EP0320453B1 - Thermally sensitive recording material - Google Patents
Thermally sensitive recording material Download PDFInfo
- Publication number
- EP0320453B1 EP0320453B1 EP88810827A EP88810827A EP0320453B1 EP 0320453 B1 EP0320453 B1 EP 0320453B1 EP 88810827 A EP88810827 A EP 88810827A EP 88810827 A EP88810827 A EP 88810827A EP 0320453 B1 EP0320453 B1 EP 0320453B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lower alkyl
- halogen
- substituted
- recording material
- unsubstituted
- 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
- 239000000463 material Substances 0.000 title claims description 20
- -1 benzotriazine compound Chemical class 0.000 claims description 55
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- 230000008878 coupling Effects 0.000 claims description 25
- 238000010168 coupling process Methods 0.000 claims description 25
- 238000005859 coupling reaction Methods 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical group 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 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 9
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 125000004442 acylamino group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000005023 xylyl group Chemical group 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 150000003931 anilides Chemical class 0.000 claims description 2
- 125000000068 chlorophenyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- OWQPOVKKUWUEKE-UHFFFAOYSA-N 1,2,3-benzotriazine Chemical class N1=NN=CC2=CC=CC=C21 OWQPOVKKUWUEKE-UHFFFAOYSA-N 0.000 description 1
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical class NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical class NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 1
- 125000006184 2,5-dimethyl benzyl group Chemical group [H]C1=C(C([H])=C(C(=C1[H])C([H])([H])[H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- VAYGAYBMJYNHMN-UHFFFAOYSA-N 2-benzyl-1,2,3,4-benzothiatriazine Chemical compound S1C2=CC=CC=C2N=NN1CC1=CC=CC=C1 VAYGAYBMJYNHMN-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- YZCNEKMCENEWRV-UHFFFAOYSA-N 2-butyl-1,2,3,4-benzothiatriazine Chemical compound C1=CC=C2N=NN(CCCC)SC2=C1 YZCNEKMCENEWRV-UHFFFAOYSA-N 0.000 description 1
- 125000006282 2-chlorobenzyl group Chemical group [H]C1=C([H])C(Cl)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- FIHCPNGHKYHQAQ-UHFFFAOYSA-N 2-cyclohexyl-1,2,3,4-benzothiatriazine Chemical compound C1CCCCC1N1N=NC2=CC=CC=C2S1 FIHCPNGHKYHQAQ-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- BTVIQJMUPGCMIR-UHFFFAOYSA-N 2-methyl-1,2,3,4-benzothiatriazine Chemical compound C1=CC=C2N=NN(C)SC2=C1 BTVIQJMUPGCMIR-UHFFFAOYSA-N 0.000 description 1
- UYNHOMDPTLPKJF-UHFFFAOYSA-N 2-phenyl-1,2,3,4-benzothiatriazine Chemical compound N1=NC2=CC=CC=C2SN1C1=CC=CC=C1 UYNHOMDPTLPKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000004688 alkyl sulfonyl alkyl group Chemical group 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007656 barbituric acids Chemical class 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
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- 150000004806 hydroxypyridines Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- XAUGWFWQVYXATQ-UHFFFAOYSA-N n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1 XAUGWFWQVYXATQ-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
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- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical class OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000007660 quinolones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FNXKBSAUKFCXIK-UHFFFAOYSA-M sodium;hydrogen carbonate;8-hydroxy-7-iodoquinoline-5-sulfonic acid Chemical class [Na+].OC([O-])=O.C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 FNXKBSAUKFCXIK-UHFFFAOYSA-M 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
Definitions
- the present invention relates to a heat-sensitive recording material having a support and a heat-sensitive layer thereon which contains a cyclic diazo component and a coupling component, characterized in that the cyclic diazo component is a benzotriazine compound of the formula is what Q -CH2-, -CO or -SO2- and R is hydrogen, hydroxyl, unsubstituted or substituted by halogen, hydroxy, cyano, lower alkoxy, lower alkylthio, C1-C8 acyloxy, lower alkoxycarbonyl or lower alkylsulfonyl alkyl or alkenyl having at most 12 carbon atoms, acyl, acyloxy or acylamino having 1 to 10 carbon atoms, cycloalkyl having 5 up to 10 carbon atoms, unsubstituted or substituted by cyano, halogen, nitro, trifluoromethyl, lower alkyl, lower alkylthio, lower alkoxy, lower
- Lower alkyl, lower alkoxy and lower alkylthio in the definition of the radicals of the benzotriazines are groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms.
- Examples for such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl or isoamyl or methoxy, ethoxy, isopropoxy, isobutoxy or tert-butoxy or methylthio, ethylthio, propylthio or butylthio.
- Halogen means for example fluorine, bromine or preferably chlorine.
- acyl in acyl, acyloxy and acylamino particularly stands for formyl, lower alkylcarbonyl, such as e.g. Acetyl or propionyl, or benzoyl.
- Further acyl residues or acyl components can be lower alkylsulfonyl, e.g. Be methylsulfonyl or ethylsulfonyl and phenylsulfonyl.
- Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.
- Q advantageously stands for -CO- or preferably -SO2-.
- the alkyl and alkenyl radicals of R can be straight-chain or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, 1,1,3 , 3-tetramethylbutyl, n-octyl, isooctyl, n-nonyl, isononyl or n-dodecyl or vinyl, allyl, 2-methallyl, 2-ethylallyl or 2-butenyl.
- alkyl radical in R is substituted, it is primarily cyanoalkyl, haloalkyl, hydroxyalkyl, alkylthioalkyl, alkoxyalkyl, alkylsulfonyloxyalkyl or alkoxycarbonylalkyl, each preferably having a total of 1 to 8, 2 to 8 or 3 to 8 carbon atoms, such as e.g.
- R can also be interrupted several times by oxygen atoms or sulfur atoms.
- cycloalkyl with the meaning of R are cyclopentyl, cycloheptyl or preferably cyclohexyl.
- the cycloalkyl radicals can contain one or more C1-C4 alkyl radicals, preferably methyl groups, and have a total of 5 to 10 carbon atoms.
- R advantageously has a total of 7 to 9 carbon atoms and generally represents ⁇ -methylbenzyl, phenethyl, phenisopropyl or primarily benzyl, which can preferably also be ring-substituted.
- Preferred substituents in the benzyl group and in the phenyl group are e.g. Halogen, methyl or methoxy.
- Examples of such araliphatic or aromatic radicals are o- or p-methylbenzyl, o- or p-chlorobenzyl, o- or p-tolyl, xylyl, o-, m- or p-chlorophenyl, o- or p-methoxyphenyl, 2 , 5-dimethylbenzyl or 2,6-dimethylphenyl.
