EP0642928B1 - Thermosensitive recording material - Google Patents

Thermosensitive recording material Download PDF

Info

Publication number
EP0642928B1
EP0642928B1 EP94114571A EP94114571A EP0642928B1 EP 0642928 B1 EP0642928 B1 EP 0642928B1 EP 94114571 A EP94114571 A EP 94114571A EP 94114571 A EP94114571 A EP 94114571A EP 0642928 B1 EP0642928 B1 EP 0642928B1
Authority
EP
European Patent Office
Prior art keywords
layer
weight
methyl
diethylamino
heat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94114571A
Other languages
German (de)
French (fr)
Other versions
EP0642928A1 (en
Inventor
Peter Dr. Wenz
Martin Dr. Schreer
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.)
Sihl GmbH
Original Assignee
Sihl 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 Sihl GmbH filed Critical Sihl GmbH
Publication of EP0642928A1 publication Critical patent/EP0642928A1/en
Application granted granted Critical
Publication of EP0642928B1 publication Critical patent/EP0642928B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B41M3/142—Security printing using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds

Definitions

  • the invention relates to a heat-sensitive recording material, on the back of which a detection layer is applied.
  • a heat-sensitive image transfer material is known, on the front of which a heat-sensitive recording layer and on the back of which are both heat and pressure-sensitive image transfer layer are arranged.
  • the image transfer layer contains wax and in microcapsules and non-encapsulated reactants which form a color when they come into contact with one another.
  • the disadvantage of this transfer material is that, in addition to the non-encapsulated reaction partners of the heat transferable image transfer layer, two different types of microcapsules must be present in the transfer layer in order to enable image recordings to be transferred due to pressure.
  • the object of the present invention is to provide a heat-sensitive recording material with a detection layer on the back of the carrier.
  • a heat-sensitive recording material with a heat-sensitive layer which contains a color former and an acidic color developer as a reaction partner, on one side of a sheet-like support material and a layer arranged on the opposite side of the support material, which is a reaction partner of the color-forming reaction in a binder contains, characterized in that the layer present on the opposite side of the carrier material is not an image transfer layer and only contains either electron-accepting acid color developer or electrons emit the color former.
  • This detection layer can be mixed with a liquid which is the reactant for the in the detection layer contains existing either acidic color developer or electron-donating color former, are activated upon contact with one another to form a color.
  • the heat-sensitive recording layer usually contains a dye precursor compound which forms a color when reacted with heat with a suitable acidic compound as reactant, one or more fusible compounds such as waxes, accelerators etc., binders, pigments and customary auxiliaries.
  • a combination of organic metal salts which take up electrons and organic reducing compounds such as phenols, chelating agents etc. can also be used as the heat-sensitive recording system in the recording layer.
  • An intermediate layer containing a binder and organic or inorganic pigments may be arranged between the sheet-like carrier material and the heat-sensitive recording layer, and a conventional protective layer may be present on the heat-sensitive recording layer.
  • the outgoing color formers contained in the electrons on the back of the carrier in the activatable recognition layer are the colorless electron-donating compounds known from heat-sensitive and pressure-sensitive recording layers, in particular triarylmethane compounds, especially fluoranes, diphenylmethane compounds, xanthene compounds, thiazine compounds and spiropyran compounds are suitable.
  • dyes based on triarylmethane for example 3,3-bis (p-dimethylaminophenyl) -6-dimethylamino-phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- ( p-Dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole -3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylaminophthalide and 3- p-dimethylaminophenyl-3- (1-
  • Lactam dyes for example rhodamine-B-anilinolactam, rhodamine (p-nitro-anilino) lactam and rhodamine (o-chloroanilino) lactam
  • fluoran dyes for example 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluoran
  • the amount of color former used can be between 60 and 95% by weight, based on the weight of the dry detection layer, and the binder content is 5-40% by weight.
  • an inorganic or organic pigment is preferably used in an amount of 30-94% by weight, the binder content again being 5-40% by weight and the color former content being set to 1-65% by weight, based in each case on the weight of the dry detection layer.
  • acid-reacting, electron-accepting color developers as are known from the heat- and pressure-sensitive recording materials, are used as reactant partners in the detection layer.
  • Phenolic resins, zinc salicylates and acid clay are particularly preferred.
  • the amount of color developer can be 60-95% by weight, based on the weight of the dry detection layer, and the binder content is generally 5-40% by weight, based on the weight of the dry detection layer.
  • an inorganic or organic pigment can be used in amounts of 20-75% by weight, the binder content again being 5-40% by weight and the color developer content being 20-75% by weight.
  • binder used in the recognition layer applied on the back of the support examples include starch, oxidized starch, esterified starch, other modified starches, hydroxyethyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymers, styrene-acrylic acid copolymers and styrene-butadiene on.
  • the detection layer can also contain customary aids.
  • auxiliaries are dispersants, wetting agents and defoaming agents in order to facilitate the application of the coating from aqueous coating compositions.
  • organic and inorganic pigments such as titanium dioxide, CaCO 3 , Al (OH) 3 , talc, oil-absorbing pigments such as SiO 2 , sodium aluminum silicate and kaolin, urea-formaldehyde, styrene etc. can be present.
  • the activatable detection layer can be applied to the back of the carrier material using a conventional coating or printing method, the application weight is 1 to 20 g / m 2 , preferably 1 to 10 g / m 2 (dry).
  • Panel-like support materials are paper or plastic film having basis weights 40-280 g / m 2 in question, preferably 50-250 g / m 2.
  • papers with an integrated watermark and colored and / or mottled fibers glowing under UV light can be used as an additional security indicator.
  • a heat-sensitive recording layer is applied in an amount of 5 g / m 2 onto a 70 g / m 2 neutral base paper.
  • the aqueous coating composition contains: 403 parts by weight water 18 parts by weight highly saponified polyvinyl alcohol 20 parts by weight Bisphenol A 7.5 parts by weight 3-N, N-diethylamino-6-methyl-7-anilinofluorane 25 parts by weight Stearic acid amide 30 parts by weight kaolin 1.5 parts by weight Network and Dispersing agents
  • the composition is prepared by first separately dispersing the reactants bisphenol A and 3-N, N-diethylamino-6-methyl-7-anilinofluoran together with portions of the binder and the pigments in PVA solution and then mixing the two dispersions and onto the coating base paper applied in an amount of 5 g / m 2 (dry) and dried and then satinized the paper.
  • an aqueous coating in an amount of 3 g / m 2 (dry) of the following composition is applied and dried: 3.75 parts by weight highly saponified polyvinyl alcohol 71.25 parts by weight water 25 parts by weight Copisil N 210 (chemically modified acid activated aluminum layer silicate based on montmorillonite, manufacturer: Süd-Chemie AG)
  • KVL 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalide
  • composition is made by dispersing the components together or separately in PVA solution in a ball mill.
  • Example 2 The procedure is as in Example 2, except that 3-N, N-di-n-butylamino-6-methyl-7-anilinofluorane is used as color former instead of KVL.
  • a gray-black color develops on the back of the thermal paper coated in this way.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Color Printing (AREA)

