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EP2329958B1 - Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de face arrière - Google Patents

Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de face arrière Download PDF

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Publication number
EP2329958B1
EP2329958B1 EP20090177677 EP09177677A EP2329958B1 EP 2329958 B1 EP2329958 B1 EP 2329958B1 EP 20090177677 EP20090177677 EP 20090177677 EP 09177677 A EP09177677 A EP 09177677A EP 2329958 B1 EP2329958 B1 EP 2329958B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
side coating
material according
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.)
Active
Application number
EP20090177677
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German (de)
English (en)
Other versions
EP2329958A1 (fr
Inventor
Karsten Lerius
Gerhard Dr. Stork
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 HiTec Paper Europe GmbH
Original Assignee
Mitsubishi HiTec Paper Europe 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 HiTec Paper Europe GmbH filed Critical Mitsubishi HiTec Paper Europe GmbH
Priority to EP20090177677 priority Critical patent/EP2329958B1/fr
Publication of EP2329958A1 publication Critical patent/EP2329958A1/fr
Application granted granted Critical
Publication of EP2329958B1 publication Critical patent/EP2329958B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • 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
    • 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
    • B41M2205/36—Backcoats; Back layers

Definitions

  • the invention relates to a heat-sensitive recording material having a substrate which carries on its first side at least one heat-sensitive recording layer, which in turn has at least one dye precursor and at least one color acceptor, which react color-forming with one another under the action of heat.
  • the substrate carries on its second side opposite the first side a backside coating.
  • a heat-sensitive recording material of the type specified above is known from DE-C-38 36 660 known.
  • the backside coating can here be formed from water-soluble high polymers, such as starch, gelatin, styrene-maleic anhydride copolymer hydrolysates or polyvinyl alcohol, and from water-insoluble polymers, such as latexes. The polymers are used alone or as a mixture.
  • the known backside coating is to prevent that when using the known recording material as a label, in particular plasticizers which are present on a provided with the label sheet can penetrate from the back of the recording layer and thus a weakening or deletion of a possible Effect typeface.
  • the barrier layer comprises substantially water-soluble polymer materials such as polyvinyl alcohol, various cellulose ethers, starch, gelatin, casein, and polyvinylpyrrolidone, as well as water-dispersed resins such as polystyrene emulsions.
  • the function of the barrier layer is to protect against materials such as oils and plasticizers, which are known to cause the image and / or decolorization of the images developed in the recording layer.
  • the backside coating of the known recording material comprises a mixture containing starch, an acrylate copolymer comprising no styrene or vinyl acetate components having a film-forming temperature of less than 5 ° C and preferably less than 2 ° C, and an alkaline catalyst such as calcium carbonate.
  • the reverse side of the proposed heat-sensitive recording material should be easy to print in the offset and flexographic printing processes without problems, which means without the occurrence of "mottling” or even "missing dots" in the sense of the present invention.
  • thermosensitive recording material with a back coat containing ethylene-vinyl alcohol copolymer (EVOH).
  • EVOH ethylene-vinyl alcohol copolymer
  • thermosensitive recording material in which the substrate is embedded in a non-claimed, but considered possible embodiment between two ozone-impermeable layers.
  • EVOH ethylene-vinyl alcohol copolymer
  • the use of ethylene-vinyl alcohol copolymer (EVOH) in a backside coating must be considered as obvious, although the Proposals of this document are not aimed at improving printing possibilities for heat-sensitive recording materials, but at improving their light resistance.
  • the at least first backcoat of the heat-sensitive recording material according to the invention comprises in a first embodiment preferably at least 90% by weight, most preferably at least 98% by weight, based in each case on the total weight of the backcoat, of the ethylene-vinyl alcohol copolymer.
  • Further constituents of this at least first backside coating are, for example, defoamers and / or agents for stabilizing the color curtain when the coating composition is applied by means of curtain or slide coaters.
  • the at least first backcoat layer comprises at least 80% by weight, based on the total weight of this backcoat layer, of the ethylene-vinyl alcohol copolymer and also of the pigment and, with very particular preference, of calcium carbonate.
  • the coating weight for the at least first ethylene-vinyl alcohol copolymer-based backcoat layer is preferably in a range of 0.9 to 5.0 g / m 2 , most preferably in a range of 1.5 to 3.5 g / m 2 .
  • Particularly suitable brushing compositions for the application of this backcoat coating are, in particular, contactless application devices such as air brushes and curtain coaters or slide coaters, without being limited to these in any way.
  • the heat-sensitive recording material according to the invention has, in addition to the first backcoat on the basis of ethylene-vinyl alcohol copolymer on another backside coating, which is then applied to the previously applied back coating with the ethylene-vinyl alcohol copolymer.
  • the further backside coating is formed as a pigmented backside coating containing calcium carbonate as a pigment.
  • the first backcoat based on ethylene-vinyl alcohol copolymer is that of the second embodiment according to paragraph [0012] which contains at least 80% by weight of the ethylene-ynyl alcohol copolymer and Pigment calcium carbonate has.
  • both the calcium carbonate optionally incorporated in the first ethylene vinyl alcohol copolymer backcoat layer and the calcium carbonate of the further backside coating have a respective average particle size (Malvern) in a preferred range of zero , 9 microns to 1.25 microns, most preferably in a range of 1.0 microns to 1.2 microns.
  • precipitated calcium carbonate in both the first backcoat on the basis of ethylene-vinyl alcohol copolymer as well as in the other backside coating is considered to be very particularly preferred, with a platelet-like particulate form being advantageous both for a particularly convincing appearance of the rear side of the invention heat-sensitive recording material as well as a good barrier effect of this back has been recognized.
  • the further backcoat layer may additionally contain, as pigment, preferably organic, so-called hollow-body pigments. It is then particularly advantageous if the pigment mixture within the further backside coating to 35 to 50 wt.% Or even better to 38 to 45 wt .-% of organic and to 65 to 50 wt .-% or even better to 62 up to 55% by weight Calcium carbonate consists, wherein the wt.% Relate to the total amount of pigment in the further backside coating.
