EP0420036A1 - Use of azo dyes in thermal transfer printing - Google Patents
Use of azo dyes in thermal transfer printing Download PDFInfo
- Publication number
- EP0420036A1 EP0420036A1 EP90118082A EP90118082A EP0420036A1 EP 0420036 A1 EP0420036 A1 EP 0420036A1 EP 90118082 A EP90118082 A EP 90118082A EP 90118082 A EP90118082 A EP 90118082A EP 0420036 A1 EP0420036 A1 EP 0420036A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- groups
- hydrogen
- phenyl
- substituted
- 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
- 239000000987 azo dye Substances 0.000 title claims abstract description 18
- 238000010023 transfer printing Methods 0.000 title claims abstract description 13
- -1 phenoxy, tolyloxy, dimethylphenyloxy, chlorophenoxy Chemical group 0.000 claims abstract description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 16
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims abstract description 6
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims abstract description 6
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims abstract description 6
- 125000005041 acyloxyalkyl group Chemical group 0.000 claims abstract description 4
- 125000005205 alkoxycarbonyloxyalkyl group Chemical group 0.000 claims abstract description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000004966 cyanoalkyl group Chemical group 0.000 claims abstract description 4
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 3
- 125000005059 halophenyl group Chemical group 0.000 claims abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000000460 chlorine Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 32
- 150000003254 radicals Chemical class 0.000 abstract description 8
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 22
- 239000000975 dye Substances 0.000 description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 17
- 239000011230 binding agent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 150000002431 hydrogen Chemical group 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 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
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000165918 Eucalyptus papuana Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 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
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000006185 dispersion Substances 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
- 150000002148 esters Chemical class 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011086 glassine Substances 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
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([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
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration 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
- 239000000025 natural resin Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- 230000003287 optical effect Effects 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
- 239000011092 plastic-coated paper Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 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
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 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
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 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
- 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
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
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to the use of azo dyes of the general formula I. for thermal transfer printing, in which the substituents have the following meaning: R1, R2 is hydrogen; Alkyl, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl groups, each of which can contain up to 20 C atoms and by phenyl, C1-C4-alkylphenyl, C1-C4-alkoxyphenyl, halophenyl , Benzyloxy, C1-C4-alkylbenzyloxy, C1-C4-alkoxybenzyloxy, halobenzyloxy, halogen, hydroxy or cyano may be substituted; Phenyl or cyclohexyl groups, which can be substituted by C1-C15 alkyl, C1-C15 alkoxy,
- thermal transfer printing In addition to lasers and IR lamps, a thermal head is used as the heat source, with which short heating pulses lasting a fraction of a second can be emitted.
- a transfer sheet which contains the dye to be transferred together with one or more binders, a carrier material and possibly other auxiliaries such as release agents or crystallization-inhibiting substances is heated from the rear through 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 previously known dyes.
- azo dyes of the formula I defined at the outset can be used advantageously for thermal transfer printing.
- 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.
- R 1 or R 2 are the alkyl groups methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl , 2-ethylhexyl or the isomer mixture isooctyl, nonyl or decyl or their isomer mixtures isononyl and isodecyl and undecyl or dodecyl.
- tridecyl or its isomer mixture isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl are also suitable.
- the alkyl groups can also be substituted by phenyl;
- Ph phenyl
- radicals R 1 or R 2 are alkoxyalkyl groups of the preferred formula II
- suitable groups W are, for example, 1,2- or 1,3-propylene, 1,2-, 1,3-, 1,4- or 2, 3-butylene, pentamethylene, hexamethylene or 2-methylpentamethylene, especially ethylene, and radicals R4, especially methyl, ethyl, propyl, butyl or phenyl, which are replaced by methyl (oxy), ethyl (oxy), propyl (oxy) or butyl (oxy ) can be substituted.
- Particularly preferred groups II are, for example: - (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 or - (CH2) 3-O- (CH2) 2-O-Ph.
- Examples of further preferred groups II are: - (CH2) 3-O-CH3, - (CH2) 3-O-C2H5, - (CH2) 3-O-C3H7, - (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)
- alkoxyalkyl groups are also suitable: - (CH2) 8-O-CH3, - (CH2) 8-O-C4H9, - (CH2) 8-O-CH2-Ph-3-C2H5, - (CH2) 4-CH (Cl) - (CH2) 3-O-CH2-Ph-3-CH3 or - (CH2) 3-CH (C4H9) -O-CH2-Ph-3-CH3.