Abstract

A thermosensitive recording material having an activatable recognition layer arranged on the side of a sheet-like support (base) material opposite to the recording layer, which recognition layer contains either an electron-absorbing acidic colour developer or an electron-releasing colour former.

Description

Gegenstand der Erfindung ist ein wärmeempfindliches Aufzeichnungsmaterial, auf dessen Trägerrückseite eine Erkennungsschicht aufgebracht ist.The invention relates to a heat-sensitive recording material, on the back of which a detection layer is applied.

Aus DE-OS-3504730 ist ein wärmeempfindliches Bildübertragungsmaterial bekannt, auf dessen Vorderseite eine wärmeempfindliche Aufzeichnungsschicht und auf dessen Rückseite eine sowohl Wärme- als auch druckempfindliche Bildübertragungsschicht angeordnet sind. Die Bildübertragungsschicht enthält Wachs und in Mikrokapseln und nicht eingekapselte Reaktionspartner, die bei Kontakt miteinander eine Farbe ausbilden. Der Nachteil dieses Übertragungsmaterials besteht darin, daß neben den nicht eingekapselten Reaktionspartnern der durch Wärmeeinwirkung übertragbaren Bildübertragungsschicht in der Übertragungsschicht noch zwei unterschiedliche Bestandteile enthaltende Sorten von Mikrokapseln vorhanden sein müssen, um eine Übertragung von Bildaufzeichnungen aufgrund von Druckeinwirkung zu ermöglichen.From DE-OS-3504730 a heat-sensitive image transfer material is known, on the front of which a heat-sensitive recording layer and on the back of which are both heat and pressure-sensitive image transfer layer are arranged. The image transfer layer contains wax and in microcapsules and non-encapsulated reactants which form a color when they come into contact with one another. The disadvantage of this transfer material is that, in addition to the non-encapsulated reaction partners of the heat transferable image transfer layer, two different types of microcapsules must be present in the transfer layer in order to enable image recordings to be transferred due to pressure.

Aufgabe der vorliegenden Erfindung ist es, ein wärmeempfindliches Aufzeichnungsmaterial mit Erkennungsschicht auf der Trägerrückseite zur Verfügung zu stellen.The object of the present invention is to provide a heat-sensitive recording material with a detection layer on the back of the carrier.

