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EP2480415B1 - Matériau d'enregistrement thermosensible pourvu d'un revêtement au verso - Google Patents

Matériau d'enregistrement thermosensible pourvu d'un revêtement au verso Download PDF

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Publication number
EP2480415B1
EP2480415B1 EP10728224.6A EP10728224A EP2480415B1 EP 2480415 B1 EP2480415 B1 EP 2480415B1 EP 10728224 A EP10728224 A EP 10728224A EP 2480415 B1 EP2480415 B1 EP 2480415B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
layer
recording material
calcium carbonate
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.)
Not-in-force
Application number
EP10728224.6A
Other languages
German (de)
English (en)
Other versions
EP2480415A1 (fr
Inventor
Gerhard Stork
Karsten Lerius
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
Publication of EP2480415A1 publication Critical patent/EP2480415A1/fr
Application granted granted Critical
Publication of EP2480415B1 publication Critical patent/EP2480415B1/fr
Not-in-force 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
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes

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 and on its second side a calcium carbonate-containing backcoat.
  • the heat-sensitive recording layer 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 backside coating of the known recording material comprises a mixture containing starch, a non-styrene or vinyl acetate acrylate copolymer having a film formation temperature less than 5 ° C and preferably less than 2 ° C and an alkaline catalyst such as calcium carbonate.
  • the first layer of the backcoat layer contains as pigment, very preferably as the only pigment, a preferably natural calcium carbonate having an average particle size preferably in a range from 1.35 ⁇ m to 2.1 ⁇ m, very particularly preferably in a range from 1.4 ⁇ m to 1.8 ⁇ m.
  • the mean particle size is determined in the present case by means of the device "Sedigraph 5100" Micromeritics GmbH, Erftstrasse 54, 41238 Mönchengladbach, Germany.
  • 60% of the calcium carbonate particles should have a particle size smaller than 2 ⁇ m.
  • styrene-butadiene latex As a binder of the first layer of the backside coating is styrene-butadiene latex as preferred, ideally supplemented with styrene-acrylate copolymer and Acrylesterpfropfpolymeren.
  • the second layer of the backcoat layer can be calcium carbonate which is preferably the only inorganic pigment which is natural or particularly preferably precipitated with an average particle size preferably in a range from 0.85 ⁇ m to 1.25 ⁇ m, very particularly preferably in a range from 0.9 ⁇ m to 1.2 ⁇ m.
  • the mean particle size is determined by means of the device "Sedigraph 5100".
  • the average particle size of the calcium carbonate of the first layer of the backside coating differs from the average particle size of the calcium carbonate of the second layer of the backside coating.
  • the particular preparations may particularly preferably differ from one another in a characteristic manner: in the first layer, preferably natural ground calcium carbonate is present, in the second layer particularly preferred precipitated calcium carbonate.
  • the precipitated calcium carbonate which is particularly preferably used in the second layer of the backcoat layer is also the particle shape in which a platelet-like particle shape is recognized as advantageous for the subsequent gloss of the backside and thus for a particularly convincing appearance of the back side of the heat-sensitive recording material of the invention has been.
  • the second layer of the backside coating additionally contains, as pigment, preferably organic, so-called hollow-body pigments. It is particularly advantageous if the pigment mixture within the second layer of the backcoat to 10 to 80 wt .-%, preferably 35 to 50 wt .-% and most preferably from 38 to 45 wt .-% of organic and 90 to 20 wt .-%, preferably to 65 to 50 wt .-% and most preferably to 62 to 55 wt .-% of calcium carbonate, wherein the wt .-% on the total amount of pigment in the second layer of the backside coating Respectively.
  • a binder of the second layer of the backside coating As a binder of the second layer of the backside coating, a combination of (carboxy) methylcellulose and styrene-butadiene latex is preferred, ideally supplemented by maize starch.
  • Another possible binder for the second layer of the backside coating is polyvinyl alcohol.
  • the basis weight of the first layer of the backside coating is preferably between 7 and 15 g / m 2 and more preferably between 8.5 and 11.5 g / m 2
  • the basis weight of the second layer of the backcoat layer is preferably between 10 and 2 g / m 2 and more preferably between 6 and 3 g / m 2 .
  • the application of the two layers can be done wet-on-wet with subsequent drying, as well as a application is possible in which the first layer is applied and dried and only then takes place application and drying of the second layer. This option is preferred in view of the achieved gloss values.
  • gloss values could be achieved which were in a preferred range of 60 to 90%, most preferably in a range of 70 to 90 %, measured according to Tappi 450 or ISO 2813 with a reflection angle of 75 °.
