JPH02281992A - Recording material - Google Patents
Recording materialInfo
- Publication number
- JPH02281992A JPH02281992A JP1104831A JP10483189A JPH02281992A JP H02281992 A JPH02281992 A JP H02281992A JP 1104831 A JP1104831 A JP 1104831A JP 10483189 A JP10483189 A JP 10483189A JP H02281992 A JPH02281992 A JP H02281992A
- Authority
- JP
- Japan
- Prior art keywords
- salicylic acid
- group
- acid
- recording material
- coloring agent
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000003872 salicylic acid derivatives Chemical class 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 4
- 239000003086 colorant Substances 0.000 claims description 39
- 239000000981 basic dye Substances 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 238000001454 recorded image Methods 0.000 abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 239000011777 magnesium Substances 0.000 abstract description 5
- 239000011135 tin Substances 0.000 abstract description 5
- 229910052718 tin Inorganic materials 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 238000005562 fading Methods 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract 1
- 150000002431 hydrogen Chemical group 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- -1 Ct~ Chemical group 0.000 description 121
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 120
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 60
- 229960004889 salicylic acid Drugs 0.000 description 60
- 239000007788 liquid Substances 0.000 description 22
- 239000000123 paper Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 239000000975 dye Substances 0.000 description 18
- 150000003751 zinc Chemical class 0.000 description 16
- 238000000034 method Methods 0.000 description 10
- 239000002775 capsule Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-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
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 2
- XQXPVVBIMDBYFF-UHFFFAOYSA-M 4-hydroxyphenylacetate Chemical compound OC1=CC=C(CC([O-])=O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-M 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 241000978776 Senegalia senegal Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000004110 Zinc silicate Substances 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 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
- 159000000007 calcium salts Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- SFIHQZFZMWZOJV-HZJYTTRNSA-N linoleamide Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(N)=O SFIHQZFZMWZOJV-HZJYTTRNSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 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
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 235000019352 zinc silicate Nutrition 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- NJNFUPWMCKHLRE-KHPPLWFESA-N (z)-n-methyloctadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NC NJNFUPWMCKHLRE-KHPPLWFESA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BDCNTSHIADXFPV-UHFFFAOYSA-N 1-chloro-4-(2-phenoxyethoxy)benzene Chemical compound C1=CC(Cl)=CC=C1OCCOC1=CC=CC=C1 BDCNTSHIADXFPV-UHFFFAOYSA-N 0.000 description 1
- IYQIAVRZWFMVGZ-UHFFFAOYSA-N 1-methoxy-4-(2-phenoxyethoxy)benzene Chemical compound C1=CC(OC)=CC=C1OCCOC1=CC=CC=C1 IYQIAVRZWFMVGZ-UHFFFAOYSA-N 0.000 description 1
- JWSWULLEVAMIJK-UHFFFAOYSA-N 1-phenylmethoxynaphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1=CC=CC=C1 JWSWULLEVAMIJK-UHFFFAOYSA-N 0.000 description 1
- PKKDWPSOOQBWFB-UHFFFAOYSA-N 2,4-dichloro-6-[(3,5-dichloro-2-hydroxyphenyl)methyl]phenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1CC1=CC(Cl)=CC(Cl)=C1O PKKDWPSOOQBWFB-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ZHBYCCVSWKWSMR-UHFFFAOYSA-N 2-hydroperoxybenzoic acid Chemical class OOC1=CC=CC=C1C(O)=O ZHBYCCVSWKWSMR-UHFFFAOYSA-N 0.000 description 1
- WSERGOXVVNJSIQ-UHFFFAOYSA-N 2-hydroxy-3,4-bis(1-phenylethyl)benzoic acid Chemical compound C=1C=C(C(O)=O)C(O)=C(C(C)C=2C=CC=CC=2)C=1C(C)C1=CC=CC=C1 WSERGOXVVNJSIQ-UHFFFAOYSA-N 0.000 description 1
- UXDLAKCKZCACAX-UHFFFAOYSA-N 2-hydroxy-3,5-bis(1-phenylethyl)benzoic acid Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(O)=O)=CC=1C(C)C1=CC=CC=C1 UXDLAKCKZCACAX-UHFFFAOYSA-N 0.000 description 1
- ZJWUEJOPKFYFQD-UHFFFAOYSA-N 2-hydroxy-3-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1O ZJWUEJOPKFYFQD-UHFFFAOYSA-N 0.000 description 1
- XGAYQDWZIPRBPF-UHFFFAOYSA-N 2-hydroxy-3-propan-2-ylbenzoic acid Chemical compound CC(C)C1=CC=CC(C(O)=O)=C1O XGAYQDWZIPRBPF-UHFFFAOYSA-N 0.000 description 1
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- ABJAMKKUHBSXDS-UHFFFAOYSA-N 3,3-bis(6-amino-1,4-dimethylcyclohexa-2,4-dien-1-yl)-2-benzofuran-1-one Chemical compound C1=CC(C)=CC(N)C1(C)C1(C2(C)C(C=C(C)C=C2)N)C2=CC=CC=C2C(=O)O1 ABJAMKKUHBSXDS-UHFFFAOYSA-N 0.000 description 1
- YEAOXMNFCSRKBV-UHFFFAOYSA-N 3,3-bis(ethenyl)-2-benzofuran-1-one Chemical compound C1=CC=C2C(C=C)(C=C)OC(=O)C2=C1 YEAOXMNFCSRKBV-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
- GNZQDEXHTZDQRB-UHFFFAOYSA-N 3-[4-(diethylamino)-2-methylphenyl]-6-(dimethylamino)-3-[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound CC1=CC(N(CC)CC)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 GNZQDEXHTZDQRB-UHFFFAOYSA-N 0.000 description 1
- ZKUWHPNJONEJEE-UHFFFAOYSA-N 3-[4-(dimethylamino)phenyl]-3-(2-methyl-1h-indol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C3=CC=CC=C3NC=2C)C2=CC=CC=C2C(=O)O1 ZKUWHPNJONEJEE-UHFFFAOYSA-N 0.000 description 1
- QRHLHCSHBDVRNB-UHFFFAOYSA-N 3-cyclohexyl-2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(C2CCCCC2)=C1O QRHLHCSHBDVRNB-UHFFFAOYSA-N 0.000 description 1
- BOTKTAZUSYVSFF-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)benzene-1,2-diol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(O)=C1 BOTKTAZUSYVSFF-UHFFFAOYSA-N 0.000 description 1
- ZTILAOCGFRDHBH-UHFFFAOYSA-N 4-(4-propan-2-yloxyphenyl)sulfonylphenol Chemical compound C1=CC(OC(C)C)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 ZTILAOCGFRDHBH-UHFFFAOYSA-N 0.000 description 1
- JSUKRBMPOXGCPR-UHFFFAOYSA-N 4-(benzenesulfonyl)phenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1 JSUKRBMPOXGCPR-UHFFFAOYSA-N 0.000 description 1
- YBOBZZSJMAWFBX-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]-phenylmethoxymethyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)OCC1=CC=CC=C1 YBOBZZSJMAWFBX-UHFFFAOYSA-N 0.000 description 1
- APRBPQIUZUZMPT-UHFFFAOYSA-N 4-benzylnaphthalene-2-carboxylic acid Chemical compound C(C1=CC=CC=C1)C1=CC(=CC2=CC=CC=C12)C(=O)O APRBPQIUZUZMPT-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- PMVVWYMWJBCMMI-UHFFFAOYSA-N 4-phenoxybutoxybenzene Chemical compound C=1C=CC=CC=1OCCCCOC1=CC=CC=C1 PMVVWYMWJBCMMI-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RNRINRUTVAFUCG-UHFFFAOYSA-N 5-(dimethylamino)-3,3-bis(1,2-dimethylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC=C2C(C3(C=4C5=CC=CC=C5N(C)C=4C)OC(=O)C4=CC=C(C=C43)N(C)C)=C(C)N(C)C2=C1 RNRINRUTVAFUCG-UHFFFAOYSA-N 0.000 description 1
- RFKNBSDIQLCADD-UHFFFAOYSA-N 5-benzyl-2-hydroxy-3-methylbenzoic acid Chemical compound OC(=O)C1=C(O)C(C)=CC(CC=2C=CC=CC=2)=C1 RFKNBSDIQLCADD-UHFFFAOYSA-N 0.000 description 1
- XAICWTLLSRXZPB-UHFFFAOYSA-N 5-tert-butyl-2-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC=C(O)C(C(O)=O)=C1 XAICWTLLSRXZPB-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-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
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 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
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- ZVSKZLHKADLHSD-UHFFFAOYSA-N benzanilide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- BPLKDVGMXNZCQO-UHFFFAOYSA-N benzyl 4-phenylmethoxybenzoate Chemical compound C=1C=C(OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 BPLKDVGMXNZCQO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- TUTWLYPCGCUWQI-UHFFFAOYSA-N decanamide Chemical compound CCCCCCCCCC(N)=O TUTWLYPCGCUWQI-UHFFFAOYSA-N 0.000 description 1
- IWGFEQWCMAADJZ-UHFFFAOYSA-N dibenzyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 IWGFEQWCMAADJZ-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001019 fluorene dye Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 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
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 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 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- HFRLHSQAZLWVEE-HZJYTTRNSA-N linoleylanilide Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)NC1=CC=CC=C1 HFRLHSQAZLWVEE-HZJYTTRNSA-N 0.000 description 1
- 230000007774 longterm Effects 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
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GKFFBAQBFJBIDR-UHFFFAOYSA-N methyl 2,2-bis(4-hydroxyphenyl)acetate Chemical compound C=1C=C(O)C=CC=1C(C(=O)OC)C1=CC=C(O)C=C1 GKFFBAQBFJBIDR-UHFFFAOYSA-N 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- ZMGJTLKSBVFOGP-KTKRTIGZSA-N n-[(z)-octadec-9-enyl]benzamide Chemical compound CCCCCCCC\C=C/CCCCCCCCNC(=O)C1=CC=CC=C1 ZMGJTLKSBVFOGP-KTKRTIGZSA-N 0.000 description 1
- NTHVNXBUGUHNAH-UHFFFAOYSA-N n-butyldodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCCC NTHVNXBUGUHNAH-UHFFFAOYSA-N 0.000 description 1
- VXUAXBGDCYWTME-UHFFFAOYSA-N n-ethyldecanamide Chemical compound CCCCCCCCCC(=O)NCC VXUAXBGDCYWTME-UHFFFAOYSA-N 0.000 description 1
- HNUFCQUTJXHEPI-UHFFFAOYSA-N n-methyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC HNUFCQUTJXHEPI-UHFFFAOYSA-N 0.000 description 1
- NOSILEXHUBACKG-UHFFFAOYSA-N n-octadecylacetamide Chemical compound CCCCCCCCCCCCCCCCCCNC(C)=O NOSILEXHUBACKG-UHFFFAOYSA-N 0.000 description 1
- CTGZVGQKTWDALN-UHFFFAOYSA-N n-octadecylcyclohexanamine Chemical compound CCCCCCCCCCCCCCCCCCNC1CCCCC1 CTGZVGQKTWDALN-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-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
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- WMIWKXQBBHIBDO-UHFFFAOYSA-N phenyl 1-hydroxy-2h-naphthalene-1-carboxylate Chemical compound C1C=CC2=CC=CC=C2C1(O)C(=O)OC1=CC=CC=C1 WMIWKXQBBHIBDO-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、記録材料に関し、特に発色性、生保存性及び
記録像の保存性に優れた記録材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a recording material, and particularly to a recording material that is excellent in color development, shelf life, and preservation of recorded images.