- alkanoyloxyalkyl, alkoxycarbonyloxyalkyl or alkoxycarbonylalkyl groups suitable as R1 or R2 are: - (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 or - (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 or - (CH2) 5-O-CO-O- (CH2) 5-CN; - (CH2) 2-CO-O-CH
- R 1 or R 2 The following halogen, hydroxyl or cyanoalkyl groups are also suitable as R 1 or R 2: - (CH2) 5-Cl, -CH (C4H9) - (CH2) 3-Cl or - (CH2) 4-CF3; - (CH2) 2-CH (CH3) -OH, - (CH2) 2-CH (C4H9) -OH or -CH (C2H5) - (CH2) 9-OH; - (CH2) 2-CN, - (CH2) 3-CN, -CH2-CH (CH3) -CH (C2H5) -CN, - (CH2) 6-CH (C2H5) -CN or - (CH2) 3-CH (CH3) - (CH2) 2-CH (CH3) -CN.
- phenyl or cyclohexyl radicals which may be present as R1 or R2 are: -Ph, -Ph-3-CH3, -Ph-4- (CH2) 10-CH3, -Ph-3- (CH2) 5-CH (CH3) -CH3, -PH-4-O-C4H9, -Ph-4- (CH2) 5-CH (C2H5) -CH3, -Ph-4-O-CH2-Ph or -Ph-4-Cl; -C6H10-4-CH3, -C6H10-4-C10H21, -C6H10-3-O-C4H9, -C6H10-3-O- (CH2) 4-CH (C2H5) -CH3 or -C6H10-4-Cl.
- a particularly preferred radical R 3 is methyl; ethyl, propyl and isopropyl are also suitable in addition to hydrogen, amino or hydroxy.
- the substituents X and Y are preferably hydrogen and nitro, and also chlorine and bromine. Further substituents X are methyl, methyloxy, ethyloxy, propyloxy, butyloxy, phenoxy, tolyloxy or dimethylphenyloxy.
- the cyano group is particularly preferred as the substituent Z, and hydrogen, acetyl and carbamoyl are also suitable.
- 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 in spite of the relatively high molecular weight, improved migration properties in the recording medium at room temperature, significantly higher lightfastness, better resistance to moisture and chemicals, better solubility in the manufacture of the printing ink, higher color strength and easier technical accessibility.
- the azo dyes I show a 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 mixed with one or more in an organic solvent such as isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or mixtures thereof
- Binders and possibly other auxiliaries such as release agents or crystallization-inhibiting substances processed into a printing ink, which preferably contains the dyes dissolved in molecular dispersion.
- 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 and ethyl hydroxyethyl cellulose, starch, alginates, alkyd resins such as polyvinyl alcohol or polyvinyl pyrrolidone, and especially polyvinyl acetate and polyvinyl butyrate.
- Cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, especially ethyl cellulose and ethyl hydroxyethyl cellulose, starch, alginates, alkyd resins such as polyvinyl alcohol or polyvinyl pyrrolidone, and especially polyvinyl acetate and poly
- polymers and copolymers of acrylates or their derivatives such as polyacrylic acid, polymethyl methacrylate or styrene acrylate copolymers, polyester resins, polyamide resins, polyurethane resins or natural resins such as e.g. Gum arabic into consideration.
- binders are often recommended, e.g. those made of ethyl cellulose and polyvinyl butyrate in a weight ratio of 2: 1.
- the weight ratio of binder to dye is usually 8: 1 to 1: 1, preferably 5: 1 to 2: 1.
- Inert carrier materials are, for example, tissue paper, blotting paper or glassine paper 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.
- 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 approximately 120 ⁇ m thick, which was coated with an 8 ⁇ m thick plastic layer (Hitachi Color Video Print Paper).
- the coated side of the encoder and slave was placed on top of one another, wrapped with aluminum foil and heated to a temperature between 70 and 80 ° C. for two minutes between two heating plates. With similar samples, this process was repeated three times at a higher temperature between 80 and 120 ° C.
- the amount of dye diffused into the plastic layer of the receiver is proportional to the optical density, which was determined as absorbance A photometrically after the respective heating to the temperatures given above.
- the temperature T * at which the extinction reaches the value 1 can also be taken from the application, ie the transmitted light intensity is one tenth of the incident light intensity.
- the azo dyes I used are divided into groups in the following tables; the variable P indicates the position of the oxdiazole residue on the phenyl nucleus of the diazo component in relation to the azo group (o: ortho, m: meta, p: para).
- binder B used in each case is also listed.