- R is primarily a 5- or 6-membered, preferably oxygen, sulfur or nitrogen-containing heterocycle of aromatic character.
- heterocycles are thienyl, furyl, furfuryl, pyrrolyl, pyrazolyl, imidazolyl or Pyridyl residues.
- R can also represent a multinuclear, heterocyclic ring system.
- This preferably contains a fused benzene or naphthalene ring, e.g. an optionally substituted benzothiophene, indolyl, benzothiazolyl, coumarin, quinoline or carbazolyl radical.
- the mono- or polynuclear, heterocyclic radicals can be substituted, in particular by halogen, hydroxyl, cyano, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl.
- the preferred heterocyclic radicals with the meaning of R are 2-furyl, furfuryl, tetrahydrofurfuryl, 2-thienyl, 2-, 3- or 4-pyridyl or 5-lower alkoxycarbonyl-2-thienyl, e.g. 5-carbomethoxy-2-thienyl.
- the substituent R is preferably lower alkyl such as methyl, ethyl or butyl, hydroxy lower alkyl such as hydroxymethyl or hydroxyethyl, cyano-lower alkyl such as cyanomethyl or cyanoethyl, acetyl, acetylamino, benzoyl, cyclohexyl, benzyl, phenyl, chlorophenyl, tolyl, xylyl , 2,6-dimethylphenyl, naphthyl, methoxyphenyl, pyridyl or furfuryl.
- the benzene ring A is preferably unsubstituted. However, it can have 1 to 4 (preferably 1 or 2) substituents. Preferred substituents are halogen, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl.
- cyclic diazo components correspond to the formula wherein Q is -CO- or preferably -SO2- and R1 is lower alkyl, halogen-lower alkyl, hydroxy-lower alkyl, cyano-lower alkyl, lower alkoxycarbonyl-lower alkyl, cyclohexyl, benzyl, naphthyl, phenyl which is unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, trifluoromethyl or lower alkylcarbonyl or a heterocyclic radical of aromatic character and the benzene nucleus B is unsubstituted or substituted by halogen, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl.
- cyclic diazo components of the formula (2) those in which the benzene nucleus B is unsubstituted or substituted by halogen and R 1 is lower alkyl, cyclohexyl, benzyl or unsubstituted or substituted by halogen, lower alkyl or lower alkoxy are preferred.
- Cyclic diazo components of the formula are of particular interest wherein R2 is lower alkyl, cyclohexyl, benzyl, phenyl or phenyl substituted by halogen, methyl or methoxy and the benzene nucleus D is unsubstituted or substituted by halogen.
- N-methyl-benzothiatriazine N-n-butyl-benzothiatriazine, N-cyclohexyl-benzothiatriazine, N-benzyl-benzothiatriazine or N-phenyl-benzothiatriazine.
- the cyclic diazo component of the formula (1) can be prepared by using an amino compound of the formula in which A, Q and R have the meaning given, diazotized and cyclized.
- Cyclic diazo components of the formulas (1) to (3) and their preparation are described, for example, in US Pat. Nos. 2,834,764, 2,402,611, 2,798,055, 2,843,588 and 2,758,115. Further references are AC Mair, MFG Stevens, J.Chem.Soc. C 1971 , 2317, Helv.Chimica Acta 68 , 892 (1985), J.Am.Chem.Soc. 77 , 6562 (1955), J.Pr.Chemie [2], 51 , (1895), 113, 132, 260, 277, 280, 52 , (1896), 379, 385, 393 and 405, 55 , 356 ( 1897) and 71 , 153 (1905).
- Suitable coupling components are all coupling components customary in azochemistry and known from the relevant literature, provided they do not contain any acidic, water-solubilizing groups such as e.g. Contain carboxyl and sulfonic acid groups.
- Examples of the coupling components mentioned are acylacetarylamides, phenols, anilines, naphthylamines, diphenylamines, naphthols, naphtholcarboxylic acid anilides, aminopyrazoles, pyrazolones, thiophenes, aminothiazoles, hydroxypyridines, pyridones, indoles, quinolones, barbituric acids or hydroxyquinolines.
- Particularly preferred coupling components are naphthols, naphthol carboxylic acid anilides and acylacetarylamides, e.g. 2-hydroxy-3-N-phenylcarbamoyl-naphthalene and acetylacet-2-methoxy-anilide.
- the proportions in which the cyclic diazo components and the coupling components are used are not critical, but the cyclic diazo components and the coupling components are preferably used in equimolar amounts.
- Both the cyclic diazo components and the coupling components can be used alone or as mixtures with one another in the heat-sensitive recording material.
- the color tone of the printed image obtained when using heat-sensitive recording materials according to the invention can be yellow, orange, pink, red or violet, depending on the coupling component used, and the color images are sharp and clear.
- the heat-sensitive recording materials according to the invention are used, for example, for recording information, for example in electronic computers, remote printers, teleprinters or in recording devices and measuring instruments, such as, for example, electrocardiographs.
- the imaging (marking) can also be done manually with a heated spring.
- Another device for generating markings using heat is laser beams.
- the heat-sensitive recording systems contain at least one support, e.g. Paper, synthetic paper or an art film and one or more temperature sensitive layers formed thereon which contain the cyclic diazo component and the coupling component.
- Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are normally water soluble, while the diazo component and the coupling component are insoluble in water. The binder should be able to disperse and fix the diazo and coupling components at room temperature.
- Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or etherified corn starch.
- hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or etherified corn starch.
- water-insoluble binders i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole
- binders soluble in non-polar or only weakly polar solvents
- Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
- the preferred arrangement is one in which the diazo component and the coupling component are contained in one layer in a water-soluble binder.
- thermoreactive layers can contain further additives.
- these layers for example talc, titanium dioxide, zinc oxide, aluminum oxide, Contain aluminum hydroxide, calcium carbonate (eg chalk), silica, clays or organic pigments such as urea-formaldehyde polymers.
- substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, benzenesulfanilide, stearic acid amide, phthalic anhydride, metal stearates, such as zinc stearate, phthalic acid nitrile or other corresponding dimethyl terephthalate products which induce the coupling of the cyclic diazo component with the coupling component.
- thermographic recording materials preferably contain waxes, for example carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde and condensates of higher fatty acids and ethylenediamine.
- the recording materials can also contain alkaline materials, such as hydroxides or carbonates of alkali metals, or preferably open or cyclic organic bases such as amines, alkanolamines, guanidines, pyridines or imidazole derivatives.