「従来の技術」
無色ないしは淡色の塩基性染料と打機ないしは無機呈色
剤との呈色反応を利用した記録材料は、感圧記録体、感
熱記録体、通電感熱記録体等をその典型例として、種々
のものが知られている。``Prior art'' Typical examples of recording materials that utilize a color reaction between a colorless or light-colored basic dye and a printing press or an inorganic coloring agent include pressure-sensitive recording materials, heat-sensitive recording materials, and electrically conductive heat-sensitive recording materials. Various types are known.
これらの記録材料には、記録濃度および記録感度が充分
であること、熱、湿度、光、薬品等の外部環境下におけ
る記録像の保存性に優れていること等の性能が要求され
ているが、現在これらを完全に満足するものは得られて
いない。These recording materials are required to have performances such as sufficient recording density and recording sensitivity, and excellent preservation of recorded images in external environments such as heat, humidity, light, and chemicals. However, at present, nothing that completely satisfies these requirements has been obtained.
−例として感熱記録体は、最近の感熱記録方式の著しい
進歩と相俟ってその利用分野や形態も多様化しており、
感熱ファクシミリや感熱プリンター用の記録媒体として
のみならずＰ ＯＳ （Ｐｏｉｎｔｏｆ ５ａｌｅｓ）
ラベルなどの新規な用途への使用も急増している。-For example, thermal recording media has been diversified in its application fields and forms, along with recent remarkable advances in thermal recording methods.
It can be used not only as a recording medium for thermal facsimiles and thermal printers, but also as a POS (Point of 5ales).
Its use in new applications such as labels is also rapidly increasing.
しかし、感熱記録体は一般に、溶剤等の影響でカブリ牽
牛じたり、記録像が変褪色を起こしてしまう等の欠点を
有している。特に、プラスチックフィルムと接触すると
記録像が著しく褪色したり、或いはジアゾ複写紙、とり
わけ複写直後のジアゾ複写紙と接触した状態で保存して
おくと、カブリ現象を極めて起こしやすい等の欠陥を有
しており、その改良が強く要請されているのが現状であ
る。However, heat-sensitive recording materials generally have drawbacks such as fogging and discoloration of recorded images due to the influence of solvents and the like. In particular, if it comes into contact with plastic film, the recorded image will fade significantly, or if it is stored in contact with diazo copy paper, especially diazo copy paper immediately after copying, it may have defects such as fogging which is extremely likely to occur. Currently, there is a strong need for improvement.
「発明が解決しようとする課題」
かかる現状に鑑み本発明者等は、塩基性染料と呈色剤と
の呈色反応を利用した記録材料において認められる上記
の如き欠陥の改良を目的として、特に呈色剤の分野を幅
広く検討した。その結果、呈色剤として下記一般式〔Ｉ
〕で表されるサリチル酸誘導体又はその多価金属塩の少
なくとも一種を使用すると、発色性や生保存性はもとよ
り記録像の保存性にも極めて優れた記録材料が得られる
ことを見出し、本発明を完成するに至った。``Problems to be Solved by the Invention'' In view of the current situation, the present inventors have particularly aimed at improving the above-mentioned defects found in recording materials that utilize the coloring reaction between basic dyes and coloring agents. The field of coloring agents was extensively studied. As a result, the following general formula [I
] It has been discovered that by using at least one salicylic acid derivative or its polyvalent metal salt represented by the following formula, a recording material which is extremely excellent not only in color development and shelf life but also in the preservation of recorded images has been developed, and the present invention has been accomplished based on this discovery. It was completed.
「課題を解決するための手段」
本発明は、無色ないしは淡色の塩基性染料と、該塩基性
染料と接触して呈色し得る呈色剤との反応を利用した記
録材料において、呈色剤として下記一般式ＣＩ）で表さ
れるサリチル酸誘導体又はその多価金属塩の少な（とも
一種を用いたことを特徴とする記録材料である。``Means for Solving the Problems'' The present invention provides a recording material that utilizes the reaction between a colorless or light-colored basic dye and a coloring agent that can change color upon contact with the basic dye. This is a recording material characterized by using at least one kind of salicylic acid derivative or its polyvalent metal salt represented by the following general formula CI).
〔式中、Ａｒは置換基を有してもよいフェニル基、置換
基を有してもよいナフチル基、又は置換基を有してもよ
い複素芳香環基を示し、Ｒはエーテル結合、エステル結
合又はアミド結合を有してもよいアルキレン基、エーテ
ル結合、エステル結合又はアミド結合を有してもよいシ
クロアルキレン基、又はエーテル結合、エステル結合又
はアミド結合を有してもよいアラルキレン基を示す。ま
た、Ｘは水素原子、アルキル基、シクロアルキル基、ア
ルケニル基、アラルキル基、アリール基、アルコキシル
基、アリールオキシ基、ニトロ基、又はハロゲン原子を
示し、ｍは１〜３の整数を示す。〕「作用」
本発明で用いられるサリチル酸誘導体は、公知の方法で
合成することができ、例えば対応するヒドロキシサリチ
ル酸誘導体をアルキル化する方法、或いは対応するフェ
ノール誘導体をカルボキシル化する方法などによって得
ることができる。[In the formula, Ar represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a heteroaromatic ring group which may have a substituent, and R represents an ether bond, an ester Indicates an alkylene group that may have a bond or an amide bond, a cycloalkylene group that may have an ether bond, an ester bond, or an amide bond, or an aralkylene group that may have an ether bond, an ester bond, or an amide bond. . Further, X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, an aryloxy group, a nitro group, or a halogen atom, and m represents an integer of 1 to 3. [Function] The salicylic acid derivative used in the present invention can be synthesized by a known method, for example, by alkylating a corresponding hydroxysalicylic acid derivative, or by carboxylating a corresponding phenol derivative. can.
上記一般式〔Ｉ〕で表されるサリチル酸誘導体において
、Ａｒは置換基を有してもよいフェニル基、置換基を有
してもよいナフチル基、又は置換基を有してもよい複素
芳香環基を示すが、これらのうちでも下記一般式（ｎ）
で表されるフェニルルケニル基、アリール基、アラルキ
ル基、アルコキシル基、アルキルチオ基、アリールオキ
シ基、アラルキルオキシ基、アルコキシカルボニル基、
アルキルカルボニル基、アルキルカルボニルオキシ基、
ニトロ基、ヒドロキシル基、又はハロゲン原子を示し、
ｎは０又は１〜５の整数を示す、〕
上記一般式（ｎ）で表されるフェニル基又はナフチル基
のうちでも、未置換のフェニル基又はナフチル基、およ
び、Ｃ８〜、のアルキル基、Ｃ７〜。In the salicylic acid derivative represented by the above general formula [I], Ar is a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a heteroaromatic ring which may have a substituent. Among these, the following general formula (n)
phenylrukenyl group, aryl group, aralkyl group, alkoxyl group, alkylthio group, aryloxy group, aralkyloxy group, alkoxycarbonyl group,
Alkylcarbonyl group, alkylcarbonyloxy group,
Represents a nitro group, hydroxyl group, or halogen atom,
n represents 0 or an integer of 1 to 5; Among the phenyl groups or naphthyl groups represented by the above general formula (n), unsubstituted phenyl groups or naphthyl groups, and C8~ alkyl groups, C7~.
のアルコキシル基、フェニル基、フェノキシ基、塩素原
子、臭素原子、又は弗素原子で置換されたフェニル基又
はナフチル基がより好ましい。More preferred are alkoxyl groups, phenyl groups, phenoxy groups, phenyl groups or naphthyl groups substituted with chlorine atoms, bromine atoms, or fluorine atoms.
また、一般式〔Ｉ〕で表されるサリチル酸誘導体におい
て、Ｒはエーテル結合、エステル結合又はアミド結合を
有してもよいアルキレン基、エーテル結合、エステル結
合又はアミド結合を有してもよいシクロアルキレン基、
又はエーテル結合、エステル結合又はアミド結合を有し
てもよいアラルキレン基を示すが、特にエーテル結合を
有してもよい０１〜１！のアルキレン基が好ましい。Furthermore, in the salicylic acid derivative represented by the general formula [I], R is an alkylene group which may have an ether bond, an ester bond or an amide bond, or a cycloalkylene group which may have an ether bond, an ester bond or an amide bond. basis,
Alternatively, 01 to 1! represents an aralkylene group which may have an ether bond, an ester bond, or an amide bond, and which may particularly have an ether bond! An alkylene group is preferred.
さらに、一般式（１）において、Ｘは水素原子、アルキ
ル基、シクロアルキル基、アルケニル基、アラルキル基
、アリール基、アルコキシル基、アリールオキシ基、ニ
トロ基、又はハロゲン原子を示すが、これらのうちでも
水素原子、Ｃ５〜２ｏのアルキル基、Ｃｓ〜７のシクロ
アルキル基、Ｃｔ〜、のアルケニル基、０１〜１０のア
ラルキル基、Ｃ，−ｔ、のアルコキシル基、フェニル基
、ナフチル基、フェノキシ基、ニトロ基、又はハロゲン
原子が好ましく、特に水素原子、Ｃ８〜、のアルキル基
、Ｃ？−Ｉｌｌのアラルキル基、Ｃ１〜６アルコキシル
基、フェニル基、フェノキシ基、塩素原子、臭素原子、
又は弗素原子がより好ましい。Furthermore, in general formula (1), X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, an aryloxy group, a nitro group, or a halogen atom; But hydrogen atom, C5~2o alkyl group, Cs~7 cycloalkyl group, Ct~, alkenyl group, 01~10 aralkyl group, C, -t, alkoxyl group, phenyl group, naphthyl group, phenoxy group , a nitro group, or a halogen atom, particularly a hydrogen atom, a C8~ alkyl group, a C? -Ill aralkyl group, C1-6 alkoxyl group, phenyl group, phenoxy group, chlorine atom, bromine atom,
Or a fluorine atom is more preferable.
一般式〔Ｉ〕で表されるサリチル酸誘導体と塩を形成す
る多価金属としては、２価、３価又は４価の金属が好ま
しく、特に亜鉛、カルシウム、アルミニウム、マグネシ
ウム、スズ、鉄がより好ましい。As the polyvalent metal that forms a salt with the salicylic acid derivative represented by the general formula [I], divalent, trivalent or tetravalent metals are preferred, and zinc, calcium, aluminum, magnesium, tin, and iron are particularly preferred. .
本発明に係るサリチル酸誘導体又はその多価金属塩を使
用した記録材料は、発色濃度が充分でしかも発色した画
像は極めて安定であり、長時間日光に曝されたり、高温
あるいは高湿度環境下に保存されても記録像が殆ど変褪
色を起こさないため、記録の長期保存という観点ですこ
ぶる有利である。The recording material using the salicylic acid derivative or its polyvalent metal salt according to the present invention has sufficient color density and the color image is extremely stable, so it cannot be exposed to sunlight for a long time or stored in a high temperature or high humidity environment. This is extremely advantageous in terms of long-term preservation of records, as the recorded images will hardly change color even if the image is exposed.
特に感熱記録体に適用した場合には、溶剤等により白紙
部が発色したり、記録像が油脂類や薬品等により変褪色
するといった欠点が解消され、呈色剤として極めて優れ
た特性を発揮するものである。In particular, when applied to heat-sensitive recording media, it eliminates the disadvantages of white paper areas becoming colored due to solvents, etc., and recorded images discoloring and fading due to oils, fats, chemicals, etc., and exhibits extremely excellent properties as a coloring agent. It is something.
