EP0462447A1 - Use of azo dyes in thermal transfer printing - Google Patents
Use of azo dyes in thermal transfer printing Download PDFInfo
- Publication number
- EP0462447A1 EP0462447A1 EP91109225A EP91109225A EP0462447A1 EP 0462447 A1 EP0462447 A1 EP 0462447A1 EP 91109225 A EP91109225 A EP 91109225A EP 91109225 A EP91109225 A EP 91109225A EP 0462447 A1 EP0462447 A1 EP 0462447A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- omega
- alkyl group
- azo dyes
- nr7r8
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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
- B41M5/388—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 impulses 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 color transferred and thus the color gradation can be specifically controlled 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 for optimum color recording must have the following properties: 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.
- 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 1 defined by definition ethyl and propyl and especially methyl are preferred.
- radicals R2 by definition, acetyl and cyano are particularly suitable.
- the C chain of said alkyl radicals R3 can be interrupted by one or two non-adjacent links -CO-, -O-CO-, -CO-O- or especially -O- and can have up to two substituents such as bromine and chlorine, hydroxy , Methyl, ethyl, phenyl or cyclohexyl; Examples include: - (CH2) 4-CO- (CH2) 4-O- (CH2) 3-O-Ph; - (CH2) 4-O-CO- (CH2) 3-O-Ph, - (CH2) 3-O-CO- (CH2) 6-O-C6H11; - (CH2) 4-CO-O- (CH2) 8-O-Ph and - (CH2) 3-CO-O- (CH2) 6-O-CH2-Ph; particularly preferred - (CH2) 3-O- (CH2) 2-O-Ph, - (CH2) 3-O- (CH2) 2-O-Ph-2-CH3, - (CH2) 3-O- (CH2) 2-O-
- Residues R4 or R5 can be especially hydrogen, chlorine and cyano, but also fluorine, bromine, nitro and trihalomethyl groups such as trifluoromethyl and trichloromethyl.
- R4 or R5 have the formulas -CO-H, -CO-R6, -O-CO-R6, -CO-OR6, -SO-OR6, -O-SO-OR6, -CO-NR7R8, -O -CO-NR7R8, -SO2-NR7R8 or -O-SO2-NR7R8; those of the formula -CO-OR6 are particularly preferred.
- the rest R6 is one of the above-listed C1-C12-alkyl groups or ⁇ -phenoxy, ⁇ -tolyloxy, ⁇ -benzyloxy or ⁇ -cyclohexyloxy-C1-C12-alkyl groups, the C chain of which each has one or two oxygen atoms can be interrupted in ether function.
- Suitable radicals R7 or R8 are the unsubstituted C1-C12 alkyl groups already mentioned.
- radicals R4 or R5 may be mentioned as examples of the radicals R4 or R5: -CO-CH3, -CO-C2H5, -CO-C6H13, -CO-C11H23, -CO- (CH2) 3-O- (CH2) 2-O-Ph, -CO- (CH2) 4-O-C3H7 and -CO- (CH2) 8-O-CH3; -O-CO-CH3, -O-CO-C4H9, -O-CO-C7H15, -O-CO- (CH2) 3-O-CH3 and -O-CO- (CH2) 4-O-C4H9; -CO-O-CH3, -CO-O-C2H5, -CO-O-C4H9, -CO-O-C6H13, -CO-O-C7H15, -CO-O- (CH2) 4-O-CH3, -CO-O-CH (CH3) -CH2-O-CH3, -CO-O- (
- Preferred azo dyes I 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 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 especially 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 polyvin
- 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 and 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 also 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 are described in EP-A-216 483.
- the thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
- the substrate to be printed for example paper, must itself be coated with a binder that absorbs the dye during the printing process.
- a binder that absorbs the dye during the printing process.
- Polymeric materials whose glass transition temperature T g 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 above 300 ° C., so that the dye transfer takes place in a maximum 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 from a binder B, each of which contained 0.25 g of azo dye I.
- the weight ratio of binder to dye was 4: 1 in each case.
- the substrate to be printed consisted of paper of approx. 120 ⁇ m thickness, 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)
Abstract
Description
Die vorliegende Erfindung betrifft die Verwendung von Azofarbstoffen der allgemeinen Formel I
für den Thermotransferdruck, in der die Substituenten folgende Bedeutung haben:
- R¹
- Wasserstoff, eine Amino-, Hydroxyl- oder C₁-C₃-Alkylgruppe;
- R²
- Wasserstoff, eine Acetyl-, Carbamoyl- oder Cyanogruppe;
- R³
- eine ω-Phenoxy-, ω-Tolyloxy-, ω-Benzyloxy- oder ω-Cyclohexyloxy-C₁-C₁₂-alkylgruppe, deren C-Kette durch ein oder zwei der folgenden nicht benachbarten Glieder
-O-, -CO-, -O-CO- oder -CO-O-
unterbrochen sein kann und die ein oder zwei der folgenden Substituenten tragen kann: Halogen, Hydroxy, C₁-C₂-Alkyl, Phenyl oder Cyclohexyl; - R⁴, R⁵
- Wasserstoff, Halogen, Cyano-, Nitro- oder Trihalogenmethylgruppen;
Reste der Formeln
-CO-H, -CO-R⁶, -O-CO-R⁶, -CO-OR⁶, -SO-OR⁶, -O-SO-OR⁶, -CO-NR⁷R⁸,
-O-CO-NR⁷R⁸, -SO₂-NR⁷R⁸ oder -O-SO₂-NR⁷R⁸
wobei - R⁶
- eine C₁-C₁₂-Alkylgruppe, eine ω-Phenoxy-, ω-Tolyloxy-, ω-Benzyloxy- oder ω-Cyclohexyloxy-C₁-C₁₂-alkylgruppe bezeichnet, wobei die C-Kette der Alkylgruppen bzw. der ω-substituierten Alkylgruppen durch ein oder zwei Sauerstoffatome in Etherfunktion unterbrochen sein kann,
