EP0909242A1 - Wärmeempfindlicher aufzeichnungsbogen - Google Patents
Wärmeempfindlicher aufzeichnungsbogenInfo
- Publication number
- EP0909242A1 EP0909242A1 EP98916894A EP98916894A EP0909242A1 EP 0909242 A1 EP0909242 A1 EP 0909242A1 EP 98916894 A EP98916894 A EP 98916894A EP 98916894 A EP98916894 A EP 98916894A EP 0909242 A1 EP0909242 A1 EP 0909242A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- parts
- heat
- sensitive recording
- protective layer
- 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.)
- Granted
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
- B41M5/40—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
-
- 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
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
-
- 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
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
Definitions
- the invention relates to a heat-sensitive recording sheet having a substrate, a heat-sensitive recording layer containing color formers and color acceptors and a pigment-containing protective layer formed on the recording layer and containing a mixture of water-soluble and water-insoluble binder.
- a heat recording sheet of the type mentioned is known from DE-A-33 03 843.
- water-soluble binder is present in the protective layer in an amount of 30 to 90% by weight, based on the total weight of the protective layer.
- the protective layer can still an aqueous emulsion of styrene-butadiene latex, styrene-acrylate or vinyl acetate in an amount of not more than 20 wt.% Of the total weight of the protective layer "included.
- Suitable fillers for the protective layer of calcium carbonate, clay, lime , Silicon dioxide, polystyrene and urea Called formaldehyde resins.
- the protective layer should contain as a pigment a silicon dioxide powder with an oil absorption of 150% or more and a bulk density of 5 ml / g or more.
- the emulsion of a graft copolymer is disclosed as an effective component of a protective layer for a heat-sensitive recording material, which is obtained by graft copolymerization of methyl (meth) acrylate, a lower hydroxyalkyl (meth) acrylate and (meth) acrylic acid with a polyvinyl alcohol in the presence of water and a neutralizing salt of diisobutylene-maleic anhydride copoly he is produced.
- the admixture of pigments is not disclosed here.
- DE-A-39 42 692 relates to the top layer of a heat-sensitive recording paper which contains at least one inorganic pigment made of calcium carbonate or silica and a water-soluble binder.
- An average particle diameter of 0.1 ⁇ m or less is given for the pigment fineness.
- latices including butadiene-styrene copolymers and butadiene-styrene copolymers, are also used as water-soluble binders.
- Acrylic acid derivatives disclosed are also used as water-soluble binders.
- the examples disclose a pigment / binder ratio of 10: 1.
- the top layer comprises colloidal inorganic silicates selected from colloidal magnesium aluminum silicates and fluorine-containing colloidal magnesium silicates or mixtures of these silicates with water-soluble high-molecular compounds or very poorly water-soluble high-molecular compounds.
- Self-crosslinking acrylic polymers are disclosed as poorly water-soluble high-molecular compounds, and as colloidal inorganic silicates: bentonite, attapulgite and dimonite. Insofar as mixtures of binders are disclosed in the examples, this is a mixture of self-crosslinking acrylic emulsions, while the mixture of water-soluble and water-insoluble binders is not disclosed.
- the ratio between the said silicates and the water-soluble or poorly water-soluble high-molecular compounds should generally be in the range between 1: 0.1 and 1:10, preferably between 1: 1 and 1: 5.
- a protective layer is known for a heat-sensitive recording material, in which acetates and formates of magnesium, calcium and aluminum are added for the accelerated crosslinking reaction of water-soluble binders.
- preferred binders are polyvinyl alcohol, modified polyvinyl alcohol and in particular with carboxyl groups, acetoacetyl groups and silicone-modified polyvinyl alcohol. The mixture of these or other binders mentioned in this document with water-insoluble binders, such as. B. latices is not disclosed in this document.
- For the protective layer is a
- Pigment / binder ratio in a wide range, namely from about 5 to about 1,000 parts by weight / 100 parts by weight of binder.
- a top layer is known from EP-A-0 344 705, in which 0.5 to 3 parts by weight of pigment are present per part by weight of binder.
- Suitable binders for the top layer include polyvinyl alcohol, carboxymethyl cellulose, starch and starch derivatives and copolymer emulsions of styrene-butadiene, vinyl acetate-ethylene, vinyl acetate-vinyl chloride-ethylene and methacrylate-butadiene.