かかる一般式〔Ｉ〕で表されるサリチル酸誘導体の具体
例としては例えば下記が挙げられる。Specific examples of the salicylic acid derivative represented by the general formula [I] include the following.
４−フェニルチオメトキシサリチル酸、５−フェニルチ
オメトキシサリチル酸、４−（２−フェニルチオエトキ
シ）サリチル酸、５−（２−フェニルチオエトキシ）サ
リチル酸、４−（３−フェニルチオプロピルオキシ）サ
リチル酸、５− （３−フェニルチオプロピルオキシ）
サリチル酸、４−（４−フェニルチオブチルオキシ）サ
リチル酸、５−（４−フェニルチオブチルオキシ）サリ
チルＬ４−（５−フェニルチオペンチルオキシ）サリチ
ルＬ５−（５−フェニルチオペンチルオキシ）サリチル
酸、４−（６−フェニルチオへキシルオキシ）サリチル
酸、５−（６−フェニルチオへキシルオキシ）サリチル
酸、４−（８−フェニルチオオクチルオキシ）サリチル
酸、５− （８−フェニルチオオクチルオキシ）サリチ
ル酸、４−（１０−フェニルチオデシルオキシ）サリチ
ル酸、５−（１０−フェニルチオデシルオキシ）サリチ
ル酸、４−（１２−フェニルチオドデシルオキシ）サリ
チル酸、５−（１２−フェニルチオドデシルオキシ）サ
リチル酸、４−（１８−フェニルチオオクタデシルオキ
シ）サリチル酸、５−（１８−フェニルチオオクタデシ
ルオキシ）サリチル酸、４−（Ｉ−メチル−１−フェニ
ルチオメトキシ）サリチル酸、５−（１−メチル−１−
フェニルチオメトキシ）サリチル酸、４−（１，１−ジ
メチル−１−フェニルチオメトキシ）サリチル酸、５−
（１，１−ジメチル−１−フェニルチオメトキシ）サリ
チル酸、４−（５−フェニルチオ−３−オキサ−ペンチ
ルオキシ）サリチル酸、５−（５−フェニルチオ−３−
オキサ−ペンチルオキシ）サリチル酸、４−（７−フェ
ニルチオ−３，５−ジオキサ−へブチルオキシ）サリチ
ル酸、５−（７−フェニルチオ−３，５−ジオキサ−へ
ブチルオキシ）サリチル酸、４−（８−フェニルチオ−
３，６−シオキサーオクチルオキシ）サリチル酸、５−
（８−フェニルチオ−３，６−シオキサーオクチルオキ
シ）サリチル酸、４−（３−フェニルチオ−２−シクロ
ヘキシルプロピルオキシ）サリチルＬ５−（３−フェニ
ルチオ−２−シクロへキシルプロピルオキシ）サリチル
酸、４− （３−フェニルチオ−２−フェニルプロピル
オキシ）サリチル酸、５−（３−フェニルチオ−２−フ
ェニルプロピルオキシ）サリチル酸、４−（２−ｏ−メ
チルフェニルチオエトキシ）サリチル酸、５−（２−ｏ
−メチルフェニルチオエトキシ）サリチル酸、４−（２
−ｍ−メチルフェニルチオエトキシ）サリチル酸、５−
（２−ｍ−メチルフェニルチオエトキシ）サリチル酸、
４−（２−ｐ−メチルフェニルチオエトキシ）サリチル
酸、５−（２−ｐ−メチルフェニルチオエトキシ）サリ
チル酸、４−（３−ｐ−メチルフェニルチオプロピルオ
キシ）サリチル酸、５−（３−ｐ−メチルフェニルチオ
プロピルオキシ）サリチル酸、４−（４−ｐ−メチルフ
ェニルチオブチルオキシ）サリチル酸、５− （４−ｐ
−メチルフェニルチオブチルオキシ）サリチル酸、４−
（２−ｐ−エチルフェニルチオエトキシ）サリチル酸、
５−（２−ｐ−エチルフェニルチオエトキシ）サリチル
酸、４−（２−ｐ−プロピルフェニルチオエトキシ）サ
リチル酸、５− （２−ｐ−プロピルフェニルチオエト
キシ）サリチル酸、４−（２−ｐ−ヘキシルフェニルチ
オエトキシ）サリチル酸、５− （２−ｐ−ヘキシルフ
ェニルチオエトキシ）サリチル酸、４−（２−０−クロ
ルフェニルチオエトキシ）サリチル酸、５（２−ｏ−ク
ロルフェニルチオエトキシ）サリチル酸、４− （２−
ｍ−クロルフェニルチオエトキシ）サリチル酸、５−（
２−ｍ−クロルフェニルチオエトキシ）サリチル酸、４
−（２−ｐ−クロルフェニルチオエトキシ）サリチル酸
、５−（２−ｐ−クロルフェニルチオエトキシ）サリチ
ル酸、４−（３−ｐ−クロルフェニルチオプロピルオキ
シ）サリチル酸、５− （３−ｐ−クロルフェニルチオ
プロピルオキシ）サリチル酸、４−（４−ｐ−クロルフ
ェニルチオブチルオキシ）サリチルＭ、５−（４−ｐ−
クロルフェニルチオブチルオキシ）サリチル酸、４−（
５−ｐ−クロルフェニルチオペンチルオキシ）サリチル
酸、５−（５−Ｐ−クロルフェニルチオペンチルオキシ
）サリチルＬ４−（６−ｐ−クロルフェニルチオへキシ
ルオキシ）サリチル酸、５−（６−ｐ−クロルフェニル
チオへキシルオキシ）サリチル酸、４−（８−ｐ−クロ
ルフェニルチオオクチルオキシ）サリチル酸、５−（８
−ｐ−クロルフェニルチオオクチルオキシ）サリチル酸
、４−（５−ｐ−クロルフェニルチオ−３−オキサ−ペ
ンチルオキシ）サリチル酸、５−（５−ｐ−クロルフェ
ニルチオ−３−オキサ−ペンチルオキシ）サリチル酸、
４−（７−ｐ−クロルフェニルチオ−３，５−ジオキサ
−へブチルオキシ）サリチル酸、５−（７−Ｐ−クロル
フェニルチオ−３，５−ジオキサ−へブチルオキシ）サ
リチル酸、４−（８−ｐ−クロルフェニルチオ−３，６
−シオキサーオクチルオキシ）サリチル酸、５−（８−
ｐ−クロルフェニルチオ−３，６−シオキサーオクチル
オキシ）サリチルＬ４−（２−ｐ−ブロモフェニルチオ
エトキシ）サリチル酸、５−（２−ｐ−ブロモフェニル
チオエトキシ）サリチル酸、４−（２−ｐ−フルオロフ
ェニルチオエトキシ）サリチル酸、５−（２−ｐ−フル
オロフェニルチオエトキシ）サリチル酸、４−（２−ｐ
−メトキシフェニルチオエトキシ）サリチル酸、５−（
２−ｐ−メトキシフェニルチオエトキシ）サリチル酸、
４−（３−ｐ−メトキシフェニルチオプロピルオキシ）
サリチル酸、５−（３−ｐ−メトキシフェニルチオプロ
ピルオキシ）サリチル酸、４−（４−ｐ−メトキシフェ
ニルチオブチルオキシ）サリチル酸、５−（４−ｐ−メ
トキシフェニルチオブチルオキシ）サリチル酸、４−
（２−ｐ−エトキシフェニルチオエトキシ）サリチル酸
、５−（２−ｐ−エトキシフェニルチオエトキシ）サリ
チル酸、４−（２−ｐ−プロピルオキシフェニルチオエ
トキシ）サリチルＬ５−（２−ｐ−プロピルオキシフェ
ニルチオエトキシ）サリチル酸、４−（２−ｐ−ヘキシ
ルオキシフェニルチオエトキシ）サリチル酸、５−（２
−ｐ−ヘキシルオキシフェニルチオエトキシ）サリチル
酸、４−（２−ｏ−ビフェニルチオエトキシ）サリチル
酸、５− （２−ｏ−ビフェニルチオエトキシ）サリチ
ル酸、４−（２−ｐ−ビフェニルチオエトキシ）サリチ
ル酸、５−（２−ｐ−ビフェニルチオエトキシ）サリチ
ル酸、４−（２−ｐ−ベンジルフェニルチオエトキシ）
サリチル酸、５−（２−ｐ−ベンジルフェニルチオエト
キシ）サリチル酸、４−（２−ｐ−フェノキシフェニル
チオエトキシ）サリチル酸、５−（２−ｐ−フェノキシ
フェニルチオエトキシ）サリチルｓ、４− （２−ｐ−
ヒドロキシフェニルチオエトキシ）サリチル酸、５−（
２−ｐ−ヒドロキシフェニルチオエトキシ）サリチル酸
、４− （２−ｐ−二トロフェニルチオエトキシ）サリ
チル酸、５−（２−ｐ−二トロフェニルチオエトキシ）
サリチル酸、４−（２−ｐ−ベンジルオキシフェニルチ
オエトキシ）サリチル酸、５−（２−ｐ−ベンジルオキ
シフェニルチオエトキシ）サリチル酸、４− ［２−（
３，５−ジメチルフェニルチオ）エトキシ］サリチル酸
、５− （２−（３，５−ジメチルフェニルチオ）エト
キシ〕サリチル酸、４−（２−（３，４，５−）ジメチ
ルフェニルチオ）エトキシ〕サリチル酸、５− （２−
（３，４，５−トリメチルフェニルチオ）エトキシ〕サ
リチル酸、４−（２−ｐ−シクロヘキシルフェニルチオ
エトキシ）サリチル酸、５−（２−ｐ−シクロヘキシル
フェニルチオエトキシ）サリチル酸、４−（２−ｐ−ア
リルフェニルチオエトキシ）サリチル酸、５−（２−ｐ
−アリルフェニルチオエトキシ）サリチル酸、４− （
２−（４−クロル−３−メチルフェニルチオ）エトキシ
〕サリチル酸、５− （２−（４−クロル−３−メチル
フェニルチオ）エトキシ〕サリチル酸、４−（２−α−
ナフチ）Ｌｔチオエトキシ）サリチル酸、５−（２−α
−ナフチルチオエトキシ）サリチル酸、４−（２−β−
ナフチルチオエトキシ）サリチル酸、５− （２−β−
ナフチルチオエトキシ）サリチル酸、４−（２−α−ピ
リジニルチオエトキシ）サリチル酸、５−（２−α−ピ
リジニルチオエトキシ）サリチル酸、３−メチル−４−
（２−フェニルチオエトキシ）サリチル酸、３−メチル
−５−（２−フェニルチオエトキシ）サリチル酸、３．
５−ジメチル−４−（２−フェニルチオエトキシ）サリ
チル酸、３−シクロヘキシル−４−（２−フェニルチオ
エトキシ）サリチル酸、３−アリル−４−（２−フェニ
ルチオエトキシ）サリチル酸、３−α。4-phenylthiomethoxysalicylic acid, 5-phenylthiomethoxysalicylic acid, 4-(2-phenylthioethoxy)salicylic acid, 5-(2-phenylthioethoxy)salicylic acid, 4-(3-phenylthiopropyloxy)salicylic acid, 5- (3-phenylthiopropyloxy)
Salicylic acid, 4-(4-phenylthiobutyloxy) salicylic acid, 5-(4-phenylthiobutyloxy) salicylic L4-(5-phenylthiopentyloxy) salicylic L5-(5-phenylthiopentyloxy) salicylic acid, 4- (6-phenylthiohexyloxy) salicylic acid, 5-(6-phenylthiohexyloxy) salicylic acid, 4-(8-phenylthiooctyloxy) salicylic acid, 5-(8-phenylthiooctyloxy) salicylic acid, 4-(10-phenyl Thiodecyloxy) salicylic acid, 5-(10-phenylthiodecyloxy) salicylic acid, 4-(12-phenylthiododecyloxy) salicylic acid, 5-(12-phenylthiododecyloxy) salicylic acid, 4-(18-phenylthiooctadecyl) oxy)salicylic acid, 5-(18-phenylthiooctadecyloxy)salicylic acid, 4-(I-methyl-1-phenylthiomethoxy)salicylic acid, 5-(1-methyl-1-
phenylthiomethoxy) salicylic acid, 4-(1,1-dimethyl-1-phenylthiomethoxy) salicylic acid, 5-
(1,1-dimethyl-1-phenylthiomethoxy)salicylic acid, 4-(5-phenylthio-3-oxapentyloxy)salicylic acid, 5-(5-phenylthio-3-
Oxapentyloxy) salicylic acid, 4-(7-phenylthio-3,5-dioxa-hebutyloxy) salicylic acid, 5-(7-phenylthio-3,5-dioxa-hebutyloxy) salicylic acid, 4-(8-phenylthio-
3,6-thioxaoctyloxy)salicylic acid, 5-
(8-phenylthio-3,6-thioxaoctyloxy) salicylic acid, 4-(3-phenylthio-2-cyclohexylpropyloxy) salicylic L5-(3-phenylthio-2-cyclohexylpropyloxy) salicylic acid, 4- ( 3-phenylthio-2-phenylpropyloxy) salicylic acid, 5-(3-phenylthio-2-phenylpropyloxy) salicylic acid, 4-(2-o-methylphenylthioethoxy) salicylic acid, 5-(2-o
-methylphenylthioethoxy)salicylic acid, 4-(2
-m-methylphenylthioethoxy)salicylic acid, 5-
(2-m-methylphenylthioethoxy) salicylic acid,
4-(2-p-methylphenylthioethoxy) salicylic acid, 5-(2-p-methylphenylthioethoxy) salicylic acid, 4-(3-p-methylphenylthiopropyloxy) salicylic acid, 5-(3-p- methylphenylthiopropyloxy) salicylic acid, 4-(4-p-methylphenylthiobutyloxy) salicylic acid, 5- (4-p