Diese Aufgabe wird gelöst durch ein wärmeempfindliches Aufzeichnungsmaterial mit einer wärmeempfindlichen Schicht, die einen Farbbildner und einen sauren Farbentwickler als Reaktionspartner enthält, auf einer Seite eines flächenförmigen Trägermaterials und einer auf der gegenüberliegenden Seite des Trägermaterials angeordneten Schicht, die einen Reaktionspartner der farbbildenden Reaktion in einem Bindemittel enthält, dadurch gekennzeichnet, daß die auf der gegenüberliegenden Seite des Trägermaterials vorhandene Schicht keine Bildübertragungsschicht ist und nur entweder Elektronen aufnehmenden sauren Farbentwickler oder Elektronen abgeben den Farbbildner enthält.This object is achieved by a heat-sensitive recording material with a heat-sensitive layer, which contains a color former and an acidic color developer as a reaction partner, on one side of a sheet-like support material and a layer arranged on the opposite side of the support material, which is a reaction partner of the color-forming reaction in a binder contains, characterized in that the layer present on the opposite side of the carrier material is not an image transfer layer and only contains either electron-accepting acid color developer or electrons emit the color former.

Diese Erkennungsschicht kann mit einer Flüssigkeit, die in gelöster Form den Reaktionspartner für den in der Erkennungsschicht vorhandenen entweder sauren Farbentwickler oder Elektronen abgebenden Farbbildner enthält, bei Kontakt miteinander unter Ausbildung einer Farbe aktiviert werden.This detection layer can be mixed with a liquid which is the reactant for the in the detection layer contains existing either acidic color developer or electron-donating color former, are activated upon contact with one another to form a color.

Aufgrund des Fehlens des Reaktionspartners in der Erkennungsschicht ist eine nicht beabsichtigte Aktivierung der Erkennungsschicht ausgeschlossen, und es sind keine Mikrokapseln mit einem Reaktionspartner erforderlich, sodaß die Erkennungsschicht mit geringem technischen Aufwand hergestellt werden kann.Due to the absence of the reaction partner in the detection layer, an unintentional activation of the detection layer is excluded, and no microcapsules with a reaction partner are required, so that the detection layer can be produced with little technical effort.

Die wärmeempfindliche Aufzeichnungsschicht enthält üblicherweise eine Farbstoffvorläuferverbindung, die bei Einwirkung von Wärme mit einer geeigneten sauren Verbindung als Reaktionspartner eine Farbe ausbildet, eine oder mehrere schmelzbare Verbindungen wie Wachse, Beschleuniger etc., Bindemittel, Pigmente und übliche Hilfsstoffe.The heat-sensitive recording layer usually contains a dye precursor compound which forms a color when reacted with heat with a suitable acidic compound as reactant, one or more fusible compounds such as waxes, accelerators etc., binders, pigments and customary auxiliaries.

Als wärmeempfindliches Aufzeichnungssystem in der Aufzeichnungsschicht kann auch eine Kombination organischer Metallsalze, die Elektronen aufnehmen, und organisch reduzierender Verbindungen wie Phenole, Chelatbildner etc. verwendet werden.A combination of organic metal salts which take up electrons and organic reducing compounds such as phenols, chelating agents etc. can also be used as the heat-sensitive recording system in the recording layer.

Zwischen dem flächenhaften Trägermaterial und wärmeempfindlicher Aufzeichnungsschicht kann eine Zwischenschicht angeordnet sein, die ein Bindemittel und organische oder anorganische Pigmente enthält, und auf der wärmeempfindlichen Aufzeichnungsschicht kann eine übliche Schutzschicht vorhanden sein.An intermediate layer containing a binder and organic or inorganic pigments may be arranged between the sheet-like carrier material and the heat-sensitive recording layer, and a conventional protective layer may be present on the heat-sensitive recording layer.

Die in der auf der Trägerrückseite in der aktivierbaren Erkennungsschicht enthaltenen Elektronen abgehenden Farbbildner sind die aus wärmeempfindlichen und druckempfindlichen Aufzeichnungsschichten bekannten farblosen Elektronen abgebenden Verbindungen, insbesondere sind Triarylmethanverbindungen, speziell Fluorane, Diphenylmethanverbindungen, Xanthenverbindungen, Thiazinverbindungen und Spiropyranverbindungen geeignet.The outgoing color formers contained in the electrons on the back of the carrier in the activatable recognition layer are the colorless electron-donating compounds known from heat-sensitive and pressure-sensitive recording layers, in particular triarylmethane compounds, especially fluoranes, diphenylmethane compounds, xanthene compounds, thiazine compounds and spiropyran compounds are suitable.