- EC ethyl cellulose
- PVB polyvinyl butyrate
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Abstract
Description
Die vorliegende Erfindung betrifft die Verwendung von Azofarbstoffen der allgemeinen Formel I
R¹, R² Wasserstoff;
Alkyl-, Alkoxyalkyl-, Alkanoyloxyalkyl-, Alkoxycarbonyloxyalkyl-, Alkoxycarbonylalkyl-, Halogenalkyl-, Hydroxyalkyl- oder Cyanoalkylgruppen, die jeweils bis zu 20 C-Atome enthalten können und durch Phenyl, C₁-C₄-Alkylphenyl, C₁-C₄-Alkoxyphenyl, Halogenphenyl, Benzyloxy, C₁-C₄-Alkylbenzyloxy, C₁-C₄-Alkoxybenzyloxy, Halogenbenzyloxy, Halogen, Hydroxy oder Cyano substituiert sein können;
Phenyl- oder Cyclohexylgruppen, die durch C₁-C₁₅-Alkyl, C₁-C₁₅-Alkoxy, Halogen oder Benzyloxy substituiert sein können; einen Rest der allgemeinen Formel II
[-W-O]n-R⁴ II
in der
W gleiche oder verschiedene C₂-C₆-Alkylengruppen bezeichnet,
n 1 bis 6 bedeutet und
R⁴ für eine C₁-C₄-Alkyl- oder Phenylgruppe, die durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiert sein kann, steht;
R³ wasserstoff, Amino-, Hydroxy- oder Alkylgruppen;
X Wasserstoff, Chlor, Brom, Nitro-, Methyl-, Phenoxy-, Tolyloxy-, Dimethylphenyloxy-, Chlorphenoxy- oder C₁-C₄-Alkoxygruppen;
Y Wasserstoff, Chlor oder Brom und
Z wasserstoff, Acetyl-, Carbamoyl- oder Cyanogruppen
sowie speziell ein Verfahren zur Übertragung dieser Azofarbstoffe durch Diffusion von einem Träger auf ein mit Kunststoff beschichtetes Papier mit Hilfe eines Thermokopfes.The present invention relates to the use of azo dyes of the general formula I.
R1, R2 is hydrogen;
Alkyl, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl groups, each of which can contain up to 20 C atoms and by phenyl, C₁-C₄-alkylphenyl, C₁-C₄-alkoxyphenyl, halophenyl , Benzyloxy, C₁-C₄-alkylbenzyloxy, C₁-C₄-alkoxybenzyloxy, halobenzyloxy, halogen, hydroxy or cyano may be substituted;
Phenyl or cyclohexyl groups, which can be substituted by C₁-C₁₅ alkyl, C₁-C₁₅ alkoxy, halogen or benzyloxy; a radical of the general formula II
[-WO] n -R⁴ II
in the
W denotes the same or different C₂-C₆ alkylene groups,
n is 1 to 6 and
R⁴ represents a C₁-C₄ alkyl or phenyl group which may be substituted by C₁-C₄ alkyl or C₁-C₄ alkoxy;
R³ is hydrogen, amino, hydroxy or alkyl groups;
X is hydrogen, chlorine, bromine, nitro, methyl, phenoxy, tolyloxy, dimethylphenyloxy, chlorophenoxy or C₁-C₄ alkoxy groups;
Y is hydrogen, chlorine or bromine and
Z is hydrogen, acetyl, carbamoyl or cyano groups
and specifically a method for transferring these azo dyes by diffusion from a support onto a plastic-coated paper using a thermal head.
Die Technik des Thermotransferdrucks ist allgemein bekannt; als Wärmequellen 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 lasers and IR lamps, a thermal head is used as the heat source, with which short heating pulses 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 through 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-152 563/1985, JP-A-262 191/1986 und JP-A-244 595/1986 bekannten und für den Thermotransferdruck empfohlenen Azopyridone zu, die den Verbindungen I ähneln, jedoch am Phenylring, der unsubstituiert oder substituiert sein kann, keinen Oxthiazolrest tragen.At the same time, these requirements are very difficult to meet. In particular, the yellow dyes previously used cannot convince. This also applies to those known from EP-A-247 737, JP-A-12 393/1986, JP-A-152 563/1985, JP-A-262 191/1986 and JP-A-244 595/1986 and azopyridones recommended for thermal transfer printing, which are similar to the compounds I but do not carry an oxthiazole residue on the phenyl ring, which may be unsubstituted or substituted.
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 Eigenschaftsprofll 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 previously known dyes.
