EP2546066A1 - Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication - Google Patents

Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication Download PDF

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Publication number
EP2546066A1
EP2546066A1 EP11173923A EP11173923A EP2546066A1 EP 2546066 A1 EP2546066 A1 EP 2546066A1 EP 11173923 A EP11173923 A EP 11173923A EP 11173923 A EP11173923 A EP 11173923A EP 2546066 A1 EP2546066 A1 EP 2546066A1
Authority
EP
European Patent Office
Prior art keywords
substrate
coating
coating composition
recording material
zinc salicylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11173923A
Other languages
German (de)
English (en)
Other versions
EP2546066B2 (fr
EP2546066B1 (fr
Inventor
Dr. Horst Heyer
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=44971135&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2546066(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Mitsubishi HiTec Paper Europe GmbH filed Critical Mitsubishi HiTec Paper Europe GmbH
Priority to PL11173923T priority Critical patent/PL2546066T5/pl
Priority to ES11173923.1T priority patent/ES2525570T5/es
Priority to EP11173923.1A priority patent/EP2546066B2/fr
Priority to EP12155798.7A priority patent/EP2546067B1/fr
Priority to ES12155798.7T priority patent/ES2477553T3/es
Priority to EP12175324.8A priority patent/EP2546068B1/fr
Publication of EP2546066A1 publication Critical patent/EP2546066A1/fr
Publication of EP2546066B1 publication Critical patent/EP2546066B1/fr
Application granted granted Critical
Publication of EP2546066B2 publication Critical patent/EP2546066B2/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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
    • 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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components