Beispielsweise Farbstoffe auf Basis Triarylmethan, z.B. 3,3-Bis(p-dimethylaminophenyl)-6-dimethylamino-phthalid, 3-(p-Dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalid, 3-(p-Dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalid, 3,3-Bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalid, 3,3-Bis (1,2-dimethylindol-3-yl)-6-dimethylaminophtalid, 3,3-Bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalid, 3,3-Bis(2-phenylindol-3-yl)-6-dimethylaminophthalid und 3-p-Dimethylaminophenyl-3-(1-methylpyrrol-3-yl)-6-dimethylaminophtalid; Diphenylmethan, 4,4-Bis-dimethylaminobenzhydrylbenzylether, N-Halophenylleucoauramin und N-2,4,5-Trichlorophenylleucoauramin; Thiazinfarbstoffe, z.B. Benzoylleucomethylenblau und p-Nitrobenzoylleucomethylenblau; Spirofarbstoffe, z.B. 3-Methyl-spiro-dinaphthopyran, 3-Ethyl-spiro-dinaphthopyran,3-Phenyl-spiro-dinaphthopyran, 3-Benzyl-spiro-dinaphthopyran, 3-Methylnaphtho(6'-methoxybenzo)spiropyran und 3-Propyl-spiro-dibenzopyran; Lactamfarbstoffe, z.B. Rhodamin-B-anilinolactam, Rhodamin(p-nitro-anilino)-lactam und Rhodamin (o-chloroanilino) lactam; und Fluoranfarbstoffe, z.B. 3-Dimethylamino-7-methoxyfluoran, 3-Diethylamino-6-methoxyfluoran, 3-Diethylamino-7-chlorofluoran, 3-Diethylamino-6-methyl-7-chlorofluoran, 3-Diethylamino-6,7-dimethylfluoran, 3-(N-Ethyl-p-toluidino)-7-methylfluoran, 3-Diethylamino-7-(N-acetyl-N-methylamino)fluoran, 3-Diethylamino-7-methylaminofluoran, 3-Diethylamino-7-dibenzylaminofluoran, 3-Diethylamino-7-(N-methyl-N-benzylamino) fluoran, 3-Diethylamino-7-(N-chloroethyl-N-methylamino)fluoran, 3-Diethylamino-7-diethylaminofluoran, 3-(N-Ethyl-p-toluidino)-6-methyl-7-phenylaminofluoran, 3-(N-Ethyl-p-toluidino)- 6-methyl-7-(phenylamino)fluoran, 3-Diethylamino-6-methyl-7-phenylaminofluoran, 3-Diethylamino-7-(2-carbomethoxyphenylamino) fluoran, 3-(N-Cyclohexyl-N-methylamino)-6-methyl-7-phenylaminofluoran, 3-Pyrrolidino-6-methyl-7-phenylaminofluoran, 3-Piperidino-6-methyl-7-phenylaminofluoran, 3-Diethylamino-6-methyl-7-xylidinofluoran, 3-Diethylamino-7-(o-chlorophenylamino)fluoran und 3-Pyrrolidino-6-methyl-7-p-butylphenylaminofluoran, 3-(N-Methyl-N-n-amylamino)-6-methyl-7-anilinofluoran, 3-(N-Ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran, 3-(N-Methyl-N-n-hexylamino)-6-methyl-7-anilinofluoran, 3-(N-Ethyl-N-n-hexylamino)-6-methyl-7-anilinofluoran und 3-(N-Ethyl-N-ethylhexylamino)-6-methyl-7-anilinofluoran. 3-N-Ethyl-N-(3'-methylbutyl)amino-6-methyl-7-anilinofluoran, 3-N-Ethyl-N-furfurylamino-6-methyl-7-anilinofluoran, 3-N,N-Diethylamino-6-methyl-7-anilinofluoran, 3-N,N-Di-n-butylamino-6-methyl-7-anilinofluoran, 3-N,N-Di-n-butylamino-7-o-chloranilinofluoran, 3-N,N-Diethylamino-7-o-chloranilino-fluoran, 3-N-Ethyl-N-i-pentylamino-6-methyl-7-anilinofluoran.For example, dyes based on triarylmethane, for example 3,3-bis (p-dimethylaminophenyl) -6-dimethylamino-phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- ( p-Dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole -3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylaminophthalide and 3- p-dimethylaminophenyl-3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide; Diphenylmethane, 4,4-bis-dimethylaminobenzhydrylbenzylether, N-halophenylleucoauramine and N-2,4,5-trichlorophenylleucoauramine; Thiazine dyes, for example benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue; Spiro dyes, e.g. 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methylnaphtho (6'-methoxybenzo) spiropyran and 3-propyl- spiro-dibenzopyran; Lactam dyes, for example rhodamine-B-anilinolactam, rhodamine (p-nitro-anilino) lactam and rhodamine (o-chloroanilino) lactam; and fluoran dyes, for example 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3- (N-ethyl-p-toluidino) -7-methylfluorane, 3-diethylamino-7- (N-acetyl-N-methylamino) fluorane, 3-diethylamino-7-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluoran, 3 -Diethylamino-7- (N-methyl-N-benzylamino) fluoran, 3-diethylamino-7- (N-chloroethyl-N-methylamino) fluoran, 3-diethylamino-7-diethylaminofluoran, 3- (N-ethyl-p- toluidino) -6-methyl-7-phenylaminofluoran, 3- (N-ethyl-p-toluidino) - 6-methyl-7- (phenylamino) fluoran, 3-diethylamino-6-methyl-7-phenylaminofluoran, 3-diethylamino- 7- (2-carbomethoxyphenylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylaminofluoran, 3-pyrrolidino-6-methyl-7-phenylaminofluoran, 3-piperidino-6-methyl-7 -phenylaminofluoran, 3-diethylamino-6-methyl-7-xylidinofluoran, 3-diethylamino-7- (o-chlorophenylamino) fluorane and 3-pyrrolidino-6-methyl-7-p-but ylphenylaminofluoran, 3- (N-methyl-Nn-amylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3- (N-methyl-Nn -hexylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-Nn-hexylamino) -6-methyl-7-anilinofluorane and 3- (N-ethyl-N-ethylhexylamino) -6-methyl-7-anilinofluorane. 3-N-ethyl-N- (3'-methylbutyl) amino-6-methyl-7-anilinofluoran, 3-N-ethyl-N-furfurylamino-6-methyl-7-anilinofluoran, 3-N, N-diethylamino- 6-methyl-7-anilinofluoran, 3-N, N-di-n-butylamino-6-methyl-7-anilinofluoran, 3-N, N-di-n-butylamino-7-o-chloroanilinofluoran, 3-N, N-diethylamino-7-o-chloroanilino-fluoran, 3-N-ethyl-Ni-pentylamino-6-methyl-7-anilinofluorane.