- R⁷
- eine C₁-C₁₂-Alkylgruppe bedeutet und
- R⁸
- für Wasserstoff oder einen der Reste R⁷ steht,
for thermal transfer printing, in which the substituents have the following meaning:
- R¹
- Hydrogen, an amino, hydroxyl or C₁-C₃ alkyl group;
- R²
- Hydrogen, an acetyl, carbamoyl or cyano group;
- R³
- a ω-phenoxy, ω-tolyloxy, ω-benzyloxy or ω-cyclohexyloxy-C₁-C₁₂-alkyl group, the C-chain through one or two of the following non-adjacent links
-O-, -CO-, -O-CO- or -CO-O-
can be interrupted and which can carry one or two of the following substituents: halogen, hydroxy, C₁-C₂-alkyl, phenyl or cyclohexyl; - R⁴, R⁵
- Hydrogen, halogen, cyano, nitro or trihalomethyl groups;
Remains of the formulas
-CO-H, -CO-R⁶, -O-CO-R⁶, -CO-OR⁶, -SO-OR⁶, -O-SO-OR⁶, -CO-NR⁷R⁸,
-O-CO-NR⁷R⁸, -SO₂-NR⁷R⁸ or -O-SO₂-NR⁷R⁸
in which - R⁶
- denotes a C₁-C₁₂-alkyl group, an ω-phenoxy, ω-tolyloxy, ω-benzyloxy or ω-cyclohexyloxy-C₁-C₁₂ alkyl group, the C chain of the alkyl groups or the ω-substituted alkyl groups being represented by a or two oxygen atoms can be interrupted in ether function,
- R⁷
- is a C₁-C₁₂ alkyl group and
- R⁸
- represents hydrogen or one of the radicals R⁷,
Die Technik des Thermotransferdrucks ist allgemein bekannt; als Wärmequelle kommt neben Laser und IR-Lampe vor allem ein Thermokopf zur Anwendung, mit dem kurze Heizimpulse der Dauer von Bruchteilen einer Sekunde abgegeben werden können.The technique of thermal transfer printing is well known; In addition to the laser and IR lamp, the main heat source used is a thermal head with which short heating impulses lasting a fraction of a second can be emitted.
Bei dieser bevorzugten Ausführungsform des Thermotransferdrucks wird ein Transferblatt, das den zu übertragenden Farbstoff zusammen mit einem oder mehreren Bindemitteln, einem Trägermaterial und eventuell weiteren Hilfsmitteln wie Trennmitteln oder kristallisationshemmenden Stoffen enthält, von der Rückseite her durch den Thermokopf erhitzt. Dabei diffundiert der Farbstoff aus dem Transferblatt in die Oberflächenbeschichtung des Substrates, z.B. in die Kunststoffschicht eines beschichteten Papiers.In this preferred embodiment of thermal transfer printing, 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.
Der wesentliche Vorteil dieses Verfahrens besteht darin, daß über die an den Thermokopf abzugebende Energie die übertragene Farbmenge und damit die Farbabstufung gezielt gesteuert werden kann.The main advantage of this method is that the amount of color transferred and thus the color gradation can be specifically controlled via the energy to be delivered to the thermal head.
Beim Thermotransferdruck werden allgemein die drei subtraktiven Grundfarben Gelb, Magenta und Cyan, gegebenenfalls zusätzlich Schwarz, verwendet, wobei die eingesetzten Farbstoffe für eine optimale Farbaufzeichnung folgende Eigenschaften aufweisen müssen: leichte thermische Transferierbarkeit, geringe Neigung zur Migration innerhalb oder aus der Oberflächenbeschichtung des Aufnahmemediums bei Raumtemperatur, hohe thermische und photochemische Stabilität sowie Resistenz gegen Feuchtigkeit und Chemikalien, keine Tendenz zur Kristallisation bei Lagerung des Transferblattes, einen geeigneten Farbton für die subtraktive Farbmischung, einen hohen molaren Absorptionskoeffizienten und leichte technische Zugänglichkeit.Thermal transfer printing generally uses the three subtractive primary colors yellow, magenta and cyan, possibly also black, whereby the dyes used for optimum color recording must have the following properties: 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.
Diese Anforderungen sind gleichzeitig nur sehr schwer zu erfüllen. Insbesondere die bislang verwendeten Gelbfarbstoffe können nicht überzeugen. Dies trifft auch für die aus den EP-A-247 737, JP-A-12 393/1986, JP-A-244 595/1986 und JP-A-262 191/1986 bekannten und für den Thermotransferdruck empfohlenen Azopyridone zu, die sich von den Verbindungen I u.a. durch die Substituenten am Pyridon-Stickstoff unterscheiden.At the same time, these requirements are very difficult to meet. In particular, the yellow dyes previously used cannot convince. This also applies to the azopyridones known from EP-A-247 737, JP-A-12 393/1986, JP-A-244 595/1986 and JP-A-262 191/1986 and recommended for thermal transfer printing differ from the compounds I inter alia by the substituents on the pyridone nitrogen.
Die Azofarbstoffe I selbst sind an sich bekannt oder nach bekannten Methoden erhältlich (EP-B-111 236).The azo dyes I themselves are known per se or can be obtained by known methods (EP-B-111 236).
Der Erfindung lag daher die Aufgabe zugrunde, für den Thermotransferdruck geeignete Gelbfarbstoffe zu finden, die dem geforderten Eigenschaftsprofil näherkommen als die bisher bekannten Farbstoffe.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.
Demgemäß wurde die Verwendung der eingangs definierten Azofarbstoffe I für den Thermotransferdruck gefunden.Accordingly, the use of the azo dyes I defined at the outset was found for thermal transfer printing.
