EP0275381B1 - Procédé pour le transfert de colorant par la chaleur - Google Patents

Procédé pour le transfert de colorant par la chaleur Download PDF

Info

Publication number
EP0275381B1
EP0275381B1 EP87116299A EP87116299A EP0275381B1 EP 0275381 B1 EP0275381 B1 EP 0275381B1 EP 87116299 A EP87116299 A EP 87116299A EP 87116299 A EP87116299 A EP 87116299A EP 0275381 B1 EP0275381 B1 EP 0275381B1
Authority
EP
European Patent Office
Prior art keywords
phenyl
alkyl
hydrogen
dye
benzyl
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
EP87116299A
Other languages
German (de)
English (en)
Other versions
EP0275381A3 (en
EP0275381A2 (fr
Inventor
Karl-Heinz Dr. Etzbach
Rüdiger Dr. Sens
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0275381A2 publication Critical patent/EP0275381A2/fr
Publication of EP0275381A3 publication Critical patent/EP0275381A3/de
Application granted granted Critical
Publication of EP0275381B1 publication Critical patent/EP0275381B1/fr
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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/3854—Dyes containing one or more acyclic carbon-to-carbon double bonds, e.g., di- or tri-cyanovinyl, methine
    • 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 present invention relates to a new method for transferring cyanovinyl dyes from a support to a plastic-coated paper by sublimation or evaporation with the aid of a thermal head.
  • a transfer sheet which contains a sublimable dye, optionally together with a binder, on a support is heated with a heating head with short heating pulses (duration: fractions of a second) from the back, the dye subliming or evaporating and opening a recording medium is transferred.
  • the main advantage of this method is that it is easy to control the amount of dye to be transferred (and thus the color gradation) by adjusting the energy to be delivered to the heating head.
  • JP-A-229 786/1985 describes dicyano and tricyanovinyl dyes, the dicyano and tricyanovinyl groups respectively being bonded to a dialkylaminophenyl radical.
  • the invention had for its object to provide a method for transferring dyes, the dyes being easily sublimable or vaporizable under the conditions of use of a thermal head, not suffering from thermal and photochemical decomposition, being able to be processed into printing inks and meeting the color requirements. They should also be technically easily accessible.
  • R1 and R2 in formula I are, for example, hydrogen; Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, fluoromethyl, chloromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, pentafluoroethyl, 2-chloro-1,1, 2,2-tetrafluoroethyl, nonafluorobutyl; 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2-sec-butoxyethyl, 2-methoxypropyl, 1-methoxyprop-2-yl, 2-methoxybutyl, 2-ethoxybutyl, 4-methoxybutyl, 4-isopropoxybutyl; Et
  • R1 and R2 in formula I also together with the nitrogen atom represent, for example, the following heterocyclic radicals: pyrrolidino, piperidino, morpholino, N-methylpiperazino, N-ethylpiperazino, N-propylpiperazino, N-isopropylpiperazino, N-butylpiperazino, N-isobutylpiperazino or N-isobutylpiperazino or N sec-butylpiperazino.
  • R3 in formula I is for example hydrogen; Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl; Benzyl; Phenyl; 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-isopropoxyphenyl, 4-butoxyphenyl, 4-isobutoxyphenyl, 4-sec-butoxyphenyl, 4-tert-butoxyphenyl, 4-pentyloxyphenyl, 4- Isopentyloxyphenyl, 4-hexyloxyphenyl; 2-dimethylaminophenyl, 4-dimethylaminophenyl, 4-diethylaminophenyl, 4-dipropylaminophenyl, 4-diisopropylaminophenyl, 4-dibutylaminophenyl, 4- (N
  • R4 in formula I represents hydrogen or cyano.
  • R5 in formula I is, for example, cyano; Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, fluoromethoxycarbonyl, chloromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, 2-fluoroethoxycarbonyl, 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 2-bromoethoxycarbonyl, 2-bromoethoxycarbonyl, 2-bromoethoxycarbonyl, 2-bromoethoxycarbonyl, 2-bromoethoxycarbonyl 2-tetrafluoroethoxycarbonyl, nonafluorobutoxycarbonyl; 2-hydroxyethoxycarbonyl, 2-hydroxypropoxycarbonyl, 3-hydroxypropoxycarbonyl, 2-hydroxybutoxycarbonyl, 4-hydroxybutoxycarbon
