EP1382459A1 - Thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff - Google Patents
Thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff Download PDFInfo
- Publication number
- EP1382459A1 EP1382459A1 EP02015885A EP02015885A EP1382459A1 EP 1382459 A1 EP1382459 A1 EP 1382459A1 EP 02015885 A EP02015885 A EP 02015885A EP 02015885 A EP02015885 A EP 02015885A EP 1382459 A1 EP1382459 A1 EP 1382459A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- recording sheet
- thermosensitive recording
- foodstuff
- substrate
- 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- Withdrawn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
- B41M5/30—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
-
- 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
- B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
-
- 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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
-
- 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 refers to a thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff.
- the thermosensitive recording sheet comprises a composition that is not detrimental according to the regulations in respect of substances in direct contact with foodstuff.
- thermoprinter For printing a label, for instance, a thermoprinter and a thermosensitive printing sheet is needed.
- the thermosensitive recording material generally comprises a supporting substrate, for example, a paper sheet, synthetic paper sheet, or plastic resin film.
- a thermosensitive image forming layer is formed on the surface of the supporting substrate.
- Said layer generally comprises a dye precursor, such as a leuco basic dye, an acidic color developing agent, such as a phenolic compound, and a binder. Colored images are recorded on such a recording material by reaction of the dye precursor with the color developing agent upon heating.
- a heat-sensitive recording material that is useful, for example, in the manufacture of labels used in connection with the sale of meat, produce, and the like.
- the material comprises a cellulosic or other suitable substrate, a thermally imprintable color producing layer, and a water-insoluble protective layer over the color-producing layer.
- the color-producing layer comprises a colorless or pale leuco dye, an acidic developer for producing an image upon heating of the recording material, a binder and a basic, particulate, neutralizing agent.
- the water-insoluble protective layer affixed to said color-producing layer comprises an organic-acid catalyzed cross-linked resin containing dispersed spacer particles.
- Such a label can be affixed to a package containing meat products. Meat discoloration beneath the label, know as "meat bloom", is avoided due to the sufficient oxygen-permeability of said label.
- the label cannot be affixed directly onto the meat because the ingredients of the thermosensitive layer, i.e. the leuco dye and the acidic developer are detrimental when in contact with meat.
- JP-09150576 discloses a heat-sensitive recording material comprising a substrate provided with a heat-sensitive color developing layer containing a colorless or light colored electron donating precursor and an electron accepting substance capable of reacting with the dye precursor upon heating to cause color development, as the main component.
- a protective layer is applied to said heat-sensitive recording layer.
- a layer containing a styrene/butadiene copolymer and a pigment is applied to the back of the substrate.
- the purpose of the backcoat layer is to provide a heat-sensitive recording material having a water-resistant seal so that it can be affixed as label to a wet surface. Said recording material can be affixed to carcass meat without causing discoloration on said meat. It is not derivable from JP-09150576 that the label has direct contact with the meat and that it is not detrimental when in contact with meat.
- DE-A-19853016 discloses a label for marking meat having a paper substrate of good printability and writability. Said paper substrate has an adhesive backside coating. Coating with the adhesive is carried out such that on each label there is at least one specific area which is coated with the adhesive and at least one specific area that is free of adhesive.
- the object of the alternating coating is to provide a substrate that can be affixed to either wet or dry meat.
- JP-51/24257 discloses a heat-sensitive recording material for the manufacture of copying paper.
- the thermosensitive layer comprises ferric stearate, white pigment, binding resin, gallic acid ester and a reaction inhibitor.
- the coating is applied so that separately a first liquid comprising ferric stearate, white pigment, binding resin and solvent, and a second liquid comprising gallic acid ester, binding resin, reaction inhibitor and solvent, are mixed and then applied to a support and dried to form a heat-sensitive layer. This is because on mixing the first liquid components and the second liquid components together in a ball mill a fogging phenomenon arises. This leads to unexpected reactions.
- reaction inhibitor is used as one of the essential components in the present invention because it inhibits the side reaction of ferric stearate and gallic acid ester in solution.
- the solvents used for preparing the coating composition are generally organic solvents and the gallic acid ester is generally soluble in these solvents.
- the object of the present invention is to provide a thermosensitive recording sheet that is not harmful in direct contact with foodstuff. Especially, the thermosensitive recording layer does not comprise any substances harmful in contact with foodstuff.
- the thermosensitive recording sheet has to be printed using conventional thermal printers.
- thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff comprising a substrate and on one surface of said substrate at least one thermosensitive layer comprising a ferric salt and a water insoluble gallic acid ester.
- a reaction inhibitor is not necessary and therefore absent in said layer.
- thermosensitive recording sheet may comprise a substrate and on one surface of said substrate at least two layers comprising a ferric salt in one layer and a gallic acid ester in the other layer.
- thermosensitive recording layer comprising a ferric salt and a gallic acid ester were applied to a substrate.
- the coating compositon of which the thermosensitive layer is applied to the substrate is preferably a water-based coating composition.
- the gallic acid ester should not be soluble in the fluid phase of the coating composition.