Bei dieser Ausführungsform der Erfindung kann die Menge des verwendeten Farbbildners in Gew. % zwischen 60 und 95 % bezogen auf das Gewicht der trockenen Erkennungsschicht liegen, der Bindemittelgehalt liegt bei 5 - 40 Gew. %. Es wird bevorzugt aus Kostengründen noch ein anorganisches oder organisches Pigment in einer Menge von 30 - 94 Gew. % verwendet, wobei der Bindemittelgehalt wieder bei 5 - 40 Gew. % liegt und der Farbbildnergehalt auf 1 - 65 Gew. % eingestellt wird, jeweils bezogen auf das Gewicht der trockenen Erkennungsschicht.In this embodiment of the invention, the amount of color former used can be between 60 and 95% by weight, based on the weight of the dry detection layer, and the binder content is 5-40% by weight. For cost reasons, an inorganic or organic pigment is preferably used in an amount of 30-94% by weight, the binder content again being 5-40% by weight and the color former content being set to 1-65% by weight, based in each case on the weight of the dry detection layer.

In der anderen Ausführungsform der Erfindung werden sauer reagierende, Elektronen annehmende Farbentwickler, wie sie aus den warme- und druckempfindlichen Aufzeichnungsmaterialien bekannt sind, als Reaktonspartner in der Erkennungsschicht eingesetzt. Besonders bevorzugt sind Phenolharze, Zinksalicylate und saurer Ton.In the other embodiment of the invention, acid-reacting, electron-accepting color developers, as are known from the heat- and pressure-sensitive recording materials, are used as reactant partners in the detection layer. Phenolic resins, zinc salicylates and acid clay are particularly preferred.

Die Menge des Farbentwicklers kann 60 - 95 Gew. % bezogen auf das Gewicht der trockenen Erkennungsschicht betragen, der Bindemittelgehalt liegt im allgemeinen bei 5 - 40 Gew. %, bezogen auf das Gewicht der tockenen Erkennungsschicht. Wiederum kann ein anorganisches oder organisches Pigment in Mengen von 20 - 75 Gew. % mitverwendet werden, wobei der Bindemittelgehalt wieder bei 5 - 40 Gew. % und der Farbentwicklergehalt bei 20 - 75 Gew. % liegen.The amount of color developer can be 60-95% by weight, based on the weight of the dry detection layer, and the binder content is generally 5-40% by weight, based on the weight of the dry detection layer. Again, an inorganic or organic pigment can be used in amounts of 20-75% by weight, the binder content again being 5-40% by weight and the color developer content being 20-75% by weight.

