EP1527900B1 - Matériau pour l'enregistrement par la chaleur, son utilisation et méthode pour sa fabrication - Google Patents

Matériau pour l'enregistrement par la chaleur, son utilisation et méthode pour sa fabrication Download PDF

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Publication number
EP1527900B1
EP1527900B1 EP04025536A EP04025536A EP1527900B1 EP 1527900 B1 EP1527900 B1 EP 1527900B1 EP 04025536 A EP04025536 A EP 04025536A EP 04025536 A EP04025536 A EP 04025536A EP 1527900 B1 EP1527900 B1 EP 1527900B1
Authority
EP
European Patent Office
Prior art keywords
recording material
material according
recording
calcium carbonate
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.)
Active
Application number
EP04025536A
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German (de)
English (en)
Other versions
EP1527900A1 (fr
Inventor
Wolfgang Dr. Wagner
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 HiTech Paper Flensburg GmbH
Stora Spezialpapiere 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.)
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Publication date
Application filed by Mitsubishi HiTech Paper Flensburg GmbH, Stora Spezialpapiere GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Priority to PL04025536T priority Critical patent/PL1527900T3/pl
Publication of EP1527900A1 publication Critical patent/EP1527900A1/fr
Application granted granted Critical
Publication of EP1527900B1 publication Critical patent/EP1527900B1/fr
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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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids

Definitions

  • the present invention relates to a recording material having a substrate and a heat-sensitive recording layer as the outer uppermost layer.
  • the heat-sensitive recording layer contains calcium carbonate and binder one or more dye precursors and a compound from the group of Np-toluenesulfonyl-N '- (3-ptoluenesulfonyloxy-phenyl) ureas, which as a developer under the influence of heat, a color-forming reaction with the or the dye precursor (s) is received.
  • the invention further relates to the use of the recording material according to the invention and to a process for its preparation.
  • EP 1 321 306 A2 proposes a very slit-resistant coating structure Adjustment of a specific wetting ability on the surface of the heat-sensitive recording material. This wettability is described by a surface tension with a minimum contact angle of 20 ° when using distilled water.
  • the known recording material preferably has a protective layer in view of the underlying object mandatory crosslinking and bonding agents in the near-surface layer on.
  • EP-A-1 208 994 discloses, for a heat-sensitive recording layer, the combination of developers of the named group with one or more pigments selected from the group consisting of aluminum hydroxide, amorphous silica, kaolin and talc.
  • the objectives of this document are the resistance to water, heat, light and plasticizer and a high recording sensitivity. According to the examples of this document, since the recording layer is covered with a protective layer which increases the manufacturing cost, the results obtained indicate that the resistance to environmental influences is not yet fully satisfactory.
  • the object of the present invention is to provide a heat-sensitive recording material which has a simple structure and can be produced at low production costs.
  • the new recording material should require no additional protective layer to cover the recording layer, but nevertheless have a high storage stability of both the recording material itself and the generated typeface and ensure good contrast between the typeface and unlabeled recording layer.
  • the labeled recording material should have good resistance to substances such as fatliquoring agents, waxes, (poly) glycols and polypropylene derivatives commonly used in leather used for making purses, wallets and slip-in cases for driver's licenses.
  • substances such as fatliquoring agents, waxes, (poly) glycols and polypropylene derivatives commonly used in leather used for making purses, wallets and slip-in cases for driver's licenses.
  • thermosensitive recording material which can be used to issue receipts such as parking tickets, receipts, guarantee documents and receipts at a cash register with a thermal printer installed therein.
  • the invention also seeks to provide a method which enables a simple and inexpensive production of the recording material according to the invention.
  • the good resistance for example, to the substances used in the production of leather, which, when storing, for example, wallet and wallet receipts, on the thermal-printed recording material, is explained by: that the anionic group in the developer molecule greatly influences the surface electrochemical character of the developer. This bonds the polar groups and reduces the polar component of the surface tension. The inventors recognized that this effect is more pronounced when there are increased amounts of calcium carbonate particles in the environment of the developer. The best results in relation to the task result when the ratio of calcium carbonate to binder in the recording layer also containing the developer and one or more dye precursors is in the range of 1.8: 1 to 3.3: 1 according to the invention.
  • a ratio of calcium carbonate to binder in a range of 2.2: 1 to 3.2: 1 has been found to be suitable.
  • the statements made here in the description as well as in the claims concerning the ratio of calcium carbonate to binder in each case refer to the "atro" weight, which means to absolutely dry parts by weight.
  • the calcium carbonate present in the recording layer is precipitated calcium carbonate.
  • the calcium carbonate has an average particle size of 0.20 ⁇ m ⁇ rounding convention, ie the range from 0.15 ⁇ m to 0.24 ⁇ m, and a specific surface area (BET) according to DIN 66132 of 10 m 2 / g ⁇ rounding convention, which has the range from 5 m 2 / g to 14 m 2 / g.
  • BET specific surface area
  • binders starch cellulose derivatives such as CMC and plastic dispersions based on acrylate, butadiene styrene, polyvinyl acetate alone or in admixture in the recording layer.
  • polyvinyl alcohol is suitable alone or in admixture with other binders.
  • it is partially or completely saponified polyvinyl alcohol, which is incorporated alone, in combination with other polyvinyl alcohols or in general with other binders in the heat-sensitive recording layer.
  • the recording layer can be present with a relatively low coating thickness, namely with a basis weight of 2.0 to 3.8 g / m 2 , in particular with a basis weight ⁇ 3.3 g / m 2 , wherein the statements made here in the description as well as in the claims relating to the surface masses of the recording layer in each case on the "atro" weight, which means to absolutely dry parts by weight, relate.
  • a relatively low coating thickness namely with a basis weight of 2.0 to 3.8 g / m 2 , in particular with a basis weight ⁇ 3.3 g / m 2
  • curtain coaters or leveling commissioned works of knife and roller doctor type are used.
  • a flat recording layer is effected which can not cause any interference with the passage of the thermal head during the thermal printing process.
  • the coating color used to form the thermosensitive recording layer is aqueous.
  • the subsequent drying of the coating color can be done by means of microwave irradiation.
  • heat is supplied, as is done by hot-air floatation dryer or contact dryer, such as drying cylinders.
  • contact dryer such as drying cylinders.
  • a combination of the listed dry processes is also conceivable.
  • an intermediate layer containing a binder and an oil-absorbing pigment is suitably disposed between the recording layer and the substrate of the recording material of the present invention.
  • an oil-absorbing pigment is suitably disposed.
  • the pigments of the intermediate layer in addition to the inorganic oil-absorbing pigments selected from the group comprising natural and calcined kaolin, silicon (di) oxide, bentonite, calcium carbonate and aluminum (di) oxide and, in particular, boehmite, organic hollow-wall pigments have proved to be preferred, the pigments can be used individually as well as in combination with each other.
  • such an intermediate layer can make a positive contribution to equalization of the substrate surface, whereby the amount of coating color necessarily to be applied for the heat-sensitive recording layer is further reduced to a preferred range of 1.0 to 3.0 g / m 2 .
  • the pigments of this intermediate layer can absorb the heat-liquefied wax components of the thermosensitive recording layer in the typeface formation, thus promoting a safe and rapid operation of the heat-induced recording.
  • the preferred intermediate layer also comprises at least one oil or wax-absorbing pigment.
  • the basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 10 g / m 2 (atro).
  • a paper web is particularly suitable, although the invention is not limited to paper as a substrate.
  • the paper web on the side opposite to the side with the recording layer may be provided with a preparation preferably based on starch, which is ideally applied in a range of 0.1 to 0.5 g / m 2 .
  • the recording material has, at least on its side provided with the recording layer, a Bekkglätte of 400 to 1000 sec.
  • the recording material preferably has a whiteness in a range of 90 to 98% as measured by ISO 2469 / ISO 2470, but D65 light is used at an observation angle of 8 °.
  • the recording material according to the invention is particularly suitable for issuing receipts, in particular for producing receipts and guarantee certificates on a cash register equipped with a thermal printer.
  • the simple structure of the recording material without protective layer and the consequently cost-effective manufacturability of considerable advantage is particularly suitable for issuing receipts, in particular for producing receipts and guarantee certificates on a cash register equipped with a thermal printer.
  • a suitable method for producing the recording material according to the invention in one of its possible embodiments initially comprises the provision of a substrate.
  • a paper web which has a surface-related mass in a range from 40 to 75 g / m 2 (atro) is particularly suitable for this purpose.
  • the components of the paper web are not restricted within the meaning of the invention, but on the one hand, in particular, a polyolefin-coated base paper or a base paper sized with an applied intermediate layer in a flattened design is recommended.
  • the base paper usually bleached and ground pulps in addition to the usual admixtures such as retention centers preferably resin glue in a range of 0.3 to 1.2 wt .-% (atro) and more preferably from 0.45 to 0.9 Wt .-% (atro), based on the solids weight of the base paper on.
  • the intermediate layer In addition to binders, there are primarily one or more inorganic oil absorption pigments and, optionally, organic voiding pigments which are then capable of reflecting heat from the thermal head for printing image formation in the recording layer, which has first penetrated the recording layer, back to the recording layer , Such ability of the cavity pigments in the intermediate layer contributes to better efficiency of the thermosensitive recording material.
  • the application of the intermediate layer is usually done with a leveling coating, as it represents, for example, a roller coater, a doctor blade or (roll) doctor blade.
  • the basis weight with which the recording layer is applied should preferably be in a range of 2.0 to 3.8 g / m 2 or less than or equal to 3.3 g / m 2 and most preferably in a range of 2, 0 to 3.3 g / m 2 (atro).
  • the recording layer is preferably applied with a curtain coater, a doctor blade or a rotary doctor applicator.
  • the subsequent drying is preferably done with a Heated hot air dryer in combination with drying cylinders, between which the formed recording material is performed meandering. Between heated air-suspended dryer and drying cylinders, the recording material can be moistened again on one or both sides. This moistening can be done with a steam box or by means of moistening cylinders or applicators.
  • both calender and calender each comprise a plurality of nips, in which the rollers for setting a suitable friction with each other and also with respect to the recording material carried through may have different speeds.
  • a substrate web is made of bleached and ground hardwood and softwood pulps with the addition of 0.6% by weight (atro) rosin size as engine sizing and other typical admixtures, based on the solids content (atro) of the substrate web, with a basis weight of (A) g / m 2 produced.
  • a calcined kaolin pigment, styrene-butadiene latex binder and starch co-binder is applied to the respective substrate webs of Examples 1 and 2 in addition to further auxiliary agents having a basis weight of 9 g / m 2 ;
  • the backing paper is provided with a starch preparation having a basis weight of 0.2 g / m 2 .
  • a heat-sensitive recording layer with a basis weight of (C) g / m 2 with the composition to be taken from Table 1 is applied by means of a coating device (B), all data being understood as parts by weight.
  • the paper web After drying the coating composition, the paper web is treated on a supercalender so that the heat-sensitive recording layer has a Bekkglätte of (D) sec.
  • the Bekkglätte is determined by the method specified in DIN 53107. For details of the measuring method, reference is made to DE 100 14 351 A1 .
  • a thermal print-out is made with a Atlantek 400 instrument from Atlantek (USA) and the print density is measured with the Gretag MacBeth TYPE D19C NB / U densitometer (Gretag MacBeth, 8105 Regensdorf, Switzerland). It was determined with a thermal head with 300 dpi at 11mJ / mm 2, a print density of (E).
  • the measurement of the surface tension was carried out with a device of the type DSA10 MK2 from KRÜSS GmbH (Hamburg). A polar fraction of the surface tension of (Y) in mN / m and a ratio of the disperse part to the polar part of the surface tension of (Z) were determined.
  • the heat-sensitive recording materials according to the invention produced in the context of Examples 1 to 3 have the required However, a simple structure, but nevertheless have a high storage stability of both the recording material itself and the generated typeface and ensure a good contrast between typeface and unlabeled recording layer. Furthermore, the recording materials according to the invention are characterized by good resistance to substances such as fatliquors, waxes, (poly) glycols and polypropylene derivatives, as are commonly used in leather for purses and wallets.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Claims (12)