- the gallic acid ester should have a solubility in water at 23°C of less than 5 g/l. It is preferred that the solubility of the gallic acid ester is less than 3,5 g/l, more preferred less than 1,5 g/l and most preferred less than 0,5 g/l in the event that both reactive compounds are present in one layer.
- gallic acid esters can be used having a higher solubility in water.
- the coating weight of the thermosensitive layer is in the range of 5 to 27 g/m 2 , preferably 10 to 22 g/m 2 , and most preferred 15 to 17 g/m 2 .
- thermosensitive recording sheet may comprise at least two layers on the same side of the substrate comprising ferric salt in one layer and gallic acid ester in the other layer.
- the coating weight of each layer is in the range of 3 to 13 g/m 2 , preferably 5 to 11 g/m 2 , and most preferred 7 to 9 g/m 2 .
- an intermediate layer is present between the layer comprising the ferric salt and the layer comprising the gallic acid ester.
- Said intermediate layer may prevent a prereaction of thermosensitive compounds. Additionally, the resistance of the thermosensitive recording sheet to chemical and environmental influence may be improved.
- Said layer can comprise binders such as nitrocellulose, polyurethane, polyvinyl alcohol, vinyl acetates, acrylic latices or mixtures thereof. Additionaly pigments such as silica, alumina or mixtures thereof can be present in said layer.
- the coating weight of said intermediate layer is in the range of 0,3 to 10 g/m 2 , preferably 0,5 to 6 g/m 2 , and most preferred 0,6 to 4 g/m 2 .
- a back-coat may be applied to the side of the substrate opposite to that comprising the layer of ferric salt and gallic acid ester.
- adhesive may be applied to the side of the substrate opposite to that comprising the thermosensitive layer of ferric salt and gallic acid ester, or to the back-coat on the side of the substrate opposite to that comprising the thermosensitive layer of ferric salt and gallic acid ester.
- the adhesive may be applied over the entire area of the side of the substrate opposite to that comprising the thermosensitive layer of ferric salt and gallic acid ester.
- the adhesive may be applied so that there is at least one specific area which is coated with the adhesive and at least one specific area that is free of the adhesive. It is preferred that the area coated with adhesive has an ellipsoidal or circular contour. The purpose of such alternating coating is to provide a thermosensitive recording sheet that can be affixed to either wet or dry meat.
- the adhesive may be any adhesive known not to be detrimental according to the regulations in respect of substances in direct contact with foodstuff, such as polyacrylic latices, derivatives of polyacrylic latices, UV-curable acrylic polymers, derivatives of UV-curable acrylic polymers, acrylic ester polymers, derivatives of acrylic ester polymers or mixtures thereof.
- thermosensitive recording sheet may be present in the thermosensitive recording sheet. It is further preferred that at least one intermediate layer is positioned between the substrate and the layer comprising the ferric salt and/or the gallic acid ester that is a thermal insulating layer known in the prior art.
- the layer may comprise a pigment such as a calcined clay, precipitated calcium carbonate, ground calcium carbonate, titanium dioxide, clay, talc, satin white, gypsum, silica, alumina, plastic pigment, hollow sphere pigment such as Ropaque® (manufactured by Rohm and Haas) or mixtures thereof. Binder, rheology modifier or wet-strength agents may also be present in said layer.
- the coating weight of said intermediate layer is in the range of 1 to 20 g/m 2 , preferably 3 to 10 g/m 2 , and most preferred 5 to 7 g/m 2 .
- a cover layer may be applied to the layer comprising the ferric salt and/or the gallic acid ester.
- the cover layer may comprise a pigment, binder or mixture thereof.
- the coating weight of the cover layer is in the range of 0,1 to 8 g/m 2 , preferably 0,5 to 5 g/m 2 , and most preferred 1 to 3 g/m 2 .
- thermosensitive recording sheet can be applied by processes known to a person skilled in the art such as meyer bar, meyer rod, curtain coating, rotogravure, flexo printing, air brush coating, air knife coating, blade coating, spray coating and combinations thereof.
- the substrate that is the carrier for at least one thermosensitive layer can be paper or board.
- the grammage of the paper or board can vary from 20-400 g/m 2 , preferably 30-200 g/m 2 , more preferred 35-150 g/m 2 , and most preferred 40-90 g/m 2 .
- the fibers used for preparing the paper or board may be of natural or artificial origin.
- a further embodiment of the substrate is to use a non-woven material, such as a valve prepared from fibers of natural or artificial origin.
- the substrate is a synthetic polymeric film, that is a PVC film, a polyethylene film (PE film), a polypropylene film, or a polyester film, like a polyethylene terephthalate film. Said film may be a unidirectional or biaxially oriented film.
- the substrate is paper or board it may have a Cobb value according to DIN 20535 after exposing the substrate for 60 seconds to water of less than 60. It is preferred that the Cobb value is less than 50, more preferred less than 40, even more preferred less than 30 and most preferred less than 20. Additionally, the substrate may be grease resistant.
- the ferric salt used in the thermosensitive recording layer may be a ferric salt of a fatty acid such as ferric stearate (iron (III) stearate).
- the gallic acid ester may be selected from lauryl gallate, stearyl gallate, octyl gallate, cetyl gallate, methyl gallate, ethyl gallate, propyl gallate and mixtures thereof.