- dispersion A 2.25 g of the cyclic diazo component of the formula 7.9 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) and 4.5 g of water are ground with glass balls down to a grain size of 2-4 ⁇ m.
- a dispersion B 3.0 g of the coupling component of the formula 10.5 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) and 6.0 g of water ground with glass balls down to a grain size of 2-4 ⁇ m.
- the two dispersions are then mixed.
- the mixture is applied to paper with a basis weight of 50 g / m2 using a doctor blade.
- the proportion of the applied material is 5 g / m2 (dry weight).
- Example 1 If the compound of the formula (4) described in Example 1 is replaced by 2.95 g of a diazo component of the formula and otherwise operates as described in Example 1, an intense red color is obtained with excellent lightfastness.
- dispersion A the compound of formula (4) described in Example 1 is replaced by the compound of formula (5) according to Example 2, and in dispersion B the coupling component of formula (21) is replaced by 2.35 g of a coupling component of the formula and otherwise operates as described in Example 1, an intense yellow color is obtained.
Description
Die vorliegende Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial mit einem Träger und einer darauf befindlichen wärmeempfindlichen Schicht, die eine cyclische Diazokomponente und eine Kupplungskomponente enthält, dadurch gekennzeichnet, dass die cyclische Diazokomponente eine Benzotriazin-Verbindung der Formel
ist, worin
Q -CH₂-, -CO oder -SO₂- und
R Wasserstoff, Hydroxyl, unsubstituiertes oder durch Halogen, Hydroxy, Cyano, Niederalkoxy, Niederalkylthio, C₁-C₈-Acyloxy, Niederalkoxycarbonyl oder Niederalkylsulfonyl substituiertes Alkyl oder Alkenyl mit höchstens 12 Kohlenstoffatomen, Acyl, Acyloxy oder Acylamino mit 1 bis 10 Kohlenstoffatomen, Cycloalkyl mit 5 bis 10 Kohlenstoffatomen, unsubstituiertes oder durch Cyano, Halogen, Nitro, Trifluormethyl, Niederalkyl, Niederalkylthio, Niederalkoxy, Niederalkylcarbonyl oder Niederalkoxycarbonyl ringsubstituiertes Phenyl, Phenylalkyl oder Naphthyl oder einen heterocyclischen Rest bedeuten und der Benzolring A unsubstituiert oder durch Halogen, Cyano, Nitro, Niederalkyl, Niederalkoxy, Niederalkylthio, Niederalkylcarbonyl oder Niederalkoxycarbonyl substituiert ist.The present invention relates to a heat-sensitive recording material having a support and a heat-sensitive layer thereon which contains a cyclic diazo component and a coupling component, characterized in that the cyclic diazo component is a benzotriazine compound of the formula
is what
Q -CH₂-, -CO or -SO₂- and
R is hydrogen, hydroxyl, unsubstituted or substituted by halogen, hydroxy, cyano, lower alkoxy, lower alkylthio, C₁-C₈ acyloxy, lower alkoxycarbonyl or lower alkylsulfonyl alkyl or alkenyl having at most 12 carbon atoms, acyl, acyloxy or acylamino having 1 to 10 carbon atoms, cycloalkyl having 5 up to 10 carbon atoms, unsubstituted or substituted by cyano, halogen, nitro, trifluoromethyl, lower alkyl, lower alkylthio, lower alkoxy, lower alkylcarbonyl or lower alkoxycarbonyl ring-substituted phenyl, phenylalkyl or naphthyl or a heterocyclic radical and the benzene ring A is unsubstituted or by halogen, cyano, nitro, lower alkyl, Lower alkoxy, lower alkylthio, lower alkylcarbonyl or lower alkoxycarbonyl is substituted.
Niederalkyl, Niederalkoxy und Niederalkylthio stellen bei der Definition der Reste der Benzotriazine solche Gruppen oder Gruppenbestandteile dar, die 1 bis 5, insbesondere 1 bis 3 Kohlenstoffatome aufweisen. Beispiele für derartige Gruppen sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, Amyl oder Isoamyl bzw. Methoxy, Ethoxy, Isopropoxy, Isobutoxy oder tert.Butoxy bzw. Methylthio, Ethylthio, Propylthio oder Butylthio.Lower alkyl, lower alkoxy and lower alkylthio in the definition of the radicals of the benzotriazines are groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms. Examples for such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl or isoamyl or methoxy, ethoxy, isopropoxy, isobutoxy or tert-butoxy or methylthio, ethylthio, propylthio or butylthio.
Halogen bedeutet beispielsweise Fluor, Brom oder vorzugsweise Chlor.Halogen means for example fluorine, bromine or preferably chlorine.
Der Ausdruck "Acyl" in Acyl, Acyloxy und Acylamino steht besonders für Formyl, Niederalkylcarbonyl, wie z.B. Acetyl oder Propionyl, oder Benzoyl. Weitere Acylreste bzw. Acylbestandteile können Niederalkylsulfonyl, wie z.B. Methylsulfonyl oder Ethylsulfonyl sowie Phenylsulfonyl sein. Benzoyl und Phenylsulfonyl können durch Halogen, Methyl, Methoxy oder Ethoxy substituiert sein.The term "acyl" in acyl, acyloxy and acylamino particularly stands for formyl, lower alkylcarbonyl, such as e.g. Acetyl or propionyl, or benzoyl. Further acyl residues or acyl components can be lower alkylsulfonyl, e.g. Be methylsulfonyl or ethylsulfonyl and phenylsulfonyl. Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.
Q steht vorteilhafterweise für -CO- oder vorzugsweise für -SO₂-.Q advantageously stands for -CO- or preferably -SO₂-.
Die Alkyl- und Alkenylreste von R können geradkettig oder verzweigt sein. Beispiele hierfür sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, tert.-Butyl, Amyl, Isoamyl, n-Hexyl, 2-Ethyl-hexyl, n-Heptyl, 1,1,3,3-Tetramethylbutyl, n-Octyl, Isooctyl, n-Nonyl, Isononyl oder n-Dodecyl bzw. Vinyl, Allyl, 2-Methallyl, 2-Ethylallyl oder 2-Butenyl.The alkyl and alkenyl radicals of R can be straight-chain or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, 1,1,3 , 3-tetramethylbutyl, n-octyl, isooctyl, n-nonyl, isononyl or n-dodecyl or vinyl, allyl, 2-methallyl, 2-ethylallyl or 2-butenyl.
