JPH043756B2 - - Google Patents
Info
- Publication number
- JPH043756B2 JPH043756B2 JP59134488A JP13448884A JPH043756B2 JP H043756 B2 JPH043756 B2 JP H043756B2 JP 59134488 A JP59134488 A JP 59134488A JP 13448884 A JP13448884 A JP 13448884A JP H043756 B2 JPH043756 B2 JP H043756B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- formula
- general formula
- compound
- acid
- 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
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- -1 cyclic alkyl Chemical group 0.000 claims description 22
- 239000012954 diazonium Substances 0.000 claims description 19
- 150000001989 diazonium salts Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 150000007514 bases Chemical class 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 7
- 125000004442 acylamino group Chemical group 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004040 coloring Methods 0.000 claims description 6
- 150000002357 guanidines Chemical class 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000010410 layer Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 7
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- IBHWREHFNDMRPR-UHFFFAOYSA-N 2,4,6-Trihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=C(O)C=C1O IBHWREHFNDMRPR-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-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
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 239000003125 aqueous solvent 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- OGLZSMPGMUDNKR-UHFFFAOYSA-N 1-(2-methylphenyl)piperidine Chemical compound CC1=CC=CC=C1N1CCCCC1 OGLZSMPGMUDNKR-UHFFFAOYSA-N 0.000 description 1
- DIWJFNNUUTXPCL-UHFFFAOYSA-M 2,3-dihydro-1,3-benzoxazole-4-diazonium;chloride Chemical compound [Cl-].N#[N+]C1=CC=CC2=C1NCO2 DIWJFNNUUTXPCL-UHFFFAOYSA-M 0.000 description 1
- RSMQFJQBYOIGGR-UHFFFAOYSA-M 2,5-diethoxy-3-(4-methylphenyl)sulfanylbenzenediazonium;chloride Chemical compound [Cl-].N#[N+]C1=CC(OCC)=CC(SC=2C=CC(C)=CC=2)=C1OCC RSMQFJQBYOIGGR-UHFFFAOYSA-M 0.000 description 1
- CATQSEUYZSHUMC-UHFFFAOYSA-M 2,5-diethoxy-4-ethylsulfanylbenzenediazonium;chloride Chemical compound [Cl-].CCOC1=CC([N+]#N)=C(OCC)C=C1SCC CATQSEUYZSHUMC-UHFFFAOYSA-M 0.000 description 1
- MSJPBYNDRJGIGX-UHFFFAOYSA-M 2,5-diethoxy-4-morpholin-4-ylbenzenediazonium;chloride Chemical compound [Cl-].C1=C([N+]#N)C(OCC)=CC(N2CCOCC2)=C1OCC MSJPBYNDRJGIGX-UHFFFAOYSA-M 0.000 description 1
- ADWMHAYGHVVKBZ-UHFFFAOYSA-N 2-(2-hydroxy-3-propylmorpholin-4-yl)naphthalene-1-carboxylic acid Chemical compound CCCC1C(O)OCCN1C1=CC=C(C=CC=C2)C2=C1C(O)=O ADWMHAYGHVVKBZ-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- OTEFEXJNJQIESQ-UHFFFAOYSA-N 3-hydroxy-n-(3-morpholin-4-ylpropyl)naphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NCCCN1CCOCC1 OTEFEXJNJQIESQ-UHFFFAOYSA-N 0.000 description 1
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 1
- CCIAVEMREXZXAK-UHFFFAOYSA-M 4-(dimethylamino)benzenediazonium;chloride Chemical compound [Cl-].CN(C)C1=CC=C([N+]#N)C=C1 CCIAVEMREXZXAK-UHFFFAOYSA-M 0.000 description 1
- GREMVPUSQUHWDU-UHFFFAOYSA-M 4-anilinobenzenediazonium;chloride Chemical compound [Cl-].C1=CC([N+]#N)=CC=C1NC1=CC=CC=C1 GREMVPUSQUHWDU-UHFFFAOYSA-M 0.000 description 1
- NUEFLEZXMKKASL-UHFFFAOYSA-M 4-benzylsulfanyl-2,5-dimethoxybenzenediazonium;chloride Chemical compound [Cl-].COC1=CC([N+]#N)=C(OC)C=C1SCC1=CC=CC=C1 NUEFLEZXMKKASL-UHFFFAOYSA-M 0.000 description 1
- YTVSBURBOWIMMD-UHFFFAOYSA-M 4-morpholin-4-ylbenzenediazonium;chloride Chemical compound [Cl-].C1=CC([N+]#N)=CC=C1N1CCOCC1 YTVSBURBOWIMMD-UHFFFAOYSA-M 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000005493 Chloridazon (aka pyrazone) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229920002085 Dialdehyde 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
- 108010010803 Gelatin Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- PVNIQBQSYATKKL-UHFFFAOYSA-N Glycerol trihexadecanoate Natural products CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- GXBDYVJMWRTUNT-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid Chemical compound C=CC=C.CC(=C)C(O)=O GXBDYVJMWRTUNT-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004227 calcium gluconate Substances 0.000 description 1
- 229960004494 calcium gluconate Drugs 0.000 description 1
- 235000013927 calcium gluconate Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates 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
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 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
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PAUDUANJHUMGII-UHFFFAOYSA-N guanidine;sulfuric acid;thiourea Chemical compound NC(N)=N.NC(N)=S.OS(O)(=O)=O PAUDUANJHUMGII-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- SRMZHGJLSDITLO-UHFFFAOYSA-N phenyl 3-hydroxynaphthalene-2-carboxylate Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)OC1=CC=CC=C1 SRMZHGJLSDITLO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 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
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000007651 thermal printing Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000002492 water-soluble polymer binding agent Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 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
- G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
(A) 発明の技術分野
本発明は感熱記録により高濃度に発色し、しか
も貯蔵保存性の優れた定着型感熱記録体に関する
ものである。
(B) 従来技術及びその問題点
近年、多量の情報をできる限り高速でハードコ
ピーとしてアウトプツトすると云う社会の要請に
応じて高速プリンター、フアクシミリ等の発達は
著しいものがある。高速プリンター、フアクシミ
リの如く電気的情報に従つて記録媒体に画像を形
成する方法として、電子写真、静電記録、放電記
録、インクジエツトおよび感熱記録等が知られて
いる。これらのなかで感熱記録法は装置が比較的
簡単であり、又、記録紙も比較的安価であること
から特に近年急速に普及している。
該感熱記録法の一つの方法として、クリスタル
バイオレツトラクトンのような発色物質とビスフ
エノールAのようなフエノール性化合物を組み合
せてなる感熱記録用シートについては、例えば特
公昭45−14039号公報に記載されておりすでに公
知である。これらの感熱記録シートは現在事務用
複写紙、各種レコーダー、心電計、電卓、コンピ
ユーターの端末機、フアクシミリ等の記録紙とし
て広く使用されている。
しかし、上記従来の方法では印字後、誤つて加
熱された場合、背景が発色して印字が読めなくな
つたり、又印字後、改ざんされる可能性があり、
その改良が強く望まれている。
本発明者等はこの問題を解決した定着可能な感
熱記録体の提供を意図して研究し、先に、ジアゾ
ニウム塩とカプラー化合物の反応を促す塩基性物
質として特定の一般式を有するグアニジン誘導体
を用いることにより、高感度でしかも貯蔵保存性
にすぐれた定着可能な感熱記録体を提供しうるこ