- the amount of the ferric salt present in the layer may be in the range of 2 to 10 wt% of the weight of the layer in total. It is preferred that the amount of the ferric salt in the layer is in the range of 4 to 9 , more preferred 5 to 8 , and most preferred 6 to 7 wt% based on the total weight of said layer.
- the amount of the gallic acid ester present in the layer may be in the range of 5 to 20 wt% of the weight of the layer in total. It is preferred that the amount of the gallic acid ester in the layer is in the range of 9 to 17 , more preferred 11 to 15 , and most preferred 12 to 14 wt% based on the total weight of said layer.
- the thermosensitive recording layer may additionally comprise compounds such as binders, pigments, rheology modifiers, dyes, polyurethanes, starches, derivatives of starches, polyvinyl acetates, copolymers of polyvinyl acetates, polyvinyl alcohols, derivatives of polyvinyl alcohols, styrene butadiene latices, acrylic latices, waxes, nitrocellulose or mixtures thereof.
- compounds such as binders, pigments, rheology modifiers, dyes, polyurethanes, starches, derivatives of starches, polyvinyl acetates, copolymers of polyvinyl acetates, polyvinyl alcohols, derivatives of polyvinyl alcohols, styrene butadiene latices, acrylic latices, waxes, nitrocellulose or mixtures thereof.
- thermosensitive recording sheet of the present invention may be affixed directly to the foodstuff.
- Foodstuff in the teaching of the present invention is any foodstuff that is adequate for human consumption. It is preferred that the foodstuff is selected from meat, sausages and similar products, fish, seafood, cheese, vegetables, fruit and baker's ware.
- thermosensitive recording sheet of the present invention is not detrimental can be conducted according to ⁇ 35 of the German "Lebensstoff- und forsussiplace Surprise", EN 1186, EN 13130 and the XXXVI. recommendation for paper and board having contact with foodstuff of the
- All following coating compositions are manufactured using procedures known to a person skilled in the art. Said coating compositions are applied to a substrate by means of meyer rod coating.
- composition of master batch A1 is given in table 1.
- Aerosol OTB was added to a dispersion unit containing a 10 wt-% aqueous solution of Mowiol 4/98 and water. After dissolving the surfactant, lauryl gallate was added and the mixture was dispersed until a homogeneous mixture was obtained.
- the composition of master batch B1 is given in table 2. Aerosol OTB was dispersed in a dispersion unit containing a 10 wt-% aqueous solution of Mowiol 4/98 and water. Iron (III) stearate, and Martinal OL Q 107 were added subsequently. The master batch B1 was dispersed until a homogeneous mixture was obtained.
- master batch A1 comprising the gallic acid ester
- master batch B1 comprising the ferric salt and binder are blended in a reaction vessel and subsequently applied to a substrate.
- the coat weight is in the range of 15 to 17 g/m 2 .
- the composition of the applied coating color and the type of substrate is given in table 3, 4 and 5.
- thermosensitive recording sheets S1 to S16 are suitable to be printed on conventional thermal printers.
- the color of the printing image is violet-black.
- the coating color A2 was manufactured in a dispersing unit by adding nitrocellulose E400, EDS-W(N), zinc stearate and lauryl gallate to acetone. The mixture was dispersed until a homogeneous dispersion was obtained.
- the composition of A2 is given in table 6.
- the coating composition A2 was applied to a PE film.
- the coating weight is 6 g/m 2 .
- the coating colors B2 to B4 were manufactured in a dispersing unit. The mixture was dispersed until a homogeneous dispersion was obtained.
- the composition of B2 to B4 is given in table 7.
- thermosensitive recording sheets are suitable to be printed on conventional thermal printers.
- the color of the printing image is violet-black.
- the coating color A3 was manufactured in a dispersing unit by adding nitrocellulose E400, EDS-W(N), zinc stearate and octyl gallate to acetone. The mixture was dispersed until a homogeneous dispersion was obtained.
- the composition of A3 is given in table 8.
- the coating color Z1 was manufactured in a dispersing unit by adding nitrocellulose E400, EDS-W(N), zinc stearate and octyl gallate to acetone. The mixture was dispersed until a homogeneous dispersion was obtained.
- the composition of Z1 is given in table 9.
- the coating composition A3 is applied to a PE film having a coating weight of 5 g/m 2 .
- the coating composition Z1 is applied to the first coating having as an intermediate coating a coating weight of 2 g/m 2 .
- the coating composition B3 (example 2) is applied to said intermediate coating having a coating weight of 6 g/m 2 .
- the obtained thermosensitive recording sheet is suitable to be printed on conventional thermal printers. The color of the printing image is violet-black.
- the coating composition A3 (example 4) is applied to a PE film having a coating weight of 5 g/m 2 .
- Setalux 6774 polyacrylate dispersion, Akzo Resins
- the coating composition B2 (example 3) is applied to said intermediate coating having a coating weight of 7 g/m 2 .
- the obtained thermosensitive recording sheet is suitable to be printed on conventional thermal printers. The color of the printing image is violet-black.
- thermosensitive recording sheet of the present invention is conforming to ⁇ 35 of the German "Lebensstoff- und forszurent Surprise", EN 1186 and EN 13130.
