EP0462447B1 - 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
EP0462447B1
EP0462447B1 EP91109225A EP91109225A EP0462447B1 EP 0462447 B1 EP0462447 B1 EP 0462447B1 EP 91109225 A EP91109225 A EP 91109225A EP 91109225 A EP91109225 A EP 91109225A EP 0462447 B1 EP0462447 B1 EP 0462447B1
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EP
European Patent Office
Prior art keywords
alkyl
hydrogen
azo dyes
formula
tolyloxy
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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.)
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EP91109225A
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German (de)
English (en)
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EP0462447A1 (fr
Inventor
Rüdiger Sens
Gunther Lamm
Karl-Heinz Etzbach
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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.
  • non-prepublished EP-A-442 466 (earlier right for the designated contracting states DE, FR and GB) uses fluorophenylazopyridone dyes for thermal transfer printing.
  • the azo dyes I themselves are known per se or can be obtained by known methods (EP-B-111 236).
  • the invention was therefore based on the object of finding suitable 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.
  • radicals R 2 by definition, acetyl and cyano are particularly suitable.
  • R 4 or R 5 radicals can be especially hydrogen, chlorine and cyano, but also fluorine, bromine, nitro and trihalomethyl groups such as trifluoromethyl and trichloromethyl.
  • R 4 or R 5 have the formulas -CO-H, -CO-R 6 , -O-CO-R 6 , -CO-OR 6 , -SO-OR 6 , -0-SO-OR 6 , -CO-NR 7 R 8 , -O-CO-NR 7 R 8 , -S0 2 -NR 7 R 8 or -0-S0 2 -NR 7 R 8 ; those of the formula -CO-OR 6 are particularly preferred.
  • the radical R 6 is one of the C 1 -C 12 -alkyl groups or ⁇ -phenoxy, ⁇ -tolyloxy, ⁇ -benzyloxy or ⁇ -cyclohexyloxy-C 1 -C 12 alkyl groups listed above, the C chain of which is in each case can be interrupted by one or two oxygen atoms in ether function.
  • Suitable radicals R 7 or R 8 are the unsubstituted C 1 -C 12 -alkyl groups already mentioned.
  • Preferred azo dyes 1 can be found in the examples.
  • the dyes I to be used according to the invention are distinguished from the 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, higher lightfastness, better resistance to moisture and chemicals, better solubility the production of the printing ink, higher color strength and easier technical accessibility.
  • the azo dyes I show significantly better color purity, in particular in dye mixtures, and give 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 crystallization inhibitors 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, ethyl hydroxyethyl cellulose and cellulose acetate hydrogen phthalate, starch, alginates, alkyd resins such as polyvinyl alcohol or polyvinyl pyrrolidone and in particular polyvinyl acetate and polyvinyl butyrate.
  • Cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, especially ethyl cellulose, ethyl hydroxyethyl cellulose and cellulose acetate hydrogen phthalate, starch, alginates, alkyd resins such as polyvinyl alcohol or poly
  • 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 1 can also be taken from the application, ie the transmitted light intensity is one tenth of the incident light intensity.
  • the smaller the temperature T * the better the thermal transferability of the investigated dye.
  • binder B used in each case is indicated.
  • EC ethyl cellulose
  • PVB polyvinyl butyrate

Landscapes

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

Claims (3)

1. Utilisation, pour l'impression par transfert thermique, de colorants azoïques de formule générale 1
Figure imgb0019
dans laquelle les substituants ont les significations suivantes:
R1 Atome d'hydrogène, groupement amino, hydroxyle ou alkyle en C1 -C3;
R2 Atome d'hydrogène, groupement acétyle, carbamoyle ou cyano;
R3 Groupement ω-phénoxy-, ω-tolyloxy-, ω-benzyloxy- ou ω-cyclohexyloxy-(alkyle en Ci-C12), dont la chaîne carbonée peut être interrompue par un ou deux des termes non voisins suivants -O-, -CO-, -O-CO- ou -CO-O-et qui peut porter un ou deux des substituants suivants: atome d'halogène, groupement hydroxy, alkyle en C1-C2, phényle ou cyclohexyle;
R4, R5 Atomes d'hydrogène, d'halogène à l'exclusion du fluor, groupements cyano, nitro ou trihalogéno méthyle; restes de formules -CO-H-, -CO-R6 , -O-CO-R6 , -CO-OR6 , -SO-OR6 , -O-SO-OR6 , -CO-NR7 R8 , -O-CO-NR7 R8 , -S02-NR7R8 ou -0-S02-NR7R8, où
R6 représente un groupement alkyle en C1 -C12, un groupement ω-phénoxy-, ω-tolyloxy-, ω-benzyloxy- ou ω-cyclohexyloxy-(alkyle en C1-C12), la chaîne carbonée des groupements alkyle ou des groupements alkyle ω-substitués pouvant être interrompue par un ou deux atomes d'oxygène dans la fonction éther,
R7 représente un groupement alkyle en C1-C1 2 et
R8 est mis pour un atome d'hydrogène ou l'un des restes R7.
2. Procédé pour le transfert de colorants azoïques par diffusion depuis un support sur un substrat enduit de matière plastique au moyen d'une tête thermique, caractérisé en ce qu'on utilise à cet effet un support sur lequel se trouvent un ou plusieurs colorants azoïques de formule I selon la revendication 1.
3. Procédé selon la revendication 2, caractérisé en ce qu'on utilise à cette fin un colorant azoïque de formule la
Figure imgb0020
dans laquelle les substituants ont les significations suivantes:
R3' Groupement ω-phénoxy-, ω-tolyloxy-, ω-benzyloxy- ou ω-cyclohexyloxy-(alkyle en Ci-C12), dont la chaîne carbonée peut être interrompue par un ou deux atomes d'oxygène dans la fonction éther;
R4', R5' Atomes d'hydrogène, de chlore ou groupements cyano; restes de formule -CO-OR6.
EP91109225A 1990-06-19 1991-06-06 Utilisation de colorants azoiques pour l'impression par transfert thermique Expired - Lifetime EP0462447B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4019419 1990-06-19
DE4019419A DE4019419A1 (de) 1990-06-19 1990-06-19 Verwendung von azofarbstoffen fuer den thermotransferdurck