とを見出してすでに提案した(特開昭57−45094、
同57−125091公報)。
しかし近年増々、感熱記録法においては発色感
度の高感度化が求められており、一般に高い発色
感度を得ようとすれば貯蔵保存性が悪化する傾向
があるが、これはジアゾニウム塩を使用する定着
型感熱記録体においても大いに認められる所であ
り、高濃度に発色して、しかも貯蔵保存性に優れ
た定着型感熱記録体が求められていた。
(C) 発明の目的
本発明の目的は感熱記録により高濃度に発色
し、しかも貯蔵保存性に優れた定着型感熱記録体
を提供する事である。
(D) 発明の構成及び作用
即ち、本発明の定着型感熱記録体は、支持体上
にジアゾニウム塩、カプラー化合物、発色助剤及
び顕色剤として熱により溶融して塩基性雰囲気を
示す有機塩基性化合物の微粒子状分散物を同一層
に、又は2層以上の別の層より成る感光感熱層と
して設けた定着型感熱記録体において、発色助剤
として下記一般式()で示される化合物を用い
ることを特徴とする。
一般式()
(式中Rはアルキル基、アラルキル基を、nは
1〜3の整数を表わす)
本発明で用いる化合物は融点40〜160℃、好ま
しくは70〜135℃の常温で固体の物質であり、水
に難溶又は不溶であり、熱溶融時にジアゾニウム
塩、カプラー化合物、及び顕色剤として使用する
有機塩基性化合物をよく溶解させるものの使用が
好ましい。
本発明に使用する化合物の具体例を表−1に示
すが、本発明はこれらに限定されるものではな
い。
表−1
エチレングリコールビス(P−ベンジルオキシカ
ルボニルフエニル)エーテル
ジエチレングリコールビス(P−ベンジルオキシ
カルボニルフエニル)エーテル
エチレングリコールビス(P−イソプロポキシカ
ルボニルフエニル)エーテル
エチレングリコールビス(P−(P−クロロベン
ジル)オキシカルボニルフエニル)エーテ
ル
エチレングリコールビス(P−n−ブトキシカル
ボニルフエニル)エーテル
エチレングリコールビス(P−(P−メチルベン
ジル)オキシカルボニルフエニル)エーテ
ル
本発明で発色助剤として用いる前記化合物は、
いずれも熱可溶融性で、かつ水難溶性又は不溶性
であり、粒径0.1〜10μの微粒子状で用いられる。
ジアゾニウム塩とカプラー化合物と本発明の発色
助剤との比率は1:(0.1〜10):(0.1〜20)(重
量)の範囲が好ましい。又、発色助剤は単独で、
もしくは必要により2種以上を組み合わせて使用
することが出来る。
本発明の発色助剤による定着型感熱記録体の発
色感度向上の効果は疎水性グアニジン誘導体のみ
ならず広く一般に公知の有機塩基性化合物を顕色
剤として使用した場合にも認められるが、特に好
ましい有機塩基性化合物として下記のグアニジン
誘導体があげられる。
一般式()
一般式()
(式中R1,R2,R3,R4およびR5は水素、炭素
数18以下のアルキル、環状アルキル、アリール、
アラルキル、アミノ、アルキルアミノ、アシルア
ミノ、カルバモイルアミノ、複素環残基を表し、
R6は低級アルキレン、フエニレン、ナフチレン、
または
(A) Technical Field of the Invention The present invention relates to a fixable heat-sensitive recording material that develops color with high density during heat-sensitive recording and has excellent storage stability. (B) Prior art and its problems In recent years, high-speed printers, facsimile machines, etc. have made remarkable progress in response to society's demand for outputting large amounts of information as hard copies as quickly as possible. Electrophotography, electrostatic recording, discharge recording, inkjet recording, thermosensitive recording, and the like are known as methods for forming images on recording media according to electrical information, such as high-speed printers and facsimiles. Among these methods, the thermal recording method has been rapidly becoming popular in recent years because the apparatus is relatively simple and the recording paper is also relatively inexpensive. As one method of the heat-sensitive recording method, a heat-sensitive recording sheet made by combining a color-forming substance such as crystal violet lactone and a phenolic compound such as bisphenol A is described in, for example, Japanese Patent Publication No. 14039/1983. It is already known. These thermosensitive recording sheets are currently widely used as office copy paper, recording paper for various recorders, electrocardiographs, calculators, computer terminals, facsimiles, and the like. However, with the above conventional method, if the background is heated incorrectly after printing, the background may become colored and the print may become unreadable, or there is a possibility that it may be tampered with after printing.
Improvements are strongly desired. The present inventors conducted research with the intention of providing a fixable heat-sensitive recording medium that solved this problem, and first developed a guanidine derivative having a specific general formula as a basic substance that promotes the reaction between a diazonium salt and a coupler compound. We have already proposed that by using the method, it is possible to provide a fixable heat-sensitive recording medium with high sensitivity and excellent storage stability (Japanese Patent Application Laid-Open No. 57-45094,
Publication No. 57-125091). However, in recent years, there has been an increasing demand for higher color development sensitivity in thermal recording methods. This is widely recognized in type thermosensitive recording materials, and there has been a demand for fixing type thermosensitive recording materials that develop color with high density and have excellent storage stability. (C) Object of the Invention The object of the present invention is to provide a fixable heat-sensitive recording material that develops color with high density during heat-sensitive recording and has excellent storage stability. (D) Structure and operation of the invention That is, the fixable heat-sensitive recording material of the present invention contains a diazonium salt, a coupler compound, a coloring aid, and an organic base as a coloring agent and an organic base that exhibits a basic atmosphere when melted by heat as a coloring agent on a support. In a fixing heat-sensitive recording material in which a fine-particle dispersion of a sexual compound is provided in the same layer or as a light- and heat-sensitive layer consisting of two or more separate layers, a compound represented by the following general formula () is used as a coloring aid. It is characterized by General formula () (In the formula, R represents an alkyl group or an aralkyl group, and n represents an integer of 1 to 3.) The compound used in the present invention is a solid substance at room temperature with a melting point of 40 to 160°C, preferably 70 to 135°C, and It is preferable to use a material that is sparingly soluble or insoluble in water, and that can well dissolve the diazonium salt, coupler compound, and organic basic compound used as a color developer during hot melting. Specific examples of compounds used in the present invention are shown in Table 1, but the present invention is not limited thereto. Table-1 Ethylene glycol bis(P-benzyloxycarbonylphenyl) ether diethylene glycol bis(P-benzyloxycarbonylphenyl) ether ethylene glycol bis(P-isopropoxycarbonylphenyl) ether ethylene glycol bis(P-(P- chlorobenzyl)oxycarbonylphenyl) ether ethylene glycol bis(P-n-butoxycarbonylphenyl) ether ethylene glycol bis(P-(P-methylbenzyl)oxycarbonylphenyl) ether The above-mentioned substances used as coloring aids in the present invention The compound is
All of them are thermofusible and poorly soluble or insoluble in water, and are used in the form of fine particles with a particle size of 0.1 to 10 μm.