  • the process according to the invention is preferably carried out by using a support on which there are dyes of the formula I in which R1 and R2 independently of one another are hydrogen, C1-C4-alkyl, benzyl, phenyl or together with the nitrogen atom a five- or six-membered saturated heterocyclic radical and R3 is hydrogen, C1-C4-alkyl, benzyl, phenyl, 4- (C1-C4-alkoxy) phenyl, 4- (C1-C4-dialkylamino) phenyl or in each case optionally substituted by methyl or chlorine or furyl or Mean thienyl.
  • the dyes of the formula I are known per se or can be obtained by methods known per se.
  • those dyes of the formula I in which R4 is hydrogen are obtained by subjecting the corresponding thiazoles which are unsubstituted in the ring position 5 to Vilsmayer formylation and reacting the resulting 5-formylthiazoles with malononitrile or the corresponding cyanoacetic acid esters.
  • the dyes transferred in the process according to the invention are generally distinguished by better sublimability, higher light fastness, higher resistance to chemical substances and less resublimation from the paper.
  • the dyes are in a suitable solvent, e.g. Chlorobenzene or isobutanol processed with a binder to form a printing ink.
  • a suitable solvent e.g. Chlorobenzene or isobutanol processed with a binder to form a printing ink.
  • the printing ink is applied to the inert carrier using a doctor blade and the dyeing is air-dried.
  • binders are ethyl cellulose, polysulfones or polyether sulfones.
  • Inert carriers are, for example, tissue paper, blotting paper, glassine paper or plastic films with good heat resistance, for example metal-coated polyester, polyamide or polyimide.
  • the thickness of the carrier is preferably 3 to 30 ⁇ m. Further carrier materials, binders and solvents suitable for the process according to the invention for the production of the printing inks are described in DE-A-3 524 519.
  • the transfer takes place by means of a thermal head, which must deliver sufficient heating power so that the dye is transferred within a few milliseconds.
  • the invention is illustrated by the following examples: In order to be able to check the transfer behavior of the dyes quantitatively and easily, the thermal transfer was carried out with large-area heating jaws instead of a thermal head. In addition, no binder was used in the production of the dye carrier to be tested.
  • 1 g of ethylene glycol, 1 g of dispersant based on a condensation product of phenol, formaldehyde and sodium bisulfite, 7.5 g of water and 0.5 g of dye of the formula I are filled into vessels together with 10 g of glass balls (2 mm ⁇ ) and after the Seal on a shaker (Red Devil®) until the average particle size of the dye is ⁇ 1 ⁇ m (duration: 8 to 12 hours depending on the dye).
  • the glass balls are sieved off, the dye dispersion obtained in this way, which is optionally diluted to twice the volume with water, is drawn off on paper using a 6 ⁇ m doctor blade and dried in air.
  • the paper layer (liver) coated with the dye to be tested is placed with the side on which the dye layer is located on an 80 ⁇ m thick polyester film (receiver) and pressed on.
  • the encoder / receiver is then wrapped with aluminum foil and heated between two heated plates for 30 seconds. The amount of dye migrated into the polyester film is determined photometrically.
  • the temperature T * [° C.] is additionally taken from the plots at which the extinction A of the colored polyester film reaches the value 1.
  • the dyes of the formula given in Table 1 below were processed according to A) and the resulting dye-coated supports according to B) were tested for the sublimation behavior.
  • the table shows the resulting color and the thermal transfer parameters T * and ⁇ E T.