- the amount of compounds migrating from said recording sheet to foodstuff is admissible for articles having direct contact with foodstuff.
- the amount of volatile isomers, isocyanates, butadiene and remaining solvent in the recording sheet of the present invention is conforming to said regulation.
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Abstract
The present invention refers to a thermosensitive recording sheet for
labeling foodstuff having direct contact with said foodstuff comprising
a substrate and on one surface of said substrate at least one
thermosensitive layer comprising a ferric salt and a gallic acid ester,
no reaction inhibitor being present in said layer.
In a further embodiment the thermosensitive recording sheet may comprise
a substrate and on one surface of said substrate at least two layers
comprising a ferric salt in one layer and a gallic acid ester in the
other layer.
Description
The present invention refers to a thermosensitive recording sheet for
labeling foodstuff having direct contact with said foodstuff. The
thermosensitive recording sheet comprises a composition that is not
detrimental according to the regulations in respect of substances in
direct contact with foodstuff.
In general, the obligation exists to identify foodstuff in the market
place to enable identification of its origin. One possibility is by
labeling said foodstuff.
The obligation to identify foodstuff is very important in the case of
meat. Generally, cattle and pigs, and other meat stock, have an
identification tag in their ear as proof of origin. Said marking allows
to trace back their origin, age, and the name of the breeder. Additional
information can also be included in such identification tag. It is
important that after slaughtering such information is transferred to the
carcass meat. Actually the veterinarian or the butcher puts down the
required information on a label and affixes it immediately onto the
meat. If these rather huge pieces of carcass meat are cut into smaller
pieces for delivery to customers the information on said label is not
transferred to the individual pieces of meat. This is so because the
information has to be copied by hand in a time consuming manner.
The thermal printing technology is known in the prior art as a very
reliable printing technology that can be carried out in environments
where other printing technologies fail. For printing a label, for
instance, a thermoprinter and a thermosensitive printing sheet is
needed.
The thermosensitive recording material generally comprises a supporting
substrate, for example, a paper sheet, synthetic paper sheet, or plastic
resin film. A thermosensitive image forming layer is formed on the
surface of the supporting substrate. Said layer generally comprises a
dye precursor, such as a leuco basic dye, an acidic color developing
agent, such as a phenolic compound, and a binder. Colored images are
recorded on such a recording material by reaction of the dye precursor
with the color developing agent upon heating.
In US-4,591,887 a heat-sensitive recording material is disclosed that is
useful, for example, in the manufacture of labels used in connection
with the sale of meat, produce, and the like. The material comprises a
cellulosic or other suitable substrate, a thermally imprintable color
producing layer, and a water-insoluble protective layer over the color-producing
layer. The color-producing layer comprises a colorless or pale
leuco dye, an acidic developer for producing an image upon heating of
the recording material, a binder and a basic, particulate, neutralizing
agent. The water-insoluble protective layer affixed to said color-producing
layer comprises an organic-acid catalyzed cross-linked resin
containing dispersed spacer particles. Such a label can be affixed to a
package containing meat products. Meat discoloration beneath the label,
know as "meat bloom", is avoided due to the sufficient oxygen-permeability
of said label. The label cannot be affixed directly onto
the meat because the ingredients of the thermosensitive layer, i.e. the
leuco dye and the acidic developer are detrimental when in contact with
meat.
JP-09150576 discloses a heat-sensitive recording material comprising a
substrate provided with a heat-sensitive color developing layer
containing a colorless or light colored electron donating precursor and
an electron accepting substance capable of reacting with the dye
precursor upon heating to cause color development, as the main
component. A protective layer is applied to said heat-sensitive
recording layer. A layer containing a styrene/butadiene copolymer and a
pigment is applied to the back of the substrate. The purpose of the
backcoat layer is to provide a heat-sensitive recording material having
a water-resistant seal so that it can be affixed as label to a wet
surface. Said recording material can be affixed to carcass meat without
causing discoloration on said meat. It is not derivable from JP-09150576
that the label has direct contact with the meat and that it is not
detrimental when in contact with meat.
DE-A-19853016 discloses a label for marking meat having a paper
substrate of good printability and writability. Said paper substrate has
an adhesive backside coating. Coating with the adhesive is carried out
such that on each label there is at least one specific area which is
coated with the adhesive and at least one specific area that is free of
adhesive. The object of the alternating coating is to provide a
substrate that can be affixed to either wet or dry meat.
JP-51/24257 discloses a heat-sensitive recording material for the
manufacture of copying paper. The thermosensitive layer comprises ferric
stearate, white pigment, binding resin, gallic acid ester and a reaction
inhibitor. The coating is applied so that separately a first liquid
comprising ferric stearate, white pigment, binding resin and solvent,
and a second liquid comprising gallic acid ester, binding resin,
reaction inhibitor and solvent, are mixed and then applied to a support
and dried to form a heat-sensitive layer. This is because on mixing the
first liquid components and the second liquid components together in a
ball mill a fogging phenomenon arises. This leads to unexpected
reactions. Additionally a reaction inhibitor is used as one of the
essential components in the present invention because it inhibits the
side reaction of ferric stearate and gallic acid ester in solution. The
solvents used for preparing the coating composition are generally
organic solvents and the gallic acid ester is generally soluble in these
solvents.