The ratio of the diazonium salt, the coupler compound, and the color development aid of the present invention is preferably in the range of 1:(0.1-10):(0.1-20) (by weight). In addition, the coloring aid is used alone,
Alternatively, two or more types can be used in combination if necessary. The effect of improving the color development sensitivity of a fixable heat-sensitive recording material by the color development aid of the present invention is observed not only when a hydrophobic guanidine derivative is used but also when a widely known organic basic compound is used as a color developer, but it is particularly preferable. Examples of organic basic compounds include the following guanidine derivatives. General formula () General formula () (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen, alkyl having 18 or less carbon atoms, cyclic alkyl, aryl,
Represents aralkyl, amino, alkylamino, acylamino, carbamoylamino, heterocyclic residue,
R 6 is lower alkylene, phenylene, naphthylene,
or
【式】(式中Xは低
級アルキレン、SO2,S2,S,O,−NH−また
は一重結合を表す)を表し、式中のアリール基は
低級アルキル、アルコキシ、ニトロ、アシルアミ
ノ、アルキルアミノ基およびハロゲンより選ばれ
る置換基を有するものも含まれる。)
本発明に使用するジアゾニウム塩としては、従
来公知のジアゾ型複写材料に用いられる化合物を
任意に使用することが出来るが、例えば次の一般
式(),(),()で示されるものを特に好適
に使用することができる。
式中、R7およびR8は炭素数1〜5のアルキル、
又はアルコキシル、又はオキシアルキル、ベンジ
ル、置換ベンジル、ベンゾイル、置換ベンゾイ
ル、フエニル基、水素原子などを示し、Y及びZ
はハロゲン原子、炭素数1〜5のアルキル、カル
ボキシル、炭素数1〜5のアルコキシル、ニト
ロ、アセトキシ基などを示し、m及びnは0又は
4以下の正整数を示す。又、XはCl-,Br-,
SO4 -,NO3 -,PF6 -,ClO4 -,BF4 -等のアニオン
やさらにZnCl2,CaCl2あるいはSnCl4等かこれら
のアニオンに付加したイオンを表わしている。
具体例として、4−N,N−ジメチルアミノベ
ンゼンジアゾニウムクロリド、3−クロル−4−
N,N−ジメチルアミノベンゼンジアゾニウムク
ロリド、4−N,N−ジエチルアミノベンゼンジ
アゾニウムクロリド、2,5−ジエトキシ−4−
N,N−ジエチルアミノベンゼンジアゾニウムク
ロリド、4−N−エチル−N−ヒドロキシエチル
アミノベンゼンジアゾニウムクロリド、4−N,
N−ジエトキシアミノベンゼンジアゾニウムクロ
リド、4−フエニルアミノベンゼンジアゾニウム
クロリド、4−N−(P−メトキシフエニル)−ア
ミノベンゼンジアゾニウムクロリドなどがある。
式中R9は−CH2CH2OCH2CH2−や−
CH2OCH2CH2−、−CH2CH2CH2CH2−などであ
る。X,Y,Z,m及びnは一般式()の場合
と同義である。
具体的化合物例としては、4−モルフオリノベ
ンゼンジアゾニウムクロリド、2,5−ジエトキ
シ−4−モルフオリノベンゼンジアゾニウムクロ
リド、4−オキサゾリジノベンゼンジアゾニウム
クロリド、3−メチル−4−ピペリジノベンゼン
ジアゾニウムクロリドなどがある。
式中、R10はアルキル基やアリール基を示す。
又、X,Y,Z,m及びnは一般式()の場合
と同義である。
具体的化合物例としては、4−エチルメルカプ
ト−2,5−ジエトキシベンゼンジアゾニウムク
ロリド、4−トリルメルカプト−2,5−ジエト
キシベンゼンジアゾニウムクロリド、4−ベンジ
ルメルカプト−2,5−ジメトキシベンゼンジア
ゾニウムクロリドなどがある。
これらのジアゾニウム塩は水又は有機溶媒中に
溶解又は適当な溶媒中に微粒子状に分散させて好
ましくは0.1〜1.0g/m2の範囲内で支持体上に塗
布することが出来る。
又、ジアゾニウム塩の安定化とプレカツプリン
グ防止の為に感光感熱層中に酸化合物を用いるこ
とも出来るが、これは、従来公知のジアゾ型複写
材料に用いられる有機、無機の酸化合物を任意に
使用することが出来、具体例を挙げると酒石酸、
クエン酸、ホウ酸、乳酸、グルコン酸、リン酸、
トリクロロ酢酸、ジクロロ酢酸、シアノ酢酸、シ
ユウ酸、マロン酸、マレイン酸等がいずれも好適
に使用される。
これらの酸化合物は有機塩基性化合物に対して
重量比で5.0〜100%の範囲内で用いるのが好まし
く、さらに好ましくは10〜50%の範囲内で使用す
るのがよい。
又、ジアゾニウム塩と反応してアゾ色素を形成
するカプラー化合物としては前記したジアゾニウ
ム塩とカツプリング可能な化合物であれば何れを
も使用できる。これらのカプラー化合物として
は、フエノール誘導体、オキシナフタレン誘導
体、活性メチレン基を含む化合物、ヘテロサイク
リツク化合物等が挙げられ、これらの具体的な化
合物としては次の如き化合物が挙げられる。
フエノール誘導体
ピロカテコール
レゾルシン
フロログリシン
ピロガロール
メタアミノフエノール
パラアミノフエノール
ジエチルアミノフエノール
N−ラウリル−パラアミノフエノール
N−アシル−メタアミノフエノール
3,3′,5−トリヒドロキシジフエニール
3,3′,5,5′−テトラヒドロキシジフエニー
ル
α−レゾルシン酸
β−レゾルシン酸
γ−レゾルシン酸
フロログルシンカルボン酸
没食子酸
オキシナフタレン誘導体
2・3−ジヒドロキシナフタレン
β−ナフトール
α−ナフトール
1・6−ジヒドロキシナフタレン
2・3−ジヒドロキシナフタレン−6−スルホ
ン酸
2−ナフトール−3・6−ジスルホン酸
1・8−ジヒドロキシナフタレン−8−スルホ
ン酸
2−ヒドロキシ−3−ナフトエ酸−N−β−ヒ
ドロキシエチル−アマイド
2−ヒドロキシ−3−ナフトエ酸−N,N−ビ
ス−β−ヒドロキシエチルアマイド
5−(パラニトロ)−ベンズアミド−1−ナフト
ール
1−ナフトール−3−(N−β−ヒドロキシエ
チル)−スルホン−アマイド
2−ヒドロキシ−3−プロピルモルホリノナフ
トエ酸
2−ヒドロキシ−3−ナフト−0−トルイジド
2−ヒドロキシ−3−ナフトエ酸モルホリノプ
ロピルアミド
2−ヒドロキシ−3−ナフトエ酸−4′−クロロ
アニリド
2−ヒドロキシ−3−ナフトエ酸−5′−クロロ
−2′,4′−ジ−メトキシアニリド
