EP0567829B1 - Process for transfer of anthraquinone dyes - Google Patents
Process for transfer of anthraquinone dyes Download PDFInfo
- Publication number
- EP0567829B1 EP0567829B1 EP93105925A EP93105925A EP0567829B1 EP 0567829 B1 EP0567829 B1 EP 0567829B1 EP 93105925 A EP93105925 A EP 93105925A EP 93105925 A EP93105925 A EP 93105925A EP 0567829 B1 EP0567829 B1 EP 0567829B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- substituted
- hydrogen
- alkoxy
- anthraquinone dyes
- 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
Links
- 238000000034 method Methods 0.000 title claims description 15
- 239000001000 anthraquinone dye Substances 0.000 title claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 47
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- -1 cyano, phenyl Chemical group 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 125000005041 acyloxyalkyl group Chemical group 0.000 claims description 4
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 4
- 125000005205 alkoxycarbonyloxyalkyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 3
- 238000000859 sublimation Methods 0.000 claims description 3
- 230000008022 sublimation Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 239000000975 dye Substances 0.000 description 20
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 19
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000010023 transfer printing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000001045 blue dye Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical class C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 1
- HPDVKZCKPOFXQA-UHFFFAOYSA-N 2-acetyl-1-aminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(C(=O)C)=CC=C3C(=O)C2=C1 HPDVKZCKPOFXQA-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001295925 Gegenes Species 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- B41M5/3852—Anthraquinone or naphthoquinone 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 present invention relates to a new method for transferring anthraquinone dyes by diffusion or sublimation from a support to a plastic-coated substrate with the aid of an energy source.
- a transfer sheet which contains a thermally transferable dye in one or more binders, optionally together with suitable auxiliaries, is supported on a support with an energy source, e.g. with a heating head or a laser, heated by short heating impulses (duration: fractions of a second) from the rear, whereby the dye migrates from the transfer sheet and diffuses into the surface coating of a recording medium, usually into the plastic layer of a coated paper.
- an energy source e.g. with a heating head or a laser
- short heating impulses duration: fractions of a second
- the color is recorded using the subtractive primary colors yellow, magenta, cyan (and possibly black).
- the invention was therefore based on the object of finding suitable blue dyes for thermal transfer printing processes which come closer to the required property profile than the dyes known hitherto.
- Suitable radicals R 1 , R 2 or R 3 are C 1 -C 20 alkyl groups, preference is given to C 1 -C 12 alkyl groups and, in the case of R 3 , C 1 -C 4 alkyl groups are particularly preferred.
- the following may be mentioned in detail: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosy
- R 1 is particularly preferably hydrogen
- R 2 is phenyl, which can be substituted by C 1 -C 4 -alkyl or -alkoxy
- R 3 C 1 -C 4 -alkyl, in particular methyl
- X in addition to cyano, is especially hydrogen.
- the anthraquinone dyes I are known per se or can be prepared by known methods.
- the anthraquinones I which have an acetyl group in the 2-position are e.g. Expediently from 1-amino-2-acetylanthraquinone (Houben-Weyl, Vol. 7 / 3c, p. 251), which can then be reacted with the desired ones in a conventional manner after bromination in the sense of a Ullmann reaction.
- anthraquinone dyes known to be used in the process according to the invention are generally distinguished by improved migration properties in the recording medium at room temperature, easier thermal transferability, higher thermal and photochemical stability, easier technical accessibility, better resistance to moisture and chemicals, higher color strength, better solubility or better suitability for subtractive color mixing (higher color purity, more favorable form of the absorption band, higher transparency in the green spectral range).
- the dyes are processed into a printing ink in a suitable organic solvent or in mixtures of solvents with one or more binders, if appropriate with the addition of auxiliaries.
- a printing ink in a suitable organic solvent or in mixtures of solvents with one or more binders, if appropriate with the addition of auxiliaries.
- the printing ink can be applied to the inert carrier using a doctor blade. The resulting color is then air dried.
- Suitable organic solvents are those in which the solubility of the dyes I generally at a temperature of 20 ° C. is greater than 1% by weight, preferably greater than 5% by weight.
- ethanol for example, ethanol, propanol, isobutanol, tetrahydrofuran, methylene chloride, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene, chlorobenzene or mixtures thereof.
- binders All resins or polymer materials which are soluble in organic solvents and bind the dye to the inert support in an abrasion-resistant manner are suitable as binders capital. Preference is given to binders which, after the printing ink has dried in air, absorb the dye in the form of a clear, transparent film without the dye crystallizing out visibly.
- Preferred binders are especially ethyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl butyrate, polyvinyl acetate, cellulose propionate and saturated linear polyesters.
- the weight ratio of binder: dye is generally 1: 1 to 10: 1.
- Suitable inert carriers are also described in EP-A-441 282 and in the patent applications cited therein.
- the thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
- thermostable plastic layers with affinity for the dyes to be transferred can be used as the dye-receiving layer, e.g. modified polycarbonate or polyester. Further details can be found in EP-A-441 282 or the patent applications cited therein.
- the dye transfer takes place with the aid of an energy source, such as a laser or, above all, a thermal head, the latter having to be able to be heated to a temperature of 300 300 ° C. so that the dye transfer can take place in the time range t: 0 ⁇ t ⁇ 15 msec.
- the dye migrates from the transfer sheet and diffuses into the surface coating of the recording medium.
