USRE34877E - Azo dyes for thermotransfer printing - Google Patents
Azo dyes for thermotransfer printing Download PDFInfo
- Publication number
- USRE34877E USRE34877E US08/166,103 US16610393A USRE34877E US RE34877 E USRE34877 E US RE34877E US 16610393 A US16610393 A US 16610393A US RE34877 E USRE34877 E US RE34877E
- Authority
- US
- United States
- Prior art keywords
- sub
- sup
- alkyl
- och
- phenyl
- 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
- 239000000987 azo dye Substances 0.000 title claims abstract description 19
- 238000007639 printing Methods 0.000 title claims abstract description 14
- 239000000460 chlorine Substances 0.000 claims description 52
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 41
- -1 aminoisothiadiazole Chemical compound 0.000 claims description 36
- 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 description 36
- 239000000975 dye Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical group 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000007651 thermal printing Methods 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 8
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 125000001544 thienyl group Chemical group 0.000 claims description 8
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 7
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- IYCKMNAVTMOAKD-UHFFFAOYSA-N 1,2-thiazol-3-amine Chemical compound NC=1C=CSN=1 IYCKMNAVTMOAKD-UHFFFAOYSA-N 0.000 claims description 6
- 125000005041 acyloxyalkyl group Chemical group 0.000 claims description 6
- 125000005205 alkoxycarbonyloxyalkyl group Chemical group 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- WIJQCPIRWXSWQG-UHFFFAOYSA-N 1,2-benzothiazol-3-amine Chemical compound C1=CC=C2C(N)=NSC2=C1 WIJQCPIRWXSWQG-UHFFFAOYSA-N 0.000 claims description 5
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims description 5
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical class NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 claims description 5
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- AEJDTVZKPNJDBM-UHFFFAOYSA-N n-[(e)-1,3-thiazol-2-yldiazenyl]aniline Chemical compound C=1C=CC=CC=1N\N=N\C1=NC=CS1 AEJDTVZKPNJDBM-UHFFFAOYSA-N 0.000 claims description 4
- FBVFGUHMGHBIID-UHFFFAOYSA-N n-[(e)-thiophen-2-yldiazenyl]aniline Chemical compound C=1C=CC=CC=1N\N=N\C1=CC=CS1 FBVFGUHMGHBIID-UHFFFAOYSA-N 0.000 claims description 4
- WHLAXDUXKMECTM-UHFFFAOYSA-N oxadiazol-4-amine Chemical compound NC1=CON=N1 WHLAXDUXKMECTM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- QUKGLNCXGVWCJX-UHFFFAOYSA-N 1,3,4-thiadiazol-2-amine Chemical compound NC1=NN=CS1 QUKGLNCXGVWCJX-UHFFFAOYSA-N 0.000 claims description 3
- ACTKAGSPIFDCMF-UHFFFAOYSA-N 1,3-oxazol-2-amine Chemical compound NC1=NC=CO1 ACTKAGSPIFDCMF-UHFFFAOYSA-N 0.000 claims description 3
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical compound NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 claims description 3
- UIWQZDKINVCVRN-UHFFFAOYSA-N [(2,2-diphenylhydrazinyl)diazenyl]benzene Chemical compound C=1C=CC=CC=1N(C=1C=CC=CC=1)NN=NC1=CC=CC=C1 UIWQZDKINVCVRN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000005059 halophenyl group Chemical group 0.000 claims description 3
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 claims description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 2
- 229950003476 aminothiazole Drugs 0.000 claims 3
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 91
- 239000001856 Ethyl cellulose Substances 0.000 description 25
- 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 25
- 229920001249 ethyl cellulose Polymers 0.000 description 25
- 235000019325 ethyl cellulose Nutrition 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 12
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 8
- 239000012362 glacial acetic acid Substances 0.000 description 8
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 125000004414 alkyl thio group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- CUWHXIJMTMMRTI-UHFFFAOYSA-N thiadiazol-4-amine Chemical class NC1=CSN=N1 CUWHXIJMTMMRTI-UHFFFAOYSA-N 0.000 description 3
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 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
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 101150108015 STR6 gene Proteins 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 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
- 150000005010 aminoquinolines 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
- 230000008901 benefit Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000012000 cholesterol Nutrition 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
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 150000008049 diazo compounds Chemical class 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
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- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005843 halogen group Chemical group 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
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- DZFWNZJKBJOGFQ-UHFFFAOYSA-N julolidine Chemical compound C1CCC2=CC=CC3=C2N1CCC3 DZFWNZJKBJOGFQ-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 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
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- 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
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- 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
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- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
Definitions
- the present invention relates to the use in thermo-transfer printing of azo dyes of the formula I ##STR2## where the substituents have the following meaning:
- R 1 is hydrogen
- cyclohexyl which may be substituted by C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy or halogen:
- phenyl which may be substituted by C 1 -C 5 -alkyl, C 1 --C 5 -alkoxy, sulfonamido or halogen;
- thienyl which may be C 1 --C 5 -alkyl- or halogen-substituted, furanyl or pyridyl;
- W is identical or different C 2 -C 6 -alkylene
- n is from 1 to 6 and
- R 4 is C 1 -C 4 -alkyl or a phenyl or benzyl group which may both be substituted by C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy;
- R 2 and R 3 are each hydrogen
- phenyl which may be substituted by C 1 -C 15 -alkyl, C 1 -C 15 -alkoxy, benzyloxy or halogen; a radical of the abovementioned formula II;
- thermotransfer printing is common knowledge; suitable heat sources besides lasers and IR lamps are in particular thermal printing heads capable of emitting short heat pulses lasting fractions of a second.
- thermotransfer printing a transfer sheet which contains the transfer dye together with one or more binders, a support material and possibly further assistants such as release agents or crystallization inhibitors is heated from the back with the thermal printing head, causing the dye to migrate out of the transfer sheet and to diffuse into the surface coating of the substrate, for example into the plastic coat of a coated sheet of paper.
- the essential advantage of this process is that the amount of dye to be transferred (and hence the color gradation) can be controlled in a specific manner via the amount of energy supplied to the thermal printing head.
- Thermal transfer printing is in general carried out using the three subtractive primaries yellow, magenta and cyan (with or without black), and the dyes used must have the following properties to ensure optimal color recording: ready thermal transferability, little tendency to migrate within or out of the surface coating of the receiving medium at room temperature, high thermal and photochemical stability, and also resistance to moisture and chemicals, no tendency to crystallize on storage of the transfer sheet, a suitable hue for subtractive color the transfer sheet, a suitable hue for subtractive color mixing, a high molar absorption coefficient, and ready industrial availability.
- magenta dyes used to date have not been fully satisfactory. This is also true for example of the azo dyes described, and recommended for thermal transfer, in U.S. Pat. No. 4,764,178, which resemble the azo dyes I and have coupling components based on aniline, tetrahydroquinoline, aminoquinoline or julolidine.
- azo dyes I themselves are known per se or obtainable by known methods, for example as described in earlier German Patent Application P 38 33 443.7, O. Annen et al., Rev. Prog. Coloration 17 (1987), 72-85, or M. A. Weaver and L. Shuttleworth, Dyes and Pigments 3 (1982), 81-121.
- thermotransfer printing It is an object of the present invention to find suitable red and blue dyes for thermotransfer printing which come closer to the required property profile than the prior art dyes.
- R 1' is C 1 -C 8 -alkyl which may be substituted by
- phenyl which may be substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or chlorine;
- R 2' and R 3' are each C 1 -C 12 -alkyl, C 1 -C 10 -alkoxy or C 1 -C 10 -cyanoalkyl or a radical of the abovementioned formula Ila;
- D' is the radical of a diazo compound III of the aniline, phenylazoaniline, aminothiophene, phenylazoaminothiophene, aminothazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxazole, aminooxadiazole, aminodiazole, aminotriazole or aminopyrrole series.
- Preferred diazo components III are:
- R 5 , R 6 and R 7 are each hydrogen, chlorine, bromine, nitro or cyano; alkyl alkoxyalkyl, alkanoyloxalkyl or alkoxycarbonylalkyl, which may each contain up to 10 carbon atoms;
- R 15 and R 16 are each alkyl or alkoxyalkyl which may each contain up to 10 carbon atoms, and
- R 16 may also be hydrogen
- R 5 may also be oxadiazole substituted in the 3-position by C 1 -C 8 -alkoxy;
- R 6 may also be a radical of the formula --CO--R 17 or --CO--OR 17 where
- R 17 is phenyl which may be substituted by C 1 -C 8 -alkyl
- R 8 is hydrogen, chlorine, cyano or thiocyanato, alkyl, alkoxy, alkylthio or alkoxyalkyl which may each contain up to 10 carbon atoms; 2-(C 1 -C 2 -alkoxycarbonyl)ethylthio; 2-(pyrrolid-1-yl)ethyl; C 5 -C 6 -cycloalkyl or -cycloalkylthio; phenyl which may be substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, benzyloxy or phenylthio; Ar-C 1 -C 4 -alkythio; Ar-C 1 -C 4 -alkoxy or Ar-C 1 -C 4 -alkylthio;
- R 9 is hydrogen, chlorine, bromine, nitro, cyano, thiocyanato or phenyl; or a radical of the formula --CO--OR 15 or --CO--NR 15 R 16 ;
- R 10 is hydrogen, chlorine, bromine, nitro, cyano or formyl; a radical of the formula --CO--OR 15 or --CO--NR 15 R 16 ; or a radical of the formula IV
- R 11 and R 12 are each hydrogen, chlorine, bromine, nitro or cyano; C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; or a radical of the formula --CO--OR 15 or --CO--NR 15 R 16 ;
- R 13 is hydrogen, chlorine, bromine or C 1 -C 4 -alkyl
- R 14 is hydrogen or cyano; or a radical of the formula --CO--OR 15 or --CO--NR 15 R 16 ;
- R 18 is cyano or formamido
- R 19 is methyl or phenyl
- X is hydrogen, chlorine or nitro
- Y is hydrogen or cyano.
- Suitable alkyl R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 15 or R 16 is in particular methyl, ethyl, propyl, ispropyl or butyl, but also isobutyl, sec.-butyl or tert.-butyl.
- R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 15 and R 16 may each also be for example pentyl, isopentyl, neopentyl, tert.-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, mixed isooctyl isomer and cyclohexyl.
