EP0909242B1 - Feuille de reproduction thermosensible - Google Patents

Feuille de reproduction thermosensible Download PDF

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Publication number
EP0909242B1
EP0909242B1 EP98916894A EP98916894A EP0909242B1 EP 0909242 B1 EP0909242 B1 EP 0909242B1 EP 98916894 A EP98916894 A EP 98916894A EP 98916894 A EP98916894 A EP 98916894A EP 0909242 B1 EP0909242 B1 EP 0909242B1
Authority
EP
European Patent Office
Prior art keywords
weight
heat
protective layer
sensitive recording
parts
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.)
Expired - Lifetime
Application number
EP98916894A
Other languages
German (de)
English (en)
Other versions
EP0909242A1 (fr
Inventor
Wolfgang Wagner
Jutta Berndt
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.)
Mitsubishi HiTech Paper Flensburg GmbH
Original Assignee
Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
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 Mitsubishi HiTech Paper Flensburg GmbH, Stora Spezialpapiere GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Publication of EP0909242A1 publication Critical patent/EP0909242A1/fr
Application granted granted Critical
Publication of EP0909242B1 publication Critical patent/EP0909242B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • B41M5/40—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 A recording sheet according to claim 1 having a substrate, one Containing color formers and color acceptors heat-sensitive recording layer and one formed on the recording layer pigment-containing protective layer that is a mixture from water-soluble and water-insoluble Contains binders.
  • a heat recording sheet of the type mentioned Art is known from DE-A-33 03 843.
  • known recording material water-soluble binder 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 also be an aqueous emulsion of styrene-butadiene latex, styrene-acrylic acid ester or vinyl acetate in an amount of no more than 20% by weight of the total weight of the protective layer contain.
  • Suitable fillers for the Protective layer calcium carbonate, clay, lime, Silicon dioxide, polystyrene and urea-formaldehyde resins called.
  • the Protective layer 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 should.
  • DE-A-39 42 692 relates to the top layer of a heat-sensitive recording paper, the at least one inorganic pigment Calcium carbonate or silica as well as a contains water-soluble binder.
  • Pigment fineness becomes an average Particle diameter of 0.1 ⁇ m or less specified.
  • As a water-soluble binder according to this script also latices, u. a. of type Butadiene-styrene copolymers and butadiene-styrene-acrylic acid derivatives disclosed. hints about Mixing of the individual types of binders however not given. The examples reveal one Pigment / binder ratio of 10: 1.
  • a cover layer is known from US-A-4,682,192 known to protect one on a substrate applied heat sensitive Recording layer serves.
  • the top layer comprises colloidal inorganic silicates selected from colloidal magnesium aluminum silicates as well fluorine-containing colloidal magnesium silicates or Mixtures of these silicates with water-soluble high molecular weight compounds or very heavy water soluble high molecular weight compounds.
  • colloidal inorganic silicates selected from colloidal magnesium aluminum silicates as well fluorine-containing colloidal magnesium silicates or Mixtures of these silicates with water-soluble high molecular weight compounds or very heavy water soluble high molecular weight compounds.
  • self-crosslinking acrylic polymers are disclosed, as colloidal inorganic silicates: bentonite, Attapulgite and dimonite.
  • mixes of Binders are disclosed in the examples, it is the mix self-crosslinking acrylic emulsions, while the Mixing of water soluble with water-insoluble binders not disclosed is.
  • Binders are according to that script Polyvinyl alcohol, modified polyvinyl alcohol and especially with carboxyl groups, Acetoacetyl groups and modified with silicone Polyvinyl alcohol. Mixing this or other binders mentioned in this document with water-insoluble binders, such as. B. Latices is not disclosed in this document.
  • a Pigment / binder ratio in a wide range Range, namely from about 5 to about 1,000 parts by weight / 100 Parts by weight of binder.
  • EP-A-0 344 705 is a top layer known, in the part by weight of binder 0.5 to 3 parts by weight of pigment are present.
  • Binders are u. a. 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 disclosed. The following are precipitated as suitable pigments Calcium carbonate, ground calcium carbonate, Talc, kaolin, silicon dioxide anhydride, Magnesium carbonate, zinc oxide, aluminum oxide and Aluminum hydroxide in addition to organic pigments called. With regard to a possibly to be made Mixture of water soluble and water-insoluble binder, the Weight ratio of these two components only is stated very generally. Are exemplary pigment-containing protective layers described that contain only water-soluble binder.
  • DE-A-40 22 537 discloses one of two layers existing protective layer. It will be water soluble and water insoluble Binder resins for the production of the protective layer disclosed and both inorganic and organic pigments for the second layer of Protective layer specified. Notes on Mixing ratio of water soluble and water-insoluble binders are the Description and claims of this document however not to be inferred.
  • Example 3 only discloses the addition of a pigment, the calculable proportion with 36% by weight pigment (Parts by dry weight, based on Total protective layer).
  • a zinc thiocyanate-antipyrine complex as a color developer DE-A-36 02 986 is essentially one protective layer consisting of water-soluble resins known, being in combination with water-soluble Resin can also be water-insoluble resin.