2−ヒドロキシ−3−ナフトエ酸−2′,5′−ジ
メトキシアニリド
2−ヒドロキシ−3−ナフトエ酸−2′−エトキ
シアニリド
2−ヒドロキシ−3−ナフトエ酸−2′−メトキ
シアニリド
2−ヒドロキシ−3−ナフトエ酸−フエニルエ
ステル
2−ヒドロキシ−3−ナフトエ酸−4′−フエノ
キシアニリド
2−ヒドロキシ−3−ナフトエ酸−4′−ベンジ
ルオキシアニリド
2−ヒドロキシ−3−ナフトエ酸−4′−フエネ
チルオキシアニリド
2−ヒドロキシ−3−ナフトエ酸−2′−ベンヂ
ルオキシアニリド
活性メチレン基を含む化合物
1−フエニル−3−メチル−ピラゾン(5)
アセトアセチツクアシツドアニリド
1−フエニル−3−カルボキシピラゾロン
アセトアセチツクアシツドシクロヘキシルアマ
イド
アセトアセチツクアシツドベンジルアマイド
シアノアセトアニリド
シアノアセトモルフオリン
4−カルボキシ−アセトアセトアニリド
ヘテロサイクリツク化合物
1−(3′−スルフオアミド)−フエニル−3−メ
チル−ピラゾロン−5
1−(4′−カルボキシエチルフエニール)−3−
ドデシル−ピラゾロン−5
これらのカプラー化合物を水又は有機溶媒に溶
解して、もしくはボールミル、サンドグラインダ
ーアトライター等の分散手段を用いて粒径10μ以
下の微粒子状分散物として感光感熱層中に含有せ
しめることが出来る。
又、カプラー化合物は必要により2種又はそれ
以上の化合物を組み合せて望みの分光吸収特性を
示す染料の組み合せを生成させてもよい。又、分
散に際してはカプラー化合物を単独で分散しても
よいが、有機塩基性化合物や本発明の発色助剤又
は、必要によりその他の添加剤と共分散すること
も出来る。
顕色剤として使用する有機塩基性化合物は支持
体への塗布時に塗液の溶媒として使用する水又は
有機溶剤に可溶であれば塗液のPHが上昇し地肌の
カブリ、貯蔵保存性の悪化の原因になるので塗層
中で不連続な微粒子状分散物として存在するのが
望ましく、又、水に対する20℃での溶解度が1.0
g/以下のものであれば耐湿熱貯蔵安定性もよ
く、脂肪族アミンやピロリジン誘導体、イミダゾ
ール誘導体、イミダゾリン誘導体、ピペリジン誘
導体等の複素環化合物も好適に使用しうるが、特
に下記一般式()及び()の疎水性グアニジ
ン誘導体を顕色剤として使用した場合には、高温
高湿下の貯蔵保存性にすぐれ、しかも高感度に発
色する定着型感熱記録体を得ることが出来る。
又、顕色剤は融点100〜170℃の範囲のものが特に
好適に使用しうる。
顕色剤はボールミル、サンドグラインダー、ア
トライター等の分散手段で単独に分散してもよい
が、カプラー化合物、本発明の発色助剤又は、そ
の他必要により添加剤等と共分散してもよい。
一般式()
一般式()
〔式中R1,R2,R3,R4およびR5は水素、炭素
数18以下のアルキル、環状アルキル、アリール、
アラルキル、アミノ、アルキルアミノ、アシルア
ミノ、カルバモイルアミノ、複素環残基を表し、
R6は低級アルキレン、フエニレン、ナフチレン、
または[Formula] (in the formula, X represents lower alkylene, SO 2 , S 2 , S, O, -NH- or a single bond), and the aryl group in the formula is lower alkyl, alkoxy, nitro, acylamino, alkylamino Also included are those having substituents selected from groups and halogens. ) As the diazonium salt used in the present invention, any compound used in conventionally known diazo type copying materials can be used. For example, compounds represented by the following general formulas (), (), () can be used. It can be used particularly preferably. In the formula, R 7 and R 8 are alkyl having 1 to 5 carbon atoms,
or alkoxyl, oxyalkyl, benzyl, substituted benzyl, benzoyl, substituted benzoyl, phenyl group, hydrogen atom, etc., and Y and Z
represents a halogen atom, alkyl having 1 to 5 carbon atoms, carboxyl, alkoxyl having 1 to 5 carbon atoms, nitro, acetoxy group, etc., and m and n represent 0 or a positive integer of 4 or less. Also, X is Cl - , Br - ,
It represents anions such as SO 4 - , NO 3 - , PF 6 - , ClO 4 - , BF 4 -, etc., as well as ions added to these anions, such as ZnCl 2 , CaCl 2 , or SnCl 4 . Specific examples include 4-N,N-dimethylaminobenzenediazonium chloride, 3-chloro-4-
N,N-dimethylaminobenzenediazonium chloride, 4-N,N-diethylaminobenzenediazonium chloride, 2,5-diethoxy-4-
N,N-diethylaminobenzenediazonium chloride, 4-N-ethyl-N-hydroxyethylaminobenzenediazonium chloride, 4-N,
Examples include N-diethoxyaminobenzenediazonium chloride, 4-phenylaminobenzenediazonium chloride, and 4-N-(P-methoxyphenyl)-aminobenzenediazonium chloride. In the formula, R 9 is −CH 2 CH 2 OCH 2 CH 2 − or −
CH 2 OCH 2 CH 2 −, −CH 2 CH 2 CH 2 CH 2 −, etc. X, Y, Z, m and n have the same meanings as in the general formula (). Specific compound examples include 4-morpholinobenzenediazonium chloride, 2,5-diethoxy-4-morpholinobenzenediazonium chloride, 4-oxazolidinobenzenediazonium chloride, and 3-methyl-4-piperidinobenzene. Examples include diazonium chloride. In the formula, R 10 represents an alkyl group or an aryl group.