- R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 15 and R 16 may each also be for example nonyl, decyl, mixed isononyl isomer or mixed isodecyl isomer.
- R 1 , R 2 and R 3 include undecyl, dodecyl, tridecyl, mixed isotridecyl isomer, tetradecyl and pentadecyl and for R 2 and R 3 additionally hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
- R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 15 or R 16 is alkoxyalkyl of preferred formula II
- suitable W is for example 1,2- and 1,3-propylene, 1,2-, 1,3-, 1,4- and 2,3-butylene, pentamethylene, hexamethylene and 2-methylpentamethylene, but in particular ethylene
- R 4 is in particular methyl, ethyl, propyl, butyl and also benzyl and phenyl which may each be substituted by methyl(oxy), ethyl(oxy), propyl(oxy) or butyl(oxy).
- Particularly preferred II is for example:
- Suitable alkoxyalkyl also includes for example:
- alkoxyalkyl groups those which contain up to 8 carbon atoms are also suitable for use as R 8 and those having up to 12 carbon atoms are also suitable for use as R 15 and R 16 .
- Preferred alkoxy R 2 , R 3 , R 8 , R 11 or R 12 is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec.-butoxy.
- R 8 and especially R 2 and R 3 may each also be for example pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, oxtyloxy or 2-ethylhexyloxy.
- R 2 and R 3 may each in addition be for example nonyloxy or decyloxy but also undecyloxy, dodecyloxy, tridecyloxy, tetradecyioxy or pentadecyloxy.
- R 8 may also be alkylthio, such as preferably methylthio, ethylthio or 2-cyanoethylthio, but also propylthio, isopropylthio, butylthio, pentylthio, hexylthio, heptythio, octylthio, 2-ethylhexylthio, 2-ethoxycarbonylethylthio or in particular 2-methoxycarbonylthio.
- alkylthio such as preferably methylthio, ethylthio or 2-cyanoethylthio, but also propylthio, isopropylthio, butylthio, pentylthio, hexylthio, heptythio, octylthio, 2-ethylhexylthio, 2-ethoxycarbonylethylthio or in particular 2-methoxycarbonylthio.
- Suitable alkanoyloxyalkyl, alkoxycarbonyloxyalkyl or alkoxycarbonylalkyl R 2 or R 3 is for example:
- Phenyl and cyclohexyl which may each be present as
- R 1 , R 2 or R 3 are for example: --Ph, --Ph--3--CH 3 , --Ph--4--(CH 2 ) 10 --CH 3 , --Ph--3--(CH 2 ) 5 --CH(CH 3 )--CH 3 , Ph--4--O--C 4 H 9 , --Ph--4--(CH 2 ) 5 --CH(C 2 H 5 )--CH 3 , --Ph--4--)---CH 2 --Ph or --Ph--4--Cl and also in the case of R 1 in particular --Ph--3--SO 2 --N(CH 3 )--CH 3 or Ph--3--SO 2 --N--((CH 2 ) 2 --O--CH 3 )--(CH 2 ) 2 --O--CH 3 ; --C 6 H 10 --4--CH 3 , --C 6 H 10 --4--C 10 H 21 , --C 6 H 10 --3-O-
- R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 or R 14 is a group of the formula --CO--OR 15 or --CO--NR 15 R 16 , particularly suitable instanccs thereof are
- Groups of the formula --SO--OR 15 or --SO 2 --OR 15 which may each be used as R 5 , R 6 , R 7 or R 8 are For example:
- R 5 , R 6 and R 7 may each also be groups of the formula --SO 2 --NR 15 R 16 , in particular --SO 2 --N(CH 3 )--CH 3 , --SO 2 --N((CH 2 ) 2 --O--CH 3 )--(CH 2 ) 2 --O--CH 3 , but also for example --SO 2 --N(C 2 H 5 )--C 2 H 5 or --SO 2 --N(C 3 H 7 )--C 3 H 7 .
- R 6 and R 10 may each also be groups of the formula IV, such as --CH ⁇ C(CN)--CN, --CH ⁇ C(CN)--CO--O--CH 3 , --CH ⁇ C(CN)--CO--O--C 2 H 5 .
- --CH ⁇ C(CN)--CO--O--C 3 H 7 --CH ⁇ --C(CN)--CO--O--C 4 H 9 , --CH ⁇ C(CN)--N(CH 3 )--CH 3 or --CH ⁇ C(CN)--N(C 2 H 5 )--C 2 H 5 .
- R 1 is particularly preferably C 1 -C 8 alkyl, especially methyl or isopropyl, cyclohexyl, phenyl, which may also be methoxy-, sulfonamido- or chlorine-substituted, or benzyl.
- Preferred R 12 further includes 3-thienyl and especially 2-thienyl. 3-furanyl and especially 2-furanyl, and also 2-pyridyl, 4-pyridyl and especially 3-pyridyl.
- R 2 or R 3 is of up to 12 carbon atoms, especially methyl, ethyl or propyl, preferred cyanoalkyl and alkoxy R 2 or R 3 is of up to 10 carbon atoms.
- Particularly preferred R 2 and R 3 each has the formula Ila with methyl or ethyl as R 4 '.
- aniline derivatives IIIa having the above-defined meanings of R 5 , R 6 and R 7
- aminothiophene derivatives IIIc having the following meanings for R 8 , R 9 and R 10 :
- R 8 is hydrogen or chlorine; alkyl, alkoxy or alkoxyalkyl, which may each contain up to 8 carbon atoms; phenyl which may be C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted, or benzyl; or a radical of the formula --CO--OR 15 ;
- R 9 is cyano or a radical of the formula --CO--OR 15 or else --CO--NR 15 R 16 ;
- R 10 is cyano, nitro, formyl or a radical of the formula IV
- aminothiazole derivatives IIIe having the following meanings for R 8 and R 10 :
- R 8 is hydrogen, chlorine, C 1 14 C 8 -alkyl, phenyl which may be C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted, benzyl, or a radical of the formula --CO--OR 15 ;
- R 10 is cyano, nitro, formyl or a radical of the formula --CO--OR 15
- R 8 is chlorine, alkyl, alkoxy, alkylthio or alkoxyalkyl which may each contain up to 8 carbon atoms, phenyl which may be C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted, benzyl or benzyloxy, and
- R 9 is cyano, nitro or a radical of the formula --CO--OR 15
- aminothiadiazole derivatives IIIk and aminoisothiadiazole derivatives IIIl having the following meaning for R 8 :
- R 8 is hydrogen, chlorine, cyano, thiocyanato, or alkyl, alkoxy, alkylthio or alkoxyalkyl, which may each contain up to 8 carbon atoms, 2-(C 1 -C 2 -alkoxycarbonyl)ethylthio, phenyl which may be C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted, benzyl, benzyloxy, or a radical of the formula --CO--OR 15 , --SO--OR 15 or --SO 2 --OR 15 .
- the dyes I to be used according to the present invention are notable for the following properties compared with prior art red and blue thermotransfer printing dyes having aniline-based coupling components: readier thermal transferability, improved migration properties in the receiving medium at room temperature, higher thermal stability, higher lightfastness, better resistance to moisture and chemicals. better solubility in printing ink preparation, higher color strength. and readier industrial accessability.
- the azo dyes I exhibit a distinctly better purity of hue, in particular in mixtures of dyes, and produce improved black prints.
- the transfer sheets required as dye donors for the thermotransfer printing process according to the present invention are prepared as follows.
- the azo dyes I are incorporated in an organic solvent, such as isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or a mixture thereof, together with one or more binders and possibly further assistants such as release agents or crystallization inhibitors to form a printing ink in which the dyes are preferably present in a molecularly dispersed, i.e. dissolved, form.
- the printing ink is then applied to an inert support and dried.
- Suitable binders for the use of the azo dyes I according to the present invention are all materials which are soluble in organic solvents and which are known to be suitable for thermotransfer printing, e.g. cellulose derivatives such as methylcellulose, hydroxypropylcellulose, cellulose acetate or cellulose acetobutyrate, but in particular ethylcellulose and ethylhydroxyethylcellulose, starch, alginates, alkyd resins and vinyl resins such as polyvinyl alcohol or polyvinylpyrrolidone but in particular polyvinyl acetate and polyvinyl butyrate.
- cellulose derivatives such as methylcellulose, hydroxypropylcellulose, cellulose acetate or cellulose acetobutyrate, but in particular ethylcellulose and ethylhydroxyethylcellulose, starch, alginates, alkyd resins and vinyl resins such as polyvinyl alcohol or polyvinylpyrrolidone but in particular polyvinyl acetate
- polymers and copolymers of acrylates and derivatives thereof such as polyacrylic acid, polymethyl methacrylate or styrene/acrylate copolymers, polyester resins, polyamide resins, polyurethane resins or natural resins such as gum arabic.
- mixtures of these binders for example mixtures of ethylcellulose and polyvinyl butyrate in a weight ratio of 2:1.
- the weight ratio of binder to dye is in general from 8:1 to 1:1, preferably from 5:1 to 2:1.
- Suitable assistants are for example release agents based on perfiuofinated alkylsulfonamidoalkyl esters or silicones as described in EP-A-127,092 and EP-A-192,435, and in particular organic additives which stop the transfer dyes from crystallizing out in the course of storage or heating of the inked ribbon, for example cholesterol or vanillin.
- Inert support materials are for example tissue, blotting or parchment paper and films made of heat resistant plastics such as polyesters, polyamides or polyimides, which films may also be metal coated.
- the inert support may additionally be coated on the side facing the thermal printing head with a lubricant in order that adhesion of the thermal printing head to the support material may be prevented.
- Suitable lubricants are for example silicones or polyurethanes as described in EP-A-216,483.
- the thickness of the dye transfer is in general from 3 to 30 ⁇ m, preferably from 5 to 10 ⁇ m.
- the substrate to be printed e.g. paper
- a plastic which receives the dye during the printing process.
- polymeric materials whose glass transition temperatures T g are within the range from 50° to 100° C.: e.g. polycarbonates and polyesters. Details may 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.
- the process according to the present invention is carried out using a thermal printing head which is heatable to above 300° C., so thai dye transfer takes not more than 15 msec.
