EP1888348A1 - The use of alginates in laser imaging - Google Patents

The use of alginates in laser imaging

Info

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Withdrawn
Application number
EP06744043A
Other languages
German (de)
French (fr)
Inventor
Joseph Gaunt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DataLase Ltd
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
Publication of EP1888348A1 publication Critical patent/EP1888348A1/en
Withdrawn legal-status Critical Current

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

A method for marking an object by directing a laser beam onto the areas of the object to be marked, wherein those areas at least comprise an alginate.

Description

THE USE OF ALGINATES IN LASER IMAGING Field of the Invention
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.
The reaction of WO02/068205 allows printing to be conducted with low maintenance costs, and avoids the need for solvents, emissions, debris and extraction. It allows on-line, non-contact coding, with reduced down-time. There is no need for the purchase of stocking of materials associated with printing. Adhesion problems and smudging can be avoided, and it is possible to code in damp conditions. Summary of the Invention
The present invention is based on the ability of particular polysaccharide moieties to undergo internal reactions on irradiation with a laser, such that a reaction product of contrasting colour is formed. According to the present invention, a method for marking an object that comprises an alginate, comprises directing a laser beam onto the areas of the object to be marked.
Depending on the nature of the components that are used, and the nature of the resulting reaction product, the product may be physiologically acceptable, or in other words edible. This means that the invention can be used in the marking of foodstuffs and pharmaceutical products such as tablets and pills. Description of the Invention
In accordance with the invention, an object may comprise an alginate moiety and a metal ion. 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. Generally, 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.
Usually the object comprises a substrate and, coated thereon, a coating. In this instance, 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) 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. Examples of preferred metal ions for use in the third embodiment include NH4 +, Li+, Na+, K+, Ca2+, Mg2+, Sr2+ and Al3+, where Na+ is particularly preferred. Cu2+ is generally less preferred, since its salts may be highly coloured. An exception is anhydrous CuSO4 (which is colourless and non-toxic) which may be a desirable additive; its use may require anhydrous solvent and non-hygroscopic materials. Alternatively, the metal ion may comprise a divalent transition metal cation, preferably from the first row of the Periodic Table. Examples of particularly preferable metal ions include Mn2+, Co2+, Fe2+, Ni2+ and Cu2+. Of these, Mn2+ and Co2+ are most preferable as their salts are generally relatively pale in colour, and Fe2+ 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.
Based on the above information, other suitable functional groups, metal ions and intensity enhancers will be known, or can be readily chosen or tested for their suitability, by those of ordinary skill in the art.
It is within the scope of the invention that 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. Using the system of the invention, 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. In a preferred embodiment, these components are formulated and used to coat a substrate. For application to the 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. Typically, the materials are formulated in an aqueous system comprising ethanol or a water/ethanol mix. Preferably, the materials are formulated to include a binder, for example polyvinyl alcohol or polyacrylic acid or cellulosic binder(s). Optionally the formulation also includes IR absorbers, which enhance the sensitivity of the coating to the wavelength of light emitted by a particular laser.
Since it may determine the clarity of the marking that can be achieved, coating may be done more than once, if desired. Further, on top of the coating, 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.
The amounts of the components that are used in the invention can readily be chosen by one of ordinary skill, having regard to the intended use. For example, a coating composition may comprise 0.1 to 20% w/v of each component.
As indicated above, an image can be formed by the application of heat. Preferably, heat is applied locally, on irradiation with a laser. Suitable lasers include those emitting at high energy, including Nd-YAG lasers and CO2 lasers, the latter typically at a wavelength of 10,600 nm. In many cases, it may be desirable to use a low-energy laser, such as diode laser, typically emitting light at a wavelength in the range of 800-1500 nm. In certain circumstances, this energy input may be insufficient to cause the desired reaction, and the composition to be irradiated then preferably comprises a suitable absorbent material.
Further additives that may be used are thus IR-absorbent materials, many of which are known. In general terms, 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. The following Examples illustrate the invention.
Example 1
When a solid sample of sodium alginate was irradiated using a Videojet Focus S10 CO2 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 CO2 laser resulted in legible dark brown/black markings. Example 3
A mixture of 50 g ethanol and 50 g water was used to dissolve 4.5 g hydroxypropylcellulose; 25 g sodium alginate was added and the resulting mixtures was stirred vigorously for 20 minutes. 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 CO2 laser resulted in legible dark brown/black markings. Example 4
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 CO2 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 hydrogen carbonate and 20 g of 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 CO2 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 CO2 laser resulted in legible, dark brown/black markings.

Claims

1. A method for marking an object by directing a laser beam onto the areas of the object to be marked, wherein those areas at least comprise an alginate.
2. A method according to claim 1, wherein the alginate is a metal alginate.
3. A method according to claim 2, wherein the metal is sodium.
4. A method according to any preceding claim, wherein the object is a pharmaceutical or foodstuff, and the reaction product is physiologically acceptable.
5. A method according to any preceding claim, wherein the object comprises a substrate and, coated thereon, a coating comprising the alginate.
6. A method according to claim 5, wherein the substrate is a tablet or pill and the coating comprises a pharmaceutical agent.
7. A method according to any preceding claim, wherein the object is wrapped or covered in a filmic material.
8. A method according to any preceding claim, wherein the object or any coating further comprises a substance comprising a second metal ion that reacts with any functional group that does not undergo reaction on laser- irradiation.
9. A method according to claim 8, wherein the amount of said substance is sufficient to enable substantially all functional groups to undergo the elimination reaction.
EP06744043A 2005-05-31 2006-05-31 The use of alginates in laser imaging Withdrawn EP1888348A1 (en)

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 (en) 2005-05-31 2006-05-31 The use of alginates in laser imaging

Publications (1)

Publication Number Publication Date
EP1888348A1 true EP1888348A1 (en) 2008-02-20

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EP06744043A Withdrawn EP1888348A1 (en) 2005-05-31 2006-05-31 The use of alginates in laser imaging
EP06744032A Withdrawn EP1888347A1 (en) 2005-05-31 2006-05-31 The use of malonates or aldonates in laser imaging

Family Applications After (1)

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EP06744032A Withdrawn EP1888347A1 (en) 2005-05-31 2006-05-31 The use of malonates or aldonates in laser imaging

Country Status (4)

Country Link
EP (2) EP1888348A1 (en)
JP (2) JP2008542077A (en)
GB (1) GB0511096D0 (en)
WO (2) WO2006129078A1 (en)

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Also Published As

Publication number Publication date
JP4827920B2 (en) 2011-11-30
WO2006129086A1 (en) 2006-12-07
EP1888347A1 (en) 2008-02-20
WO2006129078A1 (en) 2006-12-07
JP2008542077A (en) 2008-11-27
GB0511096D0 (en) 2005-07-06
JP2008545560A (en) 2008-12-18

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