- the printing ink obtained was knife-coated onto a 6 ⁇ m thick polyester film with a sliding layer on the back using a 6 ⁇ m doctor blade.
- the ink ribbons were then first blown dry with a hair dryer and then air-dried for at least 24 hours in order to remove residual amounts of solvent.
- the ink ribbons were then printed on Hitachi VY-S video print paper on a computer-controlled experimental set-up with a commercially available thermal head.
- the energy emitted by the thermal head is controlled by changing the voltage, the set pulse duration being 7 ms and only one pulse being emitted.
- the energy delivered is between 0.71 and 1.06 mJ per dot.
- the following table shows the transferred anthraquinone dyes I, their absorption maximum ⁇ max [nm] measured in methylene chloride, their half-value values HWB [cm -1 ] and their transfer data Q * [mJ / Dot] and m [1 / mJ].
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Übertragung von Anthrachinonfarbstoffen durch Diffusion oder Sublimation von einem Träger auf ein mit Kunststoff beschichtetes Substrat mit Hilfe einer Energiequelle.The present invention relates to a new method for transferring anthraquinone dyes by diffusion or sublimation from a support to a plastic-coated substrate with the aid of an energy source.
Beim Thermotransferdruckverfahren wird ein Transferblatt, das einen thermisch transferierbaren Farbstoff in einem oder mehreren Bindemittel, gegebenenfalls zusammen mit geeigneten Hilfsmitteln, auf einem Träger enthält, mit einer Energiequelle, z.B. mit einem Heizkopf oder einem Laser, durch kurze Heizimpulse (Dauer: Bruchteile einer Sekunde) von der Rückseite her erhitzt, wodurch der Farbstoff aus dem Transferblatt migriert und in die Oberflächenbeschichtung eines Aufnahmemediums, in der Regel in die Kunststoffschicht eines beschichteten Papiers, hineindiffundiert. Der wesentliche Vorteil dieses Verfahrens besteht darin, daß die Steuerung der zu übertragenden Farbstoffmenge (und damit die Farbabstufung) durch Einstellung der von der Energiequelle abzugebenden Energie leicht möglich ist.In the thermal transfer printing process, a transfer sheet which contains a thermally transferable dye in one or more binders, optionally together with suitable auxiliaries, is supported on a support with an energy source, e.g. with a heating head or a laser, heated by short heating impulses (duration: fractions of a second) from the rear, whereby the dye migrates from the transfer sheet and diffuses into the surface coating of a recording medium, usually into the plastic layer of a coated paper. 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 released from the energy source.
Allgemein wird die Farbaufzeichnung unter Verwendung der subtraktiven Grundfarben Gelb, Magenta, Cyan (und gegebenenfalls Schwarz) durchgeführt.In general, the color is recorded using the subtractive primary colors yellow, magenta, cyan (and possibly black).
Um eine optimale Farbaufzeichnung zu ermöglichen, müssen die Farbstoffe folgende Eigenschaften besitzen:
- leicht 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.
- 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 the transfer sheet is stored;
- a suitable shade for the subtractive color mixture;
- a high molar absorption coefficient.
Diese Forderungen sind erfahrungsgemäß gleichzeitig sehr schwierig zu erfüllen. Daher entsprechen die meisten der bekannten, für den thermischen Transferdruck verwendeten Blaufarbstoffe nicht dem geforderten Anforderungsprofil. Dies trifft auch auf die aus der EP-A-337 200 und den JP-A-227 948/1984, 53 563/1985, 221 287/1989 und 158 294/1991 bekannten und als Blaufarbstoffe für den Thermotransferdruck empfohlenen 1,4-Diaminoanthrachinone zu, die den im erfindungsgemäßen Verfahren eingesetzten Verbindungen I ähneln, jedoch in 2-Position einen Alkoxycarbonylrest bzw. eine Aldehydfunktion tragen.Experience has shown that these requirements are very difficult to meet at the same time. Therefore, most of the known blue dyes used for thermal transfer printing do not meet the required profile. This also applies to the 1,4- known from EP-A-337 200 and JP-A-227 948/1984, 53 563/1985, 221 287/1989 and 158 294/1991 and recommended as blue dyes for thermal transfer printing. Diaminoanthraquinones, which are similar to the compounds I used in the process according to the invention, but carry an alkoxycarbonyl radical or an aldehyde function in the 2-position.
Der Erfindung lag daher die Aufgabe zugrunde, für Thermotransferdruckverfahren geeignete Blaufarbstoffe zu finden, die dem geforderten Eigenschaftsprofil näherkommen als die bislang bekannten Farbstoffe.The invention was therefore based on the object of finding suitable blue dyes for thermal transfer printing processes which come closer to the required property profile than the dyes known hitherto.