- transfer sheets were produced from a polyester sheet from 6 to 10 ⁇ m in thickness coated with an approximately 5 ⁇ m thick transfer layer of a binder B which in each case contained about 0.25 g of azo dye I.
- the weight ratio of binder to dye was in each case 4:1, unless otherwise stated in the Tables below.
- the substrate (receiver) to be printed was paper about 120 ⁇ m in thickness which had been coated with a layer of plastic 8 ⁇ m in thickness (Hitachi Color Video Print Paper).
- Donor and receiver were placed on top of one another with the coated fronts next to each other, then wrapped in aluminum foil and heated between two hotplates at 70°-80° C. for 2 minutes. This operation was repeated three times with similar samples at a temperature within the range from 80° to 120° C., the temperature being increased each time.
- the amount of dye diffusing into the plastics layer of the receiver in the course of transfer is proportional to the optical density determined photometrically as absorbance A after each heating phase at the abovementioned temperatures.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Plural Heterocyclic Compounds (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Azo dyes useful for thermotransfer printing have the formula ##STR1##
Description
The present invention relates to the use in thermo-transfer printing of azo dyes of the formula I ##STR2## where the substituents have the following meaning:
R1 is hydrogen;
C1 -C15 -alkyl which may be substituted by phenyl or phenoxy;
cyclohexyl which may be substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy or halogen:
phenyl which may be substituted by C1 -C5 -alkyl, C1 --C5 -alkoxy, sulfonamido or halogen;
thienyl which may be C1 --C5 -alkyl- or halogen-substituted, furanyl or pyridyl;
a radical of the formula II
[--W--O].sub.n --R.sup.4 II
where
W is identical or different C2 -C6 -alkylene,
n is from 1 to 6 and
R4 is C1 -C4 -alkyl or a phenyl or benzyl group which may both be substituted by C1 -C4 -alkyl or C1 -C4 -alkoxy;
R2 and R3 are each hydrogen;
alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, which may each contain up to 15 carbon atoms and be substituted by phenyl, C1 -C4 -alkylphenyl, C1 -C4 -alkoxyphenyl, halophenyl, benzyloxy, C1 -C4 -alkylbenzyloxy, C1 -C4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano; cyclohexyl which may be substituted by C1 14 C15 -alkyl, C1 -C15 -alkoxy or halogen;
phenyl which may be substituted by C1 -C15 -alkyl, C1 -C15 -alkoxy, benzyloxy or halogen; a radical of the abovementioned formula II; and
is the radical of a diazo component III
D--NH.sub.2 III
and specifically to a process for transferring these azo dyes by diffusion from a transfer to a plastic-coated substrate with the aid of a thermal printing head.
The technique of thermotransfer printing is common knowledge; suitable heat sources besides lasers and IR lamps are in particular thermal printing heads capable of emitting short heat pulses lasting fractions of a second.
In this preferred embodiment of thermotransfer printing, a transfer sheet which contains the transfer dye together with one or more binders, a support material and possibly further assistants such as release agents or crystallization inhibitors is heated from the back with the thermal printing head, causing the dye to migrate out of the transfer sheet and to diffuse into the surface coating of the substrate, for example into the plastic coat of a coated sheet of paper.
The essential advantage of this process is that the amount of dye to be transferred (and hence the color gradation) can be controlled in a specific manner via the amount of energy supplied to the thermal printing head.
Thermal transfer printing is in general carried out using the three subtractive primaries yellow, magenta and cyan (with or without black), and the dyes used must have the following properties to ensure optimal color recording: ready thermal transferability, little tendency to migrate within or out of the surface coating of the receiving medium at room temperature, high thermal and photochemical stability, and also resistance to moisture and chemicals, no tendency to crystallize on storage of the transfer sheet, a suitable hue for subtractive color the transfer sheet, a suitable hue for subtractive color mixing, a high molar absorption coefficient, and ready industrial availability.
It is very difficult to meet all these requirements at one and the same time. In particular, the magenta dyes used to date have not been fully satisfactory. This is also true for example of the azo dyes described, and recommended for thermal transfer, in U.S. Pat. No. 4,764,178, which resemble the azo dyes I and have coupling components based on aniline, tetrahydroquinoline, aminoquinoline or julolidine.
The azo dyes I themselves are known per se or obtainable by known methods, for example as described in earlier German Patent Application P 38 33 443.7, O. Annen et al., Rev. Prog. Coloration 17 (1987), 72-85, or M. A. Weaver and L. Shuttleworth, Dyes and Pigments 3 (1982), 81-121.
It is an object of the present invention to find suitable red and blue dyes for thermotransfer printing which come closer to the required property profile than the prior art dyes.
We have found that this object is achieved by the azo dyes I defined at the beginning.
We have also found a process for transferring azo dyes by diffusion from a transfer to a plastic-coated substrate with the aid of a thermal printing head, which comprises using for this purpose a transfer on which are situated one or more of the azo dyes I defined at the beginning.
We have further found preferred embodiments of this process, which comprise using dyes of the formula Ia ##STR3## where the substituents have the following meanings:
R1' is C1 -C8 -alkyl which may be substituted by
phenyl or cyclohexyl;
phenyl which may be substituted by C1 -C4 -alkyl, C1 -C4 -alkoxy or chlorine;
thienyl;
a radical of the formula IIa ##STR4## where p is 0 or 1, q is from 1 to 4, and R4' is C1 -C4 -alkyl, phenyl or benzyl;
R2' and R3' are each C1 -C12 -alkyl, C1 -C10 -alkoxy or C1 -C10 -cyanoalkyl or a radical of the abovementioned formula Ila; and
D' is the radical of a diazo compound III of the aniline, phenylazoaniline, aminothiophene, phenylazoaminothiophene, aminothazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxazole, aminooxadiazole, aminodiazole, aminotriazole or aminopyrrole series.
Preferred diazo components III are:
aniline derivatives of the formula IIIa ##STR5## phenylazoaniline derivatives of the formula IIIb ##STR6## aminothiphene derivatives of the formula IIIc ##STR7## phenylazoaminothiophene derivatives of the formula IIId ##STR8##
Aminothiazole derivatives of the formula IIIe ##STR9## phenylazoaminothiazole derivatives of the formula IIIf ##STR10## aminoisothiazole derivatives of the formula IIIg ##STR11## aminobenzisothiazole derivatives of the formulae IIIh and IIIi ##STR12## aminothiadiazole derivatives of the formula IIIk ##STR13## aminothiadiazole derivatives of the formula IIIl ##STR14## aminopyrrole derivatives of the formula IIIm ##STR15##
Here the substituents have the following meanings:
R5, R6 and R7 are each hydrogen, chlorine, bromine, nitro or cyano; alkyl alkoxyalkyl, alkanoyloxalkyl or alkoxycarbonylalkyl, which may each contain up to 10 carbon atoms;
a radical of the formula II;
a radical of the formula --CO--OR15, --CO--NR15 R16, --SO--OR15, --SO2 --OR15 or --SO2 --NR15 R16 in which
R15 and R16 are each alkyl or alkoxyalkyl which may each contain up to 10 carbon atoms, and
R16 may also be hydrogen;
R5 may also be oxadiazole substituted in the 3-position by C1 -C8 -alkoxy;
R6 may also be a radical of the formula --CO--R17 or --CO--OR17 where
R17 is phenyl which may be substituted by C1 -C8 -alkyl;
a radical of the formula IV ##STR16## where X is cyano, --CO--OR15 or --CO--NR15 R16 ;
R8 is hydrogen, chlorine, cyano or thiocyanato, alkyl, alkoxy, alkylthio or alkoxyalkyl which may each contain up to 10 carbon atoms; 2-(C1 -C2 -alkoxycarbonyl)ethylthio; 2-(pyrrolid-1-yl)ethyl; C5 -C6 -cycloalkyl or -cycloalkylthio; phenyl which may be substituted by C1 -C4 -alkyl, C1 -C4 -alkoxy, benzyloxy or phenylthio; Ar-C1 -C4 -alkythio; Ar-C1 -C4 -alkoxy or Ar-C1 -C4 -alkylthio;
thienyl or pyridyl which may each be substituted by C1 -C4 -alkyl;
a radical of the formula II;
a radical of the formula --CO--OR15, --CO--NR15 R16, --SO--OR15 or --SO2 --OR15 ;
R9 is hydrogen, chlorine, bromine, nitro, cyano, thiocyanato or phenyl; or a radical of the formula --CO--OR15 or --CO--NR15 R16 ;
R10 is hydrogen, chlorine, bromine, nitro, cyano or formyl; a radical of the formula --CO--OR15 or --CO--NR15 R16 ; or a radical of the formula IV
R11 and R12 are each hydrogen, chlorine, bromine, nitro or cyano; C1 -C4 -alkyl or C1 -C4 -alkoxy; or a radical of the formula --CO--OR15 or --CO--NR15 R16 ;
R13 is hydrogen, chlorine, bromine or C1 -C4 -alkyl;
R14 is hydrogen or cyano; or a radical of the formula --CO--OR15 or --CO--NR15 R16 ;
R18 is cyano or formamido;
R19 is methyl or phenyl;
X is hydrogen, chlorine or nitro; and
Y is hydrogen or cyano.
Suitable alkyl R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R15 or R16 is in particular methyl, ethyl, propyl, ispropyl or butyl, but also isobutyl, sec.-butyl or tert.-butyl.
R1, R2, R3, R5, R6, R7, R8, R15 and R16 may each also be for example pentyl, isopentyl, neopentyl, tert.-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, mixed isooctyl isomer and cyclohexyl.
R1, R2, R3, R5, R6, R7, R8, R15 and R16 may each also be for example nonyl, decyl, mixed isononyl isomer or mixed isodecyl isomer.
Other possible meanings for R1, R2 and R3 include undecyl, dodecyl, tridecyl, mixed isotridecyl isomer, tetradecyl and pentadecyl and for R2 and R3 additionally hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Alkyls R2 and R3 may each also be substituted by phenyl; specific examples, where Ph=phenyl, are:
--CH2 --Ph, --CH(CH3)--Ph, --(CH2)2 --Ph,
--(CH2)4 --CH(CH3)--Ph--3--CH3,
--(CH2)3 --CH(C4 H9)--Ph--3--CH3,
--(CH2)6 --Ph--4--O--CH3.