Ist der Alkylrest in R substituiert, so handelt es sich vor allem um Cyanoalkyl, Halogenalkyl, Hydroxyalkyl, Alkylthioalkyl, Alkoxyalkyl, Alkylsulfonyloxyalkyl oder Alkoxycarbonylalkyl jeweils vorzugsweise mit insgesamt 1 bis 8, 2 bis 8 oder 3 bis 8 Kohlenstoffatomen, wie z.B. Cyanomethyl, β-Cyanoethyl, Chlormethyl, β-Chlorethyl, Hydroxymethyl, β-Hydroxyethyl, Carbomethoxymethyl, β-Methoxyethyl, β-Ethoxyethyl, γ-Methoxypropyl, Methoxybutyl oder Methylsulfonyloxyethyl. Als derartiger aliphatischer Rest kann R auch mehrmals durch Sauerstoffatome oder Schwefelatome unterbrochen sein.If the alkyl radical in R is substituted, it is primarily cyanoalkyl, haloalkyl, hydroxyalkyl, alkylthioalkyl, alkoxyalkyl, alkylsulfonyloxyalkyl or alkoxycarbonylalkyl, each preferably having a total of 1 to 8, 2 to 8 or 3 to 8 carbon atoms, such as e.g. Cyanomethyl, β-cyanoethyl, chloromethyl, β-chloroethyl, hydroxymethyl, β-hydroxyethyl, carbomethoxymethyl, β-methoxyethyl, β-ethoxyethyl, γ-methoxypropyl, methoxybutyl or methylsulfonyloxyethyl. As such an aliphatic radical, R can also be interrupted several times by oxygen atoms or sulfur atoms.
Beispiele für Cycloalkyl in der Bedeutung von R sind Cyclopentyl, Cycloheptyl oder vorzugsweise Cyclohexyl. Die Cycloalkylreste können einen oder mehrere C₁-C₄-Alkylreste, vorzugsweise Methylgruppen, enthalten und weisen insgesamt 5 bis 10 Kohlenstoffatome auf.Examples of cycloalkyl with the meaning of R are cyclopentyl, cycloheptyl or preferably cyclohexyl. The cycloalkyl radicals can contain one or more C₁-C₄ alkyl radicals, preferably methyl groups, and have a total of 5 to 10 carbon atoms.
In der Bedeutung vom Phenylalkyl weist R vorteilhafterweise insgesamt 7 bis 9 Kohlenstoffatome auf und steht in der Regel für α-Methylbenzyl, Phenethyl, Phenisopropyl oder in erster Linie für Benzyl, das bevorzugterweise auch ringsubstituiert sein kann.In the meaning of phenylalkyl, R advantageously has a total of 7 to 9 carbon atoms and generally represents α-methylbenzyl, phenethyl, phenisopropyl or primarily benzyl, which can preferably also be ring-substituted.
Bevorzugte Substituenten in der Benzylgruppe und in der Phenylgruppe sind z.B. Halogen, Methyl oder Methoxy. Beispiele für derartige araliphatische bzw. aromatische Reste sind o- oder p-Methylbenzyl, o- oder p-Chlorbenzyl, o- oder p-Tolyl, Xylyl, o-, m- oder p-Chlorphenyl, o- oder p-Methoxyphenyl, 2,5-Dimethylbenzyl oder 2,6-Dimethylphenyl.Preferred substituents in the benzyl group and in the phenyl group are e.g. Halogen, methyl or methoxy. Examples of such araliphatic or aromatic radicals are o- or p-methylbenzyl, o- or p-chlorobenzyl, o- or p-tolyl, xylyl, o-, m- or p-chlorophenyl, o- or p-methoxyphenyl, 2 , 5-dimethylbenzyl or 2,6-dimethylphenyl.
Als heterocyclischer Rest stellt R in erster Linie einen 5- oder 6-gliedrigen, vorzugsweise Sauerstoff, Schwefel oder Stickstoff aufweisenden Heterocyclus von aromatischem Charakter dar. Beispiele derartiger Heterocyclen sind Thienyl-, Furyl-, Furfuryl, Pyrrolyl-, Pyrazolyl-, Imidazolyl- oder Pyridylreste.As a heterocyclic radical, R is primarily a 5- or 6-membered, preferably oxygen, sulfur or nitrogen-containing heterocycle of aromatic character. Examples of such heterocycles are thienyl, furyl, furfuryl, pyrrolyl, pyrazolyl, imidazolyl or Pyridyl residues.
Dabei kann R auch ein mehrkerniges, heterocyclisches Ringsystem darstellen. Dieses enthält vorzugsweise einen ankondensierten Benzol- oder Naphthalinring, wie z.B. einen gegebenenfalls substituierten Benzothiophen-, Indolyl-, Benzothiazolyl-, Cumarin-, Chinolin- oder Carbazolylrest. Die ein- oder mehrkernigen, heterocyclischen Reste können substituiert sein, insbesondere durch Halogen, Hydroxyl, Cyano, Nitro, Niederalkyl, Niederalkoxy oder Niederalkoxycarbonyl. Die bevorzugten, heterocyclischen Reste in der Bedeutung von R sind 2-Furyl, Furfuryl-, Tetrahydrofurfuryl, 2-Thienyl, 2-, 3- oder 4-Pyridyl oder 5-Niederalkoxycarbonyl-2-thienyl, wie z.B. 5-Carbomethoxy-2-thienyl.R can also represent a multinuclear, heterocyclic ring system. This preferably contains a fused benzene or naphthalene ring, e.g. an optionally substituted benzothiophene, indolyl, benzothiazolyl, coumarin, quinoline or carbazolyl radical. The mono- or polynuclear, heterocyclic radicals can be substituted, in particular by halogen, hydroxyl, cyano, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl. The preferred heterocyclic radicals with the meaning of R are 2-furyl, furfuryl, tetrahydrofurfuryl, 2-thienyl, 2-, 3- or 4-pyridyl or 5-lower alkoxycarbonyl-2-thienyl, e.g. 5-carbomethoxy-2-thienyl.
Der Substituent R ist vorzugsweise Niederalkyl, wie z.B. Methyl, Ethyl oder Butyl, Hydroxy-Niederalkyl, wie z.B. Hydroxymethyl oder Hydroxyethyl, Cyanoniederalkyl, wie z.B. Cyanomethyl oder Cyanoethyl, Acetyl, Acetylamino, Benzoyl, Cyclohexyl, Benzyl, Phenyl, Chlorphenyl, Tolyl, Xylyl, 2,6-Dimethylphenyl, Naphthyl, Methoxyphenyl, Pyridyl oder Furfuryl.The substituent R is preferably lower alkyl such as methyl, ethyl or butyl, hydroxy lower alkyl such as hydroxymethyl or hydroxyethyl, cyano-lower alkyl such as cyanomethyl or cyanoethyl, acetyl, acetylamino, benzoyl, cyclohexyl, benzyl, phenyl, chlorophenyl, tolyl, xylyl , 2,6-dimethylphenyl, naphthyl, methoxyphenyl, pyridyl or furfuryl.