-methylphenylthiobutyloxy)salicylic acid, 4-
(2-p-ethylphenylthioethoxy) salicylic acid,
5-(2-p-ethylphenylthioethoxy) salicylic acid, 4-(2-p-propylphenylthioethoxy) salicylic acid, 5-(2-p-propylphenylthioethoxy) salicylic acid, 4-(2-p-hexyl phenylthioethoxy) salicylic acid, 5-(2-p-hexylphenylthioethoxy) salicylic acid, 4-(2-0-chlorophenylthioethoxy) salicylic acid, 5(2-o-chlorophenylthioethoxy) salicylic acid, 4-( 2-
m-Chlorphenylthioethoxy) salicylic acid, 5-(
2-m-chlorophenylthioethoxy)salicylic acid, 4
-(2-p-chlorophenylthioethoxy)salicylic acid, 5-(2-p-chlorophenylthioethoxy)salicylic acid, 4-(3-p-chlorophenylthiopropyloxy)salicylic acid, 5-(3-p-chloro phenylthiopropyloxy) salicylic acid, 4-(4-p-chlorophenylthiobutyloxy) salicylic M, 5-(4-p-
Chlorphenylthiobutyloxy) salicylic acid, 4-(
5-p-Chlorphenylthiopentyloxy) salicylic acid, 5-(5-P-chlorophenylthiopentyloxy) salicylic L4-(6-p-chlorophenylthiohexyloxy) salicylic acid, 5-(6-p-chlorophenyl Thiohexyloxy) salicylic acid, 4-(8-p-chlorophenylthiooctyloxy) salicylic acid, 5-(8
-p-Chlorphenylthiooctyloxy)salicylic acid, 4-(5-p-chlorophenylthio-3-oxa-pentyloxy)salicylic acid, 5-(5-p-chlorophenylthio-3-oxa-pentyloxy)salicylic acid ,
4-(7-p-Chlorphenylthio-3,5-dioxa-hebutyloxy)salicylic acid, 5-(7-P-chlorophenylthio-3,5-dioxa-hebutyloxy)salicylic acid, 4-(8-p -chlorphenylthio-3,6
-Shioxaroctyloxy)salicylic acid, 5-(8-
p-Chlorphenylthio-3,6-thioxaoctyloxy) salicylic L4-(2-p-bromophenylthioethoxy) salicylic acid, 5-(2-p-bromophenylthioethoxy) salicylic acid, 4-(2-p -fluorophenylthioethoxy) salicylic acid, 5-(2-p-fluorophenylthioethoxy) salicylic acid, 4-(2-p
-methoxyphenylthioethoxy)salicylic acid, 5-(
2-p-methoxyphenylthioethoxy) salicylic acid,
4-(3-p-methoxyphenylthiopropyloxy)
Salicylic acid, 5-(3-p-methoxyphenylthiopropyloxy) salicylic acid, 4-(4-p-methoxyphenylthiobutyloxy) salicylic acid, 5-(4-p-methoxyphenylthiobutyloxy) salicylic acid, 4-
(2-p-ethoxyphenylthioethoxy) salicylic acid, 5-(2-p-ethoxyphenylthioethoxy) salicylic acid, 4-(2-p-propyloxyphenylthioethoxy) salicylic L5-(2-p-propyloxyphenyl thioethoxy) salicylic acid, 4-(2-p-hexyloxyphenylthioethoxy) salicylic acid, 5-(2
-p-hexyloxyphenylthioethoxy) salicylic acid, 4-(2-o-biphenylthioethoxy) salicylic acid, 5-(2-o-biphenylthioethoxy) salicylic acid, 4-(2-p-biphenylthioethoxy) salicylic acid, 5-(2-p-biphenylthioethoxy) salicylic acid, 4-(2-p-benzylphenylthioethoxy)
Salicylic acid, 5-(2-p-benzylphenylthioethoxy) salicylic acid, 4-(2-p-phenoxyphenylthioethoxy) salicylic acid, 5-(2-p-phenoxyphenylthioethoxy) salicylic s, 4- (2- p-
hydroxyphenylthioethoxy) salicylic acid, 5-(
2-p-hydroxyphenylthioethoxy) salicylic acid, 4-(2-p-nitrophenylthioethoxy)salicylic acid, 5-(2-p-nitrophenylthioethoxy)
Salicylic acid, 4-(2-p-benzyloxyphenylthioethoxy) salicylic acid, 5-(2-p-benzyloxyphenylthioethoxy) salicylic acid, 4-[2-(
3,5-dimethylphenylthio)ethoxy]salicylic acid, 5-(2-(3,5-dimethylphenylthio)ethoxy)salicylic acid, 4-(2-(3,4,5-)dimethylphenylthio)ethoxy]salicylic acid , 5- (2-
(3,4,5-trimethylphenylthio)ethoxy]salicylic acid, 4-(2-p-cyclohexylphenylthioethoxy)salicylic acid, 5-(2-p-cyclohexylphenylthioethoxy)salicylic acid, 4-(2-p- Allyl phenylthioethoxy) salicylic acid, 5-(2-p
-allylphenylthioethoxy)salicylic acid, 4- (
2-(4-chloro-3-methylphenylthio)ethoxy]salicylic acid, 5-(2-(4-chloro-3-methylphenylthio)ethoxy)salicylic acid, 4-(2-α-
Naphthi) Ltthioethoxy) salicylic acid, 5-(2-α
-naphthylthioethoxy)salicylic acid, 4-(2-β-
naphthylthioethoxy)salicylic acid, 5-(2-β-
naphthylthioethoxy)salicylic acid, 4-(2-α-pyridinylthioethoxy)salicylic acid, 5-(2-α-pyridinylthioethoxy)salicylic acid, 3-methyl-4-
(2-phenylthioethoxy) salicylic acid, 3-methyl-5-(2-phenylthioethoxy) salicylic acid, 3.
5-dimethyl-4-(2-phenylthioethoxy)salicylic acid, 3-cyclohexyl-4-(2-phenylthioethoxy)salicylic acid, 3-allyl-4-(2-phenylthioethoxy)salicylic acid, 3-α.
α−ジメチルベンジル−４−（２−フェニルチオエトキ
シ）サリチル酸、３−フェニル−４−（２−フェニルチ
オエトキシ）サリチル酸、３−アセチルオキシ−４−（
２−フェニルチオエトキシ）サリチル酸、３−フェノキ
シ−４−（２−フェニルチオエトキシ）サリチル酸、４
−クロル−５−（２−フェニルチオエトキシ）サリチル
酸、５−クロル−４−（２−フェニルチオエトキシ）サ
リチル酸、４−ブロモ−５−（２−フェニルチオエトキ
シ）サリチル酸、５−ブロモ−４−（２−フェニルチオ
エトキシ）サリチル酸、３．５−ジクロル−４−（２−
フェニルチオエトキシ）サリチル酸、３−メトキシ−５
−（２−フェニルチオエトキシ）サリチル酸、５−ニト
ロ−４−（２−フェニルチオエトキシ）サリチル１４−
（２−フェニルチオアセチルオキシエトキシ）サリチル
酸、５−（２−フェニルチオアセチルオキシエトキシ）
サリチル酸、４−（３−フェニルチオアセチルオキシプ
ロピルオキシ）サリチル酸、５−（３−フェニルチオア
セチルオキシプロピルオキシ）サリチル酸、４−（２−
フェニルチオエトキシカルボニルメトキシ）サリチル酸
、５−（２−フェニルチオエトキシカルボニルメトキシ
）サリチル酸、４−（２−Ｎ−フェニルチオカルボニル
アミノエトキシ）サリチル酸、５−（２−Ｎ−フェニル
チオカルボニルアミノエトキシ）サリチル酸、４−（２
−Ｎ−フェニルチオエチルカルバモイルメトキシ）サリ
チル酸、５− （２−Ｎ−フェニルチオエチルカルバモ
イルメトキシ）サリチル酸等。α-Dimethylbenzyl-4-(2-phenylthioethoxy)salicylic acid, 3-phenyl-4-(2-phenylthioethoxy)salicylic acid, 3-acetyloxy-4-(
2-phenylthioethoxy) salicylic acid, 3-phenoxy-4-(2-phenylthioethoxy) salicylic acid, 4
-Chlor-5-(2-phenylthioethoxy)salicylic acid, 5-chloro-4-(2-phenylthioethoxy)salicylic acid, 4-bromo-5-(2-phenylthioethoxy)salicylic acid, 5-bromo-4- (2-phenylthioethoxy)salicylic acid, 3,5-dichloro-4-(2-
phenylthioethoxy) salicylic acid, 3-methoxy-5
-(2-phenylthioethoxy) salicylic acid, 5-nitro-4-(2-phenylthioethoxy) salicylic 14-
(2-phenylthioacetyloxyethoxy) salicylic acid, 5-(2-phenylthioacetyloxyethoxy)
Salicylic acid, 4-(3-phenylthioacetyloxypropyloxy) salicylic acid, 5-(3-phenylthioacetyloxypropyloxy) salicylic acid, 4-(2-
Phenylthioethoxycarbonylmethoxy) salicylic acid, 5-(2-phenylthioethoxycarbonylmethoxy) salicylic acid, 4-(2-N-phenylthiocarbonylaminoethoxy) salicylic acid, 5-(2-N-phenylthiocarbonylaminoethoxy) salicylic acid , 4-(2
-N-phenylthioethylcarbamoylmethoxy)salicylic acid, 5-(2-N-phenylthioethylcarbamoylmethoxy)salicylic acid, and the like.