  • the heat-sensitive recording layer having at least one dye precursor and at least one color acceptor, the dye precursor and color acceptor reacting color-forming with heat preferably has at least 33% by weight, most preferably 100% by weight, as color acceptor according to a first embodiment variant.
  • N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea Based on the total weight of the recording layer, the color acceptor then makes up to 32% by weight, but preferably in the range of 15 to 30% by weight, and more preferably 18 to 28.5% by weight, of the heat-sensitive recording layer out.
  • N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea which is available as Pergafast ® 201 from Ciba Specialty Chemicals Inc., is also represented as the following formula (1), although the two CH 3 end molecules are also often omitted in the literature:
  • the heat-sensitive recording layer of the heat-sensitive recording material according to the invention instead of N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea has other color acceptors, in particular 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 'Dihydroxydiphenylsulfone, N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] acetamide.
  • other color acceptors in particular selected from the list, comprising: 2 , 2-bis (4-hydroxyphenyl) propane, 4 - [(4- (1-methylethoxy)
  • 3-dibutylamino-6-methyl-7-anilinofluoran is considered to be the most suitable dye precursor used singly or in combination with other dye precursors, preferably selected from the above dye precursors.
  • the recording layer of the thermosensitive recording material of the present invention may preferably also contain sensitizers having a melting point, ideally from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, for increasing 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 useful as binders for incorporation into the heat-sensitive recording layer.
  • polyvinyl alcohol, alone or in combination with acrylate copolymer is considered to be a particularly preferred binder, which is incorporated in a proportion of from 12 to 27.5% by weight, based on the total weight of the recording layer, 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.
  • Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case calcium carbonate, preferably in an amount of from 10 to 45% by weight, based on the total weight of the recording layer, in the recording layer is to be included as being preferred.
  • a permanent color or typeface image can be formed in the recording layer under the action of heat.
  • the basis weight of the heat-sensitive recording layer is preferably between 2.5 and 12 g / m 2 and more preferably between 3 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.
  • the coating color used to form the recording layer is aqueous.
  • the subsequent drying of the coating color can be done by means of microwave irradiation. Usually and proven it is just as much to supply heat, as happens by hot-air floatation dryer or contact dryer. Also conceivable is a combination of the listed dry processes.
  • the intermediate layer is applied in a preferred embodiment with leveling coating devices, such as, for example, roller coater, doctor blade or doctor blade coaters, the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating compound necessarily to be applied to the substrate heat-sensitive recording layer reduced.
  • leveling coating devices such as, for example, roller coater, doctor blade or doctor blade coaters
  • the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating compound necessarily to be applied to the substrate heat-sensitive recording layer reduced.
  • a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
  • inorganic oil-absorbing pigments When inorganic oil-absorbing pigments are incorporated into the intermediate layer sandwiched between the recording layer and the substrate, these pigments can absorb the thermoset liquefied wax components of the thermosensitive recording layer in the typeface formation, thereby promoting still safer and faster operation of the thermally-induced recording, thus such an embodiment preferably applies.
  • inorganic pigment for the pigmented intermediate layer is calcined kaolin, which is alone or in combination with other inorganic pigments selected from the list, comprising calcium carbonate, silica, bentonite and alumina, and especially boehmite integrated.
  • the ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved when the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt .-% consists of inorganic pigment.
  • Pigment mixtures of different organic pigments are conceivable.
  • Calcined kaolin although not limited to it, when mixed with organic pigments, is the preferred inorganic pigment.
  • pigment mixtures of different inorganic pigments are also conceivable here.
  • the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results.
  • a synthetic binder with the addition of at least one natural polymer, particularly preferably starch, is a particularly suitable embodiment.
