EP1888348A1 - Utilisation d'alginates dans l'imagerie laser - Google Patents
Utilisation d'alginates dans l'imagerie laserInfo
- Publication number
- EP1888348A1 EP1888348A1 EP06744043A EP06744043A EP1888348A1 EP 1888348 A1 EP1888348 A1 EP 1888348A1 EP 06744043 A EP06744043 A EP 06744043A EP 06744043 A EP06744043 A EP 06744043A EP 1888348 A1 EP1888348 A1 EP 1888348A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- laser
- alginate
- coating
- reaction
- metal
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0511096A GB0511096D0 (en) | 2005-05-31 | 2005-05-31 | Laser imaging |
| PCT/GB2006/001982 WO2006129086A1 (fr) | 2005-05-31 | 2006-05-31 | Utilisation d'alginates dans l'imagerie laser |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1888348A1 true EP1888348A1 (fr) | 2008-02-20 |
Family
ID=34834918
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06744032A Withdrawn EP1888347A1 (fr) | 2005-05-31 | 2006-05-31 | Utilisation de malonates ou d'aldonates dans l'imagerie laser |
| EP06744043A Withdrawn EP1888348A1 (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 |
|---|---|---|---|
| EP06744032A Withdrawn EP1888347A1 (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) | WO2006129086A1 (fr) |
Families Citing this family (22)
| 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 |
| US8865620B2 (en) | 2007-03-15 | 2014-10-21 | Datalase, Ltd. | Heat-sensitive coating compositions based on resorcinyl triazine derivatives |
| EP2167323B1 (fr) | 2007-07-18 | 2018-04-04 | DataLase Ltd | Formulation de revêtement sensible au laser |
| US9045619B2 (en) | 2007-08-22 | 2015-06-02 | Datalase Ltd. | Laser-sensitive coating composition |
| EP2207933B1 (fr) | 2007-11-07 | 2014-05-21 | DataLase Ltd | Nouveaux produits fibreux |
| US8120811B2 (en) | 2007-11-21 | 2012-02-21 | Quad/Graphics, Inc. | System and method for adding data to a printed publication |
| CN102144064B (zh) * | 2008-09-03 | 2014-09-17 | 数据激光有限公司 | 激光成像纸 |
| SE0802123A2 (sv) * | 2008-10-09 | 2010-07-20 | Tetra Laval Holdings & Finance | Metod, anordning och system för informationsregis trering och informationsomvandling |
| JP5460720B2 (ja) | 2008-10-23 | 2014-04-02 | データレース リミテッド | 熱吸収添加剤 |
| US9267042B2 (en) | 2008-10-27 | 2016-02-23 | Datalase Ltd. | Coating composition for marking substrates |
| WO2010049281A1 (fr) | 2008-10-27 | 2010-05-06 | Basf Se | Composition aqueuse sensible au laser pour marquer des substrats |
| JP5671521B2 (ja) | 2009-04-02 | 2015-02-18 | データレース リミテッドDatalase Ltd. | レーザーイメージング |
| EP2553528B1 (fr) | 2010-04-01 | 2015-04-22 | Datalase Limited | Coloration de plastiques |
| ES2356013B2 (es) * | 2010-10-28 | 2011-11-15 | Laser Food 2007, S.L. | Procedimiento de marcado de frutos. |
| GB201103178D0 (en) | 2011-02-24 | 2011-04-06 | Datalase Ltd | Reversibly activatable diacetylenes |
| BR112013032524A2 (pt) | 2011-08-12 | 2017-03-01 | Tetra Laval Holding & Finance S A | uso de complexo de peroxo de molibdênio, composição, substrato, e, processo de marcação de um substrato |
| BR112013032553A2 (pt) | 2011-08-12 | 2017-01-17 | Tetra Laval Holdings & Finance | composto, composição, substrato, e, processos de marcação e de obtenção de um composto |
| 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 |
| GB201313593D0 (en) | 2013-07-30 | 2013-09-11 | Datalase Ltd | Ink for Laser Imaging |
| EP3160250B1 (fr) | 2014-06-27 | 2018-01-10 | Unilever PLC, a company registered in England and Wales under company no. 41424 of | Appareil et procédé pour la décoration de produits alimentaires |
| 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 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6608712A (fr) * | 1966-06-23 | 1966-11-25 | ||
| JPS54149617A (en) * | 1978-05-16 | 1979-11-24 | Tomoegawa Paper Co Ltd | Light heat recording material |
| JPS59120492A (ja) * | 1982-12-27 | 1984-07-12 | Pilot Ink Co Ltd | 可逆性感熱記録材料 |
| JP2834540B2 (ja) * | 1990-05-24 | 1998-12-09 | 住友ベークライト株式会社 | レーザー印字に適したエポキシ樹脂組成物 |
| DE59307983D1 (de) * | 1992-09-30 | 1998-02-19 | Ciba Geigy Ag | Konzentrierte, wässrige Flüssigformulierungen von Farbbildnern |
| US5422383A (en) * | 1993-04-22 | 1995-06-06 | Somar Corporation | Laser beam absorbing resin composition, coloring material therefor and laser beam marking method |
| JP3389073B2 (ja) * | 1997-09-18 | 2003-03-24 | 住友ベークライト株式会社 | レーザー印字用エポキシ樹脂組成物 |
| US6210472B1 (en) * | 1999-04-08 | 2001-04-03 | Marconi Data Systems Inc. | Transparent coating for laser marking |
| US6746718B2 (en) * | 2000-04-11 | 2004-06-08 | Mitsubishi Paper Mills Ltd. | Process of curtain for producing an information recording material |
| JP2004524188A (ja) * | 2001-02-28 | 2004-08-12 | シャーウッド・テクノロジー・リミテッド | レーザ印字 |
| US6846614B2 (en) * | 2002-02-04 | 2005-01-25 | Kodak Polychrome Graphics Llc | On-press developable IR sensitive printing plates |
-
2005
- 2005-05-31 GB GB0511096A patent/GB0511096D0/en not_active Ceased
-
2006
- 2006-05-31 EP EP06744032A patent/EP1888347A1/fr not_active Withdrawn
- 2006-05-31 EP EP06744043A patent/EP1888348A1/fr not_active Withdrawn
- 2006-05-31 JP JP2008514185A patent/JP4827920B2/ja active Active
- 2006-05-31 WO PCT/GB2006/001982 patent/WO2006129086A1/fr not_active Ceased
- 2006-05-31 JP JP2008514188A patent/JP2008542077A/ja not_active Withdrawn
- 2006-05-31 WO PCT/GB2006/001969 patent/WO2006129078A1/fr not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2006129086A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008545560A (ja) | 2008-12-18 |
| WO2006129086A1 (fr) | 2006-12-07 |
| EP1888347A1 (fr) | 2008-02-20 |
| GB0511096D0 (en) | 2005-07-06 |
| JP2008542077A (ja) | 2008-11-27 |
| JP4827920B2 (ja) | 2011-11-30 |
| WO2006129078A1 (fr) | 2006-12-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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| 17P | Request for examination filed |
Effective date: 20071221 |
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| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
| DAX | Request for extension of the european patent (deleted) | ||
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
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| 18W | Application withdrawn |
Effective date: 20090427 |