これらのサリチル酸誘導体及び／又はその多価金属塩は
必要に応じて二種類以上の化合物を併用することもでき
る。Two or more kinds of these salicylic acid derivatives and/or their polyvalent metal salts can be used in combination, if necessary.
本発明において、サリチル酸誘導体及び／又はその多価
金属塩の使用量については特に限定するものではないが
、一般に塩基性染料１００重量部に対して５０〜７００
重量部、好ましくは１００〜５００重量部の範囲で調節
される。In the present invention, the amount of the salicylic acid derivative and/or its polyvalent metal salt used is not particularly limited, but is generally 50 to 700 parts by weight per 100 parts by weight of the basic dye.
It is adjusted in parts by weight, preferably in the range of 100 to 500 parts by weight.
本発明では、呈色剤として一般式〔Ｉ〕で表されるサリ
チル酸誘導体及び／又はその多価金属塩を用いることで
、発色性や生保存性、特に記録像の保存性に優れた記録
材料を得ているものであるが、さらに金属化合物を併用
することでこれらの特性を一層向上させることができる
。In the present invention, by using a salicylic acid derivative represented by the general formula [I] and/or its polyvalent metal salt as a coloring agent, the recording material has excellent color development properties and raw storage stability, especially storage stability of recorded images. However, these characteristics can be further improved by using a metal compound in combination.
かかる金属化合物としては、２価、３価、又は４価の金
属、例えば亜鉛、マグネシウム、バリウム、カルシウム
、アルミニウム、スズ、チタン、ニッケル、コバルト、
マンガン、鉄等から選ばれる金属の酸化物、水酸化物、
硫化物、ハロゲン化物、炭酸塩、リン酸塩、ケイ酸塩、
硫酸塩、硝酸塩又はハロゲン錯塩等が例示できるが、こ
れらのうちでも特に亜鉛化合物が好ましい。Such metal compounds include divalent, trivalent, or tetravalent metals such as zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt,
Metal oxides and hydroxides selected from manganese, iron, etc.
sulfides, halides, carbonates, phosphates, silicates,
Examples include sulfates, nitrates, and halogen complex salts, and among these, zinc compounds are particularly preferred.
金属化合物の具体例としては、例えば酸化亜鉛、水酸化
亜鉛、アルミン酸亜鉛、硫化亜鉛、炭酸亜鉛、リン酸亜
鉛、ケイ酸亜鉛、酸化アルミニウム、酸化マグネシウム
、酸化チタン、水酸化アルミニウム、ケイ酸アルミニウ
ム、アルミノケイ酸アルミニウム、リン酸アルミニウム
、アルミン酸マグネシウム、水酸化マグネシウム、炭酸
マグネシウム、リン酸マグネシウム等が挙げられる。勿
論、これら金属化合物は二種以上を併用することもでき
る。Specific examples of metal compounds include zinc oxide, zinc hydroxide, zinc aluminate, zinc sulfide, zinc carbonate, zinc phosphate, zinc silicate, aluminum oxide, magnesium oxide, titanium oxide, aluminum hydroxide, and aluminum silicate. , aluminum aluminosilicate, aluminum phosphate, magnesium aluminate, magnesium hydroxide, magnesium carbonate, magnesium phosphate, and the like. Of course, two or more of these metal compounds can also be used in combination.
上記金属化合物の使用量については必ずしも限定するも
のではないが、通常一般式（Ｉ）で表されるサリチル酸
誘導体及び／又はその多価金属塩の１００重量部に対し
て１〜５００重量部、好ましくは５〜３００重量部程度
の範囲で調節するのが望ましい。The amount of the metal compound used is not necessarily limited, but is usually 1 to 500 parts by weight, preferably 1 to 500 parts by weight, based on 100 parts by weight of the salicylic acid derivative represented by general formula (I) and/or its polyvalent metal salt. It is desirable to adjust the amount within the range of about 5 to 300 parts by weight.
本発明の記録材料においては、所望の効果を阻害しない
範囲でサリチル酸誘導体、フェノール誘導体、フェノー
ル樹脂、酸性白土等の各種公知の呈色剤を併用すること
ができる。かかる公知の呈色剤の具体例としては、例え
ば下記が例示される。In the recording material of the present invention, various known coloring agents such as salicylic acid derivatives, phenol derivatives, phenol resins, acid clay, etc. can be used in combination within a range that does not impede the desired effect. Specific examples of such known coloring agents include the following.
酸性白土、活性白土、アクパルガイド、ベントナイト、
コロイダルシリカ、珪酸アルミニウム、珪酸マグネシウ
ム、珪酸亜鉛、珪酸スズ、焼成カオリン、タルク等の無
機呈色剤；シュウ酸、マレイン酸、酒石酸、クエン酸、
コハク酸、ステアリン酸等の脂肪族カルボン酸；安息香
酸、４−ｔｅｒｔ−ブチル安息香酸、４−クロル安息香
酸、４−ニトロ安息香酸、フタル酸、没食子酸、サリチ
ル酸、３−イソプロピルサリチル酸、３−フェニルサリ
チル酸、３−シクロへキシルサリチル酸、３，５−シー
ｔｅｒｔ−ブチルサリチル酸、３−メチル−５−ベンジ
ルサリチル酸、３−フェニル−５−（α。Acid clay, activated clay, Akpal guide, bentonite,
Inorganic coloring agents such as colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, talc; oxalic acid, maleic acid, tartaric acid, citric acid,
Aliphatic carboxylic acids such as succinic acid and stearic acid; benzoic acid, 4-tert-butylbenzoic acid, 4-chlorobenzoic acid, 4-nitrobenzoic acid, phthalic acid, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3- Phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5-(α.
α−ジメチルベンジル）サリチル酸、３，５−ジー（α
−メチルベンジル）サリチル酸、２−ヒドロキシ−１−
ベンジル−３−ナフトエ酸等の芳香族カルボン酸、４．
４’−イソプロピリデンジフェノール（ビスフェノール
Ａ）、４．４’−イソプロピリデンビス（２−クロフェ
ノール）、４゜４′−イソプロピリデンビス（２，６−
ジクロロフェノール）、４．４’−イソプロピリデンビ
ス（２，６−ジブロモフェノール）、４．４’−イソプ
ロピリデンビス（２−メチルフェノール）、４．４′−
イソプロピリデンビス（２，６−シメチルフエノール）
、４．４’−イソプロピリデンビス（２−ｔｅｒｔ−ブ
チルフェノール）、４．４’−５ｅｃ−ブチリデンジフ
ェノール、２．２−ビス（４−ヒドロキシフェニル）−
４−メチルペンタン、４．４’ −シクロヘキシリデン
ビスフェノール、４．４’−シクロヘキシリデンビス（
２−メチルフェノール） 、４−ｔｅｒｔ−ブチルフェ
ノール、４−フェニルフェノール、４−ヒドロキシジフ
ェノキシド、α−ナフトール、β−ナフトール、メチル
−４−ヒドロキシベンゾエート、ベンジル−４−ヒドロ
キシベンゾエート、２．２’−チオビス（４，６−ジク
ロロフェノール）、４−ｔｅｒｔ−オクチルカテコール
、２．２’−メチレンビス（４−クロロフェノール）、
２．２’−メチレンビス（４−メチル−６−ｔｅｒｔ−
ブチルフェノール）、２．２′−ジヒドロキシジフェニ
ール、メチル−ビス（４−ヒドロキシフェニル）アセテ
ート、エチル−ビス（４−ヒドロキシフェニル）アセテ
ート、ベンジル−ビス（４−ヒドロキシフェニル）アセ
テート、４．４’ −（Ｐ−）ユニレンジイソプロピリ
デン）ジフェノール、４．４’−（ｍ−フェニレンジイ
ソプロピリデン）ジフェノール、４−ヒドロキシジフェ
ニルスルホン、４．４’ジヒドロキシジフエニルスルホ
ン、４−ヒドロキシー４′−メチル−ジフェニルスルホ
ン、４−ヒドロキシ−４′−イソプロポキシジフェニル
スルホン、４−ヒドロキシ−３′ ４′−テトラメチ
レンジフェニルスルホン、２．２’ −ジアリル−４，
４′−ジヒドロキシジフェニルスルホン等のフェノール
性化合物；ｐ−フェニルフェノール−ホルマリン樹脂、
Ｐ−ブチルフェノール−アセチレン樹脂等のフェノール
樹脂の如き有機呈色剤の一種以上；さらにはこれら有機
呈色剤と例えば亜鉛、マグネシウム、アルミニウム、カ
ルシウム、チタン、マンガン、スズ、ニッケル等の多価
金属との塩：チオシアン酸亜鉛のアンチピリン錯体の如
き金属錯化合物等。α-dimethylbenzyl)salicylic acid, 3,5-di(α
-methylbenzyl)salicylic acid, 2-hydroxy-1-
Aromatic carboxylic acids such as benzyl-3-naphthoic acid, 4.
4'-isopropylidene diphenol (bisphenol A), 4.4'-isopropylidene bis (2-chlorophenol), 4゜4'-isopropylidene bis (2,6-
dichlorophenol), 4.4'-isopropylidene bis(2,6-dibromophenol), 4.4'-isopropylidene bis(2-methylphenol), 4.4'-
Isopropylidene bis(2,6-dimethylphenol)
, 4.4'-isopropylidenebis(2-tert-butylphenol), 4.4'-5ec-butylidenediphenol, 2.2-bis(4-hydroxyphenyl)-
4-methylpentane, 4.4'-cyclohexylidene bisphenol, 4.4'-cyclohexylidene bis(
2-methylphenol), 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-naphthol, β-naphthol, methyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, 2.2'- Thiobis(4,6-dichlorophenol), 4-tert-octylcatechol, 2,2'-methylenebis(4-chlorophenol),
2.2'-methylenebis(4-methyl-6-tert-
butylphenol), 2.2'-dihydroxydiphenyl, methyl-bis(4-hydroxyphenyl) acetate, ethyl-bis(4-hydroxyphenyl) acetate, benzyl-bis(4-hydroxyphenyl) acetate, 4.4'- (P-)unilene diisopropylidene) diphenol, 4.4'-(m-phenylene diisopropylidene) diphenol, 4-hydroxydiphenylsulfone, 4.4'dihydroxydiphenylsulfone, 4-hydroxy-4'-methyl -diphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-3'4'-tetramethylenediphenylsulfone,2,2'-diallyl-4,
Phenolic compounds such as 4'-dihydroxydiphenylsulfone; p-phenylphenol-formalin resin,
One or more organic coloring agents such as phenolic resins such as P-butylphenol-acetylene resin; and furthermore, combinations of these organic coloring agents and polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel. salts: metal complex compounds such as antipyrine complex of zinc thiocyanate, etc.
本発明の記録材料において、上記の如き特定の呈色剤と
組み合わせて使用される無色ないしは淡色の塩基性染料
としては各種のものが公知であり、例えば下記が例示さ
れる。In the recording material of the present invention, various types of colorless or light-colored basic dyes are known to be used in combination with the above-mentioned specific color formers, and the following are exemplified.