Further, X, Y, Z, m and n have the same meanings as in the general formula (). Specific compound examples include 4-ethylmercapto-2,5-diethoxybenzenediazonium chloride, 4-tolylmercapto-2,5-diethoxybenzenediazonium chloride, and 4-benzylmercapto-2,5-dimethoxybenzenediazonium chloride. and so on. These diazonium salts can be dissolved in water or an organic solvent, or dispersed in the form of fine particles in a suitable solvent, and coated onto a support preferably in a range of 0.1 to 1.0 g/m 2 . In addition, an acid compound can be used in the photosensitive and heat-sensitive layer to stabilize the diazonium salt and prevent precoupling, but this is possible by using any organic or inorganic acid compound used in conventionally known diazo type copying materials. Specific examples include tartaric acid,
Citric acid, boric acid, lactic acid, gluconic acid, phosphoric acid,
Trichloroacetic acid, dichloroacetic acid, cyanoacetic acid, oxalic acid, malonic acid, maleic acid, etc. are all preferably used. These acid compounds are preferably used in a weight ratio of 5.0 to 100%, more preferably 10 to 50%, based on the organic basic compound. Further, as the coupler compound which reacts with the diazonium salt to form an azo dye, any compound capable of coupling with the above-mentioned diazonium salt can be used. Examples of these coupler compounds include phenol derivatives, oxynaphthalene derivatives, compounds containing active methylene groups, heterocyclic compounds, and specific examples of these compounds include the following compounds. Phenol derivatives Pyrocatechol resorcin Phloroglycine Pyrogallol Meta-aminophenol Para-aminophenol Diethylaminophenol N-Lauryl-para-aminophenol N-Acyl-meta-aminophenol 3,3',5-Trihydroxydiphenyl 3,3',5,5'- Tetrahydroxydiphenyl α-resorcinic acid β-resorcinic acid γ-resorcinic acid Phloroglucinic acid Gallic acid Oxynaphthalene derivative 2,3-dihydroxynaphthalene β-naphthol α-naphthol 1,6-dihydroxynaphthalene 2,3-dihydroxy Naphthalene-6-sulfonic acid 2-naphthol-3,6-disulfonic acid 1,8-dihydroxynaphthalene-8-sulfonic acid 2-hydroxy-3-naphthoic acid-N-β-hydroxyethyl-amide 2-hydroxy-3- Naphthoic acid-N,N-bis-β-hydroxyethylamide 5-(paranitro)-benzamide-1-naphthol 1-naphthol-3-(N-β-hydroxyethyl)-sulfone-amide 2-hydroxy-3-propyl Morpholinonaphthoic acid 2-hydroxy-3-naphthoic acid-0-toluidide 2-hydroxy-3-naphthoic acid morpholinopropylamide 2-hydroxy-3-naphthoic acid-4'-chloroanilide 2-hydroxy-3-naphthoic acid-5'-chloro-2',4'-di-methoxyanilide 2-hydroxy-3-naphthoic acid-2',5'-dimethoxyanilide 2-hydroxy-3-naphthoic acid-2'-ethoxyanilide 2-hydroxy-3- Naphthoic acid-2'-methoxyanilide 2-hydroxy-3-naphthoic acid-phenyl ester 2-hydroxy-3-naphthoic acid-4'-phenoxyanilide 2-hydroxy-3-naphthoic acid-4'-benzyloxy Anilide 2-hydroxy-3-naphthoic acid-4'-phenethyloxyanilide 2-hydroxy-3-naphthoic acid-2'-benzyloxyanilide Compound containing an active methylene group 1-phenyl-3-methyl-pyrazone ( 5) Acetoacetyl acid anilide 1-phenyl-3-carboxypyrazolone acetacetyl cyclohexylamide acetyl amide benzylamide cyanoacetanilide cyanoacetomorpholin 4-carboxy-acetoacetanilide heterocyclic compound 1-(3) '-sulfoamide)-phenyl-3-methyl-pyrazolone-5 1-(4'-carboxyethyl phenyl)-3-
Dodecyl-pyrazolone-5 These coupler compounds are dissolved in water or an organic solvent, or incorporated into the light and heat sensitive layer as a fine particle dispersion with a particle size of 10 μm or less using a dispersion means such as a ball mill or a sand grinder attritor. I can do it. Further, two or more coupler compounds may be combined, if necessary, to produce a combination of dyes exhibiting desired spectral absorption characteristics. Further, during dispersion, the coupler compound may be dispersed alone, but it may also be co-dispersed with an organic basic compound, the color development aid of the present invention, or other additives if necessary. If the organic basic compound used as a color developer is soluble in the water or organic solvent used as a solvent for the coating solution when applied to the support, the pH of the coating solution will increase, causing fogging on the background and deterioration of storage stability. Therefore, it is desirable to exist as a discontinuous fine particle dispersion in the coating layer, and the solubility in water at 20°C is 1.0.
g/ or less, the humidity and heat storage stability is good, and heterocyclic compounds such as aliphatic amines, pyrrolidine derivatives, imidazole derivatives, imidazoline derivatives, piperidine derivatives, etc. can also be suitably used, but in particular, the following general formula () When the hydrophobic guanidine derivatives () and () are used as a color developer, it is possible to obtain a fixed heat-sensitive recording material which has excellent storage stability under high temperature and high humidity conditions and which develops color with high sensitivity.
Further, as the color developer, one having a melting point in the range of 100 to 170°C can be particularly preferably used. The color developer may be dispersed alone using a dispersion means such as a ball mill, a sand grinder, an attritor, or the like, but it may also be co-dispersed with a coupler compound, the color development aid of the present invention, or other additives as necessary. General formula () General formula () [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen, alkyl having 18 or less carbon atoms, cyclic alkyl, aryl,
Represents aralkyl, amino, alkylamino, acylamino, carbamoylamino, heterocyclic residue,
R 6 is lower alkylene, phenylene, naphthylene,
or
【式】(式中Xは低
級アルキレン、SO2,S2,S,O,−NH−また
は一重結合を表す)を表し、式中のアリール基は
低級アルキル、アルコキシ、ニトロ、アシルアミ
ノ、アルキルアミノ基およびハロゲンより選ばれ
る置換基を有するものも含まれる〕
その代表的な具体例を表−2に示すが、これら
に限定されるものではない。表中[Formula] (in the formula, X represents lower alkylene, SO 2 , S 2 , S, O, -NH- or a single bond), and the aryl group in the formula is lower alkyl, alkoxy, nitro, acylamino, alkylamino It also includes those having substituents selected from groups and halogens.] Typical examples are shown in Table 2, but the invention is not limited thereto. In the table
【式】 はシクロヘキシル基を表わす。 [Formula] represents a cyclohexyl group.