Außerdem wurde ein Verfahren zur Übertragung von Azofarbstoffen durch Diffusion von einem Träger auf ein mit Kunststoff beschichtetes Substrat mit Hilfe eines Thermokopfes gefunden, welches dadurch gekennzeichnet ist, daß man hierfür einen Träger verwendet, auf dem sich ein oder mehrere der eingangs definierten Azofarbstoffe I befinden.In addition, 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.
Weiterhin wurde eine bevorzugte Ausführungsform dieses Verfahrens gefunden, welche dadurch gekennzeichnet ist, daß man hierzu Farbstoffe der Formel Ia
verwendet, in der die Substituenten folgende Bedeutung haben:
- R3'
- eine ω-Phenoxy-, ω-Tolyloxy-, ω-Benzyloxy- oder ω-Cyclohexyloxy-C₁-C₁₂-alkylgruppe, deren C-Kette durch ein oder zwei Sauerstoffatome in Etherfunktion unterbrochen sein kann;
- R4', R5'
- Wasserstoff, Chlor oder eine Cyanogruppe;
Reste der Formel
-CO-OR⁶
Furthermore, a preferred embodiment of this process has been found, which is characterized in that dyes of the formula Ia
used in which the substituents have the following meaning:
- R 3 '
- a ω-phenoxy, ω-tolyloxy, ω-benzyloxy or ω-cyclohexyloxy-C₁-C₁₂-alkyl group, the C chain of which can be interrupted by one or two oxygen atoms in ether function;
- R 4 ' , R 5'
- Hydrogen, chlorine or a cyano group;
Remains of the formula
-CO-OR⁶
Unter den definitionsgemäßen Resten R¹ werden Ethyl und Propyl sowie besonders Methyl bevorzugt.Among the radicals R 1 defined by definition, ethyl and propyl and especially methyl are preferred.
Von den definitionsgemäßen Reste R² eignen sich besonders Acetyl sowie ganz besonders Cyano.Of the radicals R² by definition, acetyl and cyano are particularly suitable.
Geeignete Alkylreste R³ sind beispielsweise Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec.-Butyl, tert.-Butyl, Pentyl, Isopentyl, sec.-Pentyl, tert.-Pentyl, Hexyl, 2-Methylpentyl, Heptyl, Octyl, 2-Ethylhexyl, Nonyl, Decyl, Undecyl, Dodecyl und verzweigte Reste dieser Art, die jeweils in ω-Stellung eine Phenoxy-, Tolyloxy-, Benzyloxy- oder Cyclohexyloxygruppe tragen, wie vor allem (dabei bedeutet Ph = Phenyl und C₆H₁₁ = Cyclohexyl):
-(CH₂)₂-O-Ph, -(CH₂)₂-O-Ph-2-CH₃, -(CH₂)₂-O-Ph-3-CH₃, -(CH₂)₂-O-CH₂-Ph,
-(CH₂)₂-O-C₆H₁₁,
-(CH₂)₃-O-CH₂-Ph, -(CH₂)₃-O-C₆H₁₁,
-(CH₂)₄-O-Ph, -(CH₂)₄-O-CH₂-Ph, -(CH₂)₄-O-C₆H₁₁,
-(CH₂)₁₀-O-Ph und -(CH₂)₄-CH(C₂H₅)-CH₂-O-Ph.Suitable alkyl radicals R³ are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methyl pentyl, heptyl, octyl , 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and branched radicals of this type, each carrying a phenoxy, tolyloxy, benzyloxy or cyclohexyloxy group in the ω-position, especially (where Ph = phenyl and C₆H₁₁ = cyclohexyl ):
- (CH₂) ₂-O-Ph, - (CH₂) ₂-O-Ph-2-CH₃, - (CH₂) ₂-O-Ph-3-CH₃, - (CH₂) ₂-O-CH₂-Ph,
- (CH₂) ₂-O-C₆H₁₁,
- (CH₂) ₃-O-CH₂-Ph, - (CH₂) ₃-O-C₆H₁₁,
- (CH₂) ₄-O-Ph, - (CH₂) ₄-O-CH₂-Ph, - (CH₂) ₄-O-C₆H₁₁,
- (CH₂) ₁₀-O-Ph and - (CH₂) ₄-CH (C₂H₅) -CH₂-O-Ph.