Demgemäß wurde ein neues Verfahren zur Übertragung von Anthrachinonfarbstoffen durch Diffusion oder Sublimation von einem Träger auf ein mit Kunststoff beschichtetes Substrat mit Hilfe einer Energiequelle gefunden, welches dadurch gekennzeichnet ist, daß man einen Träger verwendet, auf dem sich ein oder mehrere Anthrachinonfarbstoffe der allgemeinen Formel I
- X
- Wasserstoff oder Cyano;
- R1 und R2
- unabhängig voneinander
- Wasserstoff;
- Alkyl, Alkanoyloxyalkyl, Alkoxycarbonyloxyalkyl oder Alkoxycarbonylalkyl, die jeweils bis zu 20 C-Atome enthalten können und durch Halogen, Hydroxy oder Cyano substituiert sein können;
- Phenyl oder Benzyl, die jeweils durch C1-C15-Alkyl oder -Alkoxy substituiert sein können;
- einen Rest der allgemeinen Formel II
[―W―O]n―R4 II
in der
- W
- gleiche oder verschiedene C2-C6-Alkylenreste bezeichnet,
- n
- 1 bis 6 bedeutet und
- R4
- für C1-C4-Alkyl oder gegebenenfalls durch C1-C4-Alkyl oder -Alkoxy substituiertes Phenyl steht;
- R3
- einen der für R1 und R2 genannten organischen Reste außer Wasserstoff.
- X
- Hydrogen or cyano;
- R 1 and R 2
- independently of each other
- Hydrogen;
- Alkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl or alkoxycarbonylalkyl, which can each contain up to 20 carbon atoms and can be substituted by halogen, hydroxy or cyano;
- Phenyl or benzyl, each of which may be substituted by C 1 -C 15 alkyl or alkoxy;
- a radical of the general formula II
[―W ― O] n ―R 4 II
in the
- W
- denotes the same or different C 2 -C 6 alkylene radicals,
- n
- 1 to 6 means and
- R 4
- represents C 1 -C 4 alkyl or phenyl optionally substituted by C 1 -C 4 alkyl or alkoxy;
- R 3
- one of the organic radicals mentioned for R 1 and R 2 , except hydrogen.
Bevorzugte Ausführungsformen dieses Verfahrens sind den Unteransprüchen zu entnehmen.Preferred embodiments of this method can be found in the subclaims.
Geeignete Reste R1, R2 oder R3 sind dabei C1-C20-Alkylgruppen, bevorzugt sind C1-C12-Alkylgruppen sowie im Fall von R3 besonders bevorzugt C1-C4-Alkylgruppen. Im einzelnen seien genannt: Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, tert.-Butyl, Pentyl, Isopentyl, sec.-Pentyl, tert.-Pentyl, Hexyl, 2-Methylpentyl, Heptyl, Octyl, 2-Ethylhexyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl sowie verzweigte Reste dieser Art.Suitable radicals R 1 , R 2 or R 3 are C 1 -C 20 alkyl groups, preference is given to C 1 -C 12 alkyl groups and, in the case of R 3 , C 1 -C 4 alkyl groups are particularly preferred. The following may be mentioned in detail: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and branched residues of this type.
Die Alkylgruppen können auch durch Halogen, Hydroxy oder Cyano substituiert sein; beispielsweise sind hier zu nennen:
- -(CH2)5-Cl, -CH(C4H9)-(CH2)3-Cl und -(CH2)4-CF3;
- -(CH2)2-CH(CH3)-OH, -(CH2)2-CH(C4H9)-OH und
- -CH(C2H5)-(CH2)9-OH;
- -(CH2)2-CN, -(CH2)3-CN, -CH2-CH(CH3)-CH(C2H5)-CN,
- -(CH2)6-CH(C2H5)-CN und
- -(CH2)3-CH(CH3)-(CH2)2-CH(CH3)-CN.
- - (CH 2 ) 5 -Cl, -CH (C 4 H 9 ) - (CH 2 ) 3 -Cl and - (CH 2 ) 4 -CF 3 ;
- - (CH 2 ) 2 -CH (CH 3 ) -OH, - (CH 2 ) 2 -CH (C 4 H 9 ) -OH and
- -CH (C 2 H 5 ) - (CH 2 ) 9 -OH;
- - (CH 2 ) 2 -CN, - (CH 2 ) 3 -CN, -CH 2 -CH (CH 3 ) -CH (C 2 H 5 ) -CN,
- - (CH 2 ) 6 -CH (C 2 H 5 ) -CN and
- - (CH 2 ) 3 -CH (CH 3 ) - (CH 2 ) 2 -CH (CH 3 ) -CN.
Als Reste R1, R2 oder R3 geeignete Alkanoyloxyalkyl-, Alkoxycarbonyloxyalkyl- und Alkoxycarbonylalkylgruppen sind beispielsweise:
- -(CH2)2-O-CO-CH3,
- -(CH2)3-O-CO-(CH2)7-CH3,
- -(CH2)2-O-CO-(CH2)3-Ph-2-O-CH3,
- -CH(CH2-Ph-3-CH3)-O-CO-C4H9 und
- -(CH2)4-O-CO-(CH2)4-CH(C2H5)-OH;
- -(CH2)2-O-CO-O-CH3,
- -(CH2)3-O-CO-O-(CH2)7-CH3,
- -CH(C2H5)-CH2-O-CO-O-C4H9,
- -(CH2)4-O-CO-O-(CH2)2-CH(CH3)-O-Ph-3-CH3 und
- -(CH2)5-O-CO-O-(CH2)5-CN;
- -(CH2)2-CO-O-CH3,
- -(CH2)3-CO-O-C4H9,
- -(CH2)3-CH(CH3)-CH2-CO-O-C4H9,
- -(CH2)3-CH(C4H9)-CH2-CO-O-C2H5,
- -(CH2)2-CO-O-(CH2)5-Ph,
- -(CH2)4-CO-O-(CH2)4-Ph-4-C4H9,
- -(CH2)3-CO-O-(CH2)4-O-Ph-3-O-CH3,
- -(CH2)2-CH(CH2OH)-(CH2)2-CO-O-C2H5,
- -CH(C2H5)-CH2-CO-O-(CH2)4-OH und
- -(CH2)3-CO-O-(CH2)6-CN.
