EP0460463B1 - Utilisation de colorants azoiques pour l'impression par transfert thermique - Google Patents

Utilisation de colorants azoiques pour l'impression par transfert thermique Download PDF

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Publication number
EP0460463B1
EP0460463B1 EP91108420A EP91108420A EP0460463B1 EP 0460463 B1 EP0460463 B1 EP 0460463B1 EP 91108420 A EP91108420 A EP 91108420A EP 91108420 A EP91108420 A EP 91108420A EP 0460463 B1 EP0460463 B1 EP 0460463B1
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EP
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Prior art keywords
alkyl
ethyl
azo dyes
oder
und
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EP91108420A
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German (de)
English (en)
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EP0460463A1 (fr
Inventor
Ruediger Sens
Helmut Reichelt
Sabine Gruettner
Karl-Heinz Etzbach
Gunther Lamm
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BASF SE
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BASF SE
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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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/388—Azo dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • the main heat source used is a thermal head with which short heating pulses lasting a fraction of a second can be emitted.
  • a transfer sheet which contains the dye to be transferred together with one or more binders, a carrier material and possibly other auxiliaries such as release agents or crystallization-inhibiting substances is heated from the rear by the thermal head.
  • the dye diffuses from the transfer sheet into the surface coating of the substrate, e.g. into the plastic layer of a coated paper.
  • the main advantage of this method is that the amount of ink transferred and thus the color gradation can be controlled in a targeted manner via the energy to be delivered to the thermal head.
  • Thermal transfer printing generally uses the three subtractive primary colors yellow, magenta and cyan, possibly also black, whereby the dyes used must have the following properties for optimal color recording: easy thermal transferability, low tendency to migrate within or from the surface coating of the recording medium at room temperature , high thermal and photochemical stability as well as resistance to moisture and chemicals, no tendency to crystallize when storing the transfer sheet, a suitable color for the subtractive color mixture, a high molar absorption coefficient and easy technical accessibility.
  • EP-A-346 729 describes azo dyes with coupling components from the diaminopyridine series for thermal transfer printing.
  • the azo dyes I themselves are known from the older German patent applications P 38 10 643.4 and P 38 16 698.4 or can be obtained by the methods mentioned there.
  • the invention was therefore based on the object of finding suitable red and yellow dyes for thermal transfer printing which come closer to the required property profile than the dyes known hitherto.
  • a method for transferring azo dyes by diffusion from a support onto a plastic-coated substrate using a thermal head was found, which is characterized in that a support is used for this purpose, on which one or more of the azo dyes I defined at the outset are located.
  • Suitable alkyl radicals R 1 or R 2 are especially methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
  • Alkyl radicals R 1 can also be pentyl, isopentyl, neopentyl, tert-pentyl, hexyl and 2-methylpentyl.
  • Suitable alkoxy radicals R 2 are, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy.
  • radical R 1 is a phenyl group bearing substituents, the following may be mentioned, for example: methyl, ethyl, methoxy, ethoxy, chlorine, bromine and cyanophenyl, the substituents of which are each in the 2, 3 or 4 position to sit.
  • Suitable alkyl radicals R 3 , R 4 , R s , R 6 , R 7 or R 8 are especially methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
  • Alkyl radicals R 3 , R 4 , R 7 or R 8 are furthermore, for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl and 2-ethylhexyl, R 3 , R 3 ', R 4 or R 4 'additionally, for example, nonyl and decyl.
  • the C chain of the alkyl radicals R 3 or R 4 is interrupted by one to three oxygen atoms
  • the following groups may be mentioned, for example: 2-methoxy, 2-ethoxy, 2-propoxy, 2-butoxyethyl, 2- and 3 -Methoxypropyl, 1-methoxyprop-2-yl, 2-ethoxypropyl, 2-propoxypropyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 4,7,10-trioxaundecyl and 4,7,10 Trioxadodecyl.
  • Suitable alkoxy radicals R 5 or R 6 are, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy.
  • the radical R 8 can, for example, also be substituted alkyl as follows: benzyl, 1- and 2-phenylethyl, fur-2-ylmethyl, 2- (fur-2-yl) ethyl, 2- (thien-2-yl) ethyl and 2 - (Pyrid-2-yl) ethyl.
  • Preferred azo dyes 1 can be found in the examples.
  • the dyes I to be used according to the invention are distinguished from the red and yellow dyes previously used for thermal transfer printing by the following properties: easier thermal transferability despite the relatively high molecular weight, improved migration properties in the recording medium at room temperature, significantly higher light fastness, better resistance to moisture and chemicals , better solubility in the production of the printing ink, higher color strength and easier technical accessibility.
  • the azo dyes 1 show a significantly better color purity, in particular in dye mixtures, and result in improved black prints.
  • the transfer sheets required as dye donors for the thermal transfer printing process according to the invention are prepared as follows:
  • the azo dyes I are dissolved in an organic solvent, e.g. Isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or mixtures thereof, processed with one or more binders and possibly other auxiliaries such as release agents or substances which hinder crystallization to give a printing ink which preferably contains the dyes in molecularly dispersed solution.
  • the printing ink is then applied to an inert support and dried.
  • Suitable binders for the use of the azo dyes I according to the invention are all materials which are soluble in organic solvents and which are known to serve for thermal transfer printing, i.e. Cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, especially ethyl cellulose and ethyl hydroxyethyl cellulose, starch, alginates, alkyd resins such as polyvinyl alcohol or polyvinyl pyrrolidone, and especially polyvinyl acetate and polyvinyl butyrate.
  • Cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, especially ethyl cellulose and ethyl hydroxyethyl cellulose, starch, alginates, alkyd resins such as polyvinyl alcohol or polyvinyl pyrrolidone, and especially polyvinyl acetate and
  • polymers and copolymers of acrylates or their derivatives such as polyacrylic acid, polymethyl methacrylate or styrene acrylate copolymers, polyester resins, polyamide resins, polyurethane resins or natural resins such as e.g. Gum arabic into consideration.
  • binders are often recommended, e.g. those made of ethyl cellulose and polyvinyl butyrate in a weight ratio of 2: 1.
  • the weight ratio of binder to dye is usually 8: 1 to 1: 1, preferably 5: 1 to 2: 1.
  • Inert carrier materials are, for example, tissue paper, blotting paper or glassine paper as well as films made of heat-resistant plastics such as polyesters, polyamides or polyimides, these films also being able to be metal-coated.
  • the inert carrier can additionally be coated with a lubricant on the side facing the thermal head in order to prevent the thermal head from sticking to the carrier material.
  • Suitable lubricants are, for example, silicones or polyurethanes, as described in EP-A-216 483.
  • the thickness of the dye carrier is generally 3 to 30 ⁇ m, preferably 5 to 10 ⁇ m.
  • the substrate to be printed for example paper, must in turn be coated with a binder which absorbs the dye during the printing process.
  • a binder which absorbs the dye during the printing process.
  • Polymeric materials whose glass transition temperature Tg is between 50 and 100 ° C., for example polycarbonates and polyester, are preferably used for this purpose. Further details can be found in EP-A-227 094, EP-A-133 012, EP-A-133 011, JP-A-199 997/1986 or JP-A 283 595/1986.
  • a thermal head which can be heated to temperatures up to over 300 ° C., so that the dye transfer takes place within a maximum time of 15 msec.
  • transfer sheets were produced in a conventional manner from 8 ⁇ m thick polyester film, which was provided with an approximately 5 ⁇ m thick transfer layer made of a binder B, which each contained 0.25 g of azo dye I.
  • the weight ratio of binder to dye was 4: 1 in each case.
  • the substrate (slave) to be printed consisted of paper of approximately 120 ⁇ m thick, which was coated with an 8 ⁇ m thick plastic layer (Hitachi Color Video Print Paper).
  • the coated side of the encoder and slave was placed on top of one another, wrapped with aluminum foil and heated to a temperature between 70 and 80 ° C. for two minutes between two heating plates. With similar samples, this process was repeated three times at a higher temperature between 80 and 120 ° C.
  • the amount of dye diffused into the plastic layer of the receiver is proportional to the optical density, which was determined as absorbance A photometrically after the respective heating to the temperatures given above.
  • the temperature T * at which the extinction reaches the value 2 can also be taken from the application, that is to say the transmitted light intensity is one hundredth of the incident light intensity.
  • the smaller the temperature T * the better the thermal transferability of the investigated dye.
  • Tables 1 to 9a list the azo dyes I tested for their thermal transfer behavior and their color.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (2)