Die C-Kette der genannten Alkylreste R³ kann durch ein oder zwei nicht benachbarte Glieder -CO-, -O-CO-, -CO-O- oder besonders -O- unterbrochen sein und kann bis zu zwei Substituenten wie Brom und Chlor, Hydroxy, Methyl, Ethyl, Phenyl oder Cyclohexyl tragen; beispielsweise sind hier zu nennen:
-(CH₂)₄-CO-(CH₂)₄-O-(CH₂)₃-O-Ph;
-(CH₂)₄-O-CO-(CH₂)₃-O-Ph, -(CH₂)₃-O-CO-(CH₂)₆-O-C₆H₁₁;
-(CH₂)₄-CO-O-(CH₂)₈-O-Ph und -(CH₂)₃-CO-O-(CH₂)₆-O-CH₂-Ph;
besonders bevorzugt -(CH₂)₃-O-(CH₂)₂-O-Ph, -(CH₂)₃-O-(CH₂)₂-O-Ph-2-CH₃,
-(CH₂)₃-O-(CH₂) ₂-O-Ph-3-CH₃,
bevorzugt -(CH₂)₃-O-(CH₂)₂-O-CH₂-Ph, -(CH₂)₃-O-(CH₂)₂-O-C₆H₁₁,
-(CH₂)₂-O-(CH₂)₂-O-Ph, -[(CH₂)₂-O]₂-(CH₂)₂-O-Ph,
-(CH₂)₃-O-CH(CH₃)-CH₂-O-Ph,
-(CH₂)₃-O-(CH₂)₂-O-(CH₂)₂-O-Ph, -(CH₂)₃-O-(CH₂)₂-O-(CH₂)₂-O-C₆H₁₁,
-(CH₂)₂-O-(CH₂)₃-O-CH₂-Ph, -(CH₂)₂-O-(CH₂)₂-CH(OH)-(CH₂)₂-O-Ph und
-(CH₂)₃-O-(CH₂)₂-CH(C₆H₁₁)-CH₂-O-Ph.The C chain of said alkyl radicals R³ can be interrupted by one or two non-adjacent links -CO-, -O-CO-, -CO-O- or especially -O- and can have up to two substituents such as bromine and chlorine, hydroxy , Methyl, ethyl, phenyl or cyclohexyl; Examples include:
- (CH₂) ₄-CO- (CH₂) ₄-O- (CH₂) ₃-O-Ph;
- (CH₂) ₄-O-CO- (CH₂) ₃-O-Ph, - (CH₂) ₃-O-CO- (CH₂) ₆-O-C₆H₁₁;
- (CH₂) ₄-CO-O- (CH₂) ₈-O-Ph and - (CH₂) ₃-CO-O- (CH₂) ₆-O-CH₂-Ph;
particularly preferred - (CH₂) ₃-O- (CH₂) ₂-O-Ph, - (CH₂) ₃-O- (CH₂) ₂-O-Ph-2-CH₃,
- (CH₂) ₃-O- (CH₂) ₂-O-Ph-3-CH₃,
preferably - (CH₂) ₃-O- (CH₂) ₂-O-CH₂-Ph, - (CH₂) ₃-O- (CH₂) ₂-O-C₆H₁₁,
- (CH₂) ₂-O- (CH₂) ₂-O-Ph, - [(CH₂) ₂-O] ₂- (CH₂) ₂-O-Ph,
- (CH₂) ₃-O-CH (CH₃) -CH₂-O-Ph,
- (CH₂) ₃-O- (CH₂) ₂-O- (CH₂) ₂-O-Ph, - (CH₂) ₃-O- (CH₂) ₂-O- (CH₂) ₂-O-C₆H₁₁,
- (CH₂) ₂-O- (CH₂) ₃-O-CH₂-Ph, - (CH₂) ₂-O- (CH₂) ₂-CH (OH) - (CH₂) ₂-O-Ph and
- (CH₂) ₃-O- (CH₂) ₂-CH (C₆H₁₁) -CH₂-O-Ph.
Reste R⁴ oder R⁵ können vor allem Wasserstoff, Chlor und Cyano, daneben auch Fluor, Brom, Nitro und Trihalogenmethylgruppen wie Trifluormethyl und Trichlormethyl sein.Residues R⁴ or R⁵ can be especially hydrogen, chlorine and cyano, but also fluorine, bromine, nitro and trihalomethyl groups such as trifluoromethyl and trichloromethyl.
Weiterhin geeignete Reste R⁴ oder R⁵ weisen die Formeln -CO-H, -CO-R⁶, -O-CO-R⁶, -CO-OR⁶, -SO-OR⁶, -O-SO-OR⁶, -CO-NR⁷R⁸, -O-CO-NR⁷R⁸, -SO₂-NR⁷R⁸ oder -O-SO₂-NR⁷R⁸ auf; dabei sind diejenigen der Formel -CO-OR⁶ besonders bevorzugt.Further suitable radicals R⁴ or R⁵ have the formulas -CO-H, -CO-R⁶, -O-CO-R⁶, -CO-OR⁶, -SO-OR⁶, -O-SO-OR⁶, -CO-NR⁷R⁸, -O -CO-NR⁷R⁸, -SO₂-NR⁷R⁸ or -O-SO₂-NR⁷R⁸; those of the formula -CO-OR⁶ are particularly preferred.
Der Rest R⁶ ist dabei eine der oben aufgeführten C₁-C₁₂-Alkylgruppen oder ω-Phenoxy-, ω-Tolyloxy-, ω-Benzyloxy- oder ω-Cyclohexyloxy-C₁-C₁₂-alkylgruppen, deren C-Kette jeweils durch ein oder zwei Sauerstoffatome in Etherfunktion unterbrochen sein kann. Geeignete Reste R⁷ oder R⁸ sind die bereits genannten unsubstituierten C₁-C₁₂-Alkylgruppen.The rest R⁶ is one of the above-listed C₁-C₁₂-alkyl groups or ω-phenoxy, ω-tolyloxy, ω-benzyloxy or ω-cyclohexyloxy-C₁-C₁₂-alkyl groups, the C chain of which each has one or two oxygen atoms can be interrupted in ether function. Suitable radicals R⁷ or R⁸ are the unsubstituted C₁-C₁₂ alkyl groups already mentioned.