３．３−ビス（ｐ−ジメチルアミノフェニル）−６−ジ
メチルアミノフタリド、３，３−ビス（Ｐ−ジメチルア
ミノフェニル）フタリド、３−（４−ジメチルアミノフ
ェニル） −３−（４−ジエチルアミノ−２−メチルフ
ェニル） −６−（ジメチルアミノ）フタリド、３−（
ｐ−ジメチルアミノフェニル’）−３−（１，２−ジメ
チルインドール−３−イル）フタリド、３−（ｐ−ジメ
チルアミノフェニル）−３−（２−メチルインドール−
３−イル）フタリド、３．３−ビス（１，２−ジメチル
インドール−３−イル）−５−ジメチルアミノフタリド
、３，３−ビス（１，２−ジメチルインドール−３−イ
ル）−６−シメチルアミノフタ＋７）’、３．３−ビス
（９−エチルカルバゾール−３−イル）−６−ジメチル
アミノフタリド、３゜３−ビス（２−フェニルインドー
ル−３−イル）−６−ジメチルアミノフタリド、３−ｐ
−ジメチルアミノフェニル−３−（１−メチルピロール
−３−イル）−６−ジメチルアミノフタリド等のトリア
リルメタン系染料、４．４’−ビス−ジメチルアミノベ
ンズヒドリルベンジルエーテル、Ｎ−ハロフェニル−ロ
イコオーラミン、Ｎ−２，４゜５−トリクロロフェニル
ロイコオーラミン等のジフェニルメタン系染料、３，３
−ビス（１，１−ビス（４−ピロリジノフェニル）エチ
レン−２−イル）−４，５，６，７−チトラプロモフタ
リド、３．３−ビス（１−（４−メトキシフェニル）−
１−（４−ジメチルアミノフェニル）エチレン−２−イ
ル）−４，５，６，７−チトラクロロフタリド、３，３
−ビス（１−（４−メトキシフェニル）−１−（４−ピ
ロリジノフェニル）エチレン−２−イル）−４，５，６
，７−チトラクロロフタリド等のジビニルフタリド系染
料、ベンゾイルロイコメチレンブルー、ｐ−ニトロベン
ゾイルロイコメチレンブルー等のチアジン系染料、３−
メチル−スピロ−ジナフトピラン、３−エチ／Ｌ／ −
スピロ−ジナフトピラン、３−フェニル−スピロ−ジナ
フトピラン、３−ベンジル−スピロ−ジナフトピラン、
３−メチル−ナフト（６′−メトキシベンゾ）スピロピ
ラン、３−プロピル−スピロ−ジベンゾピラン等のスピ
ロ系染料、ローダミン−Ｂ−アニリノラクタム、ローダ
ミン（Ｐ−ニトロアニリノ）ラクタム、ローダミン（０
−クロロアニリノ）ラクタム等のラクタム系染料、３−
ジメチルアミノ−７−メドキシフルオラン、３−ジエチ
ルアミノ−６−メドキシフルオラン、３−ジエチルアミ
ノ−７−メドキシフルオラン、３−ジエチルアミノ−７
−クロロフルオラン、３−ジエチルアミノ−６−メチル
−７−クロロフルオラン、３−ジエチルアミノ−６，７
−シメチルフルオラン、３−（Ｎ−エチル−ｐ−）ルイ
ジノ）−７メチルフルオラン、３−ジエチルアミノ−７
−Ｎ−アセチル−Ｎ−メチルアミノフルオラン、３ジエ
チルアミノ−７−Ｎ−メチルアミノフルオラン、３−ジ
エチルアミノ−７−ジベンジルアミノフルオラン、３−
ジエチルアミノ−７−Ｎ−メチル−Ｎ−ベンジルアミノ
フルオラン、３−ジエチルアミノ−７−Ｎ−クロロエチ
ル−Ｎ−メチルアミノフルオラン、３−ジエチルアミノ
−７−Ｎ−ジエチルアミノフルオラン、４−ベンジルア
ミノ−８−ジエチルアミノ−ベンゾ（ａ）フルオラン、
３− （４−（４−ジメチルアミノアニリノ）アニリノ
〕−７−クロロ−６−メチルフルオラン、８−（４−（
４−ジメチルアミノアニリノ）アニリノツーベンゾ（ａ
）フルオラン、３−（Ｎ−エチル−ｐ−１−ルイジノ）
−６−メチル−７−フェニルアミノフルオラン、３−（
Ｎ−エチル−ｐ−）ルイジノ）−６−メチル−７−（ｐ
−トルイジノ）フルオラン、３−ジエチルアミノ−６−
メチル−７−フェニルアミノフルオラン、３−ジブチル
アミノ−６−メチル−７−フェニルアミノフルオラン、
３−ジエチルアミン−７−（２−カルボメトキシ−フェ
ニルアミノ）フルオラン、３− （Ｎ−エチル−Ｎ−イ
ソアミルアミノ）−６−メチル−７−フェニルアミノフ
ルオラン、３−（Ｎ−シクロへキシル−Ｎ−メチルアミ
ノ）−６−メチル−７−フェニルアミノフルオラン、３
−ピロリジノ−６−メチル−７−フェニルアミノフルオ
ラン、３−ピペリジノ−６−メチル−７−フェニルアミ
ノフルオラン、３−ジエチルアミン−６−メチル−７−
キシリジノフルオラン、３−ジエチルアミノ−７−（ｏ
−クロロフェニルアミノ）フルオラン、３−ジブチルア
ミノ−７−（０−クロロフェニルアミノ）フルオラン、
３−（Ｎ−エチル−Ｎ−テトラヒドロフルフリルアミノ
）−６−メチル−７−フェニルアミノフルオラン、３−
（Ｎ−メチル−Ｎ−ｎ−プロピルアミノ）−６−メチル
−７−フェニルアミノフルオラン、３−（Ｎ−エチル−
Ｎ−イソブチルアミノ）−６−メチル−７−フェニルア
ミノフルオラン、３− （Ｎ−メチル−Ｎ−ｎ−へキシ
ルアミノ）−６−メチル−７−フェニルアミノフルオラ
ン、３−ジペンチルアミノ−６−メチル−７−フェニル
アミノフルオラン、３−（Ｎ−（３−エトキシプロピル
）−Ｎ−メチルアミノコ−６−メチルーフ−フェニルア
ミノフルオラン、３−〔Ｎ−エチル−Ｎ−（３−エトキ
シプロピル）アミノコ−６−メチルーフ−フェニルアミ
ノフルオラン、３−ジエチルアミノ−７−（ｍ−（トリ
フルオロメチル）フェニルアミノコフルオラン、３−ジ
エチルアミノ−７−（ｏ−フルオロフェニルアミノ）フ
ルオラン、３−ジブチルアミノ−７−（ｏ−フルオロフ
ェニルアミノ）フルオラン、３−ジエチルアミノ−６−
クロロ−７−フェニルアミノフルオラン、３−（Ｎ−エ
チル−Ｎ−ｎ−へキシルアミノ）−６−メチル−７−フ
ェニルアミノフルオラン、３−（Ｎ−エチル−Ｎ−シク
ロペンチルアミノ）−６−メチル−７−フェニルアミノ
フルオラン等のフルオラン系染料、３．６−ビス（ジメ
チルアミノ）フルオレン−９−スピロ−３’ −（６’
−ジメチルアミノ）フタリド、３−ジエチルアミノ−
６−（Ｎ−アリル−Ｎ−メチルアミノフルオレン−９−
スピロ−３’ −（６’−ジメチルアミノ）フタリド、
３゜６−ビス（ジメチルアミノ）−スピロ〔フルオレン
−９，６’ −６’ Ｈ−クロメノ（４，３−ｂ）イン
ドール）、３．６−ビス（ジメチルアミノ）−３′−メ
チル−スピロ（フルオレン−９，６′−６′Ｈ−クロメ
ノ（４，３−ｂ）インドール）、３．６−ビス（ジエチ
ルアミノ）−３′−メチル−スピロ〔フルオレン−９，
６’ −６’ Ｈ−クロメノ（４，３−ｂ）インドール
）等のフルオレン系染料等が挙げられる。勿論、これら
の染料に限定されるものではなく、二種以上の染料の併
用も可能である。3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(P-dimethylaminophenyl)phthalide, 3-(4-dimethylaminophenyl)-3-(4-diethylamino -2-methylphenyl) -6-(dimethylamino)phthalide, 3-(
p-dimethylaminophenyl')-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole-
3-yl)phthalide, 3,3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6 -dimethylaminophtha+7)', 3.3-bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 3゜3-bis(2-phenylindol-3-yl)-6- Dimethylaminophthalide, 3-p
-Triarylmethane dyes such as -dimethylaminophenyl-3-(1-methylpyrrol-3-yl)-6-dimethylaminophthalide, 4,4'-bis-dimethylaminobenzhydryl benzyl ether, N-halophenyl -Diphenylmethane dyes such as leucoauramine, N-2,4゜5-trichlorophenylleucoauramine, 3,3
-bis(1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrapromophthalide, 3,3-bis(1-(4-methoxyphenyl)-
1-(4-dimethylaminophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3,3
-bis(1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6
, divinyl phthalide dyes such as 7-titrachlorophthalide, thiazine dyes such as benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, 3-
Methyl-spiro-dinaphthopyran, 3-ethyl/L/-
Spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran,
Spiro dyes such as 3-methyl-naphtho(6'-methoxybenzo)spiropyran, 3-propyl-spiro-dibenzopyran, rhodamine-B-anilinolactam, rhodamine(P-nitroanilino)lactam, rhodamine (0
-lactam dyes such as chloroanilino)lactam, 3-
Dimethylamino-7-medoxyfluoran, 3-diethylamino-6-medoxyfluoran, 3-diethylamino-7-medoxyfluoran, 3-diethylamino-7
-Chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7
-Simethylfluorane, 3-(N-ethyl-p-)luidino)-7methylfluorane, 3-diethylamino-7
-N-acetyl-N-methylaminofluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-
Diethylamino-7-N-methyl-N-benzylaminofluorane, 3-diethylamino-7-N-chloroethyl-N-methylaminofluorane, 3-diethylamino-7-N-diethylaminofluorane, 4-benzylamino-8 -diethylamino-benzo(a)fluorane,
3-(4-(4-dimethylaminoanilino)anilino)-7-chloro-6-methylfluorane, 8-(4-(
4-dimethylaminoanilino)anilino-benzo(a
) Fluorane, 3-(N-ethyl-p-1-luidino)
-6-methyl-7-phenylaminofluorane, 3-(
N-ethyl-p-)luidino)-6-methyl-7-(p
-Toluidino)fluoran, 3-diethylamino-6-
Methyl-7-phenylaminofluorane, 3-dibutylamino-6-methyl-7-phenylaminofluorane,
3-diethylamine-7-(2-carbomethoxy-phenylamino)fluorane, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-phenylaminofluorane, 3-(N-cyclohexyl- N-methylamino)-6-methyl-7-phenylaminofluorane, 3
-pyrrolidino-6-methyl-7-phenylaminofluorane, 3-piperidino-6-methyl-7-phenylaminofluorane, 3-diethylamine-6-methyl-7-
Xylidinofluorane, 3-diethylamino-7-(o
-chlorophenylamino)fluoran, 3-dibutylamino-7-(0-chlorophenylamino)fluoran,
3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-phenylaminofluorane, 3-
(N-methyl-N-n-propylamino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-
N-isobutylamino)-6-methyl-7-phenylaminofluorane, 3-(N-methyl-Nn-hexylamino)-6-methyl-7-phenylaminofluorane, 3-dipentylamino-6- Methyl-7-phenylaminofluorane, 3-(N-(3-ethoxypropyl)-N-methylaminoco-6-methyl-phenylaminofluorane, 3-[N-ethyl-N-(3-ethoxypropyl)aminoco -6-methyl-ph-phenylaminofluorane, 3-diethylamino-7-(m-(trifluoromethyl)phenylaminocofluorane, 3-diethylamino-7-(o-fluorophenylamino)fluorane, 3-dibutylamino- 7-(o-fluorophenylamino)fluorane, 3-diethylamino-6-
Chloro-7-phenylaminofluorane, 3-(N-ethyl-N-n-hexylamino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-cyclopentylamino)-6- Fluorane dyes such as methyl-7-phenylaminofluorane, 3,6-bis(dimethylamino)fluorene-9-spiro-3'-(6'
-dimethylamino)phthalide, 3-diethylamino-
6-(N-allyl-N-methylaminofluorene-9-
spiro-3'-(6'-dimethylamino)phthalide,
3゜6-bis(dimethylamino)-spiro [fluorene-9,6'-6'H-chromeno(4,3-b)indole), 3,6-bis(dimethylamino)-3'-methyl-spiro (fluorene-9,6'-6'H-chromeno(4,3-b)indole), 3,6-bis(diethylamino)-3'-methyl-spiro[fluorene-9,
Examples include fluorene dyes such as 6'-6'H-chromeno(4,3-b)indole). Of course, the dyes are not limited to these dyes, and two or more types of dyes can be used in combination.