- - (CH 2 ) 2 -O-CO-CH 3 ,
- - (CH 2 ) 3 -O-CO- (CH 2 ) 7 -CH 3 ,
- - (CH 2 ) 2 -O-CO- (CH 2 ) 3 -Ph-2-O-CH 3 ,
- -CH (CH 2 -Ph-3-CH 3 ) -O-CO-C 4 H 9 and
- - (CH 2 ) 4 -O-CO- (CH 2 ) 4 -CH (C 2 H 5 ) -OH;
- - (CH 2 ) 2 -O-CO-O-CH 3 ,
- - (CH 2 ) 3 -O-CO-O- (CH 2 ) 7 -CH 3 ,
- -CH (C 2 H 5 ) -CH 2 -O-CO-OC 4 H 9 ,
- - (CH 2 ) 4 -O-CO-O- (CH 2 ) 2 -CH (CH 3 ) -O-Ph-3-CH 3 and
- - (CH 2 ) 5 -O-CO-O- (CH 2 ) 5 -CN;
- - (CH 2 ) 2 -CO-O-CH 3 ,
- - (CH 2 ) 3 -CO-OC 4 H 9 ,
- - (CH 2 ) 3 -CH (CH 3 ) -CH 2 -CO-OC 4 H 9 ,
- - (CH 2 ) 3 -CH (C 4 H 9 ) -CH 2 -CO-OC 2 H 5 ,
- - (CH 2 ) 2 -CO-O- (CH 2 ) 5 -Ph,
- - (CH 2 ) 4 -CO-O- (CH 2 ) 4 -Ph-4-C 4 H 9 ,
- - (CH 2 ) 3 -CO-O- (CH 2 ) 4 -O-Ph-3-O-CH 3 ,
- - (CH 2 ) 2 -CH (CH 2 OH) - (CH 2 ) 2 -CO-OC 2 H 5 ,
- -CH (C 2 H 5 ) -CH 2 -CO-O- (CH 2 ) 4 -OH and
- - (CH 2 ) 3 -CO-O- (CH 2 ) 6 -CN.
Handelt es sich bei den Resten R1, R2 oder R3 um Gruppierungen der Formel II, so sind geeignete Alkylengruppen W beispielsweise 1,2-, 1,3-, 1,4- oder 2,3-Butylen, Pentamethylen, Hexamethylen, 2-Methylpentamethylen, besonders 1,2- und 1,3-Propylen und vor allem Ethylen und Reste R4 bevorzugt Methyl, Ethyl, Propyl, Isopropyl, Butyl und Phenyl, das z.B. durch Methyl(oxy), Ethyl(oxy), Propyl(oxy) oder Butyl(oxy) substituiert sein kann, vorzugsweise jedoch unsubstituiert ist. Besonders bevorzugte Gruppierungen II sind z.B. (dabei bedeutet Ph=Phenyl):
- -(CH2)2-O-CH3, -(CH2)2-O-C2H5, -(CH2)2-O-C3H7, -(CH2)2-O-C4H9,
- -(CH2)2-O-Ph, -(CH2)2-O-CH2-Ph,
- -[(CH2)2-O]2-CH3, -[(CH2)2-O]2-Ph, -[(CH2)2-O]2-Ph-4-O-C4H9,
- -[(CH2)2-O]3-C4H9, -[(CH2)2-O]3-Ph, -[(CH2)2-O)]3-Ph-3-C4H9,
- -[(CH2)2-O]4-CH3 und
- -(CH2)3-O-(CH2)2-O-Ph.
- - (CH 2 ) 2 -O-CH 3 , - (CH 2 ) 2 -OC 2 H 5 , - (CH 2 ) 2 -OC 3 H 7 , - (CH 2 ) 2 -OC 4 H 9 ,
- - (CH 2 ) 2 -O-Ph, - (CH 2 ) 2 -O-CH 2 -Ph,
- - [(CH 2 ) 2 -O] 2 -CH 3 , - [(CH 2 ) 2 -O] 2 -Ph, - [(CH 2 ) 2 -O] 2 -Ph-4-OC 4 H 9 ,
- - [(CH 2 ) 2 -O] 3 -C 4 H 9 , - [(CH 2 ) 2 -O] 3 -Ph, - [(CH 2 ) 2 -O)] 3 -Ph-3-C 4 H 9 ,
- - [(CH 2 ) 2 -O] 4 -CH 3 and
- - (CH 2 ) 3 -O- (CH 2 ) 2 -O-Ph.