  • binder of the further backside coating is considered a combination of (carboxy) methylcellulose and styrene-butadiene latex as preferred, ideally supplemented by corn starch.
  • roll-bar coater, knife coater, curtain coater or slide coater or air brush are particularly suitable, knife coater and, in particular, roller coater coating being considered very preferred.
  • the basis weight of the further backside coating is preferably between 1 and 20 g / m 2, and more preferably between 3.0 and 8.0 g / m 2 .
  • both the first backside coating based on ethylene-vinyl alcohol copolymer and the further backside coating can be applied with two, preferably identical, coating units.
  • both backcoats wet-on-wet for which, in particular, a curtain coater system or a slide coater is offered.
  • the heat-sensitive recording layer of the heat-sensitive recording material according to the invention may likewise include in principle all color acceptors suitable for the possible, in particular the preferred, dye precursors, in particular organic color acceptors.
  • the heat-sensitive recording layer has at least one color acceptor selected from the list comprising: 2,2 bis (4-hydroxyphenyl) propane, 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol, 4-hydroxy 4'-isopropoxydiphylsulfone, 4,4'-dihydroxy-diphenylsulfone, 2,4'-dihydroxy-diphenylsulfone, N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) -thio] -acetamide and N- (p-) toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to the following formula (1),
  • N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea is known as Pergafast ® 201 from Ciba Specialty Chemicals Inc.
  • the recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness.
  • Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, Dibenzyl oxalate, benzyl naphthyl ether and diphenyl sulfone, with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 1,2-di (phenoxy) ethane being preferred.
  • Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
  • water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
  • Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer.
  • binders for incorporation into the heat-sensitive recording layer.
  • polyvinyl alcohol in conjunction with acrylate copolymer as particularly preferred binders, which are incorporated together, based on the total weight of the recording layer, in a range of 12 to 21 wt.% In the heat-sensitive recording layer.
  • the coating composition for forming the thermosensitive recording layer may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax.
  • slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax.
  • the recording layer is, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, which is preferably incorporated in the recording layer in an amount of 10 to 18% by weight, based on the total weight of the recording layer should be considered as preferred.
  • the basis weight of the heat-sensitive recording layer is usually between 2.5 and 12 g / m 2, and more preferably between 2.8 and 6.5 g / m 2 .
  • a brush for applying the heat-sensitive recording layer in particular, offer a doctor blade and (roll) doctor blade coater, curtain coater and air brush.
  • a pigment-containing intermediate layer between the substrate and the heat-sensitive recording layer.
  • pigments of the intermediate layer both organic void pigments and inorganic pigments have proven useful, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide, in particular boehmite here.
  • such an intermediate layer can make a positive contribution to the leveling of the substrate surface, which reduces the amount of coating color necessarily required for the heat-sensitive recording layer. For this reason, offer to coat the intermediate layer leveling strokes, such as roller coater, doctor blade and (roll) doctor blade coating.
  • the pigments of this intermediate layer can absorb the heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording.
  • the basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
  • the recording material according to the invention may furthermore have a protective layer which is applied to the heat-sensitive recording layer and completely or partially covers it.
  • the protective layer takes on a task, as it must also be partially fulfilled by the backside coating, namely on the one hand, the protection of the arranged below her recording layer before organic solvents as well as oils, fats, water and plasticizers.
  • paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention.
  • a paper web of bleached and ground deciduous and softwood pulps with a basis weight of 130 g / m 2 with the addition of conventional additives in conventional amounts is first prepared on a fourdrinier paper machine as a substrate.
  • a mainly calcined kaolin and organic void pigments as pigment mixture, styrene-butadiene latex as binder and starch as co-binder-containing intermediate layer of 8 g / m 2 is applied online within the paper machine with a roller blade coating unit.
  • a heat-sensitive recording layer having a basis weight of 4.2 g / m 2 is applied to the pigment-containing intermediate layer by means of a doctor blade coater.
  • the coating material used essentially contains the following components: Dye precursors: 3-dibutylamino-6-methyl-7-anilinofluoran, that is ODB-2; color acceptor: N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea, that is Pergafast® 201; sensitizer: Benzylnaphthyl ether, that is BNE; Binder: polyvinyl alcohol; co-binders: Acrylate copolymer; Pigment: Calcium carbonate.
  • a protective layer of 2.0 g / m 2 is applied by means of air brush.
  • the four coating compositions are now applied to the back of the substrate with a respective basis weight of 2 g / m 2 .
  • 0.2 ml of ethanol is applied to the respective dried backcoat of the individual samples corresponding to the two inventive examples 1 and 2 and the two comparative examples 3 and 4 with a pipette. After an exposure time of 1 minute, the ethanol is absorbed and the effect of solvent application on the heat-sensitive recording layer is visually evaluated.
  • the heat-sensitive recording layers of the two Inventive Examples 1 and 2 show no thermal reactions at all, the present invention is excellently confirmed in terms of quality.
  • Comparative Example 3 there are intense thermal reactions, this backside coating is not at all suitable to develop a far-reaching barrier effect against organic solvents with this order quantity.
  • Comparative Example 4 isolated color reaction points are formed on the heat-sensitive recording layer: below these colored dots, the back coat of the coating composition RS4 has cracks and voids due to the too high viscosity of the silanized polyvinyl alcohol. Again, the barrier effect against organic solvents is not convincing, because not without flaws.
  • thermosensitive recording material finally expected by the inventors.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (13)