また、本発明の記録材料のうちで例えば感熱記録体等に
あっては、高速記録性を得るために、記録感度向上剤と
して各種の熱可融性物質を使用することができる。かか
る熱可融性物質としては、例えばカプロン酸アミド、カ
プリン酸アミド、バルミチン酸アミド、ステアリン酸ア
ミド、オレイン酸アミド、エルシン酸アミド、リノール
酸アミド、リノール酸アミド、Ｎ−メチルステアリン酸
アミド、ステアリン酸アニリド、Ｎ−メチルオレイン酸
アミド、ベンズアニリド、リノール酸アニリド、Ｎ−エ
チルカプリン酸アミド、Ｎ−ブチルラウリン酸アミド、
Ｎ−オクタデシルアセトアミド、Ｎ−オレインアセトア
ミド、Ｎ−オレイルベンズアミド、Ｎ−ステアリルシク
ロへキシルアミド、ポリエチレングリコール、１−ベン
ジルオキシナフタレン、２−ベンジルオキシナフタレン
、１−ヒドロキシナフトエ酸フェニルエステル、１゜２
−ジフェノキシエタン、１，４−ジフェノキシブタン、
１．２−ジ（３−メチルフェノキシ）工タン、１−フェ
ノキシ−２−（４−クロロフェノキシ）エタン、１−フ
ェノキシ−２−（４−メトキシフェノキシ）エタン、テ
レフタル酸ジベンジルエステル、シュウ酸ジベンジル、
ｐ−ベンジルオキシ安息香酸ベンジルエステル等の一種
以上が例示される。Furthermore, among the recording materials of the present invention, for example, in the case of heat-sensitive recording bodies, various thermofusible substances can be used as recording sensitivity improvers in order to obtain high-speed recording properties. Such thermofusible substances include, for example, caproic acid amide, capric acid amide, balmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide, linoleic acid amide, linoleic acid amide, N-methylstearic acid amide, and stearic acid amide. Acid anilide, N-methyloleic acid amide, benzanilide, linoleic acid anilide, N-ethyl capric acid amide, N-butyl lauric acid amide,
N-octadecylacetamide, N-oleacetamide, N-oleylbenzamide, N-stearylcyclohexylamide, polyethylene glycol, 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, 1°2
-diphenoxyethane, 1,4-diphenoxybutane,
1.2-di(3-methylphenoxy)ethane, 1-phenoxy-2-(4-chlorophenoxy)ethane, 1-phenoxy-2-(4-methoxyphenoxy)ethane, terephthalic acid dibenzyl ester, oxalic acid dibenzyl,
One or more examples include p-benzyloxybenzoic acid benzyl ester.
本発明の一般式〔Ｉ〕で表されるサリチル酸誘導体及び
／又はその多価金属塩と上記の如き塩基性染料を用いた
各種の代表的な記録体について、以下に具体的に説明す
る。Various typical recording materials using the salicylic acid derivative represented by the general formula [I] and/or its polyvalent metal salt of the present invention and the basic dye as described above will be specifically explained below.
感圧記録体は例えば米国特許第２，５０５．４７０号、
同２，５０５．４７１号、同２，５０５，４８９号、同
２．５４８，３６６号、同２，７１２．５０７号、同２
，７３０，４５６号、同２，７３０゜４５７号、同３．
４１８．２５０号、同３，９２４．０２７号、同４゜０
１０．０３８号等に記載されているように種々の形態の
ものがあり、本発明はこれら各種の形態の感圧記録体に
適用できるものである。Pressure-sensitive recording bodies are disclosed, for example, in U.S. Pat. No. 2,505,470;
2,505.471, 2,505,489, 2.548,366, 2,712.507, 2
, No. 730,456, No. 2,730゜457, No. 3.
418.250, 3,924.027, 4゜0
As described in No. 10.038, there are various types of pressure-sensitive recording bodies, and the present invention can be applied to these various types of pressure-sensitive recording bodies.
一般的には、本発明のサリチル酸誘導体又はその多価金
属塩の少なくとも一種を、必要に応じて他の呈色剤や顔
料とともにスチレン・ブタジェン共重合体ラテックス、
ポリビニルアルコール等の各種バインダー中に分散させ
た呈色剤塗液を、紙、プラスチックシート、樹脂コーチ
イツト紙等の適当な支持体上に塗布することによって呈
色剤シート（所謂下用シート）が製造される。Generally, at least one of the salicylic acid derivatives or polyvalent metal salts thereof of the present invention is mixed with a styrene-butadiene copolymer latex, along with other coloring agents and pigments as necessary.
A coloring agent sheet (so-called bottom sheet) is produced by applying a coloring agent coating liquid dispersed in various binders such as polyvinyl alcohol onto a suitable support such as paper, plastic sheet, resin coated paper, etc. be done.
一方、上記呈色剤シートと組み合わせて使用される発色
剤シート（所謂上用シート）は、塩基性染料をアルキル
化ナフタレン、アルキル化ジフェニル、アルキル化ジフ
ェニルメタン、アルキル化ターフェニル等の合成油；木
綿油、ヒマシ油等の植物油；動物油；鉱物油或いはこれ
らの混合物等からなる適当な溶媒に溶解し、これをバイ
ンダー中に分散させた分散液、又は上記溶液をコアセル
ベーション法、界面重合法、１ｎ−ｓｉｔｕ法等の各種
カプセル化法によりマイクロカプセル中に含有させ、バ
インダー中に分散させた分散液を紙、プラスチックシー
ト、樹脂コーテツド紙等の適当な支持体上に塗布して製
造される。On the other hand, the color former sheet (so-called top sheet) used in combination with the above color former sheet is a synthetic oil such as basic dye, alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl; A dispersion obtained by dissolving this in a suitable solvent such as oil, vegetable oil such as castor oil; animal oil; mineral oil or a mixture thereof, or the like, and dispersing it in a binder, or the above solution can be processed by coacervation method, interfacial polymerization method, It is produced by containing it in microcapsules by various encapsulation methods such as the 1n-situ method, and coating the dispersion liquid dispersed in a binder on a suitable support such as paper, plastic sheet, resin-coated paper, etc.
勿論、支持体の片面に上記呈色剤塗液を塗布し、反対面
に染料分散液ないしは染料カプセル分散液を塗布した所
謂中用シート、更には支持体の同一面に染料カプセルと
呈色剤が混在する塗液を塗布するか、染料カプセル分散
液を塗布した上に呈色剤塗液を塗布するなどして、同一
面に染料カプセルと呈色剤を共存させた所謂単体感圧複
写シート等の各種の形態が含まれることは前述のとおり
である。Of course, there are so-called intermediate sheets in which one side of the support is coated with the coloring agent coating liquid and the other side is coated with a dye dispersion or dye capsule dispersion, and furthermore, dye capsules and coloring agent are coated on the same side of the support. A so-called single-piece pressure-sensitive copying sheet in which dye capsules and a coloring agent coexist on the same surface by applying a coating liquid containing a mixture of dye capsules and a coloring agent coating liquid on top of a dye capsule dispersion liquid. As mentioned above, various forms such as the above are included.
なお、塩基性染料と呈色剤の使用量は所望の塗布量、感
圧記録体の形態、カプセル化法、その他各種助剤を含め
た塗布液の組成、塗布方法等各種の条件により異なるの
でその条件に応じて適宜選択すればよい。The amount of basic dye and coloring agent used varies depending on various conditions such as the desired coating amount, the form of the pressure-sensitive recording medium, the encapsulation method, the composition of the coating liquid including various auxiliaries, and the coating method. It may be selected as appropriate depending on the conditions.
感熱記録体は例えば特公昭４４−３６８０号、同４４−
２７８８０号、同４５−１４０３９号、同４Ｂ −４３
８３０号、同４９−６９号、同４９−７０号、同５２−
２０１４２号等に記載されているように種々の形態のも
のがあり、本発明のサリチル酸誘導体又はその多価金属
塩はこれら各種の形態の感熱記録体に適用できる。For example, heat-sensitive recording materials are disclosed in Japanese Patent Publication Nos. 44-3680 and 44-3680.
No. 27880, No. 45-14039, No. 4B-43
No. 830, No. 49-69, No. 49-70, No. 52-
As described in No. 20142, etc., there are various forms, and the salicylic acid derivative or its polyvalent metal salt of the present invention can be applied to these various forms of heat-sensitive recording materials.
−船釣にはバインダーを溶解又は分散した媒体中に塩基
性染料と本発明のサリチル酸誘導体又はその多価金属塩
を分散させて得られる塗液を紙、プラスチックフィルム
、合成紙さらには織布シート、成形物等の適当な支持体
上に塗布すことによって本発明の感熱記録体は製造され
る。記録層中の塩基性染料と呈色剤の使用比率は特に限
定するものではないが、一般に染料１重量部に対し１〜
５０重量部、好ましくは２〜１０重量部程度の呈色剤が
用いられる。- For boat fishing, a coating liquid obtained by dispersing a basic dye and the salicylic acid derivative of the present invention or its polyvalent metal salt in a medium in which a binder is dissolved or dispersed is applied to paper, plastic film, synthetic paper, and even woven fabric sheets. The heat-sensitive recording material of the present invention is produced by coating it on a suitable support such as a molded product. The ratio of basic dye and coloring agent used in the recording layer is not particularly limited, but is generally 1 to 1 part by weight of dye.
About 50 parts by weight, preferably 2 to 10 parts by weight of the coloring agent is used.
また、発色能の改良、記録層表面の艶消し、筆記性の改
良等を目的として、無機顔料を一般に呈色剤１重量部に
対し０．１〜１０重量部、好ましくは０．５〜３重量部
程度併用することができ、更に例えば分散剤、紫外線吸
収剤、熱可融性物質、消泡剤、蛍光染料、着色染料等の
各種助剤を必要に応じて適宜併用できる。In addition, for the purpose of improving coloring ability, matting the surface of the recording layer, improving writing properties, etc., inorganic pigments are generally added in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, per 1 part by weight of the coloring agent. They can be used in combination in parts by weight, and various auxiliary agents such as dispersants, ultraviolet absorbers, thermofusible substances, antifoaming agents, fluorescent dyes, and coloring dyes can also be used in combination as necessary.