Als weitere bevorzugte Gruppen II sind beispielsweise zu nennen:
- -(CH2)3-O-CH3, -(CH2)3-O-C2H5, -(CH2)3-O-C3H7,
- -(CH2)3-O-CH(CH3)2, -(CH2)3-O-C4H9, -(CH2)3-O-Ph,
- -CH2-CH(CH3)-O-CH3, -CH2-CH(CH3)-O-C2H5, -CH2-CH(CH3)-O-C3H7,
- -CH2-CH(CH3)-O-C4H9, -CH2-CH(CH3)-O-Ph,
- -(CH2)4-O-CH3, -(CH2)4-O-C2H5, -(CH2)4-O-C4H9, -(CH2)4-O-Ph,
- -(CH2)4-O-CH2-Ph-2-O-C2H5, -(CH2)4-O-C6H10-2-C2H5,
- -[(CH2)4-O]2-C2H5, -[(CH2)2-CH(CH3)-O]2-C2H5,
- -(CH2)5-O-CH3, -(CH2)5-O-C2H5, -(CH2)5-O-C3H7, -(CH2)5-O-Ph,
- -(CH2)2-CH(C2H5)-O-CH2-Ph-3-O-C4H9, -(CH2)2-CH(C2H5)-O-CH2-Ph,
- -(CH2)6-O-C4H9, -(CH2)6-O-Ph-4-O-C4H9 und
- -(CH2)3-CH(CH3)-CH2-O-C4H9.
- - (CH 2 ) 3 -O-CH 3 , - (CH 2 ) 3 -OC 2 H 5 , - (CH 2 ) 3 -OC 3 H 7 ,
- - (CH 2 ) 3 -O-CH (CH 3 ) 2 , - (CH 2 ) 3 -OC 4 H 9 , - (CH 2 ) 3 -O-Ph,
- -CH 2 -CH (CH 3 ) -O-CH 3 , -CH 2 -CH (CH 3 ) -OC 2 H 5 , -CH 2 -CH (CH 3 ) -OC 3 H 7 ,
- -CH 2 -CH (CH 3 ) -OC 4 H 9 , -CH 2 -CH (CH 3 ) -O-Ph,
- - (CH 2 ) 4 -O-CH 3 , - (CH 2 ) 4 -OC 2 H 5 , - (CH 2 ) 4 -OC 4 H 9 , - (CH 2 ) 4 -O-Ph,
- - (CH 2 ) 4 -O-CH 2 -Ph-2-OC 2 H 5 , - (CH 2 ) 4 -OC 6 H 10 -2-C 2 H 5 ,
- - [(CH 2 ) 4 -O] 2 -C 2 H 5 , - [(CH 2 ) 2 -CH (CH 3 ) -O] 2 -C 2 H 5 ,
- - (CH 2 ) 5 -O-CH 3 , - (CH 2 ) 5 -OC 2 H 5 , - (CH 2 ) 5 -OC 3 H 7 , - (CH 2 ) 5 -O-Ph,
- - (CH 2 ) 2 -CH (C 2 H 5 ) -O-CH 2 -Ph-3-OC 4 H 9 , - (CH 2 ) 2 -CH (C 2 H 5 ) -O-CH 2 -Ph ,
- - (CH 2 ) 6 -OC 4 H 9 , - (CH 2 ) 6 -O-Ph-4-OC 4 H 9 and
- - (CH 2 ) 3 -CH (CH 3 ) -CH 2 -OC 4 H 9 .
Als Reste R1, R2 oder R3 eignen sich auch Benzyl- und vor allem Phenylgruppen, die bis zu drei C1-C15-, bevorzugt C1-C4-Alkyl- oder -Alkoxyreste tragen können, vorzugsweise jedoch zweifach oder einfach substituiert oder unsubstituiert sind. Geeignet sind z.B.:
- -Ph, -Ph-2-CH3, -Ph-3-CH3, -Ph-4-CH3, -Ph-4-(CH2)10-CH3,
- -Ph-3-(CH2)5-CH(CH3)-CH3, -Ph-4-(CH2)5-CH(C2H5)-CH3,
- -Ph-4-O-C4H9 und -Ph(2-CH3)-5-CH3;
- -CH2-Ph, -CH2-Ph-2-CH3, -CH2-Ph-3-CH3, -CH2-Ph-4-CH3,
- -CH2-Ph-3-C2H5, -CH2-Ph-3-O-CH3, -CH2-Ph-4-O-CH3,
- -CH2-Ph-4-O-C2H5 und -CH2-Ph(2-CH3)-5-CH3.
- -Ph, -Ph-2-CH 3 , -Ph-3-CH 3 , -Ph-4-CH 3 , -Ph-4- (CH 2 ) 10 -CH 3 ,
- -Ph-3- (CH 2 ) 5 -CH (CH 3 ) -CH 3 , -Ph-4- (CH 2 ) 5 -CH (C 2 H 5 ) -CH 3 ,
- -Ph-4-OC 4 H 9 and -Ph (2-CH 3 ) -5-CH 3 ;
- -CH 2 -Ph, -CH 2 -Ph-2-CH 3 , -CH 2 -Ph-3-CH 3 , -CH 2 -Ph-4-CH 3 ,
- -CH 2 -Ph-3-C 2 H 5 , -CH 2 -Ph-3-O-CH 3 , -CH 2 -Ph-4-O-CH 3 ,
- -CH 2 -Ph-4-OC 2 H 5 and -CH 2 -Ph (2-CH 3 ) -5-CH 3 .
Besonders bevorzugt bedeuten R1 Wasserstoff, R2 Phenyl, das durch C1-C4-Alkyl oder -Alkoxy substituiert sein kann, R3 C1-C4-Alkyl, insbesondere Methyl, und X neben Cyano vor allem Wasserstoff.R 1 is particularly preferably hydrogen, R 2 is phenyl, which can be substituted by C 1 -C 4 -alkyl or -alkoxy, R 3 C 1 -C 4 -alkyl, in particular methyl, and X, in addition to cyano, is especially hydrogen.