1. Utilisation, pour l'impression par transfert thermique, de colorants azoïques de formule générale 1
Figure imgb0034
dans laquelle les substituants ont les significations suivantes:
X est un reste de formule Ila ou Ilb
Figure imgb0035
où
R1 représente un atome d'hydrogène, un groupement alkyle en Ci-Ce ou un groupement phényle qui peut porter, en tant que substituant, un radical alkyle en C1-C4, alcoxy en C1-C2, un atome de chlore, de brome ou un radical cyano,
n est mis pour 1 ou 2 et
R2 représente un atome d'hydrogène, un radical alkyle en C1-C4, alcoxy en C1-C4 ou un atome de chlore ou de brome;
K est le reste d'un composant de copulation III
Figure imgb0036
de la série de l'aniline, de l'aminonaphtalène, du pyrazole, de l'hydroxypyridone ou de la tétrahydroquinoléine.
2. Procédé de transfert de colorants azoïques par diffusion à partir d'un support sur un substrat enduit de matière plastique au moyen d'une tête thermique, caractérisé en ce qu'on utilise à cette fin un support sur lequel se trouvent un ou plusieurs colorants azoïques de formule I selon la revendication 1.
EP91108420A 1990-06-06 1991-05-24 Utilisation de colorants azoiques pour l'impression par transfert thermique Expired - Lifetime EP0460463B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4018067A DE4018067A1 (de) 1990-06-06 1990-06-06 Verwendung von azofarbstoffen fuer den thermotransferdruck
DE4018067 1990-06-06