Demgemäß wurde gefunden, daß Azofarbstoffe der eingangs definierten Formel I vorteilhaft für den Thermotransferdruck verwendet werden können.Accordingly, it has been found that azo dyes of the formula I defined at the outset can be used advantageously 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 Thermokopfs 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 wurden bevorzugte Ausführungsformen dieses Verfahrens gefunden, welche dadurch gekennzeichnet sind, daß man hierzu Farbstoffe der Formel Ia
Wasserstoff;
Alkyl-, Alkoxyalkyl-, Alkanoyloxy- oder Alkoxycarbonylalkylgruppen, die jeweils bis zu 15 C-Atome enthalten können und durch Phenyl, C₁-C₄-Alkylphenyl, C₁-C₄-Alkoxyphenyl, Hydroxy oder Cyano substituiert sein können;
einen Rest der allgemeinen Formel III
[-(CH₂)₃]-O]p⁅(CH₂)₂-O]q-R4′ III,
in der p für 0 oder 1 und q für 1 bis 4 stehen und R4′ eine C₁-C₄-Alkyl- oder Phenylgruppe bezeichnet.Furthermore, preferred embodiments of this process have been found, which are characterized in that dyes of the formula Ia
Hydrogen;
Alkyl, alkoxyalkyl, alkanoyloxy or alkoxycarbonylalkyl groups, each of which can contain up to 15 carbon atoms and which can be substituted by phenyl, C₁-C₄-alkylphenyl, C₁-C₄-alkoxyphenyl, hydroxy or cyano;
a radical of the general formula III
[- (CH₂) ₃] -O] p ⁅ (CH₂) ₂-O] q -R 4 ′ III,
in which p represents 0 or 1 and q represents 1 to 4 and R 4 ' denotes a C₁-C₄ alkyl or phenyl group.
Dabei sind bevorzugte Reste R¹ oder R² die Alkylgruppen Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec-Butyl, tert-Butyl, Pentyl, Isopentyl, sec-Pentyl, tert-Pentyl, Hexyl, 2-Methylpentyl, Heptyl, Octyl, 2-Ethylhexyl oder das Isomerengemisch Isooctyl, Nonyl oder Decyl oder ihre Isomerengemische Isononyl und Isodecyl sowie Undecyl oder Dodecyl.Preferred radicals R 1 or R 2 are the alkyl groups methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl , 2-ethylhexyl or the isomer mixture isooctyl, nonyl or decyl or their isomer mixtures isononyl and isodecyl and undecyl or dodecyl.
Daneben eignen sich beispielsweise auch Tridecyl oder sein Isomerengemisch Isotridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl oder Eicosyl.In addition, for example, tridecyl or its isomer mixture isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl are also suitable.
Die Alkylgruppen können auch durch Phenyl substituiert sein; beispielsweise sind hier zu nennen (dabei bedeutet Ph = Phenyl):
-CH₂-Ph, -CH(CH₃)-Ph, -(CH₂)₂-Ph,
-(CH₂)₄-CH(CH₃)-Ph-3-CH₃,
-(CH₂)₃-CH(C₄H₉)-Ph-3-C₄H₉,
-(CH₂)₆-Ph-4-O-CH₃,
-CH(C₂H₅)-(CH₂)₃-Ph-3-O-C₂H₅ oder
-CH(C₂H₅)-(CH₂)₃-Ph-3-Cl.The alkyl groups can also be substituted by phenyl; For example, here are to be mentioned (where Ph = phenyl):
-CH₂-Ph, -CH (CH₃) -Ph, - (CH₂) ₂-Ph,
- (CH₂) ₄-CH (CH₃) -Ph-3-CH₃,
- (CH₂) ₃-CH (C₄H₉) -Ph-3-C₄H₉,
- (CH₂) ₆-Ph-4-O-CH₃,
-CH (C₂H₅) - (CH₂) ₃-Ph-3-O-C₂H₅ or
-CH (C₂H₅) - (CH₂) ₃-Ph-3-Cl.
Handelt es sich bei den Resten R¹ oder R² um Alkoxyalkylgruppen der bevorzugten Formel II, so sind geeignete Gruppen W beispielsweise 1,2- oder 1,3-Propylen, 1,2-, 1,3-, 1,4- oder 2,3-Butylen, Pentamethylen, Hexamethylen oder 2-Methylpentamethylen, besonders Ethylen, und Reste R⁴ vor allem Methyl, Ethyl, Propyl, Butyl oder Phenyl, das durch Methyl(oxy), Ethyl(oxy), Propyl(oxy) oder Butyl(oxy) substituiert sein kann. Besonders bevorzugte Gruppen II sind z.B.:
-(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 oder
-(CH₂)₃-O-(CH₂)₂-O-Ph.If the radicals R 1 or R 2 are alkoxyalkyl groups of the preferred formula II, suitable groups W are, for example, 1,2- or 1,3-propylene, 1,2-, 1,3-, 1,4- or 2, 3-butylene, pentamethylene, hexamethylene or 2-methylpentamethylene, especially ethylene, and radicals R⁴, especially methyl, ethyl, propyl, butyl or phenyl, which are replaced by methyl (oxy), ethyl (oxy), propyl (oxy) or butyl (oxy ) can be substituted. Particularly preferred groups II are, for example:
- (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 or
- (CH₂) ₃-O- (CH₂) 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-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-3-Cl,
-(CH₂)₆-O-C₄H₉, -(CH₂)₆-O-Ph-4-O-C₄H₉ oder
-(CH₂)₃-CH(CH₃)-(CH₂)-O-C₄H₉.Examples of further preferred groups II are:
- (CH₂) ₃-O-CH₃, - (CH₂) ₃-O-C₂H₅, - (CH₂) ₃-O-C₃H₇, - (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-3-Cl,
- (CH₂) ₆-O-C₄H₉, - (CH₂) ₆-O-Ph-4-O-C₄H₉ or
- (CH₂) ₃-CH (CH₃) - (CH₂) -O-C₄H₉.