Beispiele für das in der auf der Trägerrückseite aufgebrachten Erkennungsschicht verwendete Bindemittel schließen Stärke, oxidierte Stärke, veresterte Stärke, andere modifizierte Stärken, Hydroxyethylcellulose, Carboxymethylcellulose, Gelatine, Kasein, Gummiarabicum, Polyvinylalkohol, Styrol-Maleinsäureanhydridcopolymere, Styrol-Acrylsäurecopolymere und Styrol-Butadien-Copolymere ein.Examples of the binder used in the recognition layer applied on the back of the support include starch, oxidized starch, esterified starch, other modified starches, hydroxyethyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymers, styrene-acrylic acid copolymers and styrene-butadiene on.

Die Erkennungsschicht kann weiterhin übliche Hilfsmittel enthalten. Beispiele für solche Hilfmittel sind Dispergiermittel, Benetzungsmittel und Entschäumungsmittel, um das Aufbringen der Beschichtung aus wäßrigen Beschichtungszusammensetzungen zu erleichtern. Weiterhin können zusätzlich zum Binder und der aktivierbaren Reaktionskomponente organische und anorganische Pigmente wie Titandioxid, CaCO3, Al(OH)3, Talkum, ölabsorbierende Pigmente wie SiO2, Natriumaluminiumsilikat und Kaolin, Harnstoff-Formaldehyd, Styrol etc. vohanden sein.The detection layer can also contain customary aids. Examples of such auxiliaries are dispersants, wetting agents and defoaming agents in order to facilitate the application of the coating from aqueous coating compositions. In addition to the binder and the activatable reaction component, organic and inorganic pigments such as titanium dioxide, CaCO 3 , Al (OH) 3 , talc, oil-absorbing pigments such as SiO 2 , sodium aluminum silicate and kaolin, urea-formaldehyde, styrene etc. can be present.

Die aktivierbare Erkennungsschicht kann auf die Rückseite des Trägermaterials mit einem herkömmlichen Beschichtungs- oder Bedruckungsverfahren aufgebracht werden, das Auftragsgewicht liegt bei 1 - 20 g/m2, bevorzugt bei 1 - 10 g/m2 (trocken).The activatable detection layer can be applied to the back of the carrier material using a conventional coating or printing method, the application weight is 1 to 20 g / m 2 , preferably 1 to 10 g / m 2 (dry).

Als flächenhaftes Trägermaterial kommen Papier oder eine Kunststoffolie mit Flächengewichten von 40 - 280 g/m2 in Frage, bevorzugt 50 - 250 g/m2. Im Fall des Papiers können Papiere mit eingearbeitetem Wasserzeichen sowie farbigen und/oder unter UV-Licht leuchtenden Melierfasern als zusätzlichem Sicherheitskennzeichen eingesetzt werden.As Panel-like support materials are paper or plastic film having basis weights 40-280 g / m 2 in question, preferably 50-250 g / m 2. In the case of paper, papers with an integrated watermark and colored and / or mottled fibers glowing under UV light can be used as an additional security indicator.

Die Erfindung wird anhand von Beispielen näher erläutert:The invention is explained in more detail by means of examples:

Beispiel 1example 1

Auf ein 70 g/m2 neutral geleimtes Streichrohpapier wird eine wärmeempfindliche Aufzeichnungsschicht in einer Menge von 5 g/m2 aufgebracht.A heat-sensitive recording layer is applied in an amount of 5 g / m 2 onto a 70 g / m 2 neutral base paper.

Die wässrige Beschichtungszusammensetzung enthält: 403 Gew.-Teile Wasser 18 Gew.-Teile hochverseifter Polyvinylalkohol 20 Gew.-Teile Bisphenol A 7,5 Gew.-Teile 3-N,N-Diethylamino-6-methyl-7-anilinofluoran 25 Gew.-Teile Stearinsäureamid 30 Gew.-Teile Kaolin 1.5 Gew.-Teile Netz- u. Dispergierhilfsmittel The aqueous coating composition contains: 403 parts by weight water 18 parts by weight highly saponified polyvinyl alcohol 20 parts by weight Bisphenol A 7.5 parts by weight 3-N, N-diethylamino-6-methyl-7-anilinofluorane 25 parts by weight Stearic acid amide 30 parts by weight kaolin 1.5 parts by weight Network and Dispersing agents

Die Zusammensetzung wird durch zunächst getrenntes Dispergieren der Reaktionspartner Bisphenol A und 3-N,N-Diethylamino-6-methyl-7-anilinofluoran zusammen mit Anteilen des Bindemittels und der Pigmente in PVA-Lösung und anschließendem Mischen der beiden Dispersionen hergestellt und auf das Streichrohpapier in einer Menge von 5 g/m2 (trocken) aufgebracht und getrocknet und das Papier anschließend satiniert.The composition is prepared by first separately dispersing the reactants bisphenol A and 3-N, N-diethylamino-6-methyl-7-anilinofluoran together with portions of the binder and the pigments in PVA solution and then mixing the two dispersions and onto the coating base paper applied in an amount of 5 g / m 2 (dry) and dried and then satinized the paper.