  • polyvinyl acetate As water-insoluble resins called: 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 based on its opposite to the recording layer Page a the curl of the recording sheet has avoiding coating.
  • An additional one contains the intended pigment-containing protective layer as a binder, a mixture of water-soluble and water-insoluble binder, the Weight ratio of these two components only is stated very generally.
  • An exemplary Mixing with kaolin as an inorganic pigment only discloses water-soluble Binder.
  • the invention wants one heat sensitive recording material for Provide that because of the Protective layer covering protective layer in can be used in a wide variety of applications is.
  • the recording sheets according to the invention have good resistance to mechanical Influences on and are resistant to the influence of water and alcoholic Solvents.
  • Another preferred embodiment provides a portion of the water-insoluble Binder component from 32 to 50 parts by weight before while the water soluble Binder component according to the previously described embodiment is unchanged.
  • water-soluble binder are to be understood as aqueous solutions of polymers, which are used as a solution while under “Water-insoluble binders” such are understood as an aqueous dispersion / latex of polymers.
  • Networking aids are within the scope of the present invention Binding agents not included.
  • the specified protective layers on heat sensitive Recording layers are applied, the directly on the substrate, e.g. B. made of paper are applied, but they can according to one preferred embodiment in such heat-sensitive recording papers to be applied where between Paper substrate and the heat sensitive Recording layer still an intermediate layer is arranged, which contains oil-absorbing pigment.
  • the protective layer contains the one present in the protective layer Binder mixture a styrene-acrylic acid ester copolymer and / or according to another Embodiment containing an acrylamide group Copolymer of styrene / acrylic acid ester.
  • a water-soluble binder component especially polyvinyl alcohol, especially partially saponified polyvinyl alcohol.
  • a crosslinking aid e.g. B. one Melamine-formaldehyde resin or Polyamide epichlorohydrin resin.
  • Alkaline in particular has proven to be a bentonite digested bentonite has been shown to be suitable according to a further embodiment, the Pigment of the protective layer from a mixture of alkaline digested bentonite and precipitated Calcium carbonate exists.
  • It will preferably be a Calcium carbonate is used which is a particle size - Measured according to that described in DIN 66 127 Blaine method - in the range of 0.1 to 1 ⁇ m has, the range of is particularly preferred 0.1 to 0.2 ⁇ m.
  • the felled Calcium carbonate and the bentonite in the ratio of 1: 2 to 1: 3 used.
  • the above Pigments have an oil absorption capacity according to DIN 53 199 of ⁇ 100 ml / 100 g, preferably that is Oil absorption capacity ⁇ 80, very preferred ⁇ 60 ml / 100 g.
  • the protective layer the metal salt of a long chain fatty acid, especially stearic acid contains, in particular a zinc stearate, preferably in an amount ⁇ 20, in particular ⁇ 15 parts by weight, based on the total weight of the protective layer in which Protective layer is included, is preferred.
  • the protective layer is produced under Use of an aqueous coating color, which except the named binders, pigments, Crosslinking aids and fatty acid metal salts usual coating color auxiliaries and additives contains such.
  • a coating color for producing the protective layer according to the invention is produced from: Calcium carbonate (like) 10.0 parts by weight alkaline digested bentonite 23.0 parts by weight Dispersion of styrene acrylic acid ester 23.0 parts by weight Dispersion of a copolymer of acrylonitrile, methacrylamide and acrylic acid ester 17.0 parts by weight Polyvinyl alcohol 11.0 parts by weight Dispersant based on an ammonium polycarboxylate 0.2 parts by weight Zinc stearate dispersion 10.0 parts by weight Melamine formaldehyde resin 1.8 parts by weight Epichlorohydrin resin 2.7 parts by weight
  • the coating color contains a total of 1.3 Parts by weight of optical brighteners, defoamers and Metal salts, with all information on Dry weight fractions otro (oven dry) Respectively.
  • the coating color adjusted to a solids content of 10% by weight, is applied by means of 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: Calcium carbonate (precipitated) more alkaline 8.5 parts by weight Bentonite 19.0 parts by weight Dispersion of styrene acrylic acid ester 22.0 parts by weight Dispersion of a copolymer of acrylonitrile, methacrylamide and acrylic acid ester 23.0 parts by weight Polyvinyl alcohol 9.0 parts by weight Dispersant based on an ammonium polycarboxylate 0.2 parts by weight Zinc stearate dispersion 11.0 parts by weight Melamine formaldehyde resin 1.5 parts by weight Epichlorohydrin resin 2.5 parts by weight
  • the coating color contains a total of 3.3 Parts by weight of optical brighteners, defoamers and metal salts, with all information on Obtain 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: Calcium carbonate (precipitated) more alkaline 8.0 parts by weight Bentonite 23.0 parts by weight Dispersion of styrene acrylic acid ester 34.0 parts by weight Polyvinyl alcohol 15.0 parts by weight Melamine formaldehyde resin 1.6 parts by weight Zinc stearate dispersion 14.0 parts by weight Dispersant based on an ammonium polycarboxylate 0.2 parts by weight Epichlorohydrin resin 2.5 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)