Daneben sind z.B. folgende Alkoxyalkylgruppen geeignet:
-(CH₂)₈-O-CH₃, -(CH₂)₈-O-C₄H₉, -(CH₂)₈-O-CH₂-Ph-3-C₂H₅,
-(CH₂)₄-CH(Cl)-(CH₂)₃-O-CH₂-Ph-3-CH₃ oder
-(CH₂)₃-CH(C₄H₉)-O-CH₂-Ph-3-CH₃.The following alkoxyalkyl groups are also suitable:
- (CH₂) ₈-O-CH₃, - (CH₂) ₈-O-C₄H₉, - (CH₂) ₈-O-CH₂-Ph-3-C₂H₅,
- (CH₂) ₄-CH (Cl) - (CH₂) ₃-O-CH₂-Ph-3-CH₃ or
- (CH₂) ₃-CH (C₄H₉) -O-CH₂-Ph-3-CH₃.
Als Reste R¹ oder R² geeignete Alkanoyloxyalkyl-, Alkoxycarbonyloxyalkyl- oder 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 oder
-(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 oder
-(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)₅Ph,
-(CH₂)₄-CO-O-(CH₂)₄-Ph-4-C₄H₉,
-(CH₂)₃-CO-O-(CH₂)₄-O-Ph-3-CH₃,
-(CH₂)₂-CH(CH₂OH)-(CH₂)₂-CO-O-C₂H₅,
-CH(C₂H₅)-CH₂-CO-O-(CH₂)₄-OH oder
-(CH₂)₃-CO-O-(CH₂)₆-CN.Examples of alkanoyloxyalkyl, alkoxycarbonyloxyalkyl or alkoxycarbonylalkyl groups suitable as R¹ or R² are:
- (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 or
- (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 or
- (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) ₅Ph,
- (CH₂) ₄-CO-O- (CH₂) ₄-Ph-4-C₄H₉,
- (CH₂) ₃-CO-O- (CH₂) ₄-O-Ph-3-CH₃,
- (CH₂) ₂-CH (CH₂OH) - (CH₂) ₂-CO-O-C₂H₅,
-CH (C₂H₅) -CH₂-CO-O- (CH₂) ₄-OH or
- (CH₂) ₃-CO-O- (CH₂) ₆-CN.
Weiterhin eignen sich z.B. folgende Halogen-, Hydroxy- oder Cyanoalkylgruppen als Reste R¹ oder R²:
-(CH₂)₅-Cl, -CH(C₄H₉)-(CH₂)₃-Cl oder -(CH₂)₄-CF₃;
-(CH₂)₂-CH(CH₃)-OH, -(CH₂)₂-CH(C₄H₉)-OH oder -CH(C₂H₅)-(CH₂)₉-OH;
-(CH₂)₂-CN, -(CH₂)₃-CN, -CH₂-CH(CH₃)-CH(C₂H₅)-CN, -(CH₂)₆-CH(C₂H₅)-CN oder
-(CH₂)₃-CH(CH₃)-(CH₂)₂-CH(CH₃)-CN.The following halogen, hydroxyl or cyanoalkyl groups are also suitable as R 1 or R 2:
- (CH₂) ₅-Cl, -CH (C₄H₉) - (CH₂) ₃-Cl or - (CH₂) ₄-CF₃;
- (CH₂) ₂-CH (CH₃) -OH, - (CH₂) ₂-CH (C₄H₉) -OH or -CH (C₂H₅) - (CH₂) ₉-OH;
- (CH₂) ₂-CN, - (CH₂) ₃-CN, -CH₂-CH (CH₃) -CH (C₂H₅) -CN, - (CH₂) ₆-CH (C₂H₅) -CN or
- (CH₂) ₃-CH (CH₃) - (CH₂) ₂-CH (CH₃) -CN.