【式】【formula】
【式】【formula】
【式】【formula】
上記で示したこれらグアニジンの誘導体は公知
の方法ないしはそれに類似の方法で容易に合成す
ることができる。
又、本発明の感光感熱層を形成する為のバイン
ダー材料としては、水系溶媒では例えば、コーン
スターチ、アラビアゴム、にかわ、ゼラチン、カ
ゼイン、メチルセルロース、エチルセルロース、
ヒドロキシエチルセルロース、カルボキシメチル
セルロース、ポリアクリルアミド、カルボキシメ
チルデンプン、ジアルデヒドデンプン等のデンプ
ン又はその変性物及び誘導体、ポリビニルアルコ
ールもしくはその変性物及び誘導体、ポリビニル
ピロリドン、イソブチレン−無水マレイン酸共重
合物、ポリアクリル酸塩、スチレン−無水マレイ
ン酸共重合物、ポリ塩化ビニル、ポリ塩化ビニリ
デン、ポリスチレン、スチレンブタジエンゴム
(=SBR)、メタクリレートブタジエンゴム(=
MBR)、ニトリルブタジエンゴム(=NBR)ポ
リメチルメタクリレート、ポリプロピレン、ポリ
アクリロニトリル、アクリル酸エステル等の合成
樹脂エマルジヨン等が挙げられ、これらのバイン
ダー材料は単独で、もしくは混合して使用でき
る。又、有機溶媒系では上記の合成樹脂をエマル
ジヨン化せずに有機溶媒に溶解して使用すること
が出来る。
ジアゾニウム塩のカツプリング反応は水等の極
性な溶媒の下で促進されるので、ジアゾニウム塩
を用いる定着型感熱記録体の特に高温高湿下での
貯蔵保存性は低い平衡水分率を有するバインダー
材料を選択することによつても大きく改善され、
又、水系溶媒を用いた場合はホルマリン、グリオ
キザール、クロム明ばん、グルタールアルデヒ
ド、メラミン/ホルマリン樹脂、尿素/ホルマリ
ン樹脂など通常水溶性高分子バインダー材に使用
される耐水化剤を用いることによつても貯蔵保存
性を向上させることが出来る。
又、本発明の感光感熱層中に用いられる顔料の
具体例としては、カオリン、焼成カオリン、タル
ク、ろう石、ケイソウ土、スチレン樹脂粒子、炭
酸カルシウム、水酸化アルミニウム、水酸化マグ
ネシウム、炭酸マグネシウム、酸化チタン、炭酸
バリウム、尿素−ホルマリンフイラー、セルロー
スフイラー、酸化アルミニウム等が挙げられる
が、カス、ステイツキング等の熱ヘツドマツチン
グ性の観点からは特開53−118059、54−25845、
54−118846、54−118847公報記載の如き吸油度が
JIS K 5101に定める測定法において80ml〜500
ml/100gの吸油性顔料を使用するのが望ましく、
特に熱ヘツドと直接接触する層においては、焼成
カオリン、尿素−ホルマリンフイラー等で上記の
吸油量を示す吸油性顔料を使用するのが望まし
い。
その他の補助成分としては、発色抑制や発色補
助の為に塩化亜鉛、硫酸亜鉛、クエン酸ソーダ、
チオウレア硫酸グアニジン、グルコン酸カルシウ
ムや、ソルビトール、サツカローズなどの糖類な
どが用いられ、必要により紫外線防止剤を添加し
たり、又、ステイツキング改良や発色感度向上の
目的でワツクス類や金属石ケン類を使用すること
が出来る。
ワツクス類としては、具体的には、パラフイン
ワツクス、カルナウバワツクス、マイクロクリス
タリンワツクス、ポリエチレンワツクスの他、高
級脂肪酸アミド例えばステアリン酸アミド、ラウ
リルアミド、ミリスチルアミド、硬化牛脂酸アミ
ド、パルミチン酸アミド、オレイン酸アミド、ア
セトアミド、ヤシ脂肪酸アミド、又はこれらの脂
肪酸アミドのメチロール化物、メチレンビスステ
アロアミド、エチレンビスステアロアミド又高級
脂肪酸エステル等が挙げられる。
金属石鹸としては高級脂肪酸多価金属塩、即ち
ステアリン酸亜鉛、ステアリン酸アルミニウム、
ステアリン酸カルシウム、オレイン酸亜鉛等が挙
げられる。
これらは単独で分散して使用することも出来る
が、有機塩基性化合物、カプラー化合物等や、本
発明の発色助剤と共分散して使用することも出来
る。
支持体としては、紙の他に合成樹脂フイルム、
ラミネート紙等も使用出来、又、紙を支持体とし
て使用する場合、感光感熱層を支持体上に直接塗
布するとジアゾニウム塩が紙基体の空隙に浸透し
て内部まで含浸される為に多量のジアゾニウム塩
を必要とする為、感熱印字後露光による光定着の
感度が低下する場合があり、この欠点を防止する
為、必要によつては紙基体に予じめシリカゾル、
アルミナ、酸化チタン、カオリン等の空隙充てん
剤、或いはこれらとでんぷん、カゼイン、ポリビ
ニルアルコール、ポリ酢酸ビニルエマルジヨン等
の高分子材料との組み合せでプレコートし次いで
感光感熱層を塗布してもよい。
(E) 実施例
次に実施例と比較例により、本発明を更に詳細
に説明する。
実施例 1
下記の配合で感光感熱層の塗液を調製し、支持
体上に乾燥後の塗布量が9.0g/m2になるように
塗布し乾燥して定着型感熱記録体を作成する。
単位は重量部である。
水 200
クエン酸 3.0
2,5−ジエトキシ−4−モルホリノベンゼン
ジアゾニウム・テトラフルオロボレート 2
焼成カオリン 10
A 液 5
B 液 100
10%ポリビニルアルコール 200
尚、A液、B液は次の如き配合をボールミルに
て48時間粉砕分散して調製した。
A 液
2−ヒドロキシ−3−ナフトエ酸−2′−エトキ
シアニリド 10g
エチレングリコールビス(P−ベンジルオキシ
カルボニルフエニル)エーテル 10g
10%ポリビニルアルコール 5g
水 15g
B 液 These guanidine derivatives shown above can be easily synthesized by known methods or methods similar thereto. In addition, examples of binder materials for forming the photosensitive and thermosensitive layer of the present invention include cornstarch, gum arabic, glue, gelatin, casein, methylcellulose, ethylcellulose, and aqueous solvents.
Starch or its modified products and derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylamide, carboxymethyl starch, dialdehyde starch, polyvinyl alcohol or its modified products and derivatives, polyvinylpyrrolidone, isobutylene-maleic anhydride copolymer, polyacrylic acid Salt, styrene-maleic anhydride copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-butadiene rubber (=SBR), methacrylate-butadiene rubber (=
MBR), nitrile butadiene rubber (=NBR), polymethyl methacrylate, polypropylene, polyacrylonitrile, synthetic resin emulsion such as acrylic ester, etc., and these binder materials can be used alone or in combination. Furthermore, in the case of an organic solvent system, the above-mentioned synthetic resin can be used by dissolving it in an organic solvent without emulsifying it. Since the coupling reaction of diazonium salts is promoted in polar solvents such as water, the storage stability of fixed heat-sensitive recording materials using diazonium salts, especially under high temperature and high humidity conditions, is limited by the use of binder materials with a low equilibrium moisture content. It can also be greatly improved by selecting
In addition, when using an aqueous solvent, water-resistant agents such as formalin, glyoxal, chromium alum, glutaraldehyde, melamine/formalin resin, urea/formalin resin, etc., which are usually used in water-soluble polymer binders, may be used. However, it is possible to improve the storage stability. Specific examples of pigments used in the photosensitive and heat-sensitive layer of the present invention include kaolin, calcined kaolin, talc, waxite, diatomaceous earth, styrene resin particles, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, Examples include titanium oxide, barium carbonate, urea-formalin filler, cellulose filler, aluminum oxide, etc., but from the viewpoint of thermal head matching properties such as scum and statesking, JP-A No. 53-118059, 54-25845,
The oil absorption as described in 54-118846, 54-118847 is
80ml to 500 according to the measurement method specified in JIS K 5101
It is preferable to use oil-absorbing pigments of ml/100g.