--CH(C2 H5)--(CH2)3 --Ph--3--O--C2 H5 and
--CH(C2 H5)--(CH2)3 --Ph--3--Cl.
It is also possible to use for example the following halo, hydroxyl and cyanoalkyl groups as R2 or R3 :
--(CH2)5 --Cl, --CH(C4 H9)--(CH2)3 --Cl or --(CH2)4 --CF3 ;
--(CH2)2 --CH(CH3)--OH. --(CH2)2 --CH(C4 H9)--OH oder CH(C2 H5)--(CH2)9 --OH:
--(CH2)2 --CN, --(CH2)3 --CN, --CH2 --CH(CH3)--CH(C2 H5)--CN, --(CH2)6 --CH(C2 H6)--CN and
--(CH2)3 --CH(CH3)--(CH2)2 --CH(CH3)--CN.
When R1, R2, R3, R5, R6, R7, R15 or R16 is alkoxyalkyl of preferred formula II, suitable W is for example 1,2- and 1,3-propylene, 1,2-, 1,3-, 1,4- and 2,3-butylene, pentamethylene, hexamethylene and 2-methylpentamethylene, but in particular ethylene, and R4 is in particular methyl, ethyl, propyl, butyl and also benzyl and phenyl which may each be substituted by methyl(oxy), ethyl(oxy), propyl(oxy) or butyl(oxy). Particularly preferred II is for example:
--(CH2)2 --O--CH3, --(CH2)2 --O--C2 H5, --(CH2)2 --O--C3 H7, --(CH2)2 --O--C4 H9,
--(CH2)2 --O--CH2 --CH(CH3)--CH3,
--(CH2)2 --O--Ph, --(CH2)2 --O--CH2 --Ph,
--[(CH2)2 --O]2 --CH3, --[(CH2)2 --O]2 --C2 H5, --[(CH2)2 --O]2 --Ph,
--[(CH2)2 --O]2 --Ph--4--O--C4 H9,
--[(CH2)2 --O]3 --C4 H9, --[(CH2)2 --O]3 --Ph, --[(CH2)2 --O]3 --Ph--3--C4 H9,
--[(CH2)2 --O]4 --CH3,
--(CH2)3 --O--(CH 2 )2 --O--CH3, --(CH 2)3 --O--(CH2)2 --O--C2 H5,
--(CH2)3 --O--(CH2)2 --O--Ph, --(CH2)3 --O--[(CH2)2 --O]2 --CH3 and
--(CH2)3 --O--[(CH2)2 --O]2 --C2 H5.
Further preferred groups II are for example:
--(CH2)3 --O--CH3, --(CH2)3 --O--C2 H5, --(CH2)3 --O--C3 H7, --(CH2)3 --O--C4 H9,
--(CH2)3 --O--Ph, --[(CH2)3 --O]2 --CH3, --[(CH2)3 --O--]2 'C2 H5,
--CH2 --CH(CH3)--O--CH3, --CH2 --CH(CH3)--O--C2 H5, --CH2 --CH(CH3)--O--C3 H7,
--CH2 --CH(CH3)--O--C4 H9, --CH2 --CH(CH3)--O--Ph,
--(CH2)4 --O--CXH3, --(CH2)4 --O--C2 H5, --(CH2)4 --O--C4 H9,
--(CH2)4 --O--CH2 --CH(C2 H5)--C4 H9, --(CH2)4 --O--Ph,
--(CH2)4 --O--CH2 --Ph--2--O--C2 H5, --(CH2)4 --O--C6 H10 --2--C2 H5,
--[(CH2)4 --O]2 --CH3, --[(CH2)4 --O]2 --C2 H5, --[(CH2)2 --CH(CH3)--O]2 --C2 H5,
--(CH2)5 --O--CH3, --(CH2)5 --O--C2 H5, --(CH2)5 --O--C3 H7, --(CH2)5 --O--Ph,
--CH2)2 --CH(C2 H5)--O--CH2 --Ph--3--O--C4 H9, --(CH2)2 --CH(C2 H5)--O--CH2 --Ph--3--Cl,
--(CH2)6 --O--C4 H9, --(CH2)6 --O--Ph--4--O--C4 H9, --(CH2)3 --CH(CH3)--CH(CH3)--CH2 --O--C4 H9,
--(CH2)3 --O--(CH2)4 --O--CH3, --(CH2)3 --O--(CH2)4 --O--C2 H5,
--(CH2)4 --O--(CH2)3 --O--CH3 and --(CH2)4 --O--(CH2)3 --O--C2 H5.
Suitable alkoxyalkyl also includes for example:
--(CH2)8 --O--CH3, --(CH2)8 --O--C4 H9, --(CH2)8 --O--CH2 --Ph--3--C2 H5,
--(CH2)4 --CH(Cl)--(CH2)3 --O--CH2 --Ph--3--CH3 and
--(CH2)3 --CH(C4 H9)--O--CH2 --Ph--3--CH3.
Of the above-recited alkoxyalkyl groups, those which contain up to 8 carbon atoms are also suitable for use as R8 and those having up to 12 carbon atoms are also suitable for use as R15 and R16.
Preferred alkoxy R2, R3, R8, R11 or R12 is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec.-butoxy.
R8 and especially R2 and R3 may each also be for example pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, oxtyloxy or 2-ethylhexyloxy.
R2 and R3 may each in addition be for example nonyloxy or decyloxy but also undecyloxy, dodecyloxy, tridecyloxy, tetradecyioxy or pentadecyloxy.
R8 may also be alkylthio, such as preferably methylthio, ethylthio or 2-cyanoethylthio, but also propylthio, isopropylthio, butylthio, pentylthio, hexylthio, heptythio, octylthio, 2-ethylhexylthio, 2-ethoxycarbonylethylthio or in particular 2-methoxycarbonylthio.
Suitable alkanoyloxyalkyl, alkoxycarbonyloxyalkyl or alkoxycarbonylalkyl R2 or R3 is for example:
--CH2)2 --O--CO--CXH3,
--(CH2)3 --O--CO--(CH2)7 --CH3,
--(CH2)2 --O--CO--(CH2)3 --PH-2--O--CH3,
--CH(CH2 --Ph--3--CH3)--O--CO--C4 H9 and
--(CH2)4 --O--CO--(CH2)4 --CH(C2 H5)--OH;
--(CH2)2 --O--CO--O--CH3,
--(CH2)3 --O--CO--O--(CH2))7 --CH3,
--CH(C2 H5)--CH2 --O--CO--O--C4 H9,
--(CH2)4 --O--CO--O--(CH2)2 --CH(CH3)--O--Ph--3--CH3 and
--(CH2)5 --O--CO--O--(CH2)5 --CN;
--(CH2)2 --CO--O--CH3,
--(CH2)3 --CO--O--C4 H9,
--(CH2)3 --CH(CH3)--CH2 --CO--O--C4 H9,
--(CH2)3 --CH(C4 H9)--CH2 --CO--O--C2 H5,
--(CH2)2 --CO--O--(CH2)5 --Ph,
--(CH2)4 --CO--O--(CH2)4 --Ph-4C4 H9,
--(CH2)3 --CO--O--(CH2)4 --O--Ph-3--O--CH3,
--(CH2)2 --CH(CH2 OH)--(CH2)2 --CO--O--C2 H5,
--CH(C2 H5)--CH2 --CO--O--CH2)4 --OH and
--(CH2)3 --CO--O--(CH2)6 --CN.
Phenyl and cyclohexyl which may each be present as
R1, R2 or R3 are for example: --Ph, --Ph--3--CH3, --Ph--4--(CH2)10 --CH3, --Ph--3--(CH2)5 --CH(CH3)--CH3, Ph--4--O--C4 H9, --Ph--4--(CH2)5 --CH(C2 H5)--CH3, --Ph--4--)--CH2 --Ph or --Ph--4--Cl and also in the case of R1 in particular --Ph--3--SO2 --N(CH3)--CH3 or Ph--3--SO2 --N--((CH2)2 --O--CH3)--(CH2)2 --O--CH3 ; --C6 H10 --4--CH3, --C6 H10 --4--C10 H21, --C6 H10 --3--O--C4 H9, --C6 H10 --3--O--(CH2).sub. 4 --CH(C2 H5)--CH3 or --C6 H10 --4--Cl.
Where R5, R6, R7, R8, R9, R10, R11, R12 or R14 is a group of the formula --CO--OR15 or --CO--NR15 R16, particularly suitable instanccs thereof are
--CO--O--CH3, --CO--O--C2 H5, --CO--O--C3 H7,
--CO--O--C4 H9, --CO--N(CH3)--CH3 and
--CO--N(C2 H5)--C2 H5, but also for example
--CO--O--C5 H11, --CO--O--C6 H13, --CO--n(C3 H7)--C3 H7 and --CO--n(C4 H9.
Groups of the formula --SO--OR15 or --SO2 --OR15, which may each be used as R5, R6, R7 or R8 are For example:
--SO--O--CH3, --SO--O--C2 H5, --SO--O--C3 H7,
--SO2 --O--CH3, --SO2 --O--C2 H5, --SO2 --O--C3 H7.
R5, R6 and R7 may each also be groups of the formula --SO2 --NR15 R16, in particular --SO2 --N(CH3)--CH3, --SO2 --N((CH2)2 --O--CH3)--(CH2)2 --O--CH3, but also for example --SO2 --N(C2 H5)--C2 H5 or --SO2 --N(C3 H7)--C3 H7.
R6 and R10 may each also be groups of the formula IV, such as --CH═C(CN)--CN, --CH═C(CN)--CO--O--CH3, --CH═C(CN)--CO--O--C2 H5. --CH═C(CN)--CO--O--C3 H7, --CH═--C(CN)--CO--O--C4 H9, --CH═C(CN)--N(CH3)--CH3 or --CH═C(CN)--N(C2 H5)--C2 H5.
Of the aforementioned radicals, R1 is particularly preferably C1 -C8 alkyl, especially methyl or isopropyl, cyclohexyl, phenyl, which may also be methoxy-, sulfonamido- or chlorine-substituted, or benzyl. Preferred R12 further includes 3-thienyl and especially 2-thienyl. 3-furanyl and especially 2-furanyl, and also 2-pyridyl, 4-pyridyl and especially 3-pyridyl.