Die Anthrachinonfarbstoffe I sind an sich bekannt oder können nach bekannten Methoden hergestellt werden. Bei den in 2-Stellung eine Acetylgruppe aufweisenden Anthrachinonen I geht man z.B. zweckmäßigerweise von 1-Amino-2-acetylanthrachinon (Houben-Weyl, Bd. 7/3c, S. 251) aus, das dann nach Bromierung im Sinne einer Ullmann-Reaktion in üblicher Weise mit den gewünschten einen umgesetzt werden kann.The anthraquinone dyes I are known per se or can be prepared by known methods. The anthraquinones I which have an acetyl group in the 2-position are e.g. Expediently from 1-amino-2-acetylanthraquinone (Houben-Weyl, Vol. 7 / 3c, p. 251), which can then be reacted with the desired ones in a conventional manner after bromination in the sense of a Ullmann reaction.
Die beim erfindungsgemäßen Verfahren eingesetzten Farbstoffe I zeichnen sich im Vergleich zu den bekanntermaßen verwendeten Anthrachinonfarbstoffen im allgemeinen durch verbesserte Migrationseigenschaften im Aufnahmemedium bei Raumtemperatur, leichtere thermische Transferierbarkeit, höhere thermische und photochemische Stabilität, leichtere technische Zugänglichkeit, bessere Resistenz gegen Feuchtigkeit und Chemikalien, höhere Farbstärke, bessere Löslichkeit oder bessere Eignung für die subtraktive Farbmischung (höhere Farbtonreinheit, günstigere Form der Absorptionsbande, höhere Transparenz im grünen Spektralbereich) aus.Compared to the anthraquinone dyes known to be used in the process according to the invention, they are generally distinguished by improved migration properties in the recording medium at room temperature, easier thermal transferability, higher thermal and photochemical stability, easier technical accessibility, better resistance to moisture and chemicals, higher color strength, better solubility or better suitability for subtractive color mixing (higher color purity, more favorable form of the absorption band, higher transparency in the green spectral range).
Zur Herstellung der für das erfindungsgemäße Verfahren benötigten Farbstoffträger werden die Farbstoffe in einem geeigneten organischen Lösungsmittel oder in Mischungen von Lösungsmitteln mit einem oder mehreren Bindemitteln, gegebenenfalls unter Zugabe von Hilfsmitteln, zu einer Druckfarbe verarbeitet. Diese enthält den Farbstoff vorzugsweise in molekulardispers gelöster Form. Die Druckfarbe kann mittels einer Rakel auf den inerten Träger aufgetragen werden. Die erhaltene Färbung wird dann an der Luft getrocknet.To produce the dye carriers required for the process according to the invention, the dyes are processed into a printing ink in a suitable organic solvent or in mixtures of solvents with one or more binders, if appropriate with the addition of auxiliaries. This contains the dye preferably in a molecularly dispersed form. The printing ink can be applied to the inert carrier using a doctor blade. The resulting color is then air dried.
Geeignete organische Lösungsmittel sind solche, in denen die Löslichkeit der Farbstoffe I bei einer Temperatur von 20°C i.a. größer als 1 Gew.-%, vorzugsweise größer als 5 Gew.-% ist.Suitable organic solvents are those in which the solubility of the dyes I generally at a temperature of 20 ° C. is greater than 1% by weight, preferably greater than 5% by weight.
Beispielsweise seien Ethanol, Propanol, Isobutanol, Tetrahydrofuran, Methylenchlorid, Methylethylketon, Cyclopentanon, Cyclohexanon, Toluol, Chlorbenzol oder deren Mischungen genannt.For example, ethanol, propanol, isobutanol, tetrahydrofuran, methylene chloride, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene, chlorobenzene or mixtures thereof.
Als Bindemittel kommen alle Resins oder Polymermaterialien in Betracht, die in organischen Lösungsmitteln löslich sind und den Farbstoff an den inerten Träger abriebfest zu binden vermögen. Dabei werden solche Bindemittel bevorzugt, die den Farbstoff nach Trocknung der Druckfarbe an der Luft in Form eines klaren, transparenten Films aufnehmen, ohne daß dabei eine sichtbare Auskristallisation des Farbstoffs auftritt.All resins or polymer materials which are soluble in organic solvents and bind the dye to the inert support in an abrasion-resistant manner are suitable as binders capital. Preference is given to binders which, after the printing ink has dried in air, absorb the dye in the form of a clear, transparent film without the dye crystallizing out visibly.
Solche Bindemittel sind beispielsweise in der EP-A-441 282 oder den dort zitierten Patentanmeldungen genannt. Darüber hinaus sind gesättigte lineare Polyester geeignet.Such binders are mentioned for example in EP-A-441 282 or the patent applications cited therein. Saturated linear polyesters are also suitable.
Bevorzugte Bindemittel sind vor allem Ethylcellulose, Ethylhydroxyethylcellulose, Polyvinylbutyrat, Polyvinylacetat, Cellulosepropionat und gesättigte lineare Polyester.Preferred binders are especially ethyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl butyrate, polyvinyl acetate, cellulose propionate and saturated linear polyesters.
Das Gewichtsverhältnis Bindemittel:Farbstoff beträgt im allgemeinen 1:1 bis 10:1.The weight ratio of binder: dye is generally 1: 1 to 10: 1.