Landscapes

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

Claims (2)

  1. Procédé de transfert de colorants sur un papier enduit de matière plastique à partir d'un support, par sublimation ou vaporisation à l'aide d'une tête thermique, caractérisé en ce qu'on utilise un support sur lequel se trouvent des colorants de formule I
    Figure imgb0010
     dans laquelle
    R¹ et R²   sont identiques ou différents et représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène, un reste alkyle en C₁-C₄ qui est éventuellement substitué par un atome de fluor, de chlore, de brome ou par un groupement alcoxy en C₁-C₄, un reste alcényle en C₂-C₄, benzyle, phényle, cyclohexyle, ou ils forment ensemble, avec l'atome d'azote, un reste hétérocyclique saturé penta- ou hexagonal,
    R³   représente un atome d'hydrogène, un reste alkyle en C₁-C₄, benzyle, phenyle, C₁-C₆-alcoxyphényle, C₁-C₄-dialkylaminophényle, un atome d'halogène ou un reste furyle ou thiényle éventuelement substitué par un reste alkyle en C₁-C₄ ou par un atome de fluor, de chlore ou de brome,
    R⁴   représente un atome d'hydrogène ou un groupement cyano et
    R⁵   représente un groupement cyano ou le reste COOR⁶, dans lequel R⁶ est mis pour un reste alkyle en C₁-C₄, qui est éventuellement substitue par un atome de fluor, de chlore, de brome ou par un reste hydroxy, alcoxy en C₁-C₄, cycloalkyle en C₅-C₇ ou phényle, ou pour un reste cycloalkyle en C₅-C₇.
  2. Procédé selon la revendication 1, caractérisé en ce que R¹ et R² représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène, un reste alkyle en C₁-C₄, benzyle, phényle ou forment ensemble, avec l'atome d'azote, un reste hétérocyclique saturé penta- ou hexagonal, et R³ représente un atome d'hydrogène, un reste alkyle en C₁-C₄, benzyle, phényle, 4-(C₁-C₄-alcoxy)phényle, 4-(C₁-C₄-dialkylamino)phényle ou un radical furyle ou thiényle éventuellement substitué par un reste méthyle ou un atome de chlore.
EP87116299A 1986-11-13 1987-11-05 Procédé pour le transfert de colorant par la chaleur Expired - Lifetime EP0275381B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3638756 1986-11-13
DE19863638756 DE3638756A1 (de) 1986-11-13 1986-11-13 Verfahren zur uebertragung von farbstoffen

Publications (3)

Publication Number Publication Date
EP0275381A2 EP0275381A2 (fr) 1988-07-27
EP0275381A3 EP0275381A3 (en) 1989-10-04
EP0275381B1 true EP0275381B1 (fr) 1992-03-04

Family

ID=6313856

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87116299A Expired - Lifetime EP0275381B1 (fr) 1986-11-13 1987-11-05 Procédé pour le transfert de colorant par la chaleur

Country Status (4)

Country Link
US (1) US4760049A (fr)
EP (1) EP0275381B1 (fr)
JP (1) JP2574338B2 (fr)
DE (2) DE3638756A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8718431D0 (en) * 1987-08-04 1987-09-09 Ici Plc Thermal transfer printing
GB8817220D0 (en) * 1988-07-20 1988-08-24 Ici Plc Thermal transfer printing
US4891354A (en) * 1988-12-23 1990-01-02 Eastman Kodak Company Thiazolylmethylene-2-pyrazoline-5-one dye-donor element for thermal dye transfer
US4891353A (en) * 1988-12-23 1990-01-02 Eastman Kodak Company Thiazolylmethylene-3,5-pyrazolidinedione dye-donor element for thermal dye transfer
DE3928243A1 (de) * 1989-08-26 1991-02-28 Basf Ag Merocyaninartige thiazolfarbstoffe sowie ein verfahren zum thermischen transfer dieser farbstoffe
DE4003780A1 (de) * 1990-02-08 1991-08-14 Basf Ag Verwendung von azofarbstoffen fuer den thermotransferdruck
DE4005939A1 (de) * 1990-02-26 1991-08-29 Cassella Ag Verwendung von farbstoffen fuer das sublimations-transferverfahren
US5674661A (en) 1995-10-31 1997-10-07 Eastman Kodak Company Image dye for laser dye removal recording element
US20030003396A1 (en) * 2001-03-28 2003-01-02 Horst Berneth Optical data carrier comprising a merocyanine dye as light-absorbent compound in the information layer
TWI241322B (en) * 2002-12-31 2005-10-11 Ind Tech Res Inst Recording medium dye, high density blue ray recording medium and manufacturing method thereof
US7531481B2 (en) 2006-03-21 2009-05-12 Kolbo Philip A Method for transferring a dye sublimation ink image onto an elastomeric substrate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6031564A (ja) * 1983-07-28 1985-02-18 Mitsubishi Chem Ind Ltd トリシアノビニルキノリン系感熱転写記録用色素
US4698651A (en) * 1985-12-24 1987-10-06 Eastman Kodak Company Magenta dye-donor element used in thermal dye transfer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 71, Nr. 5, 4. August 1969, Seite 58, Nr. 22918y, Columbus, Ohio, US; (J.M. STRALEY et al.) 10-12-1968 *