Preferred alkyl R2 or R3 is of up to 12 carbon atoms, especially methyl, ethyl or propyl, preferred cyanoalkyl and alkoxy R2 or R3 is of up to 10 carbon atoms. Particularly preferred R2 and R3 each has the formula Ila with methyl or ethyl as R4 '.
Of the above-recited diazo components D-NH2, the following are particularly preferred:
aniline derivatives IIIa having the above-defined meanings of R5, R6 and R7
aminothiophene derivatives IIIc having the following meanings for R8, R9 and R10 :
R8 is hydrogen or chlorine; alkyl, alkoxy or alkoxyalkyl, which may each contain up to 8 carbon atoms; phenyl which may be C1 -C4 -alkyl- or C1 -C4 -alkoxy-substituted, or benzyl; or a radical of the formula --CO--OR15 ;
R9 is cyano or a radical of the formula --CO--OR15 or else --CO--NR15 R16 ; and
R10 is cyano, nitro, formyl or a radical of the formula IV
aminothiazole derivatives IIIe having the following meanings for R8 and R10 :
R8 is hydrogen, chlorine, C1 14 C8 -alkyl, phenyl which may be C1 -C4 -alkyl- or C1 -C4 -alkoxy-substituted, benzyl, or a radical of the formula --CO--OR15 ; and
R10 is cyano, nitro, formyl or a radical of the formula --CO--OR15
aminoisothiazole derivatives IIIg having the following meanings for R8 and R9 :
R8 is chlorine, alkyl, alkoxy, alkylthio or alkoxyalkyl which may each contain up to 8 carbon atoms, phenyl which may be C1 -C4 -alkyl- or C1 -C4 -alkoxy-substituted, benzyl or benzyloxy, and
R9 is cyano, nitro or a radical of the formula --CO--OR15
aminothiadiazole derivatives IIIk and aminoisothiadiazole derivatives IIIl having the following meaning for R8 :
R8 is hydrogen, chlorine, cyano, thiocyanato, or alkyl, alkoxy, alkylthio or alkoxyalkyl, which may each contain up to 8 carbon atoms, 2-(C1 -C2 -alkoxycarbonyl)ethylthio, phenyl which may be C1 -C4 -alkyl- or C1 -C4 -alkoxy-substituted, benzyl, benzyloxy, or a radical of the formula --CO--OR15, --SO--OR15 or --SO2 --OR15.
The dyes I to be used according to the present invention are notable for the following properties compared with prior art red and blue thermotransfer printing dyes having aniline-based coupling components: readier thermal transferability, improved migration properties in the receiving medium at room temperature, higher thermal stability, higher lightfastness, better resistance to moisture and chemicals. better solubility in printing ink preparation, higher color strength. and readier industrial accessability.
In addition, the azo dyes I exhibit a distinctly better purity of hue, in particular in mixtures of dyes, and produce improved black prints.
The transfer sheets required as dye donors for the thermotransfer printing process according to the present invention are prepared as follows. The azo dyes I are incorporated in an organic solvent, such as isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or a mixture thereof, together with one or more binders and possibly further assistants such as release agents or crystallization inhibitors to form a printing ink in which the dyes are preferably present in a molecularly dispersed, i.e. dissolved, form. The printing ink is then applied to an inert support and dried.
Suitable binders for the use of the azo dyes I according to the present invention are all materials which are soluble in organic solvents and which are known to be suitable for thermotransfer printing, e.g. cellulose derivatives such as methylcellulose, hydroxypropylcellulose, cellulose acetate or cellulose acetobutyrate, but in particular ethylcellulose and ethylhydroxyethylcellulose, starch, alginates, alkyd resins and vinyl resins such as polyvinyl alcohol or polyvinylpyrrolidone but in particular polyvinyl acetate and polyvinyl butyrate. It is also possible to use polymers and copolymers of acrylates and derivatives thereof, such as polyacrylic acid, polymethyl methacrylate or styrene/acrylate copolymers, polyester resins, polyamide resins, polyurethane resins or natural resins such as gum arabic.
It is frequently advisable to use mixtures of these binders, for example mixtures of ethylcellulose and polyvinyl butyrate in a weight ratio of 2:1.
The weight ratio of binder to dye is in general from 8:1 to 1:1, preferably from 5:1 to 2:1.
Suitable assistants are for example release agents based on perfiuofinated alkylsulfonamidoalkyl esters or silicones as described in EP-A-127,092 and EP-A-192,435, and in particular organic additives which stop the transfer dyes from crystallizing out in the course of storage or heating of the inked ribbon, for example cholesterol or vanillin.
Inert support materials are for example tissue, blotting or parchment paper and films made of heat resistant plastics such as polyesters, polyamides or polyimides, which films may also be metal coated.
The inert support may additionally be coated on the side facing the thermal printing head with a lubricant in order that adhesion of the thermal printing head to the support material may be prevented. Suitable lubricants are for example silicones or polyurethanes as described in EP-A-216,483.
The thickness of the dye transfer is in general from 3 to 30 μm, preferably from 5 to 10 μm.
The substrate to be printed, e.g. paper, must in turn be coated with a plastic which receives the dye during the printing process. It is preferable to use for this purpose polymeric materials whose glass transition temperatures Tg are within the range from 50° to 100° C.: e.g. polycarbonates and polyesters. Details may 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.
The process according to the present invention is carried out using a thermal printing head which is heatable to above 300° C., so thai dye transfer takes not more than 15 msec.
First, transfer sheets (donors) were produced from a polyester sheet from 6 to 10 μm in thickness coated with an approximately 5 μm thick transfer layer of a binder B which in each case contained about 0.25 g of azo dye I. The weight ratio of binder to dye was in each case 4:1, unless otherwise stated in the Tables below.
The substrate (receiver) to be printed was paper about 120 μm in thickness which had been coated with a layer of plastic 8 μm in thickness (Hitachi Color Video Print Paper).
Donor and receiver were placed on top of one another with the coated fronts next to each other, then wrapped in aluminum foil and heated between two hotplates at 70°-80° C. for 2 minutes. This operation was repeated three times with similar samples at a temperature within the range from 80° to 120° C., the temperature being increased each time.
The amount of dye diffusing into the plastics layer of the receiver in the course of transfer is proportional to the optical density determined photometrically as absorbance A after each heating phase at the abovementioned temperatures.
The plot of the logarithm of the measured absorbances A against the corresponding reciprocal of the absolute temperature is a straight line from whose slope it is possible to calculate the activation energy ΔE.sub.λ for the transfer experiment: ##EQU1##
From the plot it is additionally possible to discern the temperature T* at which the absorbance attains the value 1, i.e. at which the transmitted light intensity is one tenth of the incident light intensity. The lower the temperature T*, the better the thermal transferability of the particular dye.
The Tables which follow list the azo dyes I which were studied in respect of their thermal transfer characteristics together with their absorption maxima λmax [nm]. The λmax values were measured in methylene chloride or the stated solvent.
In addition, they list the particular binder B used employing the following abbreviations: EC=ethylcellulose, PVB=polyvinyl butyrate, MIX=EC:PVB═2:1, and VY=nylon.
If the abovementioned parameters R* [°C.] and ΔE, [kJ/mol] were measured, the values found are likewise stated.
TABLE 1
__________________________________________________________________________
##STR17## IIIa
Ex
R.sup.1
R.sup.2 R.sup.3
R.sup.5 R.sup.6
λ.sub.max [nm]
B T*[°C.]
ΔE.sub.τ
[kJ/mol]
__________________________________________________________________________
1 Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
CN H 494 EC 104 42
2 Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
##STR18## NO.sub.2
544 MS 90 71
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
##STR19## IIIb
Ex.
R.sup.2 R.sup.3
R.sup.5
R.sup.6
R.sup.7
R.sup.11
R.sup.12
R.sup.12'
λ.sub.max [nm]
B T*[°C.]