Als Hilfsmittel kommen z.B. Trennmittel in Betracht, wie sie in der EP-A-441 282 oder den dort zitierten Patentanmeldungen genannt sind. Als weitere Hilfsmittel sind besonders organische Additive zu nennen, welche das Auskristallisieren der Transferfarbstoffe bei Lagerung oder beim Erhitzen des Farbbandes verhindern, wie Cholesterin oder Vanillin.As aids, e.g. Release agents into consideration, as they are mentioned in EP-A-441 282 or the patent applications cited therein. Organic additives which prevent the transfer dyes from crystallizing out during storage or when the ink ribbon is heated, such as cholesterol or vanillin, are to be mentioned in particular.
Geeignete inerte Träger sind ebenfalls in der EP-A-441 282 und in den dort zitierten Patentanmeldungen beschrieben. Die Dicke des Farbstoff-Trägers beträgt im allgemeinen 3 bis 30 µm, vorzugsweise 5 bis 10 µm.Suitable inert carriers are also described in EP-A-441 282 and in the patent applications cited therein. The thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
Als Farbstoffnehmerschicht kommen prinzipiell alle temperaturstabilen Kunststoffschichten mit Affinität zu den zu transferierenden Farbstoffen in Betracht, z.B. modifizierte Polycarbonate oder Polyester. Weitere Einzelheiten dazu können der EP-A-441 282 oder den dort zitierten Patentanmeldungen entnommen werden.In principle, all temperature-stable plastic layers with affinity for the dyes to be transferred can be used as the dye-receiving layer, e.g. modified polycarbonate or polyester. Further details can be found in EP-A-441 282 or the patent applications cited therein.
Die Farbstoffübertragung erfolgt mit Hilfe einer Energieguelle, wie eines Lasers oder vor allem eines Thermokopfes, wobei letzterer auf eine Temperatur von ≥ 300°C aufheizbar sein muß, damit der Farbstofftransfer im Zeitbereich t: 0 < t < 15 msec erfolgen kann. Dabei migriert der Farbstoff aus dem Transferblatt und diffundiert in die Oberflächenbeschichtung des Aufnahmemediums.The dye transfer takes place with the aid of an energy source, such as a laser or, above all, a thermal head, the latter having to be able to be heated to a temperature of 300 300 ° C. so that the dye transfer can take place in the time range t: 0 <t <15 msec. The dye migrates from the transfer sheet and diffuses into the surface coating of the recording medium.
Zur Herstellung der Farbbänder wurden 10 g des Farbstoffs I, gegebenenfalls unter kurzzeitigem Erwärmen auf 80 bis 90°C, in 100 g einer 10 gew.-%igen Lösung eines Bindemittels (Vylon® 290 der Firma Toyobo) in einem Methylethylketon/Toluol/Cyclohexanon-Gemisch (4,5:2:1 v/v/v) eingerührt.To produce the ribbons, 10 g of dye I, optionally with brief heating to 80 to 90 ° C., in 100 g of a 10% strength by weight solution of a binder (Vylon® 290 from Toyobo) in a methyl ethyl ketone / toluene / cyclohexanone - Mix in (4.5: 2: 1 v / v / v).
Die erhaltene Druckfarbe wurde mit einer 6 µm Rakel auf eine 6 µm dicke Polyesterfolie mit rückseitiger Gleitschicht aufgerakelt. Die Farbbänder wurden dann zunächst 1 min mit einem Föhn trockengeblasen und dann noch mindestens 24 h an der Luft getrocknet, um Restmengen Lösungsmittel zu entfernen.The printing ink obtained was knife-coated onto a 6 μm thick polyester film with a sliding layer on the back using a 6 μm doctor blade. The ink ribbons were then first blown dry with a hair dryer and then air-dried for at least 24 hours in order to remove residual amounts of solvent.
Anschließend wurden die Farbbänder auf einer rechnergesteuerten Versuchsanordnung mit handelsüblichem Thermokopf auf Hitachi VY-S Videoprintpapier verdruckt.The ink ribbons were then printed on Hitachi VY-S video print paper on a computer-controlled experimental set-up with a commercially available thermal head.
Die durch den Thermokopf abgegebene Energie wird durch Veränderung der Spannung gesteuert, wobei die eingestellte Impulsdauer 7 ms beträgt und immer nur ein Impuls abgegeben wird. Die abgegebene Energie liegt so zwischen 0,71 und 1,06 mJ pro Dot.The energy emitted by the thermal head is controlled by changing the voltage, the set pulse duration being 7 ms and only one pulse being emitted. The energy delivered is between 0.71 and 1.06 mJ per dot.
Da die Höhe der Anfärbung direkt proportional der zugeführten Energie ist, kann ein Farbkeil erzeugt und spektroskopisch ausgewertet werden. Aus der graphischen Auftragung der Farbtiefe gegen die zugeführte Energie pro Dot wird der Q*-Wert (= Energie in mJ für den Extinktionswert 1) und die Steigung m in 1/mJ ermittelt.Since the amount of staining is directly proportional to the energy supplied, a color wedge can be generated and evaluated spectroscopically. The Q * value (= energy in mJ for the extinction value 1) and the gradient m in 1 / mJ are determined from the graphical plotting of the color depth against the energy supplied per dot.
