ株式会社 レーザー光の照射による印刷加工品の製造方法及びレーザー印刷装置
JP6204550B2 (ja) * 2016-08-24 2017-09-27 京セラドキュメントソリューションズ株式会社 レーザー光の照射による印刷加工品の製造方法

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US5421870A (en) * 1992-09-30 1995-06-06 Ciba-Geigy Corporation Concentrated aqueous liquid formulations of color formers
US20030186001A1 (en) * 2001-02-28 2003-10-02 Nazir Khan Laser coding
US20030190432A1 (en) * 2000-04-11 2003-10-09 Yasuro Yokota Process for producing information recording material and coating solutions for use therein

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US5422383A (en) * 1993-04-22 1995-06-06 Somar Corporation Laser beam absorbing resin composition, coloring material therefor and laser beam marking method
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Publication number Priority date Publication date Assignee Title
GB1155035A (en) * 1966-06-23 1969-06-11 Agfa Gevaert Nv Thermographic Recording Process
US5421870A (en) * 1992-09-30 1995-06-06 Ciba-Geigy Corporation Concentrated aqueous liquid formulations of color formers
US20030190432A1 (en) * 2000-04-11 2003-10-09 Yasuro Yokota Process for producing information recording material and coating solutions for use therein
US20030186001A1 (en) * 2001-02-28 2003-10-02 Nazir Khan Laser coding

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8865620B2 (en) 2007-03-15 2014-10-21 Datalase, Ltd. Heat-sensitive coating compositions based on resorcinyl triazine derivatives
US9045619B2 (en) 2007-08-22 2015-06-02 Datalase Ltd. Laser-sensitive coating composition
US8900414B2 (en) 2007-11-07 2014-12-02 Datalase, Ltd. Fiber products
US9607249B2 (en) 2007-11-21 2017-03-28 Quad/Graphics, Inc. System and method for adding data to a printed publication
US9047542B2 (en) 2007-11-21 2015-06-02 Quad/Graphics, Inc. System and method for adding data to a printed publication
US8637114B2 (en) 2008-09-03 2014-01-28 Datalase Ltd Laser imageable paper
WO2010026408A3 (fr) * 2008-09-03 2010-04-29 Datalase Ltd. Papier de transfert d'image par laser
US9982157B2 (en) 2008-10-27 2018-05-29 Datalase Ltd. Aqueous laser-sensitive composition for marking substrates
WO2010112940A1 (fr) 2009-04-02 2010-10-07 Datalase Ltd. Imagerie laser
WO2011121265A1 (fr) 2010-04-01 2011-10-06 Datalase Ltd. Coloration de plastiques
WO2012114121A2 (fr) 2011-02-24 2012-08-30 Datalase Ltd. Diacétylènes activables de façon réversible et leur utilisation à titre de chromogènes
US9663675B2 (en) 2013-07-30 2017-05-30 Datalase Ltd. Ink for laser imaging
EP3401372A1 (fr) 2013-07-30 2018-11-14 Datalase Limited Encre pour imagerie laser
US10798949B2 (en) 2014-06-27 2020-10-13 Conopco, Inc. Apparatus and method for the decoration of foodstuffs

Also Published As

Publication number Publication date
WO2006129078A1 (fr) 2006-12-07
EP1888347A1 (fr) 2008-02-20
JP2008542077A (ja) 2008-11-27
JP2008545560A (ja) 2008-12-18
GB0511096D0 (en) 2005-07-06
EP1888348A1 (fr) 2008-02-20
JP4827920B2 (ja) 2011-11-30

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