Particularly in the layer that is in direct contact with the heat head, it is desirable to use an oil-absorbing pigment exhibiting the above-mentioned oil absorption amount, such as calcined kaolin or urea-formalin filler. Other auxiliary ingredients include zinc chloride, zinc sulfate, sodium citrate, etc. to suppress or assist color development.
Saccharides such as guanidine thiourea sulfate, calcium gluconate, sorbitol, and sugar rose are used, and if necessary, UV inhibitors are added, and waxes and metal soaps are added to improve staining and color sensitivity. It can be used. Specific examples of waxes include paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax, and higher fatty acid amides such as stearic acid amide, laurylamide, myristylamide, hardened tallow acid amide, and palmitin. Examples include acid amide, oleic acid amide, acetamide, coconut fatty acid amide, methylolated products of these fatty acid amides, methylene bis stearamide, ethylene bis stearamide, and higher fatty acid esters. Metal soaps include higher fatty acid polyvalent metal salts, namely zinc stearate, aluminum stearate,
Examples include calcium stearate and zinc oleate. These can be used alone as dispersed, but they can also be used as co-dispersed with organic basic compounds, coupler compounds, etc., and the color development aid of the present invention. In addition to paper, synthetic resin film,
Laminated paper can also be used, and when paper is used as a support, if the photosensitive and heat-sensitive layer is applied directly onto the support, the diazonium salt will penetrate into the pores of the paper base and be impregnated into the inside, so a large amount of diazonium will be absorbed. Since salt is required, the sensitivity of light fixing due to exposure after thermal printing may be reduced. To prevent this drawback, if necessary, silica sol,
It may be precoated with a void filler such as alumina, titanium oxide, kaolin, etc., or a combination of these and a polymeric material such as starch, casein, polyvinyl alcohol, polyvinyl acetate emulsion, etc., and then a photosensitive/thermosensitive layer may be applied. (E) Examples Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1 A coating solution for a photosensitive and thermosensitive layer is prepared according to the following formulation, and coated onto a support so that the coated amount after drying is 9.0 g/m 2 and dried to prepare a fixable thermosensitive recording material. The unit is parts by weight. Water 200 Citric acid 3.0 2,5-diethoxy-4-morpholinobenzenediazonium tetrafluoroborate 2 Calcined kaolin 10 Solution A 5 Solution B 100 10% polyvinyl alcohol 200 For solutions A and B, mix the following compositions in a ball mill. The mixture was prepared by pulverization and dispersion for 48 hours. Solution A 2-hydroxy-3-naphthoic acid-2'-ethoxyanilide 10g Ethylene glycol bis(P-benzyloxycarbonylphenyl) ether 10g 10% polyvinyl alcohol 5g Water 15g Solution B
【式】 100g
(表−2の化合物(10))
10%メチルセルロース 50g
水 150g
実施例 2
実施例1においてA液でエチレングリコールビ
ス(P−ベンジルオキシカルボニルフエニル)エ
ーテルを用いる代りにジエチレングリコールビス
(P−ベンジルオキシカルボニルフエニル)エー
テルを用いる以外は実施例1と同様にして定着型
感熱記録体を作成した。
実施例 3
実施例1においてA液で2−ヒドロキシ−3−
ナフトエ酸−2′−エトキシアニリドを用いる代り
に2−ヒドロキシナフトエ酸−4′−フエノキシア
ニリドを用いる以外は実施例1と同様にして定着
型感熱記録体を作成した。
比較例 1
実施例1においてA液で本発明のエチレングリ
コールビス(P−ベンジルオキシカルボニルフエ
ニル)エーテルを除く以外は実施例1と同様にし
て定着型感熱記録体を作成した。
このようにして得られた定着型感熱記録体をフ
アクシミリ(東芝KB−4800)を使用して感熱印
字させた後全面紫外線露光にてジアゾニウム塩を
分解し定着させた。
前記の如くして得られた印字濃度をマクベス濃
度計(RD−514)にて測定した。その値を表−
3に示す。又、表−3には貯蔵保存性テストの結
果も同時に示す。
貯蔵保存性テストは塗布液を調製後塗布乾燥し
て形成したサンプルを40℃、相対湿度90%の暗所
にて24時間放置した場合の耐湿熱テストの結果を
表し、テスト後全面露光して定着し、マクベス濃
度計にて測定した地肌濃度を表−3に示す。[Formula] 100g (Compound (10) in Table 2) 10% methylcellulose 50g Water 150g Example 2 In Example 1, instead of using ethylene glycol bis(P-benzyloxycarbonylphenyl) ether in solution A, diethylene glycol bis( A fixable heat-sensitive recording material was prepared in the same manner as in Example 1 except that P-benzyloxycarbonylphenyl) ether was used. Example 3 In Example 1, 2-hydroxy-3-
A fixable heat-sensitive recording material was prepared in the same manner as in Example 1 except that 2-hydroxynaphthoic acid-4'-phenoxyanilide was used instead of naphthoic acid-2'-ethoxyanilide. Comparative Example 1 A fixable heat-sensitive recording material was prepared in the same manner as in Example 1 except that the ethylene glycol bis(P-benzyloxycarbonylphenyl) ether of the present invention was removed from Liquid A in Example 1. The thus obtained fixable heat-sensitive recording material was thermally printed using a facsimile machine (Toshiba KB-4800), and then the diazonium salt was decomposed and fixed by exposing the entire surface to ultraviolet light. The print density obtained as described above was measured using a Macbeth densitometer (RD-514). Table the value -
Shown in 3. Table 3 also shows the results of the storage stability test. The storage stability test represents the results of a humidity and heat resistance test when a sample formed by preparing a coating solution, applying it and drying it was left in a dark place at 40℃ and 90% relative humidity for 24 hours. After fixation, the skin density measured with a Macbeth densitometer is shown in Table 3.