ΔE.sub.τ
[kJ/mol]
__________________________________________________________________________
3 C.sub.2 H.sub.5
R.sup.2
Cl CN Cl OCH.sub.3
H OCH.sub.3
584 EC 96 84
4 (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H H H Br H H 538 MS 97 76
5 (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H H H Br Br H 492 EC 106 84
__________________________________________________________________________
TABLE 3 IIIc ##STR20## Ex. R.sup.1 R.sup.2 R.sup.3 R.sup.8 R.sup.10 λ.sub.max [nm] B T*[°C.] ΔE.sub.τ [kJ/mol] 6 Cyclohexyl C.sub.2 H.sub.5 R.sup.2 CH.sub.3 CN 550 MIX 90 65 7 Cyclohexyl C.sub.2 H.sub.5 R.sup.2 CH.sub.3 COOCH.sub.3 545.sup.a -- -- -- 8 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 COOCH.sub.3 544.sup.a -- -- -- 9 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3 R.sup. 2 Cl COH 580.sup.a MIX 90 88 VY 90 58 10 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 Cl CHC(CN)COO.sub.4 H.sub.9 625 VY 99 54 11 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CN 551 MIX 92 77 12 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 Cl COH 572 MIX 92 66 VY 86 40 13 CH(CH.sub.3)CH.sub.3 C.sub.2 H.sub.5 R.sup.2 CH.sub.3 CN 547 EC 90 88 14 C H(CH.sub.3)CH.sub.3 C.sub.2 H.sub.5 R.sup.2 Cl COH 572 MIX 90 50 15 CH(CH.sub.3)CH.sub.3 C.sub.2 H.sub.5 R.sup.2 CH.sub.3 CN 547 -- -- -- 16 C H(CH.sub.3)CH.sub.3 C.sub.2 H.sub.5 R.sup.2 COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 542 VY 135 50 17 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 C.sub.2 H.sub.5 R.sup.2 Cl CHC(CN)COOC.sub.4 H.sub.9 608 MIX 90** 59 18 Ph C.sub.2 H.sub.5 R.sup.2 H NO.sub.2 623 -- -- -- 19 Ph C.sub.2 H.sub.5 R.sup.2 Cl Br 559 -- -- -- 20 Ph C.sub.2 H.sub.5 R.sup.2 C l COH 602 -- -- -- 21 Ph C.sub.2 H.sub.5 R.sup.2 CH.sub.3 COOC.sub.2 H.sub.5 569 EC 132 64 22 Ph C.sub.2 H.sub.5 R.sup.2 OC.sub.2 H.sub.5 COH 598 -- -- -- 23 Ph C.sub.2 H.sub.5 R.sup.2 COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 573 VY 100 52 24 Ph (CH.sub.2).sub.3 OCH.sub. 3 C.sub.2 H.sub.5 Cl COH 574 VY 81 23 25 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOCH.sub.3 576.sup.a -- -- -- 26 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 Cl COH 606.sup.a -- -- -- 27 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 CH.sub.3 CN 582.sup.a MIX 91 64 28 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 Cl C OH 633 MIX 91 60 29 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3 OCH.sub.3 Cl CHC(CN)COOC.sub.4 H.sub.9 644 EC 130 76 30 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Cl COH 601 EC* 94 73 31 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Cl CHC(CN)COOC.sub.4 H.sub.9 653 MIX 106 46 32 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3 OCH.sub.3 Cl CHC(CN)COOC.sub.4 H.sub.9 648 MIX 122 67 33 Ph (CH.sub.2).sub.2 O[(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CN 581.sup.a -- -- -- 34 Ph (CH.sub.2).sub.2 O[(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CN 583.sup.a -- -- -- 35 Ph CH.sub.2 [(CH.sub.2).sub.2 O] .sub.2 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOC.sub.2 H.sub.5 575.sup.a -- -- -- 36 Ph CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 C COOH.sub.3 575.sup.a -- -- -- 37 Ph CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 COOC.sub.2 H.sub.5 575.sup.a -- -- -- 38 Ph-4-OCH.sub.3 C.sub.2 H.sub.5 R.sup.2 COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 591 EC 120 50 39 Ph-3-SO.sub.2 N(CH.sub.3).sub.2 C.sub.2 H.sub.5 R.sup.2 Cl COH 595 -- -- -- 40 Ph-3-SO.sub.2 N(CH.sub.3).sub.2 (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 Cl COH 596 -- -- -- 41 Ph-3-SO.sub.2 N[(CH.sub.2).sub.2 OCH.sub.3 ].sub.2 C.sub.2 H.sub.5 R.sup.2 CH.sub.3 COOCH.sub.3 586-- -- -- 42 CH.sub.2 Ph (CH.sub.2).sub.2 O C H.sub.3 R.sup.2 CH.sub.3 COOCH.sub.3 540.sup.a VY 94 51 43 CH.sub.2 OPh C.sub.2 H.sub.5 R.sup.2 CH.sub.3 CN 543.sup.a MIX 88 72 44 Thien-3-yl C.sub.2 H.sub.5 R.sup.2 CH.sub.3 COOCH.sub.3 582.sup.a -- -- -- 45 Thien-2-yl C.sub.2 H.sub.5 R.sup.2 COOC.sub.4 H.sub.9 COOC.sub.4 H.sub.9 600 MIX 94 80 46 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOC.sub.2 H.sub.5 597.sup.a -- -- -- 47 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 CN 599 -- -- -- 48 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 COOCH.sub.3 589 -- -- -- 49 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 Cl COH 631 -- -- -- 50 Thien-3-yl (CH.sub.2).sub.3 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOCH.sub.3 583.sup.a -- -- -- 51 Thien-2-yl (CH.sub.2) .sub.3 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOC.sub.2 H.sub.5 598.sup.a -- -- -- 52 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 C.sub.2 H.sub.5 Cl COH 638.sup.a -- -- -- 53 Thien-2-yl (CH.sub.2).sub.2 O(CH.sub.2)hd 2OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOCH.sub.3 599.sup.a -- -- -- 54 Thien-2-yl (CH.sub.2).sub.2 O(CH.sub.2)hd 2OCH.sub.3 C.sub.2 H.sub.5 Cl COOH 639.sup.a -- -- -- 55 Thien-2-yl (CH.sub.2).sub.2 O(CH.sub.2)hd 2OCH.sub.3 C.sub.3 H.sub.7 Cl COOH 636 MIX 91 59 56 Thien-3-yl (CH.sub.2).sub.2 O(CH.sub.2)hd 2OCH.sub.3 C.sub.3 H.sub.7 Cl COOH 619.sup.a -- -- -- 57 Furan-2-yl C.sub.2 H.sub.5 R.sup.2 CH.sub.3 CN 605.sup.a -- -- -- 58 Furan-2-yl C.sub.2 H.sub.5 R.sup.2 CH.sub.3 COOCH.sub.3 596.sup.a -- -- -- 59 Furan-2-yl (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 COOCH.sub.3 594.sup.a -- -- -- 60 Furan-2-yl (CH.sub.2). sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 Cl COH 635.sup. a -- -- -- 61 Pyrid-3-yl C.sub.2 H.sub.5 R.sup.2 Cl COH 599.sup.a -- -- .sup.a solvent 9:1 dimethylformamide/glacial acetic acid *weight ratio of binder:dye 2:1
TABLE 3a
__________________________________________________________________________
IIIc
##STR21##
ΔE.sub..
tau.
λ.sub.max
T* [kJ/
Ex.
R.sup.1 R.sup.2 R.sup.3
R.sup.8
R.sup.9 R.sup.10
[nm]
B °C.]
mol]
__________________________________________________________________________
62 Ph CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5
Cl COOCH.sub.3
COH 598.sup.a
-- -- --
63 Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
CH.sub.3
COO CH.sub.3
CN 577
VY 82
32
64 Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
Cl COOCH.sub.3
COH 611.sup.a
-- -- --
65 Ph (CH.sub.2).sub.3 OCH.sub.3
R.sup.2
CH.sub.3
COOC.sub.2 H.sub.5
CN 562.sup.a
-- -- --
66 Ph (CH.sub.2).sub.3 OCH.sub.3
C.sub.3 H.sub.7
CH.sub.3
COOC.sub.2 H.sub.5
CN 589.sup.a
-- -- --
67 Ph-4-OCH.sub.3
(CH.sub.2).sub.3 OCH.sub.3
R.sup.2
CH.sub.3
COOC.sub.2 H.sub.5
CN 567
VY 107
59
68 Thien-2-yl
CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5
CH.sub.3
COOC.sub.2 H.sub.5
CN 577
VY 105
45
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
TABLE 4
__________________________________________________________________________
##STR22## IIIe
ΔE.sub..
tau.
λ.sub.max
T* [kJ/
Ex. R.sup.1
R.sup.2 R.sup.3
R.sup.8 R.sup.10 [nm]
B [°C.]
mol]
__________________________________________________________________________
69 Ph
(CH.sub.2).sub.2 CH.sub.3
R.sup.2
H NO.sub.2 595.sup.a
-- -- --
70 Ph
(CH.sub.2).sub.2 CH.sub.3
R.sup.2
Cl COH 581
-- -- --
71 Ph
(CH.sub.2).sub.2 CH.sub.3
R.sup.2
Cl CHC(CN) COOC.sub.4 H.sub.9
637
VY 130
52
72 Thien-
C.sub.2 H.sub.5 R.sup.2
Cl CHC(CN)COOC.sub.4 H.sub.9
631
VY 125
67
3-yl
73 Thien-
C.sub.2 H.sub.5 R.sup.2
COOCH.sub.3
CN 581
-- -- --
2-yl
74 Thien-
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H NO.sub.2 626
-- -- --
2-yl
75 Thien-
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
Cl COH 593
-- -- --
3-yl
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
TABLE 5
__________________________________________________________________________
##STR23## IIIg
ΔE.sub..
tau.
λ.sub.max
T* [kJ/
Ex.
R.sup.1 R.sup.2 R.sup.3
R.sup.8 R.sup.9
[nm]
B [°C.]
mol]
__________________________________________________________________________
76 CH(CH.sub.3)CH.sub.3
C.sub.2 H.sub.5 R.sup.2
(CH.sub.2).sub.2 OCH.sub.3
CN 522
EC*
63 69
77 Cyclohexyl C.sub.2 H.sub.5 R.sup.2
CH.sub.3 CN 520
MIX
85 97
526.sup.a
VY 75 34
78 Cyclohexyl C.sub.2 H.sub.5 R.sup.2
Ph CN 529
VY 89 24
79 Cyclohexyl C.sub.2 H.sub.5 R.sup.2
(CH.sub.2).sub.2 OCH.sub.3
CN 528.sup.a
-- -- --
80 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
CH.sub.3 CN 521
VY 75 42
81 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Ph CN 524
MIX
100
80
82 Cyclohexyl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
CH.sub.3 CN 523
VY 72 38
83 Cyclohexyl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN 520
VY 75 37
84 Cyclohexyl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
Ph CN 529
VY 84 44
85 Cyclohexyl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
(CH.sub.2).sub.2 OCH.sub.3
CN 524
VY 72 33
86 Cyclohexyl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
R.sup.2
Thien-2-yl
CN 587.sup.a
-- -- --
87 Cyclohexyl CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.3 H.sub.7
Ph CN 531
VY 88 38
88 Ph C.sub.2 H.sub.5 R.sup.2
(CH.sub.2).sub.2 OCH.sub.3
CN 548
VY 89 53
89 Ph C.sub.2 H.sub.5 R.sup.2
Ph-4-SPh CN 556
EC 118
53
90 Ph-3-OCH.sub.3
C.sub.2 H.sub.5 R.sup.2
Thien-2-yl
CN 572
-- -- --
91 Ph-3-SO.sub.2 N(CH.sub.3).sub.2
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
(CH.sub.2).sub.3 OCH.sub.3
CN 548
EC*
89 32
92 CH.sub.2 OPh
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
CH.sub.3 CN 531.sup.a
-- -- --
93 Furan-2-yl C.sub.2 H.sub.5 R.sup.2
CH.sub.3 CN 578.sup.a
-- -- --
94 Furan-2-yl C.sub.2 H.sub.5 R.sup.2
(CH.sub.2).sub.2 OCH.sub.3
CN 578.sup.a
-- -- --
95 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5
CH(CH.sub.3)CH.sub.3
CN 579.sup.a
-- -- --
96 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN 581.sup.a
-- -- --
97 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3
C.sub.3 H.sub.7
C.sub.2 H.sub.5
CN 581.sup.a
-- -- --
98 Thien-3-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5
CH.sub.3 CN 562.sup.a
-- -- --
99 Thien-2-yl CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN 582.sup.a
-- -- --
100
Thien-2-yl CH.sub.2 [CH.sub. 2).sub.2 O].sub.2 CH.sub.3
C.sub.3 H.sub.7
C.sub.2 H.sub.5
CN 580.sup.a
-- -- --
101
CH(CH.sub.3)CH.sub.3
C.sub.2 H.sub.5 R.sup.2
CH.sub.3 SCN 512
EC 87 99
102
Ph C.sub.2 H.sub.5 R.sup.2
CH.sub.3 SCN 540
-- -- --
103
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
CH.sub.3 SCN 538
EC 90 57
104
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2 CH.sub.3
SCN 562 EC 88 47
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
*weight ratio of binder:dye = 2:1
TABLE 6
__________________________________________________________________________
##STR24## IIIh
Ex.