Als Beispiele für die Reste R⁴ oder R⁵ seien die folgenden Gruppierungen genannt:
-CO-CH₃, -CO-C₂H₅, -CO-C₆H₁₃, -CO-C₁₁H₂₃,
-CO-(CH₂)₃-O-(CH₂)₂-O-Ph, -CO-(CH₂)₄-O-C₃H₇ und -CO-(CH₂)₈-O-CH₃;
-O-CO-CH₃, -O-CO-C₄H₉, -O-CO-C₇H₁₅,
-O-CO-(CH₂)₃-O-CH₃ und -O-CO-(CH₂)₄-O-C₄H₉;
-CO-O-CH₃, -CO-O-C₂H₅, -CO-O-C₄H₉, -CO-O-C₆H₁₃, -CO-O-C₇H₁₅,
-CO-O-(CH₂)₄-O-CH₃, -CO-O-CH(CH₃)-CH₂-O-CH₃,
-CO-O-(CH₂)₃-O-C₄H₉, -CO-O-(CH₂)₃-O-C₆H₁₃, -CO-O-(CH₂)₂-O-(CH₂)₂-O-C₄H₉,
-CO-O-(CH₂)₂-O-Ph, -CO-O-(CH₂)₃-O-Ph, -CO-O-(CH₂)₄-O-Ph,
-CO-O-(CH₂)₄-O-C₆H₁₁ und -CO-O-(CH₂)₈-O-CH₂-Ph;
-SO-O-CH₃, -SO-O-C₂H₅, -SO-O-C₅H₁₁,
-SO-O-(CH₂)₂-O-(CH₂)₂-O-CH₃ und -SO-O-(CH₂)₄-O-C₂H₅;
-O-SO-O-CH₃, -O-SO-O-C₄H₉, -O-SO-O-C₁₀H₂₁,
-O-SO-O-(CH₂)₃-O-C₄H₉ und -O-SO-O-(CH₂)₅-O-C₃H₇;
-CO-NH-C₄H₉, -CO-NH-C₇H₁₅, -CO-NH-C₉H₁₉, -CO-NH-C₁₀H₂₁,
-CO-NH-(CH₂)₃-O-(CH₂)₂-O-C₂H₅,
-CO-N(CH₃)-C₆H₁₃, -CO-N(C₂H₅)-C₃H₇ und -CO-N(C₃H₇)-C₃H₇;
-O-CO-NH-C₆H₁₃ und -O-CO-N(C₅H₁₁)-C₅H₁₁;
-SO₂-NH-C₇H₁₅, -SO₂-NH-C₁₀H₂₁, -SO₂-NH-(CH₂)₃-O-C₂H₅,
-SO₂-N(C₄H₉)-C₄H₉ und -SO₂-N(C₃H₇)-(CH₂)₄-O-C₄H₉;
-O-SO₂-NH-C₇H₁₅ und -O-SO₂-N((CH₂)₃-O-CH₃)-(CH₂)₃-O-CH₃.The following groupings may be mentioned as examples of the radicals R⁴ or R⁵:
-CO-CH₃, -CO-C₂H₅, -CO-C₆H₁₃, -CO-C₁₁H₂₃,
-CO- (CH₂) ₃-O- (CH₂) ₂-O-Ph, -CO- (CH₂) ₄-O-C₃H₇ and -CO- (CH₂) ₈-O-CH₃;
-O-CO-CH₃, -O-CO-C₄H₉, -O-CO-C₇H₁₅,
-O-CO- (CH₂) ₃-O-CH₃ and -O-CO- (CH₂) ₄-O-C₄H₉;
-CO-O-CH₃, -CO-O-C₂H₅, -CO-O-C₄H₉, -CO-O-C₆H₁₃, -CO-O-C₇H₁₅,
-CO-O- (CH₂) ₄-O-CH₃, -CO-O-CH (CH₃) -CH₂-O-CH₃,
-CO-O- (CH₂) ₃-O-C₄H₉, -CO-O- (CH₂) ₃-O-C₆H₁₃, -CO-O- (CH₂) ₂-O- (CH₂) ₂-O-C₄H₉,
-CO-O- (CH₂) ₂-O-Ph, -CO-O- (CH₂) ₃-O-Ph, -CO-O- (CH₂) ₄-O-Ph,
-CO-O- (CH₂) ₄-O-C₆H₁₁ and -CO-O- (CH₂) ₈-O-CH₂-Ph;
-SO-O-CH₃, -SO-O-C₂H₅, -SO-O-C₅H₁₁,
-SO-O- (CH₂) ₂-O- (CH₂) ₂-O-CH₃ and -SO-O- (CH₂) ₄-O-C₂H₅;
-O-SO-O-CH₃, -O-SO-O-C₄H₉, -O-SO-O-C₁₀H₂₁,
-O-SO-O- (CH₂) ₃-O-C₄H₉ and -O-SO-O- (CH₂) ₅-O-C₃H₇;
-CO-NH-C₄H₉, -CO-NH-C₇H₁₅, -CO-NH-C₉H₁₉, -CO-NH-C₁₀H₂₁,
-CO-NH- (CH₂) ₃-O- (CH₂) ₂-O-C₂H₅,
-CO-N (CH₃) -C₆H₁₃, -CO-N (C₂H₅) -C₃H₇ and -CO-N (C₃H₇) -C₃H₇;
-O-CO-NH-C₆H₁₃ and -O-CO-N (C₅H₁₁) -C₅H₁₁;
-SO₂-NH-C₇H₁₅, -SO₂-NH-C₁₀H₂₁, -SO₂-NH- (CH₂) ₃-O-C₂H₅,
-SO₂-N (C₄H₉) -C₄H₉ and -SO₂-N (C₃H₇) - (CH₂) ₄-O-C₄H₉;
-O-SO₂-NH-C₇H₁₅ and -O-SO₂-N ((CH₂) ₃-O-CH₃) - (CH₂) ₃-O-CH₃.
Bevorzugte Azofarbstoffe I sind den Beispielen zu entnehmen.Preferred azo dyes I can be found in the examples.
Die erfindungsgemäß zu verwendenden Farbstoffe I zeichnen sich gegenüber den bisher für den Thermotransferdruck eingesetzten Gelbfarbstoffen durch folgende Eigenschaften aus: leichtere thermische Transferierbarkeit trotz des relativ hohen Molekulargewichts, verbesserte Migrationseigenschaften im Aufnahmemedium bei Raumtemperatur, höhere Lichtechtheit, bessere Resistenz gegen Feuchtigkeit und Chemikalien, bessere Löslichkeit bei der Herstellung der Druckfarbe, höhere Farbstärke sowie leichtere technische Zugänglichkeit.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.
Zudem zeigen die Azofarbstoffe I deutlich bessere Farbtonreinheit, insbesondere in Farbstoffmischungen, und ergeben verbesserte Schwarz-Drucke.In addition, the azo dyes I show significantly better color purity, in particular in dye mixtures, and give improved black prints.
Die für das erfindungsgemäße Thermotransferdruckverfahren benötigten, als Farbstoffgeber fungierenden Transferblätter werden folgendermaßen präpariert: Die Azofarbstoffe I werden in einem organischen Lösungsmittel, wie z.B. Isobutanol, Methylethylketon, Methylenchlorid, Chlorbenzol, Toluol, Tetrahydrofuran oder deren Mischungen, mit einem oder mehreren Bindemitteln sowie eventuell weiteren Hilfsmitteln wie Trennmitteln oder kristallisationshemmenden Stoffen zu einer Druckfarbe verarbeitet, welche die Farbstoffe vorzugsweise molekular-dispers gelöst enthält. Die Druckfarbe wird anschließend auf einen inerten Träger aufgetragen und getrocknet.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.