Der Benzolring A ist vorzugsweise unsubstituiert. Er kann jedoch 1 bis 4 (vorzugsweise 1 oder 2) Substituenten aufweisen. Bevorzugte Substituenten sind Halogen, Nitro, Niederalkyl, Niederalkoxy oder Niederalkoxycarbonyl.The benzene ring A is preferably unsubstituted. However, it can have 1 to 4 (preferably 1 or 2) substituents. Preferred substituents are halogen, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl.
Praktisch wichtige cyclische Diazokomponenten entsprechen der Formel
worin
Q für -CO- oder vorzugsweise -SO₂- steht und
R₁ Niederalkyl, Halogen-Niederalkyl, Hydroxy-Niederalkyl, Cyano-Niederalkyl, Niederalkoxycarbonyl-Niederalkyl, Cyclohexyl, Benzyl, Naphthyl, unsubstituiertes oder durch Halogen, Cyano, Nitro, Niederalkyl, Niederalkoxy, Trifluormethyl oder Niederalkylcarbonyl substituiertes Phenyl oder einen heterocyclischen Rest aromatischen Charakters bedeutet und der Benzolkern B unsubstituiert oder durch Halogen, Nitro, Niederalkyl, Niederalkoxy oder Niederalkoxycarbonyl substituiert ist.Practically important cyclic diazo components correspond to the formula
wherein
Q is -CO- or preferably -SO₂- and
R₁ is lower alkyl, halogen-lower alkyl, hydroxy-lower alkyl, cyano-lower alkyl, lower alkoxycarbonyl-lower alkyl, cyclohexyl, benzyl, naphthyl, phenyl which is unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, trifluoromethyl or lower alkylcarbonyl or a heterocyclic radical of aromatic character and the benzene nucleus B is unsubstituted or substituted by halogen, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl.
Unter den cyclischen Diazokomponenten der Formel (2) sind diejenigen, in denen der Benzolkern B unsubstituiert oder durch Halogen substituiert ist und R₁ Niederalkyl, Cyclohexyl, Benzyl oder unsubstituiertes oder durch Halogen, Niederalkyl oder Niederalkoxy substituiertes Phenyl darstellt, bevorzugt.Among the cyclic diazo components of the formula (2), those in which the benzene nucleus B is unsubstituted or substituted by halogen and R 1 is lower alkyl, cyclohexyl, benzyl or unsubstituted or substituted by halogen, lower alkyl or lower alkoxy are preferred.
Von besonderem Interesse sind cyclische Diazokomponenten der Formel
worin
R₂ Niederalkyl, Cyclohexyl, Benzyl, Phenyl oder durch Halogen, Methyl oder Methoxy substituiertes Phenyl bedeutet und der Benzolkern D unsubstituiert oder durch Halogen substituiert ist.Cyclic diazo components of the formula are of particular interest
wherein
R₂ is lower alkyl, cyclohexyl, benzyl, phenyl or phenyl substituted by halogen, methyl or methoxy and the benzene nucleus D is unsubstituted or substituted by halogen.
Im Vordergrund des Interesses stehen N-Methyl-benzothiatriazin, N-n-Butyl-benzothiatriazin, N-Cyclohexyl-benzothiatriazin, N-Benzyl-benzothiatriazin oder N-Phenyl-benzothiatriazin.Of primary interest are N-methyl-benzothiatriazine, N-n-butyl-benzothiatriazine, N-cyclohexyl-benzothiatriazine, N-benzyl-benzothiatriazine or N-phenyl-benzothiatriazine.
Die cyclische Diazokomponente der Formel (1) kann hergestellt werden, indem man eine Aminoverbindung der Formel
in der A, Q und R die angegebene Bedeutung haben, diazotiert und cyclisiert.The cyclic diazo component of the formula (1) can be prepared by using an amino compound of the formula
in which A, Q and R have the meaning given, diazotized and cyclized.
Cyclische Diazokomponenten der Formeln (1) bis (3) und deren Herstellung werden z.B. in den US-Patentschriften 2 834 764, 2 402 611, 2 798 055, 2 843 588 und 2 758 115 beschrieben. Weitere Literaturstellen sind A.C. Mair, M.F.G. Stevens, J.Chem.Soc. C 1971, 2317, Helv.Chimica Acta 68, 892 (1985), J.Am.Chem.Soc. 77, 6562 (1955), J.Pr.Chemie [2], 51, (1895), 113, 132, 260, 277, 280, 52, (1896), 379, 385, 393 und 405, 55, 356 (1897) und 71, 153 (1905).Cyclic diazo components of the formulas (1) to (3) and their preparation are described, for example, in US Pat. Nos. 2,834,764, 2,402,611, 2,798,055, 2,843,588 and 2,758,115. Further references are AC Mair, MFG Stevens, J.Chem.Soc. C 1971 , 2317, Helv.Chimica Acta 68 , 892 (1985), J.Am.Chem.Soc. 77 , 6562 (1955), J.Pr.Chemie [2], 51 , (1895), 113, 132, 260, 277, 280, 52 , (1896), 379, 385, 393 and 405, 55 , 356 ( 1897) and 71 , 153 (1905).
Als Kupplungskomponenten kommen alle in der Azochemie üblichen und aus der einschlägigen Literatur bekannten Kupplungskomponenten in Frage, sofern sie keine sauren, wasserlöslich machenden Gruppen wie z.B. Carboxyl- und Sulfonsäuregruppen enthalten.Suitable coupling components are all coupling components customary in azochemistry and known from the relevant literature, provided they do not contain any acidic, water-solubilizing groups such as e.g. Contain carboxyl and sulfonic acid groups.
Aus der Vielzahl der Möglichkeiten seien beispielsweise erwähnt:
Kupplungskomponenten der Benzolreihe, der Naphthalinreihe, der offenkettigen methylenaktiven Verbindungen sowie der heterocyclischen Reihe.From the multitude of possibilities, for example:
Coupling components of the benzene series, the naphthalene series, the open-chain methylene-active compounds and the heterocyclic series.