In der folgenden Tabelle sind die übertragenen Anthrachinonfarbstoffe I, ihr in Methylenchlorid gemessenes Absorptionsmaximum λmax [nm], ihre Halbswertswerte HWB [cm-1] sowie ihre Transferdaten Q* [mJ/Dot] und m [1/mJ] aufgeführt.
Claims (4)
- A process for transferring anthraquinone dyes by diffusion or sublimation from a carrier to a plastic-coated substrate with the aid of an energy source, which comprises using a carrier on which one or more anthraquinone dyes of the formula I
X is hydrogen or cyano,R1 and R2 independently of one another are each hydrogen,alkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl or alkoxycarbonylalkyl, each of which may be of up to 20 carbon atoms and may be substituted by halogen, hydroxyl or cyano,phenyl or benzyl, each of which may be substituted by C1-C15-alkyl or C1-C15-alkoxy ora radical of the formula IIwhere
[―W―O]n―R4 II
the radicals W are identical or different C2-C6-alkylene radicals,n is from 1 to 6 andR4 is C1-C4-alkyl or unsubstituted or C1-C4-alkyl-substituted or C1-C4-alkoxy-substituted phenyl, andR3 is one of the organic radicals mentioned for R1 andR2, except for hydrogen, are present. - A process as claimed in claim 1, wherein anthraquinone dyes of the formula I whereX is hydrogen or cyano,R1 and R2 independently of one another are each hydrogen,C1-C12-alkyl whose carbon chain may be interrupted by from 1 to 3 oxygen atoms as ether functions, orunsubstituted or C1-C4-alkyl-substituted or C1-C4-alkoxy-substituted phenyl, andR3 is one of the organic radicals mentioned for R1 andR2, except for hydrogen,are used for this purpose.
- A process as claimed in claim 1, wherein anthraquinone dyes of the formula I whereX is hydrogen or cyano,R1 is hydrogen,R2 is unsubstituted or C1-C4-alkyl-substituted or C1-C4-alkoxy-substituted phenyl andR3 is C1-C4-alkyl or unsubstituted or C1-C4-alkyl-substituted or C1-C4-alkoxy-substituted phenyl,are used for this purpose.
- A process as claimed in claim 1, wherein anthraquinone dyes of the formula I whereX and R1 are each hydrogen,R2 is unsubstituted or C1-C4-alkyl-substituted or C1-C4-alkoxy-substituted phenyl andR3 is methyl,are used for this purpose.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4214175 | 1992-04-30 | ||
| DE4214175A DE4214175A1 (en) | 1992-04-30 | 1992-04-30 | METHOD FOR TRANSMITTING ANTHRACHINONE DYES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0567829A1 EP0567829A1 (en) | 1993-11-03 |
| EP0567829B1 true EP0567829B1 (en) | 1997-01-22 |
Family
ID=6457784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93105925A Expired - Lifetime EP0567829B1 (en) | 1992-04-30 | 1993-04-13 | Process for transfer of anthraquinone dyes |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5302577A (en) |
| EP (1) | EP0567829B1 (en) |
| JP (1) | JPH0624158A (en) |
| DE (2) | DE4214175A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5491045A (en) * | 1994-12-16 | 1996-02-13 | Eastman Kodak Company | Image dye combination for laser ablative recording element |
| DE19716811A1 (en) † | 1997-04-22 | 1998-10-29 | Grob Gmbh & Co Kg | Transfer line |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3617173A (en) * | 1968-06-24 | 1971-11-02 | Toms River Chemical Corp | 2-benzoylanthraquinone dyes for polyester fibers |
| DE2432233A1 (en) * | 1974-07-05 | 1976-01-29 | Bayer Ag | TRANSFER PRINTING PROCEDURE |
| DE3812053A1 (en) * | 1988-04-12 | 1989-10-26 | Basf Ag | METHOD FOR TRANSMITTING DYES |
| JP3009161B2 (en) * | 1989-11-16 | 2000-02-14 | 三井化学株式会社 | Cyan heat-sensitive sublimation transfer sheet |
| DE4004612A1 (en) * | 1990-02-15 | 1991-08-22 | Basf Ag | New bi:chromophoric methine and aza-methine dyestuff cpds. and use |
| DE4031984A1 (en) * | 1990-10-09 | 1992-04-16 | Basf Ag | USE OF ANTHRACHINONE DYES FOR THERMAL TRANSFER PRINTING |
| DE4039923A1 (en) * | 1990-12-14 | 1992-06-17 | Basf Ag | USE OF ANTHRACHINONE DYES FOR THERMAL TRANSFER PRINTING |
-
1992
- 1992-04-30 DE DE4214175A patent/DE4214175A1/en not_active Withdrawn
-
1993
- 1993-03-29 US US08/038,867 patent/US5302577A/en not_active Expired - Fee Related
- 1993-04-13 DE DE59305197T patent/DE59305197D1/en not_active Expired - Lifetime
- 1993-04-13 EP EP93105925A patent/EP0567829B1/en not_active Expired - Lifetime
- 1993-04-27 JP JP5100633A patent/JPH0624158A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0567829A1 (en) | 1993-11-03 |
| US5302577A (en) | 1994-04-12 |
| DE4214175A1 (en) | 1993-11-04 |
| JPH0624158A (en) | 1994-02-01 |
| DE59305197D1 (en) | 1997-03-06 |
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