Claims (14)

  1. Feuille d'enregistrement thermosensible comprenant un substrat, une couche d'enregistrement contenant des agents chromogènes et des accepteurs de couleur, et une couche de protection contenant des pigments, formée sur la couche d'enregistrement, laquelle couche de protection contient un mélange de liants solubles dans l'eau et insolubles dans l'eau,
    caractérisée par le fait que
    le mélange de liants est constitué de 32 à 58 parties en poids de liant insoluble dans l'eau sous forme d'une dispersion de polymère, et de 8 à 16 parties en poids d'une solution aqueuse d'un polymère, rapporté à 100 parties en poids formant la couche de protection,
    la couche de protection contient, pour une fraction totale en pigments comprise entre > 20 et 40 parties en poids, de 15 à 30 parties en poids de bentonite, rapportées au poids total de la couche de protection,
    toutes les indications quantitatives se rapportant au poids sec des matériaux.
  2. Feuille d'enregistrement thermosensible selon la revendication 1, caractérisée par le fait que la couche de protection contient comme pigment supplémentaire, un ou plusieurs des pigments suivants : du carbonate de calcium naturel, du carbonate de calcium précipité, du dioxyde de silicium, de l'oxyde d'aluminium et de l'oxyde de titane.
  3. Feuille d'enregistrement thermosensible selon une des revendications 1 ou 2, caractérisée par le fait que la couche de protection contient, pour une partie en poids de mélange de liant, de 0,5 à 0,8 parties en poids de pigment.
  4. Feuille d'enregistrement thermosensible selon une des revendications 1 à 3, caractérisée par le fait que le mélange de liants est constitué de jusqu'à 50 parties en poids d'un liant insoluble dans l'eau, rapportées à 100 parties en poids de la couche de protection globale.
  5. Feuille d'enregistrement thermosensible selon une des revendications 1 à 4, caractérisée par le fait que le mélange de liant contient un copolymère de styrène et d'ester acrylique comme liant insoluble dans l'eau.
  6. Feuille d'enregistrement thermosensible selon une des revendications 1 à 4, caractérisée par le fait que le mélange de liant contient comme liant insoluble dans l'eau un copolymère d'acrylonitrile, de méthacrylamide et d'ester acrylique.
  7. Feuille d'enregistrement thermosensible selon la revendication 6, caractérisée par le fait que le copolymère d'acrylonitrile, de méthacrylamide et d'ester acrylique est auto-réticulant.
  8. Feuille d'enregistrement thermosensible selon l'une des revendications 1 à 7, caractérisée par le fait que le liant hydrosoluble est un poly(alcool vinylique).
  9. Feuille d'enregistrement thermosensible selon l'une des revendications 1 à 8, caractérisée par le fait que la couche de protection contient, rapporté à son poids total, de 1 à 5 parties en poids d'un adjuvant de réticulation.
  10. Feuille d'enregistrement thermosensible selon une des revendications 1 à 9, caractérisée par le fait que la bentonite est une bentonite attaquée par une base.
  11. Feuille d'enregistrement thermosensible selon une des revendications 1 à 10, caractérisée par le fait que le pigment de la couche de protection est un mélange de bentonite et de carbonate de calcium précipité.
  12. Feuille d'enregistrement thermosensible selon la revendication 11, caractérisée par le fait que le rapport carbonate de calcium précipité/bentonite est compris entre 1/2 et 1/3.
  13. Feuille d'enregistrement thermosensible selon l'une des revendications 1 à 12, caractérisée par le fait que le pigment de la couche de protection a une capacité d'absorption d'huile, déterminée selon la norme DIN 53 199, inférieure à 100 ml/100 g.
  14. Feuille d'enregistrement thermosensible selon une des revendications 1 à 13, caractérisée par le fait que la couche de protection contient moins de 20 parties en poids, rapporté à son poids total, d'un sel métallique d'un acide gras supérieur et/ou d'une cire.
EP98916894A 1997-04-02 1998-03-06 Feuille de reproduction thermosensible Expired - Lifetime EP0909242B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19713590A DE19713590C1 (de) 1997-04-02 1997-04-02 Wärmeempfindlicher Aufzeichnungsbogen
DE19713590 1997-04-02
PCT/EP1998/001319 WO1998043824A1 (fr) 1997-04-02 1998-03-06 Feuille de reproduction thermosensible