  1. Matériau d'enregistrement ayant un substrat et une couche d'enregistrement thermosensible, formant couche supérieure isolante vers l'extérieur, contenant :
    a) un ou plusieurs précurseurs de couleurs,
    b) à titre de révélateur, un composé provenant du groupe des N-p-toluènesulfonyl-N'-(3-p-toluènesulfonyloxyphényl)urées, qui entre en réaction colorante avec le ou les précurseurs colorants sous l'action de la chaleur,
    c) du carbonate de calcium,
    d) des liants,
    caractérisé en ce que
    e) la couche d'enregistrement présente une partie polaire de tension superficielle de 5 à 9,5 mN/m d'après Owens-Wendt et le rapport entre la partie dispersée et la partie polaire se situe entre 3,5 : 1 et 7,0 : 1,
    f) le rapport carbonate de calcium : liants dans la couche d'enregistrement se situe dans une plage allant de 1,8 : 1 à 3,3 : 1 et
    g) le carbonate de calcium est présent en tant qu'unique pigment dans la couche d'enregistrement.
  2. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que le carbonate de calcium est du carbonate de calcium précipité.
  3. Matériau d'enregistrement selon l'une des revendications 1 à 2, caractérisé en ce que le liant est l'alcool polyvinylique ou en contient.
  4. Matériau d'enregistrement selon l'une des revendications 1 à 3, caractérisé en ce que le carbonate de calcium présente une taille moyenne de particules de 0,20 µm et une surface spécifique (BET) d'après la norme DIN 66132 de 10 m2/g.
  5. Matériau d'enregistrement selon l'une des revendications 1 à 4, caractérisé en ce que la couche d'enregistrement est déposée avec un grammage de 2,0 à 3,8 g/m2.
  6. Matériau d'enregistrement selon l'une des revendications 1 à 5, caractérisé en ce que la couche d'enregistrement est déposée avec un grammage ≤ 3,3 g/m2.
  7. Matériau d'enregistrement selon l'une des revendications 1 à 6, caractérisé en ce qu'une couche intermédiaire contenant des liants et un pigment lipoabsorbant est disposée entre la couche d'enregistrement et le substrat.
  8. Matériau d'enregistrement selon l'une des revendications 1 à 7, caractérisé en ce qu'au moins la face du matériau d'enregistrement dotée de la couche d'enregistrement présente un lissé Bekk de 400 à 1000 sec.
  9. Matériau d'enregistrement selon l'une des revendications 1 à 8, caractérisé en ce que le matériau d'enregistrement présente, immédiatement après une impression réalisée avec une énergie de 10 à 11,5 mJ/mm2 à une résolution de 300 dpi, une densité graphique de 1,20 à 1,35 ODU.
  10. Matériau d'enregistrement selon l'une des revendications 1 à 9, caractérisé en ce que le matériau d'enregistrement présente une blancheur dans la plage de 90 à 98 % d'après la norme ISO 2469/ ISO 2470.
  11. Utilisation du matériau d'enregistrement selon l'une des revendications 1 à 10 pour l'édition de tickets de caisse sur une caisse enregistreuse équipée d'une imprimante thermique.
  12. Procédé de fabrication d'un matériau d'enregistrement thermosensible d'après l'une des revendications 1 à 10, comprenant les étapes de procédés suivantes :
    • application en grande surface d'une masse de couchage aqueuse contenant les composants indiqués dans les revendications 1 à 4, sur un substrat, en particulier une bande de papier, avec un grammage, tel qu'il est indiqué dans les revendications 5 et 6,
    • égalisation et séchage de la masse de couchage appliquée,
    caractérisé en ce que
    • le matériau d'enregistrement est lissé au moins sur sa face ayant été dotée de la masse de couchage.
EP04025536A 2003-10-28 2004-10-27 Matériau pour l'enregistrement par la chaleur, son utilisation et méthode pour sa fabrication Active EP1527900B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04025536T PL1527900T3 (pl) 2003-10-28 2004-10-27 Termoczuły materiał do zapisu, jego zastosowanie i sposób wytwarzania