  • a protective layer is preferably applied on the heat-sensitive recording layer. It is considered to be particularly preferred if the protective layer comprises at least 60% by weight, based on the total amount of binder in the protective layer, of diacetone-modified polyvinyl alcohol as binder.
  • the protective layer of the heat-sensitive recording material according to the invention comprises, in addition to the diacetone-modified polyvinyl alcohol in a first possible embodiment, further binders, in particular mixtures of different carboxyl-group- or silanol-modified polyvinyl alcohols. These then make up a maximum of 40 wt .-%, preferably at most 15 wt .-%, - based on the total amount of binder in the protective layer - from.
  • the protective layer of the heat-sensitive recording material according to the invention has as binders exclusively diacetone-modified polyvinyl alcohol.
  • diacetone-modified polyvinyl alcohol is the sole binder in the protective layer covering the heat-sensitive recording layer
  • the binder content in the Protective layer in a range of 35 to 65 wt .-%, based on the total weight of the protective layer.
  • Suitable crosslinking aids in the protective layer are, in particular, those selected from the group comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine-formaldehyde. It is also possible to use mixtures of different crosslinking aids.
  • the ratio of the weight% of the binder, especially the diacetone-modified polyvinyl alcohol, to the crosslinking aid is in a range of 20: 1 to 5: 1, and more preferably in a range of 12: 1 to 7 : 1 is.
  • the protective layer additionally and preferably contains an inorganic pigment.
  • the inorganic pigment is selected from the group comprising silica, aluminum hydroxide, bentonite, calcium carbonate, kaolin or a mixture of said inorganic pigments.
  • roller coater, knife coater, curtain coater or air brush are particularly suitable as coating devices for applying the protective layer covering the heat-sensitive recording layer.
  • the basis weight of the protective layer is preferably between 1.0 and 3.0 g / m 2 and more preferably between 1.6 and 2.3 g / m 2 .
  • films and paper and most preferably, a base-paper coating base paper are suitable, without, however, being limited in any way.
  • the substrate is a paper web with a proportion of recycled fibers of at least 70 wt .-%, based on the total pulp content in the paper web.
  • a paper pulp of bleached eucalyptus pulps and softwood pulps together with water is applied in a mixing chest. Further constituents of the pulp are further resin size for engine sizing with an amount of 0.6% by weight (atro), based on the total weight of the pulp, and optionally further customary additives, such as, for example, pigments and / or optical brighteners. After completion of the pulp this is then fed to a fourdrinier paper machine, where it is processed into a paper web with a basis weight of 69 g / m 2 .
  • a paper web prepared in accordance with the descriptions of the previous paragraphs [0044] to [0047] is now provided with various backside coatings by single or double use of a roll bar coater, so as to obtain samples of thermosensitive recording materials on one of the two examples of the invention and on the other of the four comparative examples to obtain.
  • the following backside coatings are applied: ⁇ u> Table 1: ⁇ / u> Backside coating ...
  • Used recipe Example 1, according to the invention ..., first layer, order: 10 g / m 2 recipe ..., second layer, application: 3.2 g / m 2 recipe Example 2, according to the invention ..., first layer, order: 10 g / m 2 recipe ..., second layer, application: 3.2 g / m 2 recipe Comparative Example 1 ..., first layer, order: 10 g / m 2 recipe ..., second location --- Comparative Example 2 ..., first layer, order: 10 g / m 2 recipe ..., second layer, application: 3.2 g / m 2 recipe Comparative Example 3 ..., first location --- ..., second location --- Comparative Example 4 ..., first layer, order: 15 g / m 2 recipe ..., second location ---
  • Table 1 in conjunction with the two paragraphs [0049] and [0051] shows that only samples of examples 1 and 2 according to the invention have a two-layer backcoat whose two layers have different calcium carbonates.
  • the difference between the calcium carbonates in the two layers is thus on the one hand in particular that the average particle size of the respective calcium carbonate in the two layers is different, namely in the first layer greater than in the second layer, and on the other with regard to the inventive example 1 in the first layer of natural calcium carbonate, in the second layer of precipitated calcium carbonate.
  • Samples of Comparative Examples 1 and 4 have only a single-layer back coating, samples of Comparative Example 3 no back coating at all.
  • the samples of Comparative Example 2 have a two-layer back coating, but the two layers have the same calcium carbonates.
  • the samples of all the examples are still calendered, the calender used for this purpose having 2 nips with a central steel roll and two adjacent polymer rolls, with a line pressure of 150 bar in each nip , The inlet temperature in the calender is measured at 36 ° C.