  1. Matériau d'enregistrement thermosensible avec un substrat,
    - qui porte sur sa première face au moins une couche d'enregistrement thermosensible avec au moins un précurseur de colorant et au moins un accepteur de couleur, le précurseur de colorant et l'accepteur de couleur réagissant l'un avec l'autre sous l'effet de la chaleur, formant une couleur,
    - et qui porte sur sa deuxième face au moins un premier revêtement de face arrière qui contient un copolymère éthylène-alcool vinylique (EVOH),
    caractérisé en ce que le matériau d'enregistrement thermosensible contient un revêtement supplémentaire de face arrière, déposé sur le premier revêtement de face arrière appliqué précédemment, le revêtement supplémentaire de face arrière contenant du carbonate de calcium.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le au moins premier revêtement de face arrière contient le copolymère éthylène-alcool vinylique à raison d'au moins 80 % en poids.
  3. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le au moins premier revêtement de face arrière contient un pigment.
  4. Matériau d'enregistrement thermosensible selon la revendication 3, caractérisé en ce que le au moins premier revêtement de face arrière contient comme pigment du carbonate de calcium.
  5. Matériau d'enregistrement thermosensible selon la revendication 4, caractérisé en ce que la taille particulaire moyenne du carbonate de calcium contenu dans le revêtement de face arrière comportant le copolymère éthylène-alcool vinylique (EVOH), est comprise dans une plage de 0,9 µm à 1,25 µm.
  6. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la taille particulaire moyenne du carbonate de calcium contenu dans le revêtement supplémentaire de face arrière est comprise dans une plage de 0,9 µm à 1,25 µm.
  7. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le carbonate de calcium contenu dans le revêtement de face arrière comportant le copolymère éthylène-alcool vinylique (EVOH) et le carbonate de calcium dans le revêtement supplémentaire de face arrière sont identiques du point de vue de leur forme d'élaboration respective et du point de vue des caractéristiques physiques respectives.
  8. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le carbonate de calcium du revêtement supplémentaire de face arrière est précipité.
  9. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le revêtement supplémentaire de face arrière contient comme pigments, outre le carbonate de calcium, également des pigments organiques à corps creux.
  10. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le au moins premier revêtement de face arrière contient le copolymère éthylène-alcool vinylique à raison d'au moins 90 % en poids.
  11. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le au moins premier revêtement de face arrière contient le copolymère éthylène-alcool vinylique à raison d'au moins 98 % en poids.
  12. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 11, caractérisé en ce que le matériau d'enregistrement thermosensible présente une couche intermédiaire contenant des pigments et disposée entre substrat et couche d'enregistrement thermosensible.
  13. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le matériau d'enregistrement thermosensible présente une couche protectrice recouvrant la couche d'enregistrement thermosensible.
EP20090177677 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de face arrière Active EP2329958B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20090177677 EP2329958B1 (fr) 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de face arrière