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10350406 2003-10-28
DE10350406 2003-10-28

Publications (2)

Publication Number Publication Date
EP1527900A1 EP1527900A1 (fr) 2005-05-04
EP1527900B1 true EP1527900B1 (fr) 2006-10-18

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ID=34399583

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04025536A Active EP1527900B1 (fr) 2003-10-28 2004-10-27 Matériau pour l'enregistrement par la chaleur, son utilisation et méthode pour sa fabrication

Country Status (5)

Country Link
EP (1) EP1527900B1 (fr)
AT (1) ATE342808T1 (fr)
DE (1) DE502004001785D1 (fr)
ES (1) ES2273142T3 (fr)
PL (1) PL1527900T3 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9827569D0 (en) 1998-12-16 1999-02-10 Ciba Geigy Ag Heat sensitive recording material
DE10014351A1 (de) 2000-03-24 2001-09-27 Mitsubishi Hitec Paper Flensbu Aufzeichnungspapier zum rückseitigen Bedrucken
EP1208994B2 (fr) 2000-11-24 2011-05-25 Oji Paper Co., Ltd. Matériau thermosensible pour l'enregistrement
JP2003182235A (ja) 2001-12-20 2003-07-03 Fuji Photo Film Co Ltd 感熱記録材料

Also Published As

Publication number Publication date
ATE342808T1 (de) 2006-11-15
DE502004001785D1 (de) 2006-11-30
PL1527900T3 (pl) 2007-02-28
EP1527900A1 (fr) 2005-05-04
ES2273142T3 (es) 2007-05-01

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