- Precipitated calcium carbonate, ground calcium carbonate, talc, kaolin, silicon dioxide anhydride, magnesium carbonate, zinc oxide, aluminum oxide and aluminum hydroxide in addition to organic pigments are suitable pigments called.
- the weight ratio of these two components being stated only very generally.
- Protective layers containing pig that only contain water-soluble binders are described as examples.
- DE-A-40 22 537 discloses a protective layer consisting of two layers. Although they become water-soluble and water-insoluble
- Binder resins for the production of the protective layer are disclosed and both inorganic and organic pigments are specified for the second layer of the protective layer.
- information on the mixing ratio of water-soluble and water-insoluble binders cannot be found in the description and claims of this document. Only example 3 discloses the addition of a pigment, the calculable fraction being 36% by weight of pigment (dry weight parts, based on the total protective layer).
- a protective layer consisting essentially of water-soluble resins is known, and in combination with water-soluble resin water-insoluble resin can also be present.
- Calcium carbonate, silicon dioxide, zinc oxide, titanium oxide, Aluminum hydroxide, zinc hydroxide, barium sulfate, alumina, talc, surface-treated calcium carbonate, surface-treated silicon dioxide, urea-formaldehyde resin, styrene / methacrylic acid copolymers and polystyrene are disclosed.
- water-insoluble resins polyvinyl acetate, polyurethanes, styrene / butadiene copolymers, polyacrylic acid, polyacrylic acid esters, vinyl chloride / vinyl acetate copolymers, polybutyl methacrylate, ethylene / vinyl acetate copolymers and styrene / butadiene / acrylic derivative copolymers.
- Bentonite as a pigment component of the protective layer is not mentioned.
- EP-A-0 518 552 discloses a heat-sensitive recording material which has a coating on its side opposite the recording layer which prevents the recording sheet from curling.
- An additionally provided pigment-containing protective layer contains as a binder a mixture of water-soluble and water-insoluble binder, the weight ratio of these two components being stated only very generally.
- An exemplary mixture with kaolin as an inorganic pigment only discloses water-soluble binders.
- the object of the invention is therefore to provide a - heat-sensitive recording sheet with a further improved protective layer, which meets the following requirements Fulfills:
- the protective layer should consist of only one layer and be producible in one operation
- the protective layer should be able to be produced using aqueous solutions and polymer dispersions
- the protective layer should have improved resistance to grease, oil, water and alcohol,
- the protective layer of the heat-sensitive recording paper should be easy to print using the : wet offset process
- the protective layer should on the one hand provide good coverage of the heat-sensitive layer arranged beneath it, so that the heat-sensitive recording material conveys a bright appearance and a graying of the surface which is often caused by the recording layer does not appear; on the other hand, the
- the recording layer is not so strongly covered by the protective layer that the recording quality is influenced and the legibility of the typeface produced is impaired
- the heat-sensitive recording sheet is also intended for use as a label, price label, receipt, to be printed by thermal printing, Invoice or ticket may be suitable.
- the invention aims to provide a heat-sensitive recording material which can be used in a wide variety of fields of application due to the cover layer covering the recording layer.
- the inventors have now recognized that the desired goals can be achieved essentially by using a binder mixture in the cover layer which contains water-insoluble predominantly and water-soluble binders to a lesser extent and that - compared to the known protective layers - furthermore the proportion of the binder compared to the pigment proportion is increased. Based on this finding, the invention provides for a heat-sensitive recording sheet with a substrate, a heat-sensitive recording layer containing color formers and color acceptors and a pigment-containing protective layer formed on the recording layer and containing a mixture of water-soluble and water-insoluble binder
- the binder mixture based on 100 parts by weight of the total weight of the protective layer, consists of 32 to 58 parts by weight of water-insoluble and 8 to 16 parts by weight of water-soluble binder, - the protective layer with a total pigment content of> 20 to 40 parts by weight,
- the typeface of the heat-sensitive recording layer is still legible, but on the other hand it also has a sufficiently high smudge resistance of stamp imprints and on the other hand also a good one
- the recording sheets according to the invention have good resistance to mechanical influences and are resistant to the influence of water and alcoholic solvents.
- natural calcium carbonate, in particular in finely ground form, as well as silicon dioxide, aluminum oxide and titanium oxide have also been found.
- the protective layer has also proven expedient for the protective layer to contain 0.5 to 0.8 part by weight of pigment per part by weight of binder mixture.
- a further preferred embodiment provides a proportion of the water-insoluble binder component of 32 to 50 parts by weight, while the water-soluble binder component is unchanged in accordance with the embodiment described above.