Publications (2)

Publication Number Publication Date
EP0909242A1 EP0909242A1 (fr) 1999-04-21
EP0909242B1 true EP0909242B1 (fr) 2001-01-03

Family

ID=7825224

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98916894A Expired - Lifetime EP0909242B1 (fr) 1997-04-02 1998-03-06 Feuille de reproduction thermosensible

Country Status (4)

Country Link
EP (1) EP0909242B1 (fr)
DE (2) DE19713590C1 (fr)
ES (1) ES2154495T3 (fr)
WO (1) WO1998043824A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002068207A1 (fr) 2001-02-23 2002-09-06 Mitsubishi Hitec Paper Flensburg Gmbh Materiau d'enregistrement sensible a la chaleur et son utilisation
WO2002074550A1 (fr) 2001-03-16 2002-09-26 Mitsubishi Hitec Paper Flensburg Gmbh Feuille d'enregistrement thermosensible et son utilisation
EP1925459A2 (fr) 2006-11-24 2008-05-28 Mitsubishi Hitec Paper Flensburg GmbH Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authentification

Families Citing this family (5)

* Cited by examiner, † Cited by third party
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
DE20117479U1 (de) * 2001-10-25 2003-03-06 Hummel GmbH & Co., 71106 Magstadt Veredeltes Thermopapier
DE102008007596B4 (de) 2008-02-06 2010-08-05 Kanzan Spezialpapiere Gmbh Verfahren zur Herstellung von thermischen Aufzeichnungsmaterialien, insbesondere von Thermopapieren und Aufzeichnungsmaterial
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)

* Cited by examiner, † Cited by third party
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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002068207A1 (fr) 2001-02-23 2002-09-06 Mitsubishi Hitec Paper Flensburg Gmbh Materiau d'enregistrement sensible a la chaleur et son utilisation
DE10108982A1 (de) * 2001-02-23 2002-09-12 Mitsubishi Hitec Paper Flensbu Wärmeempfindliches Aufzeichnungsmaterial und seine Verwendung
WO2002074550A1 (fr) 2001-03-16 2002-09-26 Mitsubishi Hitec Paper Flensburg Gmbh Feuille d'enregistrement thermosensible et son utilisation
US7049267B2 (en) 2001-03-16 2006-05-23 Mitsubishi Hitec Paper Flensburg Gmbh Heat-sensitive recording sheet and the use thereof
EP1925459A2 (fr) 2006-11-24 2008-05-28 Mitsubishi Hitec Paper Flensburg GmbH Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authentification

Also Published As

Publication number Publication date
EP0909242A1 (fr) 1999-04-21
DE19713590C1 (de) 1998-10-29
WO1998043824A1 (fr) 1998-10-08
ES2154495T3 (es) 2001-04-01
DE59800418D1 (de) 2001-02-08

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