Phenyl- oder Cyclohexylreste, die als Reste R¹ oder R² enthalten sein können, sind beispielsweise folgende:
-Ph, -Ph-3-CH₃, -Ph-4-(CH₂)₁₀-CH₃, -Ph-3-(CH₂)₅-CH(CH₃)-CH₃,
-PH-4-O-C₄H₉, -Ph-4-(CH₂)₅-CH(C₂H₅)-CH₃, -Ph-4-O-CH₂-Ph oder -Ph-4-Cl;
-C₆H₁₀-4-CH₃, -C₆H₁₀-4-C₁₀H₂₁, -C₆H₁₀-3-O-C₄H₉,
-C₆H₁₀-3-O-(CH₂)₄-CH(C₂H₅)-CH₃ oder -C₆H₁₀-4-Cl.Examples of phenyl or cyclohexyl radicals which may be present as R¹ or R² are:
-Ph, -Ph-3-CH₃, -Ph-4- (CH₂) ₁₀-CH₃, -Ph-3- (CH₂) ₅-CH (CH₃) -CH₃,
-PH-4-O-C₄H₉, -Ph-4- (CH₂) ₅-CH (C₂H₅) -CH₃, -Ph-4-O-CH₂-Ph or -Ph-4-Cl;
-C₆H₁₀-4-CH₃, -C₆H₁₀-4-C₁₀H₂₁, -C₆H₁₀-3-O-C₄H₉,
-C₆H₁₀-3-O- (CH₂) ₄-CH (C₂H₅) -CH₃ or -C₆H₁₀-4-Cl.
Besonders bevorzugter Rest R³ ist Methyl, ebenfalls geeignet sind neben Wasserstoff, Amino oder Hydroxy auch Ethyl, Propyl und Isopropyl.A particularly preferred radical R 3 is methyl; ethyl, propyl and isopropyl are also suitable in addition to hydrogen, amino or hydroxy.
Für die Substituenten X und Y kommen vorzugsweise Wasserstoff und Nitro, daneben auch Chlor und Brom in Betracht. Als weitere Substituenten X sind Methyl, Methyloxy, Ethyloxy, Propyloxy, Butyloxy, Phenoxy, Tolyloxy oder Dimethylphenyloxy zu nennen.The substituents X and Y are preferably hydrogen and nitro, and also chlorine and bromine. Further substituents X are methyl, methyloxy, ethyloxy, propyloxy, butyloxy, phenoxy, tolyloxy or dimethylphenyloxy.
Als Substituent Z besonders bevorzugt ist die Cyanogruppe, außerdem eignen sich Wasserstoff, Acetyl und Carbamoyl.The cyano group is particularly preferred as the substituent Z, and hydrogen, acetyl and carbamoyl are also suitable.
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, wesentlich 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 in spite of the relatively high molecular weight, improved migration properties in the recording medium at room temperature, significantly higher lightfastness, better resistance to moisture and chemicals, better solubility in the manufacture of the printing ink, higher color strength and easier technical accessibility.
Zudem zeigen die Azofarbstoffe I eine deutlich bessere Farbtonreinheit, insbesondere in Farbstoffmischungen, und ergeben verbesserte Schwarz-Drucke.In addition, the azo dyes I show a 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 molekulardispers 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 mixed with one or more in an organic solvent such as isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or mixtures thereof Binders and possibly other auxiliaries such as release agents or crystallization-inhibiting substances processed into a printing ink, which preferably contains the dyes dissolved in molecular dispersion. 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 und Ethylhydroxyethylcellulose, 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 and ethyl hydroxyethyl cellulose, 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.
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 approximately 120 µm thick, 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 ΔEτ 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, umso 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 den folgenden Tabellen sind die eingesetzten Azofarbstoffe I in Gruppen eingeteilt; die Variable P gibt die Position des Oxdiazolrestes am Phenylkern der Diazokomponente in Bezug auf die Azogruppe an (o: ortho, m: meta, p: para).The azo dyes I used are divided into groups in the following tables; the variable P indicates the position of the oxdiazole residue on the phenyl nucleus of the diazo component in relation to the azo group (o: ortho, m: meta, p: para).
Zudem ist das jeweils verwendete Bindemittel B aufgeführt. Dabei bedeutet: EC = Ethylcellulose, PVB = Polyvinylbutyrat, MS = EC:PVB = 2:1.The binder B used in each case is also listed. Here means: EC = ethyl cellulose, PVB = polyvinyl butyrate, MS = EC: PVB = 2: 1.
Weitere charakteristische Daten sind die in Methylenchlorid gemessenen Absorptionsmaxima λmax[nm] und die bereits erwähnten Parameter T*[°C] und ΔEτ[kcal/mol].