Definitions

  • the invention also relates to a method for producing a recording material for the pressure-induced formation of a typeface to the same extent.
  • zinc benzoates are generally known as color acceptors in color-reactive recording materials.
  • the non-generic EP 1 375 182A1 the zinc 4-nitrobenzoate, which is not identical to zinc salicylate, as a developer component in heat-sensitive recording materials.
  • zinc benzoates, and also those color developers, which include the zinc salicylate proposed here are generally disclosed as components of color-reactive recording materials, without being concerned with possible concentrations in the color reaction layers.
  • the recording material proposed here is formed from a web-shaped substrate, on the front side of which a first coating composition is applied for forming a so-called CF layer as a possibility of a color reaction layer .
  • CF layers are understood as meaning layers having color developers (colorants or color acceptors) which can be formed as color developer pigment or, as in the case according to the invention, as oil-soluble acidic organic substances and which are admixed with suitable dye precursors, preferably leuco dyes a color reaction, in which a color complex is formed.
  • organic color acceptors well known in the art include phenolic substances such as phenol, resorcinol, naphthols and salicylic acid, which may also be alkyl substituted and may be present as monomers, oligomers or polymers (resins).
  • the recording material proposed here is formed from a web-shaped substrate, on the front side of which a coating composition is applied for forming a so-called SC layer as a further possibility of a color reaction layer .
  • SC layers are understood as meaning layers which contain a zinc salicylate as well as at least one color acceptor as well as encapsulated dye precursors for the purposes of the present invention.
  • Silica, kaolin, aluminum (hydr) oxide and, in particular, natural calcium carbonate are suitable as inorganic pigment within this backside coating, and it is also conceivable to mix these inorganic pigments with one another or with other inorganic pigments. If, in addition to the previously disclosed pigments, other pigments are to be used within the backside coating, it is preferred if these other inorganic pigments in a wt .-% relative mixing ratio to silica, aluminum (hydr) or especially natural calcium carbonate between 1: 4 and 1:25 are incorporated within the second coating composition.
  • Styrene-acrylate latex, starch, polyvinyl alcohol and very particularly preferably styrene-butadiene latex are suitable as binders within this backside coating.
  • Wax and / or AKD glue are used in particular as a means of hydrophobing the pigmented coating.
  • the recording material proposed here is formed from a sheet-like material Substrate, on the front side as a first coating composition, the composition for forming the coating with zinc salicylate as at least one color acceptor is applied to form a CF layer, while on the back of the substrate, a so-called CB layer (coated back) is formed.
  • CB layer recording materials which have on the front side a CF layer with color acceptors or color acceptors and on the backside a CB layer are referred to as so-called CFB materials , sheets or sheets.
  • the CB layer contains microcapsules containing dye precursors in a suitable solvent.
  • the application of a localized pressure to the CB coating causes the microcapsules to break up, resulting in a release of the previously encapsulated dye precursors. Then come dye precursors from the microcapsules of the CB or SC layer in contact with the zinc salicylate as at least one color acceptor within the CF or SC layer, it leads to the formation of a color reaction, which takes place exactly where previously by the Pressure exerted the microcapsules are broken: usually this happens along a script line, which is formed by inscription using a pen or typewriter.
  • the CF coatings and / or the CB coatings are underlaminated with barrier-forming intermediate coatings, which means that the barrier-forming intermediate coatings between substrate and CF coating and / or are formed between the substrate and the CB coating.
  • the dye precursors are encapsulated in microcapsules having the size and leuco dyes preferably used therein are largely not restricted.
  • those microcapsules which have a wall material of melamine-formaldehyde resin with a preferred average capsule size in a range in particular of 4 to 6 ⁇ m are particularly well-proven.
  • the capsule contents are preferably diisopropylnaphthalene oil (KMC oil Rütgers Novares GmbH, Duisburg - Germany) is used, which contains as dye precursor leuco dyes in a range of 4 to 7.5 wt .-%.
  • KMC oil Rütgers Novares GmbH Duisburg - Germany
  • dye precursor leuco dyes in a range of 4 to 7.5 wt .-%.
  • the zinc salicylate coating additionally comprises at least one inorganic pigment selected from the list comprising: natural kaolin, calcined kaolin, silicic acid, talc, natural calcium carbonate, precipitated calcium carbonate and aluminum (hydr) oxide. It is irrelevant whether the coating with the zinc salicylate is formed on a web-like substrate, in the substrate and coating with the zinc salicylate to a recording material according to the first embodiment proposed here, concerning a CF coating, second embodiment, a SC Coating, or third embodiment, concerning a CFB recording material.
  • at least one inorganic pigment selected from the list comprising: natural kaolin, calcined kaolin, silicic acid, talc, natural calcium carbonate, precipitated calcium carbonate and aluminum (hydr) oxide. It is irrelevant whether the coating with the zinc salicylate is formed on a web-like substrate, in the substrate and coating with the zinc salicylate to a recording material according to the first embodiment proposed here, concerning a CF coating, second embodiment, a SC Coating, or third
  • the zinc salicylate coating contains a pigment mixture, the pigment mixture containing at least one inorganic pigment selected from the list comprising: natural kaolin, calcined kaolin, silicic acid, talc, natural calcium carbonate, precipitated calcium carbonate and aluminum (hydroxide.
  • the zinc salicylate coating comprises a pigment mixture of exactly two substantially different inorganic pigments, each selected from the list, comprising: natural kaolin, calcined kaolin, silica, talc, natural calcium carbonate, precipitated calcium carbonate and aluminum ( hydroxide.