Als Bindemittel für die erfindungsgemäße Verwendung der Azofarbstoffe I eignen sich alle in organischen Lösungsmitteln löslichen Materialien, die bekanntermaßen für den Thermotransferdruck dienen, also z.B. Cellulosederivate wie Methylcellulose, Hydroxypropylcellulose, Celluloseacetat oder Celluloseacetobutyrat, vor allem Ethylcellulose, Ethylhydroxyethylcellulose und Celluloseacetathydrogenphthalat, Stärke, Alginate, Alkydharze wie Polyvinylalkohol oder Polyvinylpyrrolidon sowie besonders Polyvinylacetat und Polyvinylbutyrat. Daneben kommen Polymere und Copolymere von Acrylaten oder deren Derivaten wie Polyacrylsäure, Polymethylmethacrylat- oder Styrolacrylatcopolymere, Polyesterharze, Polyamidharze, Polyurethanharze oder natürliche Harze wie z.B. Gummi Arabicum in Betracht.Suitable binders for the use of 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 especially polyvinyl acetate and polyvinyl butyrate. In addition there are 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.
Häufig empfehlen sich Mischungen dieser Bindemittel, z.B. solche aus Ethylcellulose und Polyvinylbutyrat im Gewichtsverhältnis 2 : 1.Mixtures of these binders are often recommended, e.g. those made of ethyl cellulose and polyvinyl butyrate in a weight ratio of 2: 1.
Das Gewichtsverhältnis von Bindemittel zu Farbstoff beträgt in der Regel 8 : 1 bis 1 : 1, vorzugsweise 5 : 1 bis 2 : 1.The weight ratio of binder to dye is usually 8: 1 to 1: 1, preferably 5: 1 to 2: 1.
Als Hilfsmittel werden z.B. Trennmittel auf der Basis von perfluorierten Alkylsulfonamidoalkylestern oder Siliconen, wie sie in der EP-A-227 092 bzw. der EP-A-192 435 beschrieben sind, und besonders organische Additive, welche das Auskristallisieren der Transferfarbstoffe bei Lagerung und Erhitzung des Farbbandes verhindern, beispielsweise Cholesterin oder Vanillin, verwendet.As aids, e.g. Release agents based on perfluorinated alkylsulfonamidoalkyl esters or silicones as described in EP-A-227 092 or EP-A-192 435, and especially organic additives which prevent the transfer dyes from crystallizing out when the ribbon is stored and heated, for example cholesterol or vanillin used.
Inerte Trägermaterialien sind beispielsweise Seiden-, Lösch- oder Pergaminpapier sowie Folien aus wärmebeständigen Kunststoffen wie Polyestern, Polyamiden oder Polyimiden, wobei diese Folien auch metallbeschichtet sein können.Inert carrier materials are, for example, tissue paper, blotting paper or glassine paper and films made of heat-resistant plastics such as polyesters, polyamides or polyimides, these films also being able to be metal-coated.
Der inerte Träger kann auf der dem Thermokopf zugewandten Seite zusätzlich mit einem Gleitmittel beschichtet werden, um ein Verkleben des Thermokopfes mit dem Trägermaterial zu verhindern. Geeignete Gleitmittel sind beispielsweise Silicone oder Polyurethane, wie sie in der EP-A-216 483 beschrieben sind.The inert carrier can also 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 are described in EP-A-216 483.
Die Stärke des Farbstoffträgers beträgt im allgemeinen 3 bis 30 µm, bevorzugt 5 bis 10 µm.The thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
Das zu bedruckende Substrat, z.B. Papier, muß seinerseits mit einem Bindemittel beschichtet sein, welches den Farbstoff beim Druckvorgang aufnimmt. Vorzugsweise verwendet man hierzu polymere Materialien, deren Glasumwandlungstemperatur Tg zwischen 50 und 100°C beträgt, also z.B. Polycarbonate und Polyester. Näheres hierzu ist den EP-A-227 094, EP-A-133 012, EP-A-133 011, JP-A-199 997/1986 oder JP-A 283 595/1986 zu entnehmen.The substrate to be printed, for example paper, must itself be coated with a binder that absorbs the dye during the printing process. Polymeric materials whose glass transition temperature T g 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.
Für das erfindungsgemäße Verfahren wird ein Thermokopf eingesetzt, der auf Temperaturen bis über 300°C aufheizbar ist, so daß der Farbstofftransfer in einer Zeit von maximal 15 msec erfolgt.For the process according to the invention, a thermal head is used which can be heated to temperatures above 300 ° C., so that the dye transfer takes place in a maximum of 15 msec.
Es wurden zunächst in üblicher Weise Transferblätter (Geber) aus Polyesterfolie von 8 µm Stärke hergestellt, die mit einer ca. 5 µm starken Transferschicht aus einem Bindemittel B versehen war, welche jeweils 0,25 g Azofarbstoff I enthielt. Das Gewichtsverhältnis Bindemittel zu Farbstoff betrug jeweils 4 : 1.Initially, transfer sheets (donors) were produced in a conventional manner from 8 µm thick polyester film, which was provided with an approximately 5 µm thick transfer layer made from a binder B, each of which contained 0.25 g of azo dye I. The weight ratio of binder to dye was 4: 1 in each case.
Das zu bedruckende Substrat (Nehmer) bestand aus Papier von ca. 120 µm Stärke, das mit einer 8 µm dicken Kunststoffschicht beschichtet war (Hitachi Color Video Print Paper).The substrate to be printed (taker) consisted of paper of approx. 120 µm thickness, which was coated with an 8 µm thick plastic layer (Hitachi Color Video Print Paper).