Publications (2)

Publication Number Publication Date
EP0460463A1 EP0460463A1 (fr) 1991-12-11
EP0460463B1 true EP0460463B1 (fr) 1994-12-14

Family

ID=6407854

Family Applications (1)

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EP91108420A Expired - Lifetime EP0460463B1 (fr) 1990-06-06 1991-05-24 Utilisation de colorants azoiques pour l'impression par transfert thermique

Country Status (4)

Country Link
US (1) US5200386A (fr)
EP (1) EP0460463B1 (fr)
JP (1) JPH04232093A (fr)
DE (2) DE4018067A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4112654A1 (de) * 1991-04-18 1992-10-22 Basf Ag Verfahren zur uebertragung von methinfarbstoffen
JP3136711B2 (ja) * 1991-11-28 2001-02-19 ソニー株式会社 熱転写方法、熱転写用印画紙、及び熱転写用インクリボン
GB9407665D0 (en) * 1994-04-18 1994-06-08 Zeneca Ltd Dye diffusion thermal transfer printing
US5693766A (en) * 1994-04-18 1997-12-02 Zeneca Limited Dye diffusion thermal transfer printing
GB9806810D0 (en) * 1998-03-31 1998-05-27 Zeneca Ltd Compositions
JP4512053B2 (ja) * 2006-02-28 2010-07-28 富士フイルム株式会社 感熱転写方式を用いた画像形成方法
EP2868702A1 (fr) * 2013-10-29 2015-05-06 DyStar Colours Distribution GmbH Colorants dispersives, leur préparation et utilisation
CN105820596B (zh) * 2016-04-22 2017-12-22 深圳市国华光电科技有限公司 一种四氢喹啉类染料、油墨和电润湿显示器

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3481596D1 (de) * 1983-07-25 1990-04-19 Dainippon Printing Co Ltd Blatt zur verwendung im thermotransferdruck.
GB8504518D0 (en) * 1985-02-21 1985-03-27 Ici Plc Thermal transfer dyesheet
GB8521327D0 (en) * 1985-08-27 1985-10-02 Ici Plc Thermal transfer printing
US4695286A (en) * 1985-12-24 1987-09-22 Eastman Kodak Company High molecular weight polycarbonate receiving layer used in thermal dye transfer
US4740496A (en) * 1985-12-24 1988-04-26 Eastman Kodak Company Release agent for thermal dye transfer
US4698651A (en) * 1985-12-24 1987-10-06 Eastman Kodak Company Magenta dye-donor element used in thermal dye transfer
DE3630279A1 (de) * 1986-09-05 1988-03-17 Basf Ag Verfahren zur uebertragung von farbstoffen
DE3810643A1 (de) * 1988-03-29 1989-10-12 Basf Ag Isothiazolazofarbstoffe
DE3816698A1 (de) * 1988-05-17 1989-11-30 Basf Ag Azofarbstoffe der 5-aminoisothiazolreihe
DE3820313A1 (de) * 1988-06-15 1989-12-21 Basf Ag Verfahren zur uebertragung von azofarbstoffen mit einer pyridin-kupplungskomponente

Also Published As

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JPH04232093A (ja) 1992-08-20
DE4018067A1 (de) 1991-12-12
US5200386A (en) 1993-04-06
DE59103852D1 (de) 1995-01-26
EP0460463A1 (fr) 1991-12-11

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