  • the zinc salicylate coating contains a pigment mixture exclusively of natural kaolin and precipitated calcium carbonate.
  • the experiments and trial preparations preceding the invention showed that the Inventor places a particular preference on a coating with the zinc salicylate as at least one color acceptor containing as pigment a pigment mixture of natural kaolin and precipitated calcium carbonate wherein the weight percent mixing ratio of natural kaolin and precipitated calcium carbonate ranges from 2: 1 to 1: 2.
  • the zinc zinc coating contains Salicylate preferably includes at least one binder selected from the list comprising: styrene-butadiene latex, styrene-acrylate latex, starch, polyvinyl alcohol.
  • styrene-butadiene latex which is used in particular together with starch.
  • the invention also relates, to the same extent, to a method for producing a recording material for the pressure-induced formation of a typeface in all the embodiments and variants already proposed here.
  • the formation of the web-like substrate is done for example on a paper machine, in which at least one upstream Mischbütte a paper pulp of different pulps, optionally groundwood, fillers and water is applied and where to this paper pulp before being fed to the paper machine preferably further ingredients such as resin glue for engine sizing and other customary additives, such as pigments, shading dyes and / or optical brighteners are added.
  • a paper machine in which at least one upstream Mischbütte a paper pulp of different pulps, optionally groundwood, fillers and water is applied and where to this paper pulp before being fed to the paper machine preferably further ingredients such as resin glue for engine sizing and other customary additives, such as pigments, shading dyes and / or optical brighteners are added.
  • the first coating composition preferably applied to the front of the substrate using a coating unit, the coating unit preferably selected from the list, comprising: roller coater, roller blade coater, knife coater, air brush and most preferably curtain coater.
  • the first coating composition used to form a color reaction layer is preferably aqueous.
  • the subsequent drying of the first coating composition is usually carried out by a method in which heat is supplied, as is done by hot-air floatation dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the color reaction layer thus formed is preferably at least slightly frosted.
  • the basis weight of the color reaction layer of the first coating composition is preferably from 3.2 to 7.2 g / m 2, and more preferably from 3.4 to 4.8 g / m 2 .
  • the application of the second coating composition to form a pigmented and preferably hydrophobic coating on the back side of the substrate is preferably accomplished by means of a coater selected from the list comprising: roller coater, curtain coater, doctor blade and doctor blade coater.
  • the second coating composition used to form this pigmented backside coating is also preferably aqueous.
  • the subsequent drying of the second coating composition after the application is again usually carried out by a method in which heat is supplied, as is done by hot-air floatation dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of the pigmented backcoat of the second coating composition is preferably between 2.5 and 4.2 g / m 2, and more preferably between 2.7 and 3.7 g / m 2 .
  • the application of the third coating composition to form a CB layer on the back surface of the substrate is preferably accomplished by means of a coater selected from the list comprising: roller coater, curtain coater, doctor blade and doctor blade coater.
  • a coater selected from the list comprising: roller coater, curtain coater, doctor blade and doctor blade coater.
  • a curtain coater both in its design as Schlitzg teller with downwardly open color head from which immediately forms the color curtain, as well as in its design as Gleit vombe harsher, in which the paint head is the coating mass on an inclined flow sheet, from where forming the color curtain, excellent product and especially machine running properties could be observed within the coating process, eventually leading to a particularly homogeneous appearance of the CB coating from the third coating composition.
  • the third coating composition used to form the CB layer is preferably aqueous.
  • the subsequent drying of the second coating composition after the application is again usually carried out by a method in which heat is supplied, as is done by hot-air floatation dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of the pigmented backcoat of the second coating composition is preferably between 2.2 and 6.2 g / m 2, and more preferably between 2.4 and 3.8 g / m 2 .
  • a paper web of bleached and ground deciduous and softwood pulps having a basis weight of 67 g / m 2 with conventional additives and in particular with the addition of resin size for engine sizing is produced as a web-shaped substrate and at the end of the paper machine as a semi-finished product rolled up on a spool.
  • a second coating composition to form a pigmented and hydrophobic Applied coating.
  • the second coating composition contains as main constituents natural calcium carbonate as pigment, styrene-acrylate latex and starch as binder mixture and AKD glue as a means for hydrophobizing the pigmented backcoat. While the back coating is applied at a basis weight of 3.0 g / m 2 , the basis weight for the color reaction layer is 4.0 g / m 2 .
  • the color reaction layer is alternatively formed from seven different first coating compositions, these coating compositions differing as shown in Table 2 below.
  • Table 2 ⁇ / u> component Amount [wt%]
  • Inventive Example 1 Inventive Example 2
  • Comparative Example 1 Comparative Example 2 Comparative Example 3
  • Comparative Example 4 Precipitated calcium carbonate 37.8 --- --- 37.8 36.6 75.4 --- Natural kaolin 37.8 --- --- 37.8 36.6 --- 75.4 calcined kaolin --- 23.0 31.0 --- --- --- --- aluminum hydroxide --- 53.7 --- --- --- --- talc --- 46.5 --- --- --- --- Strength 4.5 3.8 --- 4.5 4.4 4.5 4.5 Styrene-butadiene latex 7.6 --- 6.2 7.5 7.3 7.5 Styrene-acrylate latex --- 6.9 --- --- --- --- --- --- --- --- --- --- --- --- --- ---