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

Claims (10)

  1. Matériau d'enregistrement thermosensible avec un substrat,
    qui porte sur sa première face au moins une couche d'enregistrement thermosensible dotée d'au moins un précurseur de couleur et au moins un accepteur de couleur, le précurseur de couleur et l'accepteur de couleur réagissant ensemble sous l'action de la chaleur de manière chromogène,
    et qui porte sur sa deuxième face un revêtement de face arrière contenant du carbonate de calcium,
    caractérisé en ce que le revêtement de face arrière est formé d'au moins deux couches, une première couche étant appliquée plus près du substrat et une deuxième couche étant appliquée plus loin du substrat, et
    la première couche contient un premier carbonate de calcium,
    la deuxième couche contient un deuxième carbonate de calcium, qui est différent du premier carbonate de calcium.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le premier carbonate de calcium se distingue du deuxième carbonate de calcium concernant la taille moyenne des particules.
  3. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le premier carbonate de calcium se distingue du deuxième carbonate de calcium concernant sa préparation.
  4. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la deuxième couche contient en outre des pigments à corps creux.
  5. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la deuxième couche contient comme liant la combinaison composée de la (carboxy-)méthylcellulose et du latex styrène-butadiène.
  6. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'entre le substrat et la couche d'enregistrement thermosensible est appliquée une couche intermédiaire pigmentée.
  7. Matériau d'enregistrement thermosensible selon la revendication 6, caractérisé en ce que la couche intermédiaire pigmentée contient comme pigment un mélange de kaolin calciné et de pigments à corps creux.
  8. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la couche d'enregistrement thermosensible comporte comme récepteur de couleur, au moins 331/3 % en poids, rapporté à la proportion totale des récepteurs de couleur dans la couche d'enregistrement thermosensible, de la N-(p-toluènesulfonyle)-N'-3-(p-toluènesulfonyle-oxy-phényle)-urée.
  9. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'une couche de protection est appliquée sur la couche d'enregistrement thermosensible.
  10. Matériau d'enregistrement thermosensible selon la revendication 9, caractérisé en ce que la couche de protection contient comme liant un alcool polyvinylique modifié à la diacétone.
EP10728224.6A 2009-09-21 2010-06-30 Matériau d'enregistrement thermosensible pourvu d'un revêtement au verso Not-in-force EP2480415B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009041998 2009-09-21
PCT/EP2010/059258 WO2011032738A1 (fr) 2009-09-21 2010-06-30 Matériau d'enregistrement thermosensible pourvu d'un revêtement au verso

Publications (2)

Publication Number Publication Date
EP2480415A1 EP2480415A1 (fr) 2012-08-01
EP2480415B1 true EP2480415B1 (fr) 2013-08-14

Family

ID=42199274

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10728224.6A Not-in-force EP2480415B1 (fr) 2009-09-21 2010-06-30 Matériau d'enregistrement thermosensible pourvu d'un revêtement au verso

Country Status (3)

Country Link
US (1) US8637431B2 (fr)
EP (1) EP2480415B1 (fr)
WO (1) WO2011032738A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57146686A (en) 1981-03-05 1982-09-10 Ricoh Co Ltd Thermal recording type label sheet
SE500916C2 (sv) 1986-06-16 1994-10-03 Ricoh Kk Termokänsligt registreringsmaterial med registreringsskikt innehållande fluorescensfärgämneskomposition
JPS63209990A (ja) 1987-02-27 1988-08-31 Fuji Photo Film Co Ltd 感熱記録紙
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

Also Published As

Publication number Publication date
US8637431B2 (en) 2014-01-28
EP2480415A1 (fr) 2012-08-01
WO2011032738A1 (fr) 2011-03-24
US20120225774A1 (en) 2012-09-06

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