Geber und Nehmer wurden mit der beschichteten Seite aufeinander gelegt, mit Aluminiumfolie umwickelt und für 2 min zwischen zwei Heizplatten auf eine Temperatur zwischen 70 und 80°C erhitzt. Mit gleichartigen Proben wurde dieser Vorgang dreimal bei jeweils höherer Temperatur zwischen 80 und 120°C wiederholt.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.
Die hierbei in die Kunststoffschicht des Nehmers diffundierte Farbstoffmenge ist proportional der optischen Dichte, die als Extinktion A photometrisch nach dem jeweiligen Erhitzen auf die oben angegebenen Temperaturen bestimmt wurde.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.
Die Auftragung des Logarithmus der gemessenen Extinktionswerte A gegen die zugehörige reziproke absolute Temperatur ergibt Geraden, aus deren Steigung die Aktivierungsenergie ΔET für das Transferexperiment zu berechnen ist:
Der Auftragung kann zusätzlich die Temperatur T* entnommen werden, bei der die Extinktion den Wert 1 erreicht, d.h., die durchgelassene Lichtintensität ein Zehntel der eingestrahlten Lichtintensität beträgt. Je kleinere Werte die Temperatur T* annimmt, um so besser ist die thermische Transferierbarkeit des untersuchten Farbstoffs.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.
In der folgenden Tabelle sind die bezüglich ihres Thermotransferverhaltens untersuchten Azofarbstoffe I mit den zugehörigen in Methylenchlorid gemessenen Absorptionsmaxima λmax [nm] aufgeführt.The following table shows the azo dyes I investigated with regard to their thermal transfer behavior, with the associated absorption maxima λ max [nm] measured in methylene chloride.
Zudem ist das jeweils verwendete Bindemittel B angegeben. Dabei bedeutet: EC = Ethylcellulose, PVB = Polyvinylbutyrat, MS = EC:PVB = 2:1.In addition, the binder B used in each case is indicated. Here means: EC = ethyl cellulose, PVB = polyvinyl butyrate, MS = EC: PVB = 2: 1.
Weiterhin aufgelistete charakteristische Daten sind die bereits erwähnten Parameter T* [°C] und ΔET [kcal/mol].
Claims (3)
-O-, -CO-, -O-CO- oder -CO-O-
unterbrochen sein kann und die ein oder zwei der folgenden Substituenten tragen kann: Halogen, Hydroxy, C₁-C₂-Alkyl, Phenyl oder Cyclohexyl;
Reste der Formeln
-CO-H, -CO-R⁶, -O-CO-R⁶, -CO-OR⁶, -SO-OR⁶, -O-SO-OR⁶,
-CO-NR⁷R⁸, -O-CO-NR⁷R⁸, -SO₂-NR⁷R⁸ oder -O-SO₂-NR⁷R⁸
wobei
-O-, -CO-, -O-CO- or -CO-O-
can be interrupted and which can carry one or two of the following substituents: halogen, hydroxy, C₁-C₂-alkyl, phenyl or cyclohexyl;
Remains of the formulas
-CO-H, -CO-R⁶, -O-CO-R⁶, -CO-OR⁶, -SO-OR⁶, -O-SO-OR⁶,
-CO-NR⁷R⁸, -O-CO-NR⁷R⁸, -SO₂-NR⁷R⁸ or -O-SO₂-NR⁷R⁸
in which
Reste der Formel
-CO-OR⁶
Remains of the formula
-CO-OR⁶
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4019419 | 1990-06-19 | ||
| DE4019419A DE4019419A1 (en) | 1990-06-19 | 1990-06-19 | USE OF AZO DYES FOR THERMAL TRANSFER PRINT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0462447A1 true EP0462447A1 (en) | 1991-12-27 |
| EP0462447B1 EP0462447B1 (en) | 1994-12-21 |
Family
ID=6408614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91109225A Expired - Lifetime EP0462447B1 (en) | 1990-06-19 | 1991-06-06 | Use of azo dyes in thermal transfer printing |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5204312A (en) |
| EP (1) | EP0462447B1 (en) |
| JP (1) | JPH04232781A (en) |
| DE (2) | DE4019419A1 (en) |
Cited By (1)
| 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 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835708B2 (en) | 2001-03-07 | 2004-12-28 | Nippon Shokubai Co., Ltd. | Graft polymer composition and its production process and uses |
| JP5634019B2 (en) * | 2008-10-14 | 2014-12-03 | キヤノン株式会社 | Dye compound and ink containing the dye compound |
| CN105504858A (en) * | 2016-01-27 | 2016-04-20 | 杭州福莱蒽特精细化工有限公司 | Single azo based pyridine ketone dye and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2951403A1 (en) * | 1979-12-20 | 1981-06-25 | Basf Ag, 6700 Ludwigshafen | Phenyl-azo pyridine dyestuff cpds. esp. useful for polyester - are phenyl-or phenoxy-alkoxy-alkyl hydroxy phenyl-azo methyl cyano pyridone cpds. |
| EP0247737A1 (en) * | 1986-05-27 | 1987-12-02 | Imperial Chemical Industries Plc | Thermal transfer printing |
| JPS6339380A (en) * | 1986-08-04 | 1988-02-19 | Mitsubishi Chem Ind Ltd | Thermal transfer sheet |
| EP0302627A2 (en) * | 1987-08-04 | 1989-02-08 | Imperial Chemical Industries Plc | Thermal transfer printing |
| EP0319234A2 (en) * | 1987-12-03 | 1989-06-07 | MITSUI TOATSU CHEMICALS, Inc. | Coloring method by use of new yellow dyestuff and coloring transfer material for thermal transfer using this method |
| EP0323259A2 (en) * | 1987-12-29 | 1989-07-05 | Matsushita Electric Industrial Co., Ltd. | Dye transfer type thermal printing sheets |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3244960A1 (en) * | 1982-12-04 | 1984-06-07 | Basf Ag, 6700 Ludwigshafen | PYRIDONE DYES |
| DE3481596D1 (en) * | 1983-07-25 | 1990-04-19 | Dainippon Printing Co Ltd | SHEET FOR USE IN THERMAL TRANSFER PRINTING. |
| JPS6112393A (en) * | 1984-06-29 | 1986-01-20 | Mitsui Toatsu Chem Inc | Yellowish-hue thermal transfer coloring material |
| GB8504518D0 (en) * | 1985-02-21 | 1985-03-27 | Ici Plc | Thermal transfer dyesheet |