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20090177677 EP2329958B1 (fr) 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de face arrière

Publications (2)

Publication Number Publication Date
EP2329958A1 EP2329958A1 (fr) 2011-06-08
EP2329958B1 true EP2329958B1 (fr) 2012-10-03

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FI123323B (fi) * 2011-06-14 2013-02-28 Teknologian Tutkimuskeskus Vtt Piilokuvioiden muodostaminen huokoisille substraateille

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Publication number Priority date Publication date Assignee Title
SE500916C2 (sv) 1986-06-16 1994-10-03 Ricoh Kk Termokänsligt registreringsmaterial med registreringsskikt innehållande fluorescensfärgämneskomposition
JP2528905B2 (ja) 1987-10-27 1996-08-28 三菱製紙株式会社 感熱記録体の製造方法
JPH04364983A (ja) * 1991-06-12 1992-12-17 Oji Paper Co Ltd 感熱記録体
JPH1024657A (ja) * 1996-05-10 1998-01-27 Mitsubishi Paper Mills Ltd 感熱記録材料およびその製造方法
DE59800342D1 (de) 1997-09-12 2000-12-21 Mitsubishi Hitec Paper Flensbu Wärmeempfindlicher aufzeichnungsbogen mit einer rückseitenbeschichtung die stärke, ein acrylatcopolymer und einen alkalischen katalysator enthält

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