- water-soluble binders are understood to mean aqueous solutions of polymers which are used as a solution, while “water-insoluble binders” are to be understood as those which are present as an aqueous dispersion / latex of polymers.
- Crosslinking aids are not included in the binders in the context of the present invention.
- the specified protective layers can be applied to heat-sensitive recording layers which are applied directly to the substrate, e.g. B. are made of paper, but they can according to a preferred embodiment in such heat-sensitive recording papers are used in which an intermediate layer which contains oil-absorbent pigment is arranged between the paper substrate and the heat-sensitive recording layer.
- the binder mixture present in the protective layer contains a styrene-acrylic acid ester copolymer and / or according to a further embodiment a copolymer of styrene / acrylic acid residues containing acrylamide groups.
- a heat-sensitive recording sheet in which the binder mixture contains a copolymer of acrylonitrile, methacrylamide and acrylic ester has proven to be particularly suitable for further improving the resistance to the effects of fats, oils, alcohol and acids.
- a copolymer of this type which is self-crosslinking is very particularly preferred.
- polyvinyl alcohol in particular partially saponified polyvinyl alcohol, has proven to be a water-soluble binder component.
- a crosslinking aid for. B. a melamine-formaldehyde resin or Polyamide epichlorohydrin resin.
- an alkaline digested bentonite has proven to be suitable as bentonite, wherein according to a further embodiment the pigment of the protective layer consists of a mixture of bentonite alkaline digested and precipitated calcium carbonate.
- a calcium carbonate is preferably used which has a particle size - measured according to the Blaine method described in DIN 66 127 - in the range from 0.1 to 1 ⁇ m, the range from 0.1 to 0.2 ⁇ m being particularly preferred.
- the precipitated calcium carbonate and the bentonite are preferably used in a ratio of 1: 2 to 1: 3.
- the pigments given above have an oil absorption capacity according to DIN 53 199 of ⁇ 100 ml / 100 g, preferably the oil absorption capacity is ⁇ 80, very preferred
- the protective layer contains the metal salt of a long chain fatty acid, especially stearic acid, especially a zinc stearate, preferably in an amount
- ⁇ 20, in particular ⁇ 15 parts by weight, based on the total weight of the protective layer, contained in the protective layer is preferred.
- the range from 2.5 to 5 g / m 2 has proven to be a suitable application weight of the protective layer. proven in particular from 3.5 to 4.5 g / m 2 .
- the protective layer is produced using an aqueous coating color which, in addition to the abovementioned binders, pigments, crosslinking aids and fatty acid metal salts, also contains conventional coating color aids and additives, such as, for. B. dispersants, thickeners, defoamers, optical brighteners and metal salts to accelerate the crosslinking of
- Crosslinking aids in an amount of not more than 10 parts by weight, preferably not more than 7 parts by weight, calculated as dry parts by weight, of 100 parts by weight of the protective layer.
- a coating color for producing the protective layer according to the invention is produced from:
- Ammonium polycarboxylates 0.2 parts by weight
- Zinc stearate dispersion 10.0 parts by weight
- the coating color contains a total of 1.3 parts by weight of optical brighteners, defoamers and metal salts, all the information relating to dry weight parts otro (oven-dry).
- the coating color adjusted to a solids content of 10% by weight, is applied with an air brush in an amount of 4 g / m 2 to the recording layer of a commercially available, heat-sensitive recording sheet.
- a coating color for producing the protective layer according to the invention is produced from:
- Acrylic acid ester 23.0 parts by weight Polyvinyl alcohol 9.0 parts by weight
- Ammonium polycarboxylates 0.2 parts by weight
- Zinc stearate dispersion 11.0 parts by weight
- the coating color contains a total of 3.3 parts by weight of optical brighteners, defoamers and metal salts, all the information relating to dry weight fractions.
- the coating color set to a solids content of 12% by weight is applied in an amount of 3.8 g / m 2 to the recording layer of a commercially available heat-sensitive recording sheet.
- a coating color for producing the protective layer according to the invention is produced from:
- Zinc stearate dispersion 14.0 parts by weight
- the coating color is also added:
- optical brighteners defoamers, thickening aids and a metal salt to accelerate the crosslinking in a total amount of 1.7 parts by weight.