The object of the present invention is to provide a thermosensitive
recording sheet that is not harmful in direct contact with foodstuff.
Especially, the thermosensitive recording layer does not comprise any
substances harmful in contact with foodstuff. The thermosensitive
recording sheet has to be printed using conventional thermal printers.
This object is attained by a thermosensitive recording sheet for
labeling foodstuff having direct contact with said foodstuff comprising
a substrate and on one surface of said substrate at least one
thermosensitive layer comprising a ferric salt and a water insoluble
gallic acid ester. A reaction inhibitor is not necessary and therefore
absent in said layer. In a further embodiment the thermosensitive
recording sheet may comprise a substrate and on one surface of said
substrate at least two layers comprising a ferric salt in one layer and
a gallic acid ester in the other layer.
It was unexpectedly found that a reaction inhibitor is not required in a
coating composition and the resulting coating comprising ferric salt and
a water insoluble gallic acid ester. The disadvantageous fogging
phenomenon of the prior art compositions was not observed if a
thermosensitive recording layer comprising a ferric salt and a gallic
acid ester were applied to a substrate. The coating compositon of which
the thermosensitive layer is applied to the substrate is preferably a
water-based coating composition. The gallic acid ester should not be
soluble in the fluid phase of the coating composition. The gallic acid
ester should have a solubility in water at 23°C of less than 5 g/l. It
is preferred that the solubility of the gallic acid ester is less than
3,5 g/l, more preferred less than 1,5 g/l and most preferred less than
0,5 g/l in the event that both reactive compounds are present in one
layer.
In the event that the gallic acid ester and the ferric salt are present
in different layers, alternatively gallic acid esters can be used having
a higher solubility in water.
The coating weight of the thermosensitive layer is in the range of 5 to
27 g/m2, preferably 10 to 22 g/m2, and most preferred 15 to 17 g/m2.
The thermosensitive recording sheet may comprise at least two layers on
the same side of the substrate comprising ferric salt in one layer and
gallic acid ester in the other layer. The coating weight of each layer
is in the range of 3 to 13 g/m2, preferably 5 to 11 g/m2, and most
preferred 7 to 9 g/m2.
In a preferred embodiment an intermediate layer is present between the
layer comprising the ferric salt and the layer comprising the gallic
acid ester. Said intermediate layer may prevent a prereaction of
thermosensitive compounds. Additionally, the resistance of the
thermosensitive recording sheet to chemical and environmental influence
may be improved. Said layer can comprise binders such as nitrocellulose,
polyurethane, polyvinyl alcohol, vinyl acetates, acrylic latices or
mixtures thereof. Additionaly pigments such as silica, alumina or
mixtures thereof can be present in said layer. The coating weight of
said intermediate layer is in the range of 0,3 to 10 g/m2, preferably 0,5
to 6 g/m2, and most preferred 0,6 to 4 g/m2.
In a further embodiment a back-coat may be applied to the side of the
substrate opposite to that comprising the layer of ferric salt and
gallic acid ester.
Additionally, adhesive may be applied to the side of the substrate
opposite to that comprising the thermosensitive layer of ferric salt and
gallic acid ester, or to the back-coat on the side of the substrate
opposite to that comprising the thermosensitive layer of ferric salt and
gallic acid ester. The adhesive may be applied over the entire area of
the side of the substrate opposite to that comprising the
thermosensitive layer of ferric salt and gallic acid ester. In a
preferred embodiment the adhesive may be applied so that there is at
least one specific area which is coated with the adhesive and at least
one specific area that is free of the adhesive. It is preferred that the
area coated with adhesive has an ellipsoidal or circular contour. The
purpose of such alternating coating is to provide a thermosensitive
recording sheet that can be affixed to either wet or dry meat. The
adhesive may be any adhesive known not to be detrimental according to
the regulations in respect of substances in direct contact with
foodstuff, such as polyacrylic latices, derivatives of polyacrylic
latices, UV-curable acrylic polymers, derivatives of UV-curable acrylic
polymers, acrylic ester polymers, derivatives of acrylic ester polymers
or mixtures thereof.
Other layers may be present in the thermosensitive recording sheet. It
is further preferred that at least one intermediate layer is positioned
between the substrate and the layer comprising the ferric salt and/or
the gallic acid ester that is a thermal insulating layer known in the
prior art. Thus, the layer may comprise a pigment such as a calcined
clay, precipitated calcium carbonate, ground calcium carbonate, titanium
dioxide, clay, talc, satin white, gypsum, silica, alumina, plastic
pigment, hollow sphere pigment such as Ropaque® (manufactured by Rohm and
Haas) or mixtures thereof. Binder, rheology modifier or wet-strength
agents may also be present in said layer. The coating weight of said
intermediate layer is in the range of 1 to 20 g/m2, preferably 3 to 10
g/m2, and most preferred 5 to 7 g/m2.
Additionally, a cover layer may be applied to the layer comprising the
ferric salt and/or the gallic acid ester. The cover layer may comprise a
pigment, binder or mixture thereof. The coating weight of the cover
layer is in the range of 0,1 to 8 g/m2, preferably 0,5 to 5 g/m2, and
most preferred 1 to 3 g/m2.