Auf der der wärmeempfindlichen Aufzeichnungsschicht gegenüberliegenden Seite des Trägers wird eine wäßrige Beschichtung in einer Menge von 3 g/m2 (trocken) folgender Zusammensetzung aufgebracht und getrocknet: 3,75 Gew.-Teile hochverseifter Polyvinylalkohol 71,25 Gew.-Teile Wasser 25 Gew.-Teile Copisil N 210 (chem. modif. sauer aktiviertes Aluminium-Schichtsilikat auf Montmorillonit-Basis, Hersteller: Süd-Chemie AG) On the side of the support opposite the heat-sensitive recording layer, an aqueous coating in an amount of 3 g / m 2 (dry) of the following composition is applied and dried: 3.75 parts by weight highly saponified polyvinyl alcohol 71.25 parts by weight water 25 parts by weight Copisil N 210 (chemically modified acid activated aluminum layer silicate based on montmorillonite, manufacturer: Süd-Chemie AG)

Zur Herstellung einer Testflüssigkeit werden 0,1 g KVL (= 3,3-bis-(4-dimethylaminophenyl)-6-dimethylaminophthalid in 1,5 g Toluol/MEK-Gemisch (Massenverhältnis 9 : 2) gelöst und mit einem Pinsel auf die beschichtete Trägerrückseite aufgetragen.
Es entwickelt sich eine blaue Farbe.To prepare a test liquid, 0.1 g KVL (= 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalide) is dissolved in 1.5 g toluene / MEK mixture (mass ratio 9: 2) and brushed onto the coated back of the carrier applied.
A blue color develops.

Beispiel 2Example 2

Auf die Rückseite des gemäß Beispiel 1 hergestellten Thermopapiers wird eine wäßrige Beschichtung in einer Menge von 3 g/m2 (trocken) folgender Zusammensetzung aufgebracht und getrocknet: 4,1 Gew.-Teile hochverseifter Polyvinylalkohol 19,7 Gew.-Teile calc. Kaolin 79 Gew.-Teile Wasser 1,1 Gew.-Teile KVL On the back of the thermal paper produced according to Example 1, an aqueous coating in an amount of 3 g / m 2 (dry) of the following composition is applied and dried: 4.1 parts by weight highly saponified polyvinyl alcohol 19.7 parts by weight calc. kaolin 79 parts by weight water 1.1 parts by weight KVL

Die Zusammensetzung wird durch gemeinsames oder getrenntes Dispergieren der Komponenten in PVA-Lösung in einer Kugelmühle hergestellt.The composition is made by dispersing the components together or separately in PVA solution in a ball mill.

Zur Herstellung einer Testflüssigkeit werden 0,1 g Bisphenol A in 2 g Isopropanol gelöst und mit einem Pinsel auf die beschichtete Trägerrückseite aufgetragen. Es ergibt sich eine blaue Färbung.To prepare a test liquid, 0.1 g bisphenol A is dissolved in 2 g isopropanol and applied to the coated back of the carrier with a brush. The result is a blue color.

Beispiel 3Example 3

Es wird wie in Beispiel 2 verfahren, lediglich wird anstelle von KVL 3-N,N-di-n-butylamino-6-methyl-7-anilinofluoran als Farbbildner eingesetzt. Beim Bestreichen mit der gemäß Beispiel 2 hergestellten Testflüssigkeit entwickelt sich eine grau-schwarze Färbung auf der so beschichteten Thermopapierrückseite.The procedure is as in Example 2, except that 3-N, N-di-n-butylamino-6-methyl-7-anilinofluorane is used as color former instead of KVL. When coated with the test liquid prepared according to Example 2, a gray-black color develops on the back of the thermal paper coated in this way.