| JPH0741746B2 (en) * | 1985-02-28 | 1995-05-10 | 大日本印刷株式会社 | Thermal transfer image receiving sheet |
| JPS61244595A (en) * | 1985-04-24 | 1986-10-30 | Mitsubishi Chem Ind Ltd | Pyridone azo coloring matter for thermal transfer recording |
| JPS61262191A (en) * | 1985-05-16 | 1986-11-20 | Sumitomo Chem Co Ltd | Sublimable transfer body |
| JPH0714665B2 (en) * | 1985-06-10 | 1995-02-22 | 大日本印刷株式会社 | Heat transfer sheet |
| 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 |
| EP0442466B1 (en) * | 1990-02-14 | 1995-01-18 | Mitsubishi Chemical Corporation | Thermal transfer recording sheet and ink composition for producing the same |
-
1990
- 1990-06-19 DE DE4019419A patent/DE4019419A1/en not_active Withdrawn
-
1991
- 1991-06-06 EP EP91109225A patent/EP0462447B1/en not_active Expired - Lifetime
- 1991-06-06 DE DE59103964T patent/DE59103964D1/en not_active Expired - Lifetime
- 1991-06-12 US US07/714,021 patent/US5204312A/en not_active Expired - Fee Related
- 1991-06-18 JP JP3145742A patent/JPH04232781A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2951403A1 (en) * | 1979-12-20 | 1981-06-25 | Basf Ag, 6700 Ludwigshafen | Phenyl-azo pyridine dyestuff cpds. esp. useful for polyester - are phenyl-or phenoxy-alkoxy-alkyl hydroxy phenyl-azo methyl cyano pyridone cpds. |
| EP0247737A1 (en) * | 1986-05-27 | 1987-12-02 | Imperial Chemical Industries Plc | Thermal transfer printing |
| JPS6339380A (en) * | 1986-08-04 | 1988-02-19 | Mitsubishi Chem Ind Ltd | Thermal transfer sheet |
| EP0302627A2 (en) * | 1987-08-04 | 1989-02-08 | Imperial Chemical Industries Plc | Thermal transfer printing |
| EP0319234A2 (en) * | 1987-12-03 | 1989-06-07 | MITSUI TOATSU CHEMICALS, Inc. | Coloring method by use of new yellow dyestuff and coloring transfer material for thermal transfer using this method |
| EP0323259A2 (en) * | 1987-12-29 | 1989-07-05 | Matsushita Electric Industrial Co., Ltd. | Dye transfer type thermal printing sheets |
Cited By (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0462447B1 (en) | 1994-12-21 |
| JPH04232781A (en) | 1992-08-21 |
| DE59103964D1 (en) | 1995-02-02 |
| US5204312A (en) | 1993-04-20 |
| DE4019419A1 (en) | 1992-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0416434B1 (en) | Triazole pyridine dyes and a thermal transfer process of methine dyes | |
| EP0258856B1 (en) | Dye transfer method | |
| DE3829918C2 (en) | Heat-sensitive transfer material | |
| EP0441282B1 (en) | Bichromophore methine and azamethine dyestuffs and a process for their transfer | |
| EP0346729B1 (en) | Azo dye transfer process with a pyridine coupling component | |
| EP0439200B1 (en) | Transfer process using methine dyes containing bichromophoric cyano-groups | |
| DE68908996T2 (en) | Heat sensitive transfer material. | |
| EP0437282B1 (en) | Bichromophore methine dyes containing cyano groups and a process for their transfer | |
| EP0460463B1 (en) | Use of azo dyes in thermal transfer printing | |
| EP0441208B1 (en) | Use of azo-dyes for thermal transfer printing | |
| EP0462447B1 (en) | Use of azo dyes in thermal transfer printing | |
| EP0344592B2 (en) | Process for azo dye transfer | |
| EP0480252B1 (en) | Pyridone dyes and a method for their thermal transfer | |
| EP0479076B1 (en) | Process for transfer of indoaniline dyestuffs | |
| EP0480278B1 (en) | Use of anthraquinone dyestuffs for thermal transfer printing | |
| EP0420036B1 (en) | Use of azo dyes in thermal transfer printing | |
| EP0490225B1 (en) | Use of anthraquinone dyerstuffs for thermal transfer printing | |
| EP0442360A1 (en) | Process for transfer of azo dyes | |
| DE69001477T2 (en) | HEAT TRANSFER SHEET. | |
| DE3881603T2 (en) | Transfer pressure through heat. | |
| EP0567829B1 (en) | Process for transfer of anthraquinone dyes | |
| EP0479068B1 (en) | Quinoline methin dyes and process for their thermal transfer | |
| EP0509302A1 (en) | Process for transfer of methine dyes |
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 |
|
| 17P | Request for examination filed |
Effective date: 19910810 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE FR GB IT LI |
|
| 17Q | First examination report despatched |
Effective date: 19931105 |
|
| 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 |
|
| REF | Corresponds to: |
Ref document number: 59103964 Country of ref document: DE Date of ref document: 19950202 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19950111 |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
| 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 | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19970529 Year of fee payment: 7 |
|
| 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: 19980630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980630 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20010515 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20010604 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20010628 Year of fee payment: 11 |
|
| 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: 20020606 |
|
| 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: 20020615 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20020606 |
|
| 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: 20030228 |
|
| 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: 20050606 |