【表】
実施例 4
ジアゾニウム塩を含有する層を次の配合で調整
し、支持体上に乾燥後の塗布量が2.0g/m2にな
るように塗布する。
クエン酸 2g
チオウレア 2g
2,5−ジエトキシ−4−モルホリノベンゼン
ジアゾニウム・テトラフルオロボレート 2g
焼成カオリン 4g
10%ポリビニルアルコール 30g
水 100ml
上記にて作成した層上に次の配合で調製した顕
色剤を含有する層の塗液を、乾燥後の塗布量が
8.0g/m2になるように塗布して定着型感熱記録
体を作成する。
水 100g
焼成カオリン 20g
A液 5g
B液 100g
10%ポリビニルアルコール 120g
50%メラミンホルマリン系耐水化剤 2g
尚、A液、B液、は実施例1と同じ配合をボー
ルミルにて48時間粉砕分散して調製した。
実施例 5
実施例4において、A液、B液の配合が実施例
2と同じ以外は実施例4と同様にして定着型感熱
記録体を作成した。
実施例 6
実施例4において、A液、B液の配合が実施例
3と同じ以外は実施例4と同様にして定着型感熱
記録体を作成した。
比較例 2
実施例4において、A液、B液の配合が比較例
1と同じ以外は実施例4と同様にして定着型感熱
記録体を作成した。
このようにして得られたジアゾ定着型感熱記録
体をフアクシミリ(東芝KD−4800)を使用して
感熱印字させた後全面紫外線露光にてジアゾニウ
ム塩を分解し定着させた。
前記の如くして得られた印字濃度をマクベス濃
度計(RD−514)にて測定し、その値を表−4
に示す。
又、表−4には貯蔵保存性テストの結果も同時
に示す。
貯蔵保存性テストは塗布液を調製後塗布乾燥し
て形成したサンプルを40℃、相対湿度90%の暗所
にて24時間放置する耐湿熱テストとサンプルを60
℃の乾燥器に24時間放置する耐熱テストの結果を
表し、それぞれ処理後全面露光して定着し、マク
ベス濃度計にて測定した地肌濃度を表−4に示
す。[Table] Example 4 A layer containing a diazonium salt is prepared according to the following formulation and coated on a support so that the coating weight after drying is 2.0 g/m 2 . Citric acid 2g Thiourea 2g 2,5-diethoxy-4-morpholinobenzenediazonium tetrafluoroborate 2g Calcined kaolin 4g 10% polyvinyl alcohol 30g Water 100ml Contains a color developer prepared with the following formulation on the layer created above. The coating amount of the coating layer after drying is
A fixing type heat-sensitive recording material is prepared by applying it at a concentration of 8.0 g/m 2 . Water 100g Calcined kaolin 20g Part A 5g Part B 100g 10% polyvinyl alcohol 120g 50% melamine formalin waterproofing agent 2g For parts A and B, the same formulation as in Example 1 was ground and dispersed in a ball mill for 48 hours. Prepared. Example 5 A fixable heat-sensitive recording material was prepared in the same manner as in Example 4, except that the formulations of liquid A and liquid B were the same as in Example 2. Example 6 A fixable heat-sensitive recording material was prepared in the same manner as in Example 4, except that the formulations of liquid A and liquid B were the same as in Example 3. Comparative Example 2 A fixable heat-sensitive recording material was prepared in the same manner as in Example 4, except that the formulations of liquid A and liquid B were the same as in comparative example 1. The thus obtained diazo-fixed heat-sensitive recording material was thermally printed using a facsimile (Toshiba KD-4800), and then the entire surface was exposed to ultraviolet light to decompose and fix the diazonium salt. The print density obtained as described above was measured using a Macbeth densitometer (RD-514), and the values are shown in Table 4.
Shown below. Table 4 also shows the results of the storage stability test. The storage stability test consists of a moisture and heat resistance test in which the sample is prepared by preparing the coating solution, applied and dried, and left in a dark place at 40℃ and 90% relative humidity for 24 hours.
Table 4 shows the results of a heat resistance test in which the samples were left in a dryer at ℃ for 24 hours. After each treatment, the entire surface was exposed to light and fixed, and the background density was measured using a Macbeth densitometer.
【表】
(F) 発明の効果
表−3、表−4に示す如く、本発明の一般式
()で表わされる化合物を定着型感熱記録体に
添加することにより、高濃度に発色し、しかも貯
蔵保存性にすぐれた定着型感熱記録体を得ること
ができた。[Table] (F) Effects of the Invention As shown in Tables 3 and 4, by adding the compound represented by the general formula () of the present invention to a fixing type heat-sensitive recording material, color can be developed with high density, and It was possible to obtain a fixable heat-sensitive recording material with excellent storage stability.
Claims (1)
剤、及び顕色剤として熱により溶融して塩基性雰
囲気を示す有機塩基性化合物の微粒子状分散物を
同一の層又は2層以上の別の層より成る感光感熱
層として、支持体上に設けた定着型感熱記録体に
おいて、該発色助剤が下記一般式()で示され
る化合物であることを特徴とする定着型感熱記録
体。 一般式() (式中Rはアルキル基、アラルキル基を、nは
1〜3の整数を表わす)。 2 ジアゾニウム塩又はカプラー化合物の少くと
もいずれか一方が不連続状の微粒子状分散物とし
て感光感熱層中に含有される特許請求の範囲第1
項記載の定着型感熱記録体。 3 有機塩基性化合物が下記一般式()又は
()で表わされる疎水性グアニジン誘導体であ
る特許請求の範囲第2項記載の定着型感熱記録
体。 一般式() 一般式() (式中R1,R2,R3,R4およびR5は水素、炭素
数18以下のアルキル、環状アルキル、アリール、
アラルキル、アミノ、アルキルアミノ、アシルア
ミノ、カルバモイルアミノ、複素環残基を表し、
R6は低級アルキレン、フエニレン、ナフチレン
または【式】(式中Xは低 級アルキレン、SO2,S2,S,O,−NH−また
は一重結合を表す)を表し、式中のアリール基は
低級アルキル、アルコキシ、ニトロ、アシルアミ
ノ、アルキルアミノ基およびハロゲンより選ばれ
る置換基を有するものも含まれる。)。[Scope of Claims] 1. A fine particle dispersion of a diazonium salt, a coupler compound, a coloring aid, and an organic basic compound that melts with heat and exhibits a basic atmosphere as a color developer in the same layer or in two or more layers. A fixing heat-sensitive recording material provided on a support as a photosensitive heat-sensitive layer consisting of a separate layer, wherein the coloring aid is a compound represented by the following general formula (). General formula () (In the formula, R represents an alkyl group or an aralkyl group, and n represents an integer of 1 to 3). 2. Claim 1, in which at least one of the diazonium salt and the coupler compound is contained in the light and heat sensitive layer as a discontinuous fine particle dispersion.
The fixing type heat-sensitive recording material described in Section 1. 3. The fixable heat-sensitive recording material according to claim 2, wherein the organic basic compound is a hydrophobic guanidine derivative represented by the following general formula () or (). General formula () General formula () (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen, alkyl having 18 or less carbon atoms, cyclic alkyl, aryl,
Represents aralkyl, amino, alkylamino, acylamino, carbamoylamino, heterocyclic residue,
R 6 represents lower alkylene, phenylene, naphthylene, or [Formula] (wherein X represents lower alkylene, SO 2 , S 2 , S, O, -NH-, or a single bond), and the aryl group in the formula is lower Also included are those having substituents selected from alkyl, alkoxy, nitro, acylamino, alkylamino groups and halogen. ).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59134488A JPS6112390A (en) | 1984-06-29 | 1984-06-29 | Fixable-type thermal recording material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59134488A JPS6112390A (en) | 1984-06-29 | 1984-06-29 | Fixable-type thermal recording material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6112390A JPS6112390A (en) | 1986-01-20 |
JPH043756B2 true JPH043756B2 (en) | 1992-01-24 |
Family
ID=15129496
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59134488A Granted JPS6112390A (en) | 1984-06-29 | 1984-06-29 | Fixable-type thermal recording material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6112390A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0199876A (en) * | 1987-10-13 | 1989-04-18 | Fuji Photo Film Co Ltd | Recording material |
-
1984
- 1984-06-29 JP JP59134488A patent/JPS6112390A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS6112390A (en) | 1986-01-20 |
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