Beispiele für die genannten Kupplungskomponenten sind Acylacetarylamide, Phenole, Aniline, Naphthylamine, Diphenylamine, Naphthole, Naphtholcarbonsäureanilide, Aminopyrazole, Pyrazolone, Thiophene, Aminothiazole, Hydroxypyridine, Pyridone, Indole, Chinolone, Barbitursäuren oder Hydroxychinoline.Examples of the coupling components mentioned are acylacetarylamides, phenols, anilines, naphthylamines, diphenylamines, naphthols, naphtholcarboxylic acid anilides, aminopyrazoles, pyrazolones, thiophenes, aminothiazoles, hydroxypyridines, pyridones, indoles, quinolones, barbituric acids or hydroxyquinolines.
Besonders bevorzugte Kupplungskomponenten sind Naphthole, Naphtholcarbonsäureanilide und Acylacetarylamide, wie z.B. 2-Hydroxy-3-N-phenylcarbamoyl-naphthalin und Acetylacet-2-methoxy-anilid.Particularly preferred coupling components are naphthols, naphthol carboxylic acid anilides and acylacetarylamides, e.g. 2-hydroxy-3-N-phenylcarbamoyl-naphthalene and acetylacet-2-methoxy-anilide.
Die Mengenverhältnisse, in denen die cyclischen Diazokomponenten und die Kupplungskomponenten verwendet werden, sind nicht kritisch, jedoch verwendet man vorzugsweise die cyclischen Diazokomponenten und die Kupplungskomponenten in äquimolaren Mengen.The proportions in which the cyclic diazo components and the coupling components are used are not critical, but the cyclic diazo components and the coupling components are preferably used in equimolar amounts.
Sowohl die cyclischen Diazokomponenten als auch die Kupplungskomponenten können für sich allein oder als Mischungen untereinander in dem wärmeempfindlichen Aufzeichnungsmaterial eingesetzt werden.Both the cyclic diazo components and the coupling components can be used alone or as mixtures with one another in the heat-sensitive recording material.
Der Farbton des bei der Verwendung von erfindungsgemässen wärmeempfindlichen Aufzeichnungsmaterialien erhaltenen Druckbildes, kann je nach der verwendeten Kupplungskomponente gelb, orange, rosa, rot oder violett sein und die Farbbilder sind scharf und klar.The color tone of the printed image obtained when using heat-sensitive recording materials according to the invention can be yellow, orange, pink, red or violet, depending on the coupling component used, and the color images are sharp and clear.
Die erfindungsgemässen wärmeempfindlichen Aufzeichnungsmaterialien werden beispielsweise zum Aufzeichnen von Informationen, z.B. in elektronischen Rechnern, Ferndruckern, Fernschreibern oder in Aufzeichnungsgeräten und Messinstrumenten, wie z.B. Elektrocardiographen, verwendet. Die Bilderzeugung (Markierung) kann auch manuell mit einer erhitzten Feder erfolgen. Eine weitere Einrichtung zur Erzeugung von Markierungen mittels Wärme sind Laserstrahlen.The heat-sensitive recording materials according to the invention are used, for example, for recording information, for example in electronic computers, remote printers, teleprinters or in recording devices and measuring instruments, such as, for example, electrocardiographs. The imaging (marking) can also be done manually with a heated spring. Another device for generating markings using heat is laser beams.
Die wärmeempfindlichen Aufzeichnungssysteme enthalten mindestens einen Schichtträger, wie z.B. Papier, synthetisches Papier oder eine Kunstfolie und eine oder mehrere darauf ausgebildete temperaturempfindliche Schichten, welche die cyclische Diazokomponente und die Kupplungskomponente enthalten.The heat-sensitive recording systems contain at least one support, e.g. Paper, synthetic paper or an art film and one or more temperature sensitive layers formed thereon which contain the cyclic diazo component and the coupling component.
Vorzugsweise werden zur Herstellung des thermoreaktiven Aufzeichnungsmaterials schmelzbare, filmbildende Bindemittel verwendet. Diese Bindemittel sind normalerweise wasserlöslich, während die Diazokomponente und die Kupplungskomponente in Wasser unlöslich sind. Das Bindemittel sollte in der Lage sein, die Diazo- und Kupplungskomponenten bei Raumtemperatur zu dispergieren und zu fixieren.Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are normally water soluble, while the diazo component and the coupling component are insoluble in water. The binder should be able to disperse and fix the diazo and coupling components at room temperature.
Bei Einwirkung von Wärme erweicht oder schmilzt das Bindemittel, so dass die Diazokomponente mit der Kupplungskomponente in Kontakt kommt und sich durch Kupplung eine Farbe bildet. Wasserlösliche oder mindestens in Wasser quellbare Bindemittel sind z.B. hydrophile Polymerisate, wie Polyvinylalkohol, Polyacrylsäure, Hydroxyethylcellulose, Methylcellulose, Carboxymethylcellulose, Polyacrylamid, Polyvinylpyrrolidon, carboxylierte Butadien-Styrolcopolymerisate, Gelatine, Stärke oder veretherte Maisstärke.When exposed to heat, the binder softens or melts, so that the diazo component comes into contact with the coupling component and a color forms as a result of the coupling. Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or etherified corn starch.
Wenn die Diazokomponente und die Kupplungskomponente in zwei getrennten Schichten vorliegen, können in Wasser unlösliche Bindemittel, d.h. in nichtpolaren oder nur schwach polaren Lösungsmitteln lösliche Bindemittel, wie z.B. Naturkautschuk, synthetischer Kautschuk, chlorierter Kautschuk, Alkydharze, Polystyrol, Styrol/Butadien-Mischpolymerisate, Polymethylacrylate, Ethylcellulose, Nitrocellulose und Polyvinylcarbazol verwendet werden. Die bevorzugte Anordnung ist jedoch diejenige, bei der die Diazokomponente und die Kupplungskomponente in einer Schicht in einem wasserlöslichen Bindemittel enthalten sind.If the diazo component and the coupling component are in two separate layers, water-insoluble binders, i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used. However, the preferred arrangement is one in which the diazo component and the coupling component are contained in one layer in a water-soluble binder.