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19713590 | 1997-04-02 | ||
DE19713590A DE19713590C1 (de) | 1997-04-02 | 1997-04-02 | Wärmeempfindlicher Aufzeichnungsbogen |
PCT/EP1998/001319 WO1998043824A1 (de) | 1997-04-02 | 1998-03-06 | Wärmeempfindlicher aufzeichnungsbogen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0909242A1 true EP0909242A1 (de) | 1999-04-21 |
EP0909242B1 EP0909242B1 (de) | 2001-01-03 |
Family
ID=7825224
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98916894A Expired - Lifetime EP0909242B1 (de) | 1997-04-02 | 1998-03-06 | Wärmeempfindlicher aufzeichnungsbogen |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0909242B1 (de) |
DE (2) | DE19713590C1 (de) |
ES (1) | ES2154495T3 (de) |
WO (1) | WO1998043824A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7008902B2 (en) | 2001-02-23 | 2006-03-07 | Mitsubishi Hitec Paper Flensburg Gmbh | Thermosensitive recording material and use thereof |
DE102008007596A1 (de) | 2008-02-06 | 2009-08-20 | Kanzan Spezialpapiere Gmbh | Verfahren zur Herstellung von thermischen Aufzeichnungsmaterialien, insbesondere von Thermopapieren |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19933139A1 (de) * | 1999-07-19 | 2001-01-25 | Agfa Gevaert Ag | Stabile Pigmentdispersion und damit hergestelltes strahlungsempfindliches Aufzeichnungsmaterial |
DE10051294C1 (de) * | 2000-10-16 | 2002-04-18 | Mitsubishi Hitec Paper Flensbu | Wärmeempfindlicher Aufzeichnungsbogen und seine Verwendung |
DE10113286A1 (de) | 2001-03-16 | 2002-10-02 | Mitsubishi Hitec Paper Flensbu | Wärmeempfindlicher Aufzeichnungsbogen und seine Verwendung |
DE20117479U1 (de) * | 2001-10-25 | 2003-03-06 | Hummel Gmbh & Co | Veredeltes Thermopapier |
DE102006056003B4 (de) | 2006-11-24 | 2008-08-14 | Mitsubishi Hitec Paper Flensburg Gmbh | Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal |
DE102018102177A1 (de) | 2018-01-31 | 2019-08-01 | Mitsubishi Hitec Paper Europe Gmbh | Beschichtungszusammensetzung, wärmeempfindliche Aufzeichnungsschicht, wärmeempfindliches Aufzeichnungsmaterial sowie entsprechende Verwendungen und Verfahren |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4682192A (en) * | 1984-07-31 | 1987-07-21 | Nippon Kayaku Kabushiki Kaisha | Heat-sensitive recording sheet |
JPH0667671B2 (ja) * | 1985-02-01 | 1994-08-31 | 株式会社リコー | 感熱記録材料 |
JPH01301368A (ja) * | 1988-05-31 | 1989-12-05 | Kanzaki Paper Mfg Co Ltd | 感熱記録体 |
JPH04364983A (ja) * | 1991-06-12 | 1992-12-17 | Oji Paper Co Ltd | 感熱記録体 |
DE19542598A1 (de) * | 1995-11-15 | 1997-05-22 | Feldmuehle Ag Stora | Wärmeempfindlicher Aufzeichnungsbogen |
-
1997
- 1997-04-02 DE DE19713590A patent/DE19713590C1/de not_active Expired - Fee Related
-
1998
- 1998-03-06 WO PCT/EP1998/001319 patent/WO1998043824A1/de active IP Right Grant
- 1998-03-06 DE DE59800418T patent/DE59800418D1/de not_active Expired - Lifetime
- 1998-03-06 ES ES98916894T patent/ES2154495T3/es not_active Expired - Lifetime
- 1998-03-06 EP EP98916894A patent/EP0909242B1/de not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9843824A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7008902B2 (en) | 2001-02-23 | 2006-03-07 | Mitsubishi Hitec Paper Flensburg Gmbh | Thermosensitive recording material and use thereof |
DE102008007596A1 (de) | 2008-02-06 | 2009-08-20 | Kanzan Spezialpapiere Gmbh | Verfahren zur Herstellung von thermischen Aufzeichnungsmaterialien, insbesondere von Thermopapieren |
Also Published As
Publication number | Publication date |
---|---|
WO1998043824A1 (de) | 1998-10-08 |
DE59800418D1 (de) | 2001-02-08 |
DE19713590C1 (de) | 1998-10-29 |
ES2154495T3 (es) | 2001-04-01 |
EP0909242B1 (de) | 2001-01-03 |
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