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Color Printing (AREA)
EP11173923.1A 2011-07-14 2011-07-14 Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication Active EP2546066B2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PL11173923T PL2546066T5 (pl) 2011-07-14 2011-07-14 Materiał rejestrujący wrażliwy na ciśnienie i jego sposób otrzymywania
ES11173923.1T ES2525570T5 (es) 2011-07-14 2011-07-14 Material de impresión piezosensible y procedimiento para su producción
EP11173923.1A EP2546066B2 (fr) 2011-07-14 2011-07-14 Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication
ES12155798.7T ES2477553T3 (es) 2011-07-14 2012-02-16 Procedimiento para la preparación de un material de registro sensible a la presión
EP12155798.7A EP2546067B1 (fr) 2011-07-14 2012-02-16 Méthode pour la fabrication d'un matériau pour l'enregistrement sensible à la pression
EP12175324.8A EP2546068B1 (fr) 2011-07-14 2012-07-06 Matériel d'enregistrement pour formation induite par pression d'un sigle et procédé de fabrication d'un tel matériel d'enregistrement

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11173923.1A EP2546066B2 (fr) 2011-07-14 2011-07-14 Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication

Publications (3)

Publication Number Publication Date
EP2546066A1 true EP2546066A1 (fr) 2013-01-16
EP2546066B1 EP2546066B1 (fr) 2014-09-10
EP2546066B2 EP2546066B2 (fr) 2018-06-27

Family

ID=44971135

Family Applications (3)

Application Number Title Priority Date Filing Date
EP11173923.1A Active EP2546066B2 (fr) 2011-07-14 2011-07-14 Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication
EP12155798.7A Active EP2546067B1 (fr) 2011-07-14 2012-02-16 Méthode pour la fabrication d'un matériau pour l'enregistrement sensible à la pression
EP12175324.8A Active EP2546068B1 (fr) 2011-07-14 2012-07-06 Matériel d'enregistrement pour formation induite par pression d'un sigle et procédé de fabrication d'un tel matériel d'enregistrement

Family Applications After (2)

Application Number Title Priority Date Filing Date
EP12155798.7A Active EP2546067B1 (fr) 2011-07-14 2012-02-16 Méthode pour la fabrication d'un matériau pour l'enregistrement sensible à la pression
EP12175324.8A Active EP2546068B1 (fr) 2011-07-14 2012-07-06 Matériel d'enregistrement pour formation induite par pression d'un sigle et procédé de fabrication d'un tel matériel d'enregistrement

Country Status (3)

Country Link
EP (3) EP2546066B2 (fr)
ES (2) ES2525570T5 (fr)
PL (1) PL2546066T5 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014108341A1 (de) * 2014-06-13 2015-12-17 Papierfabrik August Koehler Se CF-Papier
EP2979888A1 (fr) 2014-07-29 2016-02-03 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la chaleur ayant un dérivé d'acide salicylique comme développeur (de couleur) pouvant réagir à un précurseur de colorant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4257935A (en) * 1975-11-28 1981-03-24 Sumitomo Naugatuck Co., Ltd. Color developing sheet for pressure-sensitive recording systems
EP0360522A2 (fr) * 1988-09-16 1990-03-28 The Mead Corporation Composition révélatrice
EP0485064A1 (fr) * 1990-11-07 1992-05-13 The Standard Register Company Encre auto-chromogène pour l'impression contenant un pourcentage élevé de solides
EP1375182A1 (fr) 2001-04-04 2004-01-02 Nippon Soda Co., Ltd. Mat riau et feuille d'enregistrement
EP2161255A1 (fr) 2002-03-14 2010-03-10 Nippon Soda Co., Ltd. Composés phénoliques et matériaux d'enregistrement les contenant