Publications (2)

Publication Number Publication Date
EP0462447A1 EP0462447A1 (fr) 1991-12-27
EP0462447B1 true EP0462447B1 (fr) 1994-12-21

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Country Status (4)

Country Link
US (1) US5204312A (fr)
EP (1) EP0462447B1 (fr)
JP (1) JPH04232781A (fr)
DE (2) DE4019419A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5929218A (en) * 1996-05-08 1999-07-27 Hansol Paper Co., Ltd. Pyridone-based yellow monoazo dye for use in thermal transfer and ink compositions comprising same
US6835708B2 (en) 2001-03-07 2004-12-28 Nippon Shokubai Co., Ltd. Graft polymer composition and its production process and uses
JP5634019B2 (ja) * 2008-10-14 2014-12-03 キヤノン株式会社 色素化合物並びに該色素化合物を含有するインク
CN105504858A (zh) * 2016-01-27 2016-04-20 杭州福莱蒽特精细化工有限公司 一种单偶氮基吡啶酮染料及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442466A1 (fr) * 1990-02-14 1991-08-21 Mitsubishi Chemical Corporation Feuille d'enregistrement pour le transfert thermique et composition d'encre pour la produire

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2951403A1 (de) * 1979-12-20 1981-06-25 Basf Ag, 6700 Ludwigshafen Pyridonfarbstoffe
DE3244960A1 (de) * 1982-12-04 1984-06-07 Basf Ag, 6700 Ludwigshafen Pyridonfarbstoffe
DE3481596D1 (de) * 1983-07-25 1990-04-19 Dainippon Printing Co Ltd Blatt zur verwendung im thermotransferdruck.
JPS6112393A (ja) * 1984-06-29 1986-01-20 Mitsui Toatsu Chem Inc 黄色系熱転写用色材
GB8504518D0 (en) * 1985-02-21 1985-03-27 Ici Plc Thermal transfer dyesheet
JPH0741746B2 (ja) * 1985-02-28 1995-05-10 大日本印刷株式会社 熱転写受像シート
JPS61244595A (ja) * 1985-04-24 1986-10-30 Mitsubishi Chem Ind Ltd 感熱転写記録用ピリドンアゾ系色素
JPS61262191A (ja) * 1985-05-16 1986-11-20 Sumitomo Chem Co Ltd 昇華転写体
JPH0714665B2 (ja) * 1985-06-10 1995-02-22 大日本印刷株式会社 被熱転写シ−ト
GB8521327D0 (en) * 1985-08-27 1985-10-02 Ici Plc Thermal transfer printing
US4740496A (en) * 1985-12-24 1988-04-26 Eastman Kodak Company Release agent for thermal dye transfer
US4695286A (en) * 1985-12-24 1987-09-22 Eastman Kodak Company High molecular weight polycarbonate receiving layer used in thermal dye transfer
GB8612778D0 (en) * 1986-05-27 1986-07-02 Ici Plc Thermal transfer printing
JPH085253B2 (ja) * 1986-08-04 1996-01-24 三菱化学株式会社 感熱転写記録用色素及び感熱転写シート
GB8817224D0 (en) * 1987-08-04 1988-08-24 Ici Plc Thermal transfer printing
JP2966849B2 (ja) * 1987-12-03 1999-10-25 三井化学株式会社 黄色系昇華転写用色材
US4985396A (en) * 1987-12-29 1991-01-15 Matsushita Electric Industrial Co., Ltd Dye transfer type thermal printing sheets

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442466A1 (fr) * 1990-02-14 1991-08-21 Mitsubishi Chemical Corporation Feuille d'enregistrement pour le transfert thermique et composition d'encre pour la produire

Also Published As

Publication number Publication date
EP0462447A1 (fr) 1991-12-27
DE59103964D1 (de) 1995-02-02
DE4019419A1 (de) 1992-01-02
US5204312A (en) 1993-04-20
JPH04232781A (ja) 1992-08-21

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