R.sup.1 R.sup.2 R.sup.3
X X' λ.sub.max [nm]
__________________________________________________________________________
105
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H H 573.sup.a
106
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Cl H 579.sup.a
107
Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5
H H 574.sup.a
108
Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
NO.sub.2
H 629.sup.a
109
Ph-4-O CH.sub.3
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Cl N 594.sup.a
110
Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H H 594.sup.a
111
Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Cl H 602.sup.a
112
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
H H 597.sup.a
113
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
Cl H 605.sup.a
114
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
R.sup.2
Cl H 606.sup.a
115
Thien-2-yl
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5
H H 598.sup.a
116
Thien-2-yl
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
Cl H 598.sup.a
117
Thien-2-yl
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
H Cl 606.sup.a
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
TABLE 7
__________________________________________________________________________
##STR25## IIIi
Ex.
R.sup.1
R.sup.2 R.sup.3
Y λ.sub.max [nm]
B T*[°C.]
ΔE.sub.τ [kJ/mol]
__________________________________________________________________________
118
CH.sub.3
C.sub.2 H.sub.5 R.sup.2
CN 591 EC*
130 44
119
Ph C.sub.2 H.sub.5 R.sup.2
H 583 -- -- --
120
Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
CN 622.sup.a
-- -- --
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide glacial acetic acid
*weight ratio of binder:dye = 2.1
TABLE 8
__________________________________________________________________________
##STR26## IIIk
Ex.
R.sup.1
R.sup.2 R.sup.3
R.sup.8
λ.sub.max [nm]
B T*[°C.]
ΔE.sub.τ [kJ/mol]
__________________________________________________________________________
121
PH C.sub.2 H.sub.5
R.sup.2
Ph 531 EC 94 68
122
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Ph 533.sup.a
-- -- --
123
Cyclohexyl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Ph 508.sup.a
-- -- --
124
Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Ph 556.sup.a
-- -- --
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
TABLE 9
__________________________________________________________________________
##STR27## IIIl
Ex.
R.sup.1
R.sup.2 R.sup.3
R.sup.8 λ.sub.max [nm]
B T*[°C.]
ΔE.sub.τ
[kJ/mol]
__________________________________________________________________________
125
Ph C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 COOCH.sub.3
535 EC 110 72
126
Ph C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 CN
536 EC 103 47
127
Ph C.sub.2 H.sub.5
R.sup.2
SCH.sub.3 533 -- -- --
128
Ph C.sub.2 H.sub.5
R.sup.2
CH.sub.3 524 -- -- --
129
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
S(CH.sub.2).sub.2 COOCH.sub.3
535 MIX
87 71
130
Cyclohexyl
C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 COOCH.sub.3
519.sup.a
-- -- --
131
Cyclohexyl
C.sub.2 H.sub.5
R.sup.2
SCH.sub.3 518.sup.a
-- -- --
132
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 COOCH.sub.3
558 VY 93 61
133
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 CN
560 EC 105 42
134
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2
SCH.sub.3 557 EC 126 62
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
*weight ratio of binder:dye = 2:1
TABLE 10
__________________________________________________________________________
##STR28## IIIm
Ex.
R.sup.1
R.sup.2
R.sup.3
R.sup.18
R.sup.19
λ.sub.max [nm]
B T*[°C.]
ΔE.sub.τ [kJ/mol]
__________________________________________________________________________
135
Ph C.sub.2 H.sub.5
R.sup.2
CN Ph 567 MIX
106 37
136
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2
CONH.sub.2
CH.sub.3
573 -- -- --
__________________________________________________________________________
TABLE 11 ##STR29## IIIg Ex. R.sup.1 R.sup.2 R.sup.3 R.sup.8 R.sup.9 Hue 137 P h (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 H red 138 Ph (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 Cl red 139 Ph (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 Br red 140 Ph (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 CN violet 141 Ph (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 SCN violet 142 P h (CH.sub.2).sub.2 OCH.sub.3 R.sup. 2 C.sub.2 H.sub.5 CN violet 143 Ph (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH(CH.sub.3)CH.sub.3 CN violet 144 Ph ( CH.sub.2).sub.2 OCH.sub.3 R.sup.2 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 CN bluish red 145 Ph (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CH.sub.3 SCN violet 146 Ph (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Ph CN violet 147 Ph (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CN violet 148 Ph (CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN violet 149 Ph (CH.sub.2).sub.3 OC.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CN violet 150 Ph (CH.sub.2).sub.3 OC.sub.2 H.sub.5 CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CN violet 151 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 ( CH.sub.2).sub.2 OCH.sub.3Ph CN violet 152 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3Ph CN violet 153 Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Ph CN violet 154 Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CN violet 155 Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN violet 156 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 Ph CN violet 157 Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.3 CH.sub.3 Ph CN violet 158 Ph-4-Cl (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 (CH.sub.2).sub.2 OCH.sub.3 CN violet 159 Ph-4-Cl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN violet 160 Ph-4-OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CN violet 161 Ph-4-OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN violet 162 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3R.sup.2 CH.sub.3 SCN violet 163 Thien-2-yl (CH.sub.2).sub.2 O CH.sub.3R.sup.2 CH.sub.3 CN reddish blue 164 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3R.sup.2 C.sub.2 H.sub.5 CN reddish blue 165 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3R.sup.2 C.sub.3 H.sub.7 CN reddish blue 166 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3R.sup.2 C H(CH.sub.3)CH.sub.3 CN reddish blue 167 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3R.sup.2 (CH.sub.2).sub.2 OCH.sub.3 CN navy 168 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3R.sup.2 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 CN navy 169 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CH.sub.3 SCN reddish blue 170 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Ph CN reddish blue 171 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Ph SCN reddish blue 172 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CN navy 173 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 CN navy 174 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 175 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 Thien-2-yl CN blue 176 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 177 Thien-2-yl (CH.sub.2).sub.3 OC.sub.2 H.sub.5 (CH.sub.2).sub.3 OCH.sub.3 Thien-3-yl CN blue 178 Thien-2-yl (CH.sub.2).sub.3 OC.sub.2 H.sub.5 (CH.sub.2).sub. 3 OCH.sub.3 ( CH.sub.2).sub.2 OCH.sub.3 CN navy 179 Thien-2-yl (CH.sub.2).sub.3 OC.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 ##STR30## CN reddish blue 180 Thien-2-yl (CH.sub.2).sub.3 OC.sub.2 H.sub.5 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 181 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 SCN bluish violet 182 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 Ph CN reddish blue 183 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 184 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 Thien-2-yl CN blue 185 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 CH(CH.sub.3)CH.sub.3 CN navy 186 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 Ph CN reddish blue 187 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 (CH.sub.2).sub.2 OCH.sub.3 CN navy 188 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 CN navy 189 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 190 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.2 O CH.sub.3 Thien-2-yl CN reddish blue 191 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Thien-3-yl CN blue 192 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 Ph CN reddish blue 193 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 194 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 Thien-3-yl CN blue 195 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.3 H.sub.7 (CH.sub.2).sub.2 OCH.sub.3 CN navy 196 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3 OCH.sub.3 Ph CN reddish blue 197 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3 OCH.sub.3 Pyrid-3-yl CN reddish blue 198 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 Ph CN reddish blue 199 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Thien-2-yl CN reddish blue 200 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Thien-3-yl CN reddish blue 201 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 C.sub.2 H.sub.5 Ph CN reddish blue 202 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 C.sub.2 H.sub.5 Thien-2-yl CN blue 203 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 C.sub.2 H.sub.5 Thien-3-yl CN blue
TABLE 12
__________________________________________________________________________
##STR31## IIII
Ex.
R.sup.1 R.sup.2 R.sup.3 R.sup.8 Hue
__________________________________________________________________________
204
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2 SCH.sub.3 reddish violet
205
Ph (CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 OCH.sub.3
SCH.sub.3 violet
206
Ph (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
S(CH.sub.2).sub.2 COOCH.sub.3
violet
207
Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
Ph SCH.sub.3 violet
208
Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5
Ph SCH.sub.3 violet
209
Ph-4-OCH.sub.3
(CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 OCH.sub.3
SCH.sub.3 violet
210
Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2 SCH.sub.3 reddish blue
211
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
R.sup.2 SCH.sub.3 reddish blue
212
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 OCH.sub.3
SC.sub.2 H.sub.5 reddish blue
213
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 OC.sub.2 H.sub.5
SCH.sub.3 bluish violet
214
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
S(CH.sub.2).sub.2 COOCH.sub.3
bluish violet
215
Thien-2-yl
(CH.sub.2).sub.3 OC.sub.2 H.sub.5
C.sub.2 H.sub.5
S(CH.sub.2).sub.2 COOCH.sub.3
bluish violet
216
Thien-2-yl
[(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5
SCH.sub.3 bluish violet
217
Thien-2-yl
[(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5
(CH.sub.2).sub.3 OCH.sub.3
SCH.sub.3 bluish violet
218
Thien-2-yl
[(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5
C.sub.2 H.sub.5
SCH.sub.3 bluish
__________________________________________________________________________
violet
Claims (3)
1. A process comprising printing a substrate by thermotransfer printing with a transfer dye which is an azo dye of the general formula I ##STR32## in which the substituents have the following meanings: R1 is hydrogen;
C1 -C15 -alkyl, C1 -C15 -alkyl substituted by phenyl or phenoxy; cyclohexyl, cyclohexyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy or halogen;
phenyl, phenyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy, sulfonamido or halogen;
thienyl, thienyl substituted by C1 -C5 -alkyl or halogen; furanyl or pyridyl;
a radical of the formula II
[--W--O].sub.n --R.sup.4 II
where
W is identical or different C2 -C6 -alkylene,
n is from 1 to 6 and
R4 is C1 -C4 -alkyl, phenyl or benzyl; phenyl or benzyl substituted by C1 -C4 -alkyl or C1 -C4 -alkoxy;
R2 and R3 are each hydrogen;
alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, each containing up to 15 carbon atoms;
alkyl, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, each containing up to 15 carbon atoms, substituted by phenyl, C1 -C4 -alkylphenyl, C1 -C4 -alkoxyphenyl, halophenyl, benxyloxy, C1 -C4 -alkylbenzyloxy, C1 -C4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano;
cyclohexyl, cyclohexyl substituted by C1 -C15 -alkyl, C1 -C15 -alkoxy or halogen;
phenyl, phenyl substituted by C1 -C15 -alkyl, C1 -C15 -alkoxy, benzyloxy or halogen;
a radical of the above-mentioned formula II; and
D is the radical of a diazo component III.