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360548A (en) † 1980-10-24 1982-11-23 The Standard Register Company Self-contained covert image
JPS6013839B2 (ja) † 1980-11-12 1985-04-09 十條製紙株式会社 感圧複写用顕色シ−ト
GB2106529B (en) * 1981-08-05 1985-06-12 Monsanto Co Solvent systems containing a high proportion of diluent for pressure-sensitive copying systems
JP2828634B2 (ja) † 1988-07-18 1998-11-25 王子製紙株式会社 感圧複写用呈色紙
JP2786510B2 (ja) † 1989-11-22 1998-08-13 株式会社三光開発科学研究所 顕色剤水分散液の製造方法及びそれを用いた感圧記録紙
DE4224719C3 (de) † 1992-07-27 2002-03-07 Mitsubishi Hitec Paper Bielefe Verfahren zur Herstellung einer eine CF-Schicht aufweisenden Papierbahn für druckempfindliches Durchschreibepapier
DE4342140C2 (de) † 1993-12-10 1997-03-06 Zanders Feinpapiere Ag Aufzeichnendes Blatt für druckempfindliche Aufzeichnungssysteme
JP2002347339A (ja) † 2001-05-30 2002-12-04 Oji Paper Co Ltd 感圧記録紙およびその製造方法
JP2005111695A (ja) † 2003-10-03 2005-04-28 Nippon Paper Industries Co Ltd 感圧複写用顕色シート
CN101373183B (zh) † 2008-08-01 2012-04-18 东莞市天盛特种纸制品有限公司 用基准纸检测无碳复写纸cb面和cf面显色方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4257935A (en) * 1975-11-28 1981-03-24 Sumitomo Naugatuck Co., Ltd. Color developing sheet for pressure-sensitive recording systems
EP0360522A2 (fr) * 1988-09-16 1990-03-28 The Mead Corporation Composition révélatrice
EP0485064A1 (fr) * 1990-11-07 1992-05-13 The Standard Register Company Encre auto-chromogène pour l'impression contenant un pourcentage élevé de solides
EP1375182A1 (fr) 2001-04-04 2004-01-02 Nippon Soda Co., Ltd. Mat riau et feuille d'enregistrement
EP2161255A1 (fr) 2002-03-14 2010-03-10 Nippon Soda Co., Ltd. Composés phénoliques et matériaux d'enregistrement les contenant

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014108341A1 (de) * 2014-06-13 2015-12-17 Papierfabrik August Koehler Se CF-Papier
US10718089B2 (en) 2014-06-13 2020-07-21 Papierfabrik August Koehler Se CF paper
EP2979888A1 (fr) 2014-07-29 2016-02-03 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la chaleur ayant un dérivé d'acide salicylique comme développeur (de couleur) pouvant réagir à un précurseur de colorant
US10131169B2 (en) 2014-07-29 2018-11-20 Mitsubish HiTec Paper Europe GmbH Heat-sensitive recording material with salicylic acid derivative as (color) developer reactive with a dye precursor

Also Published As

Publication number Publication date
ES2525570T5 (es) 2018-11-07
EP2546068A1 (fr) 2013-01-16
PL2546066T3 (pl) 2015-02-27
ES2477553T3 (es) 2014-07-17
PL2546066T5 (pl) 2018-10-31
EP2546067B1 (fr) 2014-04-09
EP2546066B2 (fr) 2018-06-27
EP2546068B1 (fr) 2014-09-10
EP2546067A1 (fr) 2013-01-16
EP2546066B1 (fr) 2014-09-10
ES2525570T3 (es) 2014-12-26

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