Claims (4)
R¹, R² Wasserstoff;
Alkyl-, Alkoxyalkyl-, Alkanoyloxyalkyl-, Alkoxycarbonyloxyalkyl-, Alkoxycarbonylalkyl-, Halogenalkyl-, Hydroxyalkyl- oder Cyanoalkylgruppen, die jeweils bis zu 20°C-Atome enthalten können und durch Phenyl, C₁-C₄-Alkylphenyl, C₁-C₄-Alkoxyphenyl, Halogenphenyl, Benzyloxy, C₁-C₄-Alkylbenzyloxy, C₁-C₄-Alkoxybenzyloxy, Halogenbenzyloxy, Halogen, Hydroxy oder Cyano substituiert sein können;
Phenyl- oder Cyclohexylgruppen, die durch C₁-C₁₅-Alkyl, C₁-C₁₅-Alkoxy, Halogen oder Benzyloxy substituiert sein können;
einen Rest der allgemeinen Formel II
[-W-O]n-R⁴ II
in der
W gleiche oder verschiedene C₂-C₆-Alkylengruppen bezeichnet,
n 1 bis 6 bedeutet und
R⁴ für eine C₁-C₄-Alkyl- oder Phenylgruppe, die durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiert sein kann, steht;
R³ Wasserstoff, Amino-, Hydroxy- oder Alkylgruppen;
X Wasserstoff, Chlor, Brom, Nitro-, Methyl-, Phenoxy-, Tolyloxy-, Dimethylphenyloxy-, Chlorphenoxy- oder C₁-C₄-Alkoxygruppen;
Y Wasserstoff, Chlor oder Brom und
Z Wasserstoff, Acetyl-, Carbamoyl- oder Cyanogruppen.1. Use of azo dyes of the general formula I
R1, R2 is hydrogen;
Alkyl, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl groups, each of which can contain up to 20 ° C. atoms and by phenyl, C₁-C₄-alkylphenyl, C₁-C₄-alkoxyphenyl, Halophenyl, benzyloxy, C₁-C₄-alkylbenzyloxy, C₁-C₄-alkoxybenzyloxy, halobenzyloxy, halogen, hydroxy or cyano may be substituted;
Phenyl or cyclohexyl groups, which can be substituted by C₁-C₁₅ alkyl, C₁-C₁₅ alkoxy, halogen or benzyloxy;
a radical of the general formula II
[-WO] n -R⁴ II
in the
W denotes the same or different C₂-C₆ alkylene groups,
n is 1 to 6 and
R⁴ represents a C₁-C₄ alkyl or phenyl group which may be substituted by C₁-C₄ alkyl or C₁-C₄ alkoxy;
R³ is hydrogen, amino, hydroxy or alkyl groups;
X is hydrogen, chlorine, bromine, nitro, methyl, phenoxy, tolyloxy, dimethylphenyloxy, chlorophenoxy or C₁-C₄ alkoxy groups;
Y is hydrogen, chlorine or bromine and
Z is hydrogen, acetyl, carbamoyl or cyano groups.
R1′, R2′ Wasserstoff;
Alkyl-, Alkoxyalkyl-, Alkanoyloxy- oder Alkoxycarbonylalkylgruppen, die jeweils bis zu 15°C Atome enthalten können und durch Phenyl, C₁-C₄-Alkylphenyl, C₁-C₄-Alkoxyphenyl, Hydroxy oder Cyano substituiert sein können;
einen Rest der allgemeinen Formel III
[-(CH₂)₃-O]p⁅(CH₂)₂-O]q-R4′ III,
in der p für 0 oder 1 und q für 1 bis 4 stehen und R4′ eine C₁-C₄-Alkyl- oder Phenylgruppe bezeichnet.4. The method according to claim 2, characterized in that for this purpose an azo dye of the formula Ib
R 1 ′ , R 2 ′ hydrogen;
Alkyl, alkoxyalkyl, alkanoyloxy or alkoxycarbonylalkyl groups, each of which can contain up to 15 ° C atoms and can be substituted by phenyl, C₁-C₄-alkylphenyl, C₁-C₄-alkoxyphenyl, hydroxy or cyano;
a radical of the general formula III
[- (CH₂) ₃-O] p ⁅ (CH₂) ₂-O] q -R 4 ′ III,
in which p represents 0 or 1 and q represents 1 to 4 and R 4 ' denotes a C₁-C₄ alkyl or phenyl group.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3932523 | 1989-09-29 | ||
| DE3932523A DE3932523A1 (en) | 1989-09-29 | 1989-09-29 | USE OF AZO DYES FOR THERMAL TRANSFER PRINTING |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0420036A1 true EP0420036A1 (en) | 1991-04-03 |
| EP0420036B1 EP0420036B1 (en) | 1994-05-18 |
Family
ID=6390467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90118082A Expired - Lifetime EP0420036B1 (en) | 1989-09-29 | 1990-09-20 | Use of azo dyes in thermal transfer printing |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5093308A (en) |
| EP (1) | EP0420036B1 (en) |
| JP (1) | JPH03126591A (en) |
| DE (2) | DE3932523A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2320990B2 (en) | 2008-08-29 | 2023-05-31 | Corindus, Inc. | Catheter control system and graphical user interface |