Die thermoreaktiven Schichten können weitere Zusätze enthalten. Zur Verbesserung des Weissgrades, zur Erleichterung des Bedruckens der Papiere und zur Verhinderung des Festklebens der erhitzten Feder können diese Schichten, z.B. Talk, Titandioxyd, Zinkoxyd, Aluminiumoxyd, Aluminiumhydroxyd, Calciumcarbonat (z.B. Kreide), Silica, Tone oder auch organische Pigmente, wie z.B. Harnstoff-Formaldehydpolymerisate enthalten. Um zu bewirken, dass nur innerhalb eines begrenzten Temperaturbereichs die Farbe gebildet wird, können Substanzen, wie Harnstoff, Thioharnstoff, Diphenylthioharnstoff, Acetamid, Acetanilid, Benzolsulfanilid, Stearinsäureamid, Phthalsäureanhydrid, Metallstearate, wie z.B. Zinkstearat, Phthalsäurenitril, Dimethylterephthalat oder andere entsprechende, schmelzbare Produkte, welche die Kupplung der cyclischen Diazokomponente mit der Kupplungskomponente induzieren, zugesetzt werden. Bevorzugt enthalten die thermographischen Aufzeichnungsmaterialien Wachse, z.B. Carnaubawachs, Montanwachs, Paraffinwachs, Polyethylenwachs, Kondensate höherer Fettsäureamide und Formaldehyde und Kondensate höherer Fettsäuren und Ethylendiamin. Gewünschtenfalls können die Aufzeichnungsmaterialien auch alkalische Materialien, wie z.B. Hydroxyde oder Carbonate von Alkalimetallen oder vorzugsweise offene oder cyclische organische Basen wie Amine, Alkanolamine, Guanidine, Pyridine oder Imidazolderivate enthalten.The thermoreactive layers can contain further additives. To improve the degree of whiteness, to facilitate printing on the papers and to prevent the heated spring from sticking, these layers, for example talc, titanium dioxide, zinc oxide, aluminum oxide, Contain aluminum hydroxide, calcium carbonate (eg chalk), silica, clays or organic pigments such as urea-formaldehyde polymers. In order to ensure that the color is formed only within a limited temperature range, substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, benzenesulfanilide, stearic acid amide, phthalic anhydride, metal stearates, such as zinc stearate, phthalic acid nitrile or other corresponding dimethyl terephthalate products which induce the coupling of the cyclic diazo component with the coupling component. The thermographic recording materials preferably contain waxes, for example carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde and condensates of higher fatty acids and ethylenediamine. If desired, the recording materials can also contain alkaline materials, such as hydroxides or carbonates of alkali metals, or preferably open or cyclic organic bases such as amines, alkanolamines, guanidines, pyridines or imidazole derivatives.
In den folgenden Beispielen beziehen sich die angegebenen Prozentsätze, wenn nichts anderes angegeben ist, auf das Gewicht und Teile sind Gewichtsteile.In the following examples, the percentages given are by weight and parts are parts by weight unless otherwise specified.
Zur Herstellung einer Dispersion A werden:
2,25 g der cyclischen Diazokomponente der Formel
7,9 g einer 10%igen wässrigen Lösung von Polyvinylalkohol (Polyviol VO3/140) und
4,5 g Wasser mit Glaskugeln bis zu einer Korngrösse von 2-4 µm gemahlen.To prepare dispersion A:
2.25 g of the cyclic diazo component of the formula
7.9 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) and
4.5 g of water are ground with glass balls down to a grain size of 2-4 µm.
Zur Herstellung einer Dispersion B werden:
3,0 g der Kupplungskomponente der Formel
10,5 g einer 10%igen wässrigen Lösung von Polyvinylalkohol (Polyviol VO3/140) und
6,0 g Wasser mit Glaskugeln bis zu einer Korngrösse von 2-4 µm gemahlen.To prepare a dispersion B:
3.0 g of the coupling component of the formula
10.5 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) and
6.0 g of water ground with glass balls down to a grain size of 2-4 µm.
Anschliessend werden die beiden Dispersionen vermischt.The two dispersions are then mixed.
Das Gemisch wird auf ein Papier mit einem Flächengewicht von 50 g/m² mit einem Rakel aufgetragen. Der Anteil des aufgebrachten Materials beträgt 5 g/m² (Trockengewicht).The mixture is applied to paper with a basis weight of 50 g / m² using a doctor blade. The proportion of the applied material is 5 g / m² (dry weight).
Beim Entwickeln mit einer Heizplatte (Kontaktzeit 0,1 Sekunden) entwickelt sich rasch ein roter Farbton ab 100°C, dessen volle Farbstärke bei 200°C erreicht wird.When developing with a heating plate (contact time 0.1 seconds), a red color quickly develops from 100 ° C, the full color strength of which is reached at 200 ° C.
Ersetzt man die im Beispiel 1 beschriebene Verbindung der Formel (4) durch 2,95 g einer Diazokomponente der Formel
und verfährt im übrigen wie im Beispiel 1 beschrieben, so erhält man eine intensiv rote Färbung mit hervorragender Lichtechtheit.If the compound of the formula (4) described in Example 1 is replaced by 2.95 g of a diazo component of the formula
and otherwise operates as described in Example 1, an intense red color is obtained with excellent lightfastness.
Ersetzt man in der Dispersion A die im Beispiel 1 beschriebene Verbindung der Formel (4) durch die Verbindung der Formel (5) gemäss Beispiel 2 und in der Dispersion B die Kupplungskomponente der Formel (21) durch 2,35 g einer Kupplungskomponente der Formel
und verfährt im übrigen wie im Beispiel 1 beschrieben, so erhält man eine intensiv gelbe Färbung.In dispersion A, the compound of formula (4) described in Example 1 is replaced by the compound of formula (5) according to Example 2, and in dispersion B the coupling component of formula (21) is replaced by 2.35 g of a coupling component of the formula
and otherwise operates as described in Example 1, an intense yellow color is obtained.
Entsprechende intensive und lichtechte rote bzw. gelbe Färbungen werden erhalten, wenn in den Beispielen 1 und 3 anstelle der verwendeten Diazokomponente die in der folgenden Tabelle aufgeführten Diazokomponenten der Formel
eingesetzt werden.
be used.
Claims (10)
- A heat-sensitive recording material comprising a base and, on top of the said base, a heat-sensitive layer containing a cyclic diazo component and a coupling component, wherein the cyclic diazo component is a benzotriazine compound of the formula
R is hydrogen, hydroxyl, or alkyl or alkenyl having at most 12 carbon atoms, each unsubstituted or substituted by halogen, hydroxyl, cyano, lower alkoxy, lower alkylthio, C₁-C₈acyloxy, lower alkoxycarbonyl or lower alkylsulfonyl, or is acyl, acyloxy or acylamino each having 1 to 10 carbon atoms, or cycloalkyl having 5 to 10 carbon atoms, or phenyl, phenylalkyl or naphthyl, each unsubstituted or ring-substituted by cyano, halogen, nitro, trifluoromethyl, lower alkyl, lower alkylthio, lower alkoxy, lower alkylcarbonyl or lower alkoxycarbonyl, or is a heterocyclic radical, and
the benzene ring A is unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, lower alkythio, lower alkylcarbonyl or lower alkoxycarbonyl. - A recording material according to claim 1, wherein R in formula (1) is lower alkyl, hydroxy-lower alkyl, cyano-lower alkyl, acetyl, acetylamino, benzoyl, cyclohexyl, benzyl, phenyl, chlorophenyl, tolyl, xylyl, naphthyl, methoxyphenyl, pyridyl or furfuryl.