All layers present in the thermosensitive recording sheet can be applied
by processes known to a person skilled in the art such as meyer bar,
meyer rod, curtain coating, rotogravure, flexo printing, air brush
coating, air knife coating, blade coating, spray coating and
combinations thereof.
The substrate that is the carrier for at least one thermosensitive layer
can be paper or board. The grammage of the paper or board can vary from
20-400 g/m2, preferably 30-200 g/m2, more preferred 35-150 g/m2, and most
preferred 40-90 g/m2. The fibers used for preparing the paper or board
may be of natural or artificial origin. A further embodiment of the
substrate is to use a non-woven material, such as a valve prepared from
fibers of natural or artificial origin. It is also possible that the
substrate is a synthetic polymeric film, that is a PVC film, a
polyethylene film (PE film), a polypropylene film, or a polyester film,
like a polyethylene terephthalate film. Said film may be a
unidirectional or biaxially oriented film.
If the substrate is paper or board it may have a Cobb value according to
DIN 20535 after exposing the substrate for 60 seconds to water of less
than 60. It is preferred that the Cobb value is less than 50, more
preferred less than 40, even more preferred less than 30 and most
preferred less than 20. Additionally, the substrate may be grease
resistant.
The ferric salt used in the thermosensitive recording layer may be a
ferric salt of a fatty acid such as ferric stearate (iron (III)
stearate).
The gallic acid ester may be selected from lauryl gallate, stearyl
gallate, octyl gallate, cetyl gallate, methyl gallate, ethyl gallate,
propyl gallate and mixtures thereof.
The amount of the ferric salt present in the layer may be in the range
of 2 to 10 wt% of the weight of the layer in total. It is preferred that
the amount of the ferric salt in the layer is in the range of 4 to 9 ,
more preferred 5 to 8 , and most preferred 6 to 7 wt% based on the total
weight of said layer.
The amount of the gallic acid ester present in the layer may be in the
range of 5 to 20 wt% of the weight of the layer in total. It is
preferred that the amount of the gallic acid ester in the layer is in
the range of 9 to 17 , more preferred 11 to 15 , and most preferred 12
to 14 wt% based on the total weight of said layer. The thermosensitive
recording layer may additionally comprise compounds such as binders,
pigments, rheology modifiers, dyes, polyurethanes, starches, derivatives
of starches, polyvinyl acetates, copolymers of polyvinyl acetates,
polyvinyl alcohols, derivatives of polyvinyl alcohols, styrene butadiene
latices, acrylic latices, waxes, nitrocellulose or mixtures thereof.
The thermosensitive recording sheet of the present invention may be
affixed directly to the foodstuff. Foodstuff in the teaching of the
present invention is any foodstuff that is adequate for human
consumption. It is preferred that the foodstuff is selected from meat,
sausages and similar products, fish, seafood, cheese, vegetables, fruit
and baker's ware.
The assessment that the thermosensitive recording sheet of the present
invention is not detrimental can be conducted according to § 35 of the
German "Lebensmittel- und Bedarfsgegenständegesetz", EN 1186, EN 13130
and the XXXVI. recommendation for paper and board having contact with
foodstuff of the ISEGA (XXXVI Empfehlung - Papiere, Kartons und Pappen
für den Lebensmittelkontakt; 202. Mitteilung: Bundesgesundheitsbild-Gesundheitsforsch-Gesundheitsschutz
5/2001 44:546). Said recommendations
regulate the properties of substances admissible for direct contact with
foodstuff. The thermosensitive recording sheet of the present invention
conforms to said recommendations.
The present invention is illustrated by the following examples.
All following coating compositions are manufactured using procedures
known to a person skilled in the art. Said coating compositions are
applied to a substrate by means of meyer rod coating.
Compound | A1 [wt-%] |
10 wt-% aqueous solution of Mowiol® 4/98 | 42 |
Aerosol OTB | 0,2 |
lauryl gallate | 26,3 |
water | rest |
The composition of master batch A1 is given in table 1. Aerosol OTB was
added to a dispersion unit containing a 10 wt-% aqueous solution of
Mowiol 4/98 and water. After dissolving the surfactant, lauryl gallate
was added and the mixture was dispersed until a homogeneous mixture was
obtained.
Compound | B1 [wt-%] |
10 wt-% aqueous solution of Mowiol® 4/981 | 27,8 |
Aerosol OTB | 0,3 |
iron (III) stearate | 6,8 |
Martinal OL Q 107 | 32,3 |
water | rest |
The composition of master batch B1 is given in table 2. Aerosol OTB was
dispersed in a dispersion unit containing a 10 wt-% aqueous solution of
Mowiol 4/98 and water. Iron (III) stearate, and Martinal OL Q 107 were
added subsequently. The master batch B1 was dispersed until a
homogeneous mixture was obtained.
For manufacture of a thermal sensitive recording sheet master batch A1
comprising the gallic acid ester, master batch B1 comprising the ferric
salt and binder are blended in a reaction vessel and subsequently
applied to a substrate. The coat weight is in the range of 15 to 17 g/m2.