| JP5634019B2 (en) * | 2008-10-14 | 2014-12-03 | キヤノン株式会社 | Dye compound and ink containing the dye compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0216483A1 (en) * | 1985-08-27 | 1987-04-01 | Zeneca Limited | Thermal transfer printing |
| EP0301752A2 (en) * | 1987-07-30 | 1989-02-01 | Zeneca Limited | 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 |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4505975A (en) * | 1981-07-25 | 1985-03-19 | Sony Corporation | Thermal transfer printing method and printing paper therefor |
| DE3244960A1 (en) * | 1982-12-04 | 1984-06-07 | Basf Ag, 6700 Ludwigshafen | PYRIDONE DYES |
| US4555427A (en) * | 1983-07-25 | 1985-11-26 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transferable sheet |
| DE3481598D1 (en) * | 1983-07-25 | 1990-04-19 | Dainippon Printing Co Ltd | SHEET FOR USE IN THERMAL TRANSFER PRINTING. |
| US4927666A (en) * | 1983-07-25 | 1990-05-22 | Dai Nippon Insatsu Kabushiki Kaisha | Image-receiving sheet |
| JPS60152563A (en) * | 1984-01-20 | 1985-08-10 | Mitsubishi Chem Ind Ltd | Pyridone-based thermal transfer recording dye and thermal transfer sheet |
| JPS6112393A (en) * | 1984-06-29 | 1986-01-20 | Mitsui Toatsu Chem Inc | Yellowish-hue thermal transfer coloring material |
| JPS6112392A (en) * | 1984-06-29 | 1986-01-20 | Mitsui Toatsu Chem Inc | Reddish-hue thermal transfer coloring material |
| JPS6131293A (en) * | 1984-07-24 | 1986-02-13 | Sharp Corp | Thermal recording method |
| 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 dye for thermal transfer recording |
| JPS61262191A (en) * | 1985-05-16 | 1986-11-20 | Sumitomo Chem Co Ltd | Sublimable transfer body |
| JPH0764123B2 (en) * | 1985-05-23 | 1995-07-12 | 大日本印刷株式会社 | Thermal transfer sheet |
| JPH0714665B2 (en) * | 1985-06-10 | 1995-02-22 | 大日本印刷株式会社 | Heat transfer sheet |
| GB8518572D0 (en) * | 1985-07-23 | 1985-08-29 | Ici Plc | Anthraquinone dye |
| US4695286A (en) * | 1985-12-24 | 1987-09-22 | Eastman Kodak Company | High molecular weight polycarbonate receiving layer used in thermal dye transfer |
| GB8612668D0 (en) * | 1986-05-23 | 1986-07-02 | Turnright Controls | Electronic time switch |
| GB8612778D0 (en) * | 1986-05-27 | 1986-07-02 | Ici Plc | Thermal transfer printing |
| US4985396A (en) * | 1987-12-29 | 1991-01-15 | Matsushita Electric Industrial Co., Ltd | Dye transfer type thermal printing sheets |
| US4985397A (en) * | 1988-10-03 | 1991-01-15 | Ricoh Company, Ltd. | Thermal image transfer recording system |
| GB8826455D0 (en) * | 1988-11-11 | 1988-12-14 | Ici Plc | Dyesheet |
| EP0384040B1 (en) * | 1989-02-24 | 1994-01-26 | Agfa-Gevaert N.V. | Dye-donor element for thermal dye sublimation transfer |
-
1989
- 1989-09-29 DE DE3932523A patent/DE3932523A1/en not_active Withdrawn
-
1990
- 1990-09-20 EP EP90118082A patent/EP0420036B1/en not_active Expired - Lifetime
- 1990-09-20 DE DE59005730T patent/DE59005730D1/en not_active Expired - Lifetime
- 1990-09-28 JP JP2257626A patent/JPH03126591A/en active Pending
- 1990-09-28 US US07/590,130 patent/US5093308A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0216483A1 (en) * | 1985-08-27 | 1987-04-01 | Zeneca Limited | Thermal transfer printing |
| EP0301752A2 (en) * | 1987-07-30 | 1989-02-01 | Zeneca Limited | 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 |
Non-Patent Citations (2)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 10, no. 159 (M-486)(2215) 07 Juni 1986, & JP-A-61 12392 (MITSUI TOATSU KAGAKU K.K.) 20 Januar 1986, * |
| PATENT ABSTRACTS OF JAPAN vol. 11, no. 125 (M-582)(2572) 18 April 1987, & JP-A-61 268494 (DAINIPPON PRINTING CO LTD) 27 November 1986, * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3932523A1 (en) | 1991-04-11 |
| EP0420036B1 (en) | 1994-05-18 |
| US5093308A (en) | 1992-03-03 |
| DE59005730D1 (en) | 1994-06-23 |
| JPH03126591A (en) | 1991-05-29 |
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