- A recording material according to claim 1, wherein R in formula (1) is hydroxyl, acetoxy, benzyloxy, vinyl, methylsulfonyloxyethyl or tolylsulfonyloxyethyl.
- A recording material according to any one of claims 1 to 3, wherein Q is -CO- or -SO₂-.
- A recording material according to any one of claims 1 to 4, wherein the benzene ring A in formula (1) is unsubstituted or substituted by halogen, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl.
- A recording material according to claim 1, wherein the cyclic diazo component has the formula
R₁ is lower alkyl, halogeno-lower alkyl, hydroxy-lower alkyl, cyano-lower alkyl, lower alkoxy-carbonyl-lower alkyl, cyclohexyl, benzyl, naphthyl, phenyl which is unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, trifluoromethyl or lower alkylcarbonyl, or is a heterocyclic radical of aromatic character, and the benzene ring B is unsubstituted or substituted by halogen, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl. - A recording material according to claim 6, wherein R₁ in formula (2) is lower alkyl, cyclohexyl, benzyl, phenyl or phenyl substituted by halogen, lower alkyl or lower alkoxy, and the benzene ring B is unsubstituted or substituted by halogen.
- A recording material according to claim 1, wherein the cyclic diazo component has the formula
- A recording material according to any one of claims 1 to 8, wherein the coupling component is a naphthol, naphtholcarboxylic acid anilide or acylacetarylamide compound.
- A recording material according to any one of claims 1 to 9, which contains, in addition to the diazo and coupling components, at least one binder in at least one layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH484987 | 1987-12-11 | ||
| CH4849/87 | 1987-12-11 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0320453A2 EP0320453A2 (en) | 1989-06-14 |
| EP0320453A3 EP0320453A3 (en) | 1990-08-08 |
| EP0320453B1 true EP0320453B1 (en) | 1993-10-20 |
Family
ID=4283627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88810827A Expired - Lifetime EP0320453B1 (en) | 1987-12-11 | 1988-12-01 | Thermally sensitive recording material |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4957847A (en) |
| EP (1) | EP0320453B1 (en) |
| JP (1) | JPH021370A (en) |
| CA (1) | CA1315549C (en) |
| DE (1) | DE3885068D1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679494A (en) * | 1994-02-16 | 1997-10-21 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material comprising a diazonium salt, a coupler and a benzotriazole compound |
| US5424268A (en) * | 1994-05-13 | 1995-06-13 | Polaroid Corporation | Imaging medium and process |
| US5773186A (en) * | 1996-02-19 | 1998-06-30 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
| JPH11109554A (en) * | 1997-10-01 | 1999-04-23 | Fuji Photo Film Co Ltd | Photosensitive and thermosensitive recording material, and dye |
| JP2002326457A (en) * | 2001-04-27 | 2002-11-12 | Fuji Photo Film Co Ltd | Heat-sensitive recording material |
| JP2003050442A (en) * | 2001-06-01 | 2003-02-21 | Fuji Photo Film Co Ltd | Recording material |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2402611A (en) * | 1942-06-04 | 1946-06-25 | Eastman Kodak Co | Cyclic diazo compounds |
| US2411811A (en) * | 1945-02-01 | 1946-11-26 | Gen Aniline & Film Corp | Light-sensitive materials |
| BE468903A (en) * | 1945-08-18 | |||
| US2843588A (en) * | 1953-02-26 | 1958-07-15 | Bayer Ag | Derivatives of thiophosphoric acid |
| US2798055A (en) * | 1954-12-14 | 1957-07-02 | American Cyanamid Co | Rubber compositions containing triazine blowing agents and process for producing cellular rubber therefrom |
| US2834764A (en) * | 1954-12-14 | 1958-05-13 | American Cyanamid Co | Polymerization process employing n-substituted-benzosulfotriazine polymerization catalysts |
| US2758115A (en) * | 1955-02-10 | 1956-08-07 | Bayer Ag | Derivatives of thiophosphoric acid |
| DE2363675A1 (en) * | 1973-12-21 | 1975-06-26 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC MATERIAL WITH NEW 2-AEQUIVALENT YELLOW COUPLERS |
| IT1018702B (en) * | 1974-06-26 | 1977-10-20 | Minnesota Mining & Mfg | PHOTOGRAPHIC COPULANTS PIVALILACETA NILIDIC PHOTOGRAPHIC ELEMENTS THAT INCLUDE SUCH COPULANTS E.O THE COLORS FORMED FOR THE CHROME GENO DEVELOPMENT OF SAID COPULANTS AND METHOD FOR FORMING A PHOTOGRAPHIC IMAGE CA WITH DYES IN THE PRESENCE OF DETECT COOLANTS |
| DE2556620A1 (en) * | 1975-12-16 | 1977-06-30 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC MATERIAL |
| JPS554060A (en) * | 1978-06-27 | 1980-01-12 | Asahi Chem Ind Co Ltd | Dry type image forming material |
| DE2840381A1 (en) * | 1978-09-16 | 1980-04-03 | Agfa Gevaert Ag | METHOD FOR PRODUCING 2-EQUIVALENT YELLOW COUPLERS |
| JPS58128896A (en) * | 1982-01-27 | 1983-08-01 | Toppan Printing Co Ltd | Thermally developable diazo-type recording medium |
| JPS60214990A (en) * | 1984-03-26 | 1985-10-28 | Fuji Photo Film Co Ltd | Photosensitive thermal recording material |
| JPS60240491A (en) * | 1984-05-16 | 1985-11-29 | Fuji Photo Film Co Ltd | Thermal recording material |
-
1988
- 1988-12-01 EP EP88810827A patent/EP0320453B1/en not_active Expired - Lifetime
- 1988-12-01 DE DE88810827T patent/DE3885068D1/en not_active Expired - Fee Related
- 1988-12-02 US US07/278,989 patent/US4957847A/en not_active Expired - Fee Related
- 1988-12-09 CA CA000585417A patent/CA1315549C/en not_active Expired - Fee Related
- 1988-12-09 JP JP63310246A patent/JPH021370A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH021370A (en) | 1990-01-05 |
| DE3885068D1 (en) | 1993-11-25 |
| EP0320453A2 (en) | 1989-06-14 |
| EP0320453A3 (en) | 1990-08-08 |
| US4957847A (en) | 1990-09-18 |
| CA1315549C (en) | 1993-04-06 |
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