The composition of the applied coating color and the type of substrate
is given in table 3, 4 and 5.
Compound | S1 [pbw] | S2 [pbw] | S3 [pbw] | S4 [pbw] | S5 [pbw] | S6 [pbw] | S7 [pbw] |
Substrate | paper | paper | paper | paper | paper | paper | paper |
A1 | 2 | 1,3 | 1 | 1 | 1 | 1 | 1 |
B1 | 2 | 2 | 2 | 2 | 2 | 1 | |
APU 1012 | 1 | 2 | 1 | 1 | |||
Acronal S728 | 1 | 2 | |||||
Neocryl XK14 | 2 |
Compound | S8 [pbw] | S9 [pbw] | S10 [pbw] | S11 [pbw] | S12 [pbw] | S13 [pbw] | S14 [pbw] |
Substrate | paper | paper | PE film | paper | paper | PE film | PE film |
A1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
B1 | 4 | 4 | 4 | 2 | 1 | 2 | 2 |
APU 1012 | 1,5 | 1 | 3 | 3 | 2 | 2 | |
Setalux 6774 EBL | 4 | ||||||
Neocryl XK14 |
Compound | S15 [pbw] | S16 [pbw] |
Substrate | PE film | PE film |
A1 | 1 | 1 |
B1 | 2 | 2 |
UC 80 | 2 | |
U911 | 2 |
The thermosensitive recording sheets S1 to S16 are suitable to be
printed on conventional thermal printers. The color of the printing
image is violet-black.
The coating color A2 was manufactured in a dispersing unit by adding
nitrocellulose E400, EDS-W(N), zinc stearate and lauryl gallate to
acetone. The mixture was dispersed until a homogeneous dispersion was
obtained. The composition of A2 is given in table 6.
Compound | A2 [wt-/00] |
nitrocellulose E400 | 8,2 |
EDS-W(N) | 2,2 |
zinc stearate | 3,8 |
lauryl gallate | 13,4 |
acetone | 72,4 |
The coating composition A2 was applied to a PE film. The coating weight
is 6 g/m2.
The coating colors B2 to B4 were manufactured in a dispersing unit. The
mixture was dispersed until a homogeneous dispersion was obtained. The
composition of B2 to B4 is given in table 7.
Compound | B2 [wt-%] | B3 [wt-%] | B4 [wt-%] |
Mowital B30T | 4,9 | ||
nitrocellulose E375 | 5,3 | ||
Vinapas UW10 | 6,2 | ||
Martinal OLQ 107 | 18,9 | 18,9 | |
Sipernat P820 | 10 | ||
EDS-W (N) | 5,3 | 5,3 | 2,7 |
zinc stearate | 0,3 | ||
iron (III) stearate | 4,9 | 4,9 | 4,2 |
ethanol | 65,8 | ||
acetone | 65,6 | 76,6 |
Either the coating composition B2, B3 or B4 were applied to the coated
side of the substrate according example 2. The coating weight is 6 g/m2.
The obtained thermosensitive recording sheets are suitable to be printed
on conventional thermal printers. The color of the printing image is
violet-black.
The coating color A3 was manufactured in a dispersing unit by adding
nitrocellulose E400, EDS-W(N), zinc stearate and octyl gallate to
acetone. The mixture was dispersed until a homogeneous dispersion was
obtained. The composition of A3 is given in table 8.
Compound | A3 [wt-%] |
nitrocellulose E400 | 8,2 |
EDS-W(N) | 2,2 |
zinc stearate | 3,8 |
octyl gallate | 13,4 |
acetone | 72,4 |
The coating color Z1 was manufactured in a dispersing unit by adding
nitrocellulose E400, EDS-W(N), zinc stearate and octyl gallate to
acetone. The mixture was dispersed until a homogeneous dispersion was
obtained. The composition of Z1 is given in table 9.
Compound | Z1 [wt-%] |
nitrocellulose E400 | 16,3 |
EDS-W(N) | 3,2 |
zinc stearate | 0,4 |
Sipernat P820 | 14,7 |
acetone | 65,5 |
The coating composition A3 is applied to a PE film having a coating
weight of 5 g/m2. The coating composition Z1 is applied to the first
coating having as an intermediate coating a coating weight of 2 g/m2. The
coating composition B3 (example 2) is applied to said intermediate
coating having a coating weight of 6 g/m2.
The obtained thermosensitive recording sheet is suitable to be printed on conventional thermal printers. The color of the printing image is violet-black.
The obtained thermosensitive recording sheet is suitable to be printed on conventional thermal printers. The color of the printing image is violet-black.
The coating composition A3 (example 4) is applied to a PE film having a
coating weight of 5 g/m2. Setalux 6774 (polyacrylate dispersion, Akzo
Resins) is applied as intermediate coating to the first coating having a
coating weight of 3 g/m2. The coating composition B2 (example 3) is
applied to said intermediate coating having a coating weight of 7 g/m2.
The obtained thermosensitive recording sheet is suitable to be printed
on conventional thermal printers. The color of the printing image is
violet-black.
The thermosensitive recording sheet of the present invention is
conforming to § 35 of the German "Lebensmittel- und Bedarfsgegenständegesetz",
EN 1186 and EN 13130.