D--NH.sub.2 III
.Iadd.wherein D is the radical of a diazo component III of the aminothiophene, phenylazoaminothiophene, aminothiazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxazole, aminooxadiazole, aminodiazole, aminotriazole or aminopyrrole series..Iaddend.
2. A process comprising transferring an azo dye or dyes by diffusiton from a transfer to a plastic-coated substrate by means of a thermal printing head, wherein said azo dye or dyes is or are of the formula I ##STR33## in which the substituents have the following meanings: R1 on is hydrogen;
C1 -C15 -alkyl, C1 -C15 -alkyl substituted by phenyl or phenoxy; cyclohexyl, cyclohexyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy or halogen;
phenyl, phenyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy, sulfonamido or halogen;
thienyl, thienyl substituted by C1 -C5 -alkyl or halogen; furanyl or pyridyl;
a radical of the formula II
[--W--O].sub.n --R.sup.4 II
where
W is identical or different C2 -C6 -alkylene,
n is from 1 to 6 and
R4 is C1 -C4 -alkyl, phenyl or benzyl; phenyl or benzyl substituted by C1 -C4 -alkyl or C1 -C4 -alkoxy;
R2 and R3 are each hydrogen;
alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, each containing up to 15 carbon atoms;
alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, each containing up to 15 carbon atoms, substituted by phenyl, C1 -C4 -alkylphenyl, C1 -C4 -alkoxyphenyl, halophenyl, benzyloxy, C1 -C4 -alkylbenzyloxy, C1 -C4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano;
cyclohexyl, cyclohexyl substituted by C1 -C15 -alkyl, C1 -C15 -alkoxy or halogen;
phenyl, phenyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy, C1 -C15 -alkoxy, benzyloxy or halogen;
a radical of the above-mentioned formula II; and
D is the radical of a diazo component III
D--NH.sub.2 III
.Iadd.wherein D is the radical of a diazo component III of the aminothiophene, phenylazominothiophene, aminothiazole, phenylazominothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxazole, aminooxadiazole, aminoidazole, aminotriazole or aminopyrrole series..Iaddend.
3. A process as claimed is claim 2, wherein the azo dye or dyes has the formula Ia ##STR34## where the substituents have the following meanings: R1 is C1 14 C8 -alkyl, C1 -C8 -alkyl substituted by phenyl or phenoxy;
cyclohexyl;
phenyl, phenyl substituted by C1 -C4 -alkyl, C1 -C4 -alkoxy or chlorine;
thienyl;
a radical of the formula IIa ##STR35## where p is 0 or 1, q is from 1 to 4, and
R4' is C1 -C4 -alkyl, phenyl or benzyl;
R2' and R3' are each C1 -C12 -alkyl, C1 -C10 -alkoxy or C1 -C10 -cyanoalklyl or a radical of the above-mentioned formula IIa; and
D' is the radical of a diazo component III of the .[.aniline, phenylazoaniline..]. aminothiophene, phenylazoaminothiophene, aminothiazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazle, aminooxadiazole, aminodiazole, aminotriazole or aminopyrrole series.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/166,103 USRE34877E (en) | 1990-02-08 | 1993-12-14 | Azo dyes for thermotransfer printing |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4003780 | 1990-02-08 | ||
| DE4003780A DE4003780A1 (en) | 1990-02-08 | 1990-02-08 | USE OF AZO DYES FOR THERMAL TRANSFER PRINTING |
| US07/652,771 US5158928A (en) | 1990-02-08 | 1991-02-08 | Azo dyes for thermotransfer printing |
| US08/166,103 USRE34877E (en) | 1990-02-08 | 1993-12-14 | Azo dyes for thermotransfer printing |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/652,771 Reissue US5158928A (en) | 1990-02-08 | 1991-02-08 | Azo dyes for thermotransfer printing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE34877E true USRE34877E (en) | 1995-03-14 |
Family
ID=6399696
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/652,771 Ceased US5158928A (en) | 1990-02-08 | 1991-02-08 | Azo dyes for thermotransfer printing |
| US08/166,103 Expired - Lifetime USRE34877E (en) | 1990-02-08 | 1993-12-14 | Azo dyes for thermotransfer printing |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/652,771 Ceased US5158928A (en) | 1990-02-08 | 1991-02-08 | Azo dyes for thermotransfer printing |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US5158928A (en) |
| EP (1) | EP0441208B1 (en) |
| JP (1) | JP3001991B2 (en) |
| DE (2) | DE4003780A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100081823A1 (en) * | 2008-09-29 | 2010-04-01 | Abdullah Mohamed Asiri | Azo dyes |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4112654A1 (en) * | 1991-04-18 | 1992-10-22 | Basf Ag | METHOD FOR TRANSMITTING METHINE DYES |
| DE4426023A1 (en) * | 1994-07-22 | 1996-01-25 | Basf Ag | Azo dyes with a coupling component from the aminothiazole series |
| DE19611351A1 (en) * | 1996-03-22 | 1997-09-25 | Basf Ag | Dye mixtures containing thienyl and / or thiazole azo dyes |
| WO2002080152A2 (en) * | 2001-03-28 | 2002-10-10 | Bayer Aktiengesellschaft | Optical data carrier that contains a heterocyclic azo dye as the light-absorbing compound in the information layer |
| US20080081766A1 (en) * | 2006-09-29 | 2008-04-03 | Fujifilm Corporation | Image-forming method using heat-sensitive transfer system |
| EP1974948A3 (en) | 2007-03-29 | 2012-02-08 | FUJIFILM Corporation | Image-forming method using heat-sensitive transfer system |
| JP2008265319A (en) * | 2007-03-29 | 2008-11-06 | Fujifilm Corp | Thermal transfer ink sheet and image formation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60239291A (en) * | 1984-05-11 | 1985-11-28 | Mitsubishi Chem Ind Ltd | Coloring matter for thermal recording |
| EP0192435A2 (en) * | 1985-02-21 | 1986-08-27 | Imperial Chemical Industries Plc | Thermal transfer dyesheet |
| EP0275381A2 (en) * | 1986-11-13 | 1988-07-27 | BASF Aktiengesellschaft | Dye transfer process |
| US4933226A (en) * | 1989-12-11 | 1990-06-12 | Eastman Kodak Company | Thermal print element comprising a magenta 3-aryl-2-arylazo-5-aminothiazole or aminothiophene dye stabilized with a cyan indoaniline dye |
| US5101035A (en) * | 1989-08-26 | 1992-03-31 | Basf Aktiengesellschaft | Merocyanine-like thiazole dyes and thermal transfer thereof |
-
1990
- 1990-02-08 DE DE4003780A patent/DE4003780A1/en not_active Withdrawn
-
1991
- 1991-01-26 EP EP91101022A patent/EP0441208B1/en not_active Expired - Lifetime
- 1991-01-26 DE DE59101521T patent/DE59101521D1/en not_active Expired - Lifetime
- 1991-02-06 JP JP3015400A patent/JP3001991B2/en not_active Expired - Lifetime
- 1991-02-08 US US07/652,771 patent/US5158928A/en not_active Ceased
-
1993
- 1993-12-14 US US08/166,103 patent/USRE34877E/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60239291A (en) * | 1984-05-11 | 1985-11-28 | Mitsubishi Chem Ind Ltd | Coloring matter for thermal recording |
| EP0192435A2 (en) * | 1985-02-21 | 1986-08-27 | Imperial Chemical Industries Plc | Thermal transfer dyesheet |
| EP0275381A2 (en) * | 1986-11-13 | 1988-07-27 | BASF Aktiengesellschaft | Dye transfer process |
| US5101035A (en) * | 1989-08-26 | 1992-03-31 | Basf Aktiengesellschaft | Merocyanine-like thiazole dyes and thermal transfer thereof |
| US4933226A (en) * | 1989-12-11 | 1990-06-12 | Eastman Kodak Company | Thermal print element comprising a magenta 3-aryl-2-arylazo-5-aminothiazole or aminothiophene dye stabilized with a cyan indoaniline dye |
Non-Patent Citations (4)
| Title |
|---|
| Derwent Japanese Patents Report, vol. 79, No. 46, 14 Dec. 1979, London, GB, Seite 2 Canon K.K.: "Heat-Sensitive Sheet for Latent Image Production". |
| Derwent Japanese Patents Report, vol. 79, No. 46, 14 Dec. 1979, London, GB, Seite 2 Canon K.K.: Heat Sensitive Sheet for Latent Image Production . * |
| Patent Abstracts of Japan, vol. 10, No. 109 (M 472) (2166), 23 Apr. 1986. * |
| Patent Abstracts of Japan, vol. 10, No. 109 (M-472) (2166), 23 Apr. 1986. |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100081823A1 (en) * | 2008-09-29 | 2010-04-01 | Abdullah Mohamed Asiri | Azo dyes |
| US8258300B2 (en) | 2008-09-29 | 2012-09-04 | King Abdulaziz University | Azo dyes |
Also Published As
| Publication number | Publication date |
|---|---|
| US5158928A (en) | 1992-10-27 |
| EP0441208A1 (en) | 1991-08-14 |
| EP0441208B1 (en) | 1994-05-04 |
| DE59101521D1 (en) | 1994-06-09 |
| JP3001991B2 (en) | 2000-01-24 |
| DE4003780A1 (en) | 1991-08-14 |
| JPH04357088A (en) | 1992-12-10 |
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