Also Published As

Publication number Publication date
DE3777142D1 (en) 1992-04-09
EP0275381A3 (en) 1989-10-04
EP0275381A2 (fr) 1988-07-27
JP2574338B2 (ja) 1997-01-22
DE3638756A1 (de) 1988-05-26
US4760049A (en) 1988-07-26
JPS63141799A (ja) 1988-06-14

Similar Documents

Publication Publication Date Title
EP0416434B1 (fr) Colorants triazolopyridiniques ainsi qu'un procédé de transfert thermique de colorants méthiniques
EP0258856B2 (fr) Méthode de transfert de colorant
EP0582579B1 (fr) Colorants a base de n-aminopyridone
EP0275381B1 (fr) Procédé pour le transfert de colorant par la chaleur
EP0346729B1 (fr) Procédé de transfert de colorants azoiques avec un composant de couplage pyridine
DE3644369A1 (de) Verfahren zur uebertragung von kationischen farbstoffen in ihrer deprotonierten, elektrisch neutralen form
EP0415203B1 (fr) Colorants thiazoliques du type merocyanine ainsi qu'un procédé de transfert thermique de ces colorants
EP0569785B1 (fr) Mélanges de colorants pour le transfert de colorants
DE4004614A1 (de) Verfahren zur uebertragung von bichromophoren cyanogruppen enthaltenden methinfarbstoffen
EP0906370B1 (fr) Colorants a base de pyridone
EP0442360B1 (fr) Procédé de transfert de colorants azoiques
EP0480252B1 (fr) Colorants pyridones et un procédé pour leur transfert thermique
EP0344592B1 (fr) Procédé de transfert de colorants azoiques
EP0479076B1 (fr) Procédé pour le transfert des colorants indoanilines
DE3880270T2 (de) Thermische farbstoffuebertragungsschicht.
DE3812053A1 (de) Verfahren zur uebertragung von farbstoffen
EP0509302B1 (fr) Procédé pour le transfert de colorants méthiniques
EP0479068B1 (fr) Colorants de type quinoléine méthine et procédé pour leur transformation thermique
EP0384225A1 (fr) Application de colorants pour le procédé de transfert par sublimation
EP0745107A1 (fr) Colorants de triazolopyridine
DE4114456A1 (de) N-aminopyridonfarbstoffe

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: A2

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

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

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

17P Request for examination filed

Effective date: 19890822

17Q First examination report despatched

Effective date: 19910521

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

ITF It: translation for a ep patent filed

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

REF Corresponds to:

Ref document number: 3777142

Country of ref document: DE

Date of ref document: 19920409

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
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
EAL Se: european patent in force in sweden

Ref document number: 87116299.6

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

Ref country code: SE

Payment date: 19971028

Year of fee payment: 11

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

Ref country code: CH

Payment date: 19971105

Year of fee payment: 11

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: 19981106

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: 19981130

Ref country code: CH

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

Effective date: 19981130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed

Ref document number: 87116299.6

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

Ref country code: FR

Payment date: 20011017

Year of fee payment: 15

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

Ref country code: GB

Payment date: 20011102

Year of fee payment: 15

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

Ref country code: DE

Payment date: 20011121

Year of fee payment: 15

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: GB

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

Effective date: 20021105

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 THE APPLICANT RENOUNCES

Effective date: 20021213

GBPC Gb: european patent ceased through non-payment of renewal fee
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: 20030731

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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: 20051105