The amount of compounds migrating from said recording sheet to foodstuff is admissible for articles having direct contact with foodstuff. Furthermore, the amount of volatile isomers, isocyanates, butadiene and remaining solvent in the recording sheet of the present invention is conforming to said regulation.
The amount of compounds migrating from said recording sheet to foodstuff is admissible for articles having direct contact with foodstuff. Furthermore, the amount of volatile isomers, isocyanates, butadiene and remaining solvent in the recording sheet of the present invention is conforming to said regulation.
Claims (13)
- Thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff comprising a substrate and on one surface of said substrate at least one thermosensitive layer comprising a ferric salt and a water-insoluble gallic acid ester, no reaction inhibitor being present in said layer.
- Thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff comprising a substrate and on one surface of said substrate at least two layers comprising a ferric salt in one layer and a gallic acid ester in the other layer.
- Thermosensitive recording sheet according to claim 2,
characterized in that at least one intermediate layer is present between the layer comprising a ferric salt and the layer comprising the gallic acid ester. - Thermosensitive recording sheet according to any of the preceding claims, characterized in that an adhesive is present on the side of the substrate opposite to the side of the substrate having thereon the layer comprising the ferric salt and/or the gallic acid ester.
- Thermosensitive recording sheet according to any of the preceding claims, characterized in that at least one thermal insulating layer is present between the substrate and the layer comprising the ferric salt and/or the gallic acid ester.
- Thermosensitive recording sheet according to any of the preceding claims, characterized in that a cover layer is present on the coating comprising the ferric salt and/or the gallic acid ester.
- Thermosensitive recording sheet according to any of the preceding claims, characterized in that the ferric salt is ferric stearate.
- Thermosensitive recording sheet according to any of the preceding claims, characterized in that the gallic acid ester is selected from the group consisting of lauryl gallate, stearyl gallate, cetyl gallate, octyl gallate, methyl gallate, ethyl gallate, propyl gallate and mixtures thereof.
- Thermosensitive recording sheet according to any of the preceding claims, characterized in that the amount of the ferric salt in the layer is in the range of 2 to 10 percent by weight based on the total weight of said layer.
- Thermosensitive recording sheet according to any of the preceding claims, characterized in that the amount of the gallic acid ester in the layer is in the range of 5 to 20 percent by weight based on the total weight of said layer.
- Thermosensitive recording sheet according to any of the preceding claims, characterized in that the substrate is selected from paper, board, nonwoven material and synthetic polymeric film.
- Use of the thermosensitive recording sheet according to any of the preceding claims for labeling foodstuff by directly affixing the thermosensitive recording sheet to the foodstuff.
- Use of the thermosensitive recording sheet according to claim 12, characterized in that the foodstuff is selected from meat, sausages and similar products, fish, seafood, cheese, vegetables, fruit and baker's ware.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02015885A EP1382459A1 (en) | 2002-07-17 | 2002-07-17 | Thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02015885A EP1382459A1 (en) | 2002-07-17 | 2002-07-17 | Thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1382459A1 true EP1382459A1 (en) | 2004-01-21 |
Family
ID=29762634
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02015885A Withdrawn EP1382459A1 (en) | 2002-07-17 | 2002-07-17 | Thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff |
Country Status (1)
Country | Link |
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EP (1) | EP1382459A1 (en) |
Cited By (7)
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---|---|---|---|---|
WO2008091858A2 (en) * | 2007-01-23 | 2008-07-31 | President & Fellows Of Harvard College | Non-invasive optical analysis using surface enhanced raman spectroscopy |
US7586601B2 (en) | 2005-06-14 | 2009-09-08 | Ebstein Steven M | Applications of laser-processed substrate for molecular diagnostics |
US7715003B2 (en) | 2005-06-14 | 2010-05-11 | President & Fellows Of Harvard College | Metalized semiconductor substrates for raman spectroscopy |
US7864312B2 (en) | 2007-07-30 | 2011-01-04 | President And Fellows Of Harvard College | Substrates for Raman spectroscopy having discontinuous metal coatings |
EP2325018A1 (en) * | 2009-11-24 | 2011-05-25 | Mondi Uncoated Fine & Kraft Paper GmbH | Thermally sensitive recording material |
US8184284B2 (en) | 2005-06-14 | 2012-05-22 | Ebstein Steven M | Laser-processed substrate for molecular diagnostics |
WO2017081064A1 (en) * | 2015-11-11 | 2017-05-18 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
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US7969570B2 (en) | 2005-06-14 | 2011-06-28 | Ebstein Steven M | Applications of laser-processed substrate for molecular diagnostics |
US8325339B2 (en) | 2005-06-14 | 2012-12-04 | Ebstein Steven M | Applications of laser-processed substrate for molecular diagnostics |
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US7715003B2 (en) | 2005-06-14 | 2010-05-11 | President & Fellows Of Harvard College | Metalized semiconductor substrates for raman spectroscopy |
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CN108290435B (en) * | 2015-11-11 | 2020-03-24 | 奥古斯特科勒纸厂欧洲公司 | Thermosensitive recording material |
US11084308B2 (en) | 2015-11-11 | 2021-08-10 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
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