Claims (2)

  1. Thermosensitive recording material comprising a heat sensitive recording layer on one side of a sheet-like support material and a layer on the opposite side of the support material which comprises within a binder a reaction partner of a colour forming reaction between a colour former and an acid acceptor as reactive partners,
    characterized in that
    the layer which is provided on the opposite side of the support material is not a recording transfer layer and which comprises only electrons accepting acid acceptor or electrons delivering colour former.
  2. Thermosensitive recording material of claim 1,
    characterized in that
    the sheet-like support material is of paper or a plastic film in the form of a web or a sheet having a weight per unit area from 40 to 280 g/m2.
EP94114571A 1993-09-15 1994-09-15 Thermosensitive recording material Expired - Lifetime EP0642928B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4331260A DE4331260C2 (en) 1993-09-15 1993-09-15 Heat-sensitive recording material with a recognition layer on the back
DE4331260 1993-09-15

Publications (2)

Publication Number Publication Date
EP0642928A1 EP0642928A1 (en) 1995-03-15
EP0642928B1 true EP0642928B1 (en) 1997-08-06

Family

ID=6497738

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94114571A Expired - Lifetime EP0642928B1 (en) 1993-09-15 1994-09-15 Thermosensitive recording material

Country Status (4)

Country Link
EP (1) EP0642928B1 (en)
AT (1) ATE156426T1 (en)
DE (2) DE4331260C2 (en)
ES (1) ES2107096T3 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19832003A1 (en) * 1998-07-16 2000-02-03 Kanzan Spezialpapiere Gmbh Multi-layer sheet material with safety marks and method of manufacture
DE19838894A1 (en) * 1998-08-27 2000-03-09 Stora Spezialpapiere Gmbh Heat sensitive recording material
DE10113286A1 (en) * 2001-03-16 2002-10-02 Mitsubishi Hitec Paper Flensbu Heat sensitive recording sheet and its use
DE102007006059A1 (en) * 2007-02-02 2008-08-07 Peter Dr. Schneider Design for producing thermal paper, has layer, which is applied to thermal layer, where acid component is introduced into auxiliary layer with acid color developer of thermal layer

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60168690A (en) * 1984-02-13 1985-09-02 Mitsubishi Paper Mills Ltd Pressure-sensitive colorless thermal transfer recording paper
US5198410A (en) * 1992-02-19 1993-03-30 Eastman Kodak Company Thermal dye transfer receiving element with backing layer

Also Published As

Publication number Publication date
ES2107096T3 (en) 1997-11-16
DE59403624D1 (en) 1997-09-11
EP0642928A1 (en) 1995-03-15
DE4331260C2 (en) 1995-10-05
DE4331260A1 (en) 1995-03-16
ATE156426T1 (en) 1997-08-15

Similar Documents

Publication Publication Date Title
US4948775A (en) Heat-sensitive record material
DE2919521C2 (en) Recording material for use in a pressure-sensitive copier system
DE4316880C2 (en) Thermosensitive recording material
DE3601525A1 (en) HEAT SENSITIVE AND HEAT TRANSFERABLE RECORD SHEET
US4626877A (en) Heat-sensitive recording material
DE3240623C2 (en)
EP0642928B1 (en) Thermosensitive recording material
DE60315695T2 (en) HEAT-SENSITIVE RECORDING MEDIUM
US4946823A (en) Heat-sensitive record material
US4771033A (en) Heat-sensitive record material
DE102008007596B4 (en) Process for the preparation of thermal recording materials, in particular thermal papers and recording materials
DE3703486A1 (en) HEAT SENSITIVE RECORDING MATERIAL
DE60103135T2 (en) TWO-WAY SELF-TAGING PAPER CONTAINING HOLLOW MICROBALLS
DE3911199C2 (en)
US4910184A (en) Heat-sensitive recording materials
US5017545A (en) Heat sensitive recording material
US5143890A (en) Heat sensitive recording material
DE69106149T3 (en) Heat-sensitive recording material.
DE4009187C1 (en) Heat-transfer data recording material - comprises carrier paper coated with thermal data recording layer contg. colourless dye precursor and acidic component
DE3827060C2 (en)
JP2617505B2 (en) Multicolor thermal recording medium
JP2766296B2 (en) Manufacturing method of thermal recording film
JP3052446B2 (en) Thermal recording medium
JPH04232774A (en) Pressure-sensitive recording sheet for preventing alteration
JP2893649B2 (en) Thermal recording medium

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE ES FR GB IT LI SE

17P Request for examination filed

Effective date: 19950526

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19960723

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RENKER GMBH

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SIHL GMBH

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT CH DE ES FR GB IT LI SE

REF Corresponds to:

Ref document number: 156426

Country of ref document: AT

Date of ref document: 19970815

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59403624

Country of ref document: DE

Date of ref document: 19970911

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19971001

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: PATENTANWALTSBUERO JEAN HUNZIKER

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2107096

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20000727

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000802

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20000816

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000913

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20000918

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000928

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20001025

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010915

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010916

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010916

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010930

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020501

EUG Se: european patent has lapsed

Ref document number: 94114571.6

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010915

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020531

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20021011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050915