本発明の感熱記録体は上述の如（、一般に塩基性染料と
呈色剤の微粒子を分散させた塗液を支持体に塗布するこ
とによって製造されるが、塩基性染料と呈色剤のそれぞ
れを別個に分散せしめている２種の塗液を支持体に重ね
塗りしてもよく、含浸、抄き込みによって製造すること
も勿論可能である。The heat-sensitive recording material of the present invention is manufactured by coating a support with a coating liquid in which fine particles of a basic dye and a coloring agent are dispersed, as described above. The support may be overcoated with two types of coating liquids in which these are separately dispersed, and it is of course also possible to produce the support by impregnation or rolling.
その他塗液の調製方法、塗布方法等についても特に限定
されるものではなく、塗布量も一般に乾燥重量で２〜１
２ｇ／ｒｒｆ程度塗布される。更に記録層上に記録層を
保護する等の目的でオーバーコート層を設けたり、支持
体に下塗り層を設けることも勿論可能で、感熱記録体製
造分野における各種の公知技術が適宜付加し得るもので
ある。There are no particular restrictions on the preparation method or application method of the coating liquid, and the amount applied is generally 2 to 1 on dry weight.
Approximately 2g/rrf is applied. Furthermore, it is of course possible to provide an overcoat layer on the recording layer for the purpose of protecting the recording layer, or to provide an undercoat layer on the support, and various known techniques in the field of heat-sensitive recording material manufacturing can be added as appropriate. It is.
なお、バインダーとしては例えばデンプン類、セルロー
ス類、蛋白質類、アラビアゴム、ポリビニルアルコール
、スチレン−無水マレイン酸共重合体塩、スチレン−ブ
タジェン共重合体エマルジョン、酢ビー無水マレイン酸
共重合体塩、ポリアクリル酸塩等が適宜選択して用いら
れる。Examples of binders include starches, celluloses, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salts, styrene-butadiene copolymer emulsions, acetic acid and maleic anhydride copolymer salts, and polyvinyl alcohol. Acrylates and the like are appropriately selected and used.
通電感熱記録体は例えば特開昭４９−１１３４４号、同
５０−４８９３０号等に記載の方法によって製造される
。一般に、導電性物質、塩基性染料及び呈色剤をバイン
ダーと共に分散した塗液を紙等の適当な支持体に塗布す
るか、支持体に導電性物質を塗布して導電層を形成し、
その上に染料、呈色剤及びバインダーを分散した塗液を
塗布することによって製造される。なお、染料と呈色剤
が共に７０〜１２０°Ｃといった好ましい温度領域で溶
融しない場合には、適当な熱可融性物質を併用すること
によりジュール熱に対する感度を調整することができる
。The electrically conductive heat-sensitive recording material is manufactured, for example, by the method described in JP-A-49-11344 and JP-A-50-48930. Generally, a coating liquid in which a conductive substance, a basic dye, and a coloring agent are dispersed together with a binder is applied to a suitable support such as paper, or a conductive substance is applied to the support to form a conductive layer.
It is manufactured by applying a coating liquid containing a dye, a coloring agent, and a binder dispersed thereon. Incidentally, if both the dye and the coloring agent do not melt in the preferred temperature range of 70 to 120°C, sensitivity to Joule heat can be adjusted by using an appropriate thermofusible substance in combination.
「実施例」
以下に実施例を示し、本発明をより具体的に説明するが
、勿論これらに限定されるものではない。"Example" The present invention will be described in more detail with reference to Examples below, but the present invention is of course not limited to these.
また、特に断らない限り例中の部及び％はそれぞれ重量
部及び重量％を示す。Further, unless otherwise specified, parts and % in the examples indicate parts by weight and % by weight, respectively.
実施例１
３−（Ｎ−エチル−Ｎ−イソアミルアミノ）−６−メチ
ル−７−フエニルアミツフルオラン６部をイソプロピル
化ナフタレンｌＯＯ部に溶解し、等電点８のビッグスキ
ンゼラチン２５部とアラビアゴム２５部を溶解した３５
０部の温水（５０°Ｃ）中に添加し乳化分散した。この
乳化液にｌ０００部の温水を加え酢酸でｐＨを４に調節
してから１０℃まで冷却し、ゲルタールアルデヒドの２
５％水溶液１０部を加えカプセルを硬化した。このカプ
セル含有塗液を４５ ｇ／ｒｒｆの原紙の片面に乾燥重
量が５ｇ／ｒｒｆとなるように塗工し、発色剤シートを
得た。Example 1 6 parts of 3-(N-ethyl-N-isoamylamino)-6-methyl-7-phenylamitofluorane were dissolved in 100 parts of isopropylated naphthalene, and 25 parts of big skin gelatin with an isoelectric point of 8 were dissolved. 35 by dissolving 25 parts of gum arabic
It was added to 0 parts of warm water (50°C) and emulsified and dispersed. Add 1000 parts of warm water to this emulsion, adjust the pH to 4 with acetic acid, cool it to 10°C, and add geltaraldehyde 2.
10 parts of a 5% aqueous solution was added to harden the capsules. This capsule-containing coating liquid was coated on one side of a 45 g/rrf base paper so that the dry weight was 5 g/rrf to obtain a color former sheet.
一方、水２００部に４−（２−フェニルチオエトキシ）
サリチル酸の亜鉛塩２０部、カオリ７８０部、スチレン
−ブタジェン共重合体エマルジョン（５０％固形分）３
０部を分散した呈色剤塗液を、４５ｇ／ｒｒｆの原紙に
乾燥重量が５ｇ／ｒｒｆとなるように塗工し、呈色剤シ
ートを得た。Meanwhile, 4-(2-phenylthioethoxy) in 200 parts of water
20 parts of zinc salt of salicylic acid, 780 parts of kaoli, styrene-butadiene copolymer emulsion (50% solids) 3
A coloring agent coating liquid in which 0 parts of the coloring agent was dispersed was applied to a 45g/rrf base paper so that the dry weight was 5g/rrf to obtain a coloring agent sheet.
このようにして調製した発色剤シートと呈色剤シートと
を、カプセル塗布面と呈色剤塗布面が相対向するように
重ね、筆記・加圧したところ、瞬時に黒色の印像が得ら
れた。この像は濃度が高く、耐光性に優れていた。When the thus prepared coloring agent sheet and coloring agent sheet were stacked so that the capsule-coated surface and the coloring agent-coated surface faced each other, and writing and pressure were applied, a black image was instantly obtained. Ta. This image had high density and excellent light resistance.
実施例２〜４
実施例１の呈色剤シート作成において、４−（２−フェ
ニルチオエトキシ）サリチル酸の亜鉛塩２０部の代わり
に、下記の呈色剤を用いた以外は実施例１と同様にして
３種類の呈色剤シートを得た。Examples 2 to 4 Same as Example 1 except that the following coloring agent was used instead of 20 parts of zinc salt of 4-(2-phenylthioethoxy)salicylic acid in preparing the coloring agent sheet of Example 1. Three types of coloring agent sheets were obtained.
実施例２ ： ４− （３−フェニルチオプロピルオキ
シ）サリチル酸の亜鉛塩 ２０部
実ｍ例３ ： ４− （２−ｐ−メトキシフェニルチオ
エトキシ）サリチル酸の亜鉛塩
２０部
実施例４：３．５−ビス（α−メチルベンジル）サリチ
ル酸の亜鉛塩 １０部
４−（２−フェニルチオエトキシ）
サリチル酸の亜鉛塩 １０部
これらの呈色剤シートを用い、実施例１と同様にして発
色させると、いずれの場合も瞬時に黒色の印像が得られ
た。これらの像はいずれも濃度が高（、しかも耐光性に
優れていた。Example 2: 20 parts of zinc salt of 4-(3-phenylthiopropyloxy)salicylic acid Example 3: 20 parts of zinc salt of 4-(2-p-methoxyphenylthioethoxy)salicylic acid Example 4: 3.5 -10 parts of zinc salt of bis(α-methylbenzyl)salicylic acid 10 parts of zinc salt of 4-(2-phenylthioethoxy) salicylic acid When these coloring agent sheets are used to develop color in the same manner as in Example 1, In this case, a black image was also obtained instantly. All of these images had high density (and excellent light resistance).
実施例５
■ Ａ液調製
３−（Ｎ−エチル−Ｎ−イソアミルアミノ）−６−メチ
ル−７−フェニルアミノフルオラン１０部
１．２−シ（３−メチルフェノキシ）エタン２０部
メチルセルロース ５％水溶液 ２０部水
１１０部この
組成物をサンドミルで平均粒子径が２μｍとなるまで粉
砕した。Example 5 ■ Preparation of liquid A 3-(N-ethyl-N-isoamylamino)-6-methyl-7-phenylaminofluorane 10 parts 1.2-cy(3-methylphenoxy)ethane 20 parts Methyl cellulose 5% aqueous solution 20 parts water
110 parts of this composition was ground in a sand mill until the average particle size was 2 μm.
■ Ｂ液調製
４−（２−フェニルチオエトキシ）サリチル酸３０部
メチルセルロース ５％水溶液 ６０部水
１１０部この
組成物をサンドミルで平均粒子径が３μｍとなるまで粉
砕した。■ Preparation of Solution B 4-(2-phenylthioethoxy)salicylic acid 30 parts Methylcellulose 5% aqueous solution 60 parts water
110 parts of this composition was ground in a sand mill until the average particle size was 3 μm.
■ 記録層の形成
Ａ液１６０部、Ｂ液２００部、酸化珪素顔料（吸油量：
１８０ｍ１／１００ｇ）３０部、２０％酸化澱粉水溶
液１５０部、水２１０部を混合・撹拌し塗液とした。得
られた塗液を５０ ｇ／ｎ（の原紙に乾燥重量が６．０
ｇ／ｒｔｉとなるように塗布・乾燥して感熱記録紙を得
た。■ Formation of recording layer 160 parts of liquid A, 200 parts of liquid B, silicon oxide pigment (oil absorption:
180 m1/100 g), 150 parts of a 20% oxidized starch aqueous solution, and 210 parts of water were mixed and stirred to prepare a coating liquid. The resulting coating liquid was applied to 50 g/n (dry weight of 6.0 g/n) of base paper.
A heat-sensitive recording paper was obtained by coating and drying so as to give g/rti.
実施例６〜２１
実施例５のＢ液調製において、４−（２−フェニルチオ
エトキシ）サリチル酸の代わりに、下記の化合物を用い
た以外は、実施例５と同様にして１６種類の感熱記録紙
を得た。Examples 6 to 21 Sixteen types of thermal recording paper were prepared in the same manner as in Example 5, except that the following compound was used instead of 4-(2-phenylthioethoxy)salicylic acid in the preparation of liquid B in Example 5. I got it.
実施例６：４−（４−フェニルチオブチルオキシ）サリ
チル酸
実施例７：４−（２−ｐ−メチルフェニルチオエトキシ
）サリチル酸
実施４ｊＡ１８ ： ４− （４−ｐ−クロルフェニル
チオブトキシ）サリチル酸
実施例９：４−（２−ｐ−メトキシフェニルチオエトキ
シ）サリチル酸
実施例１０１−（２−ｐ−ビフェニルチオエトキシ）サ
リチル酸
実施例１１：５−（２−フェニルチオエトキシ）サリチ
ル酸
実施例１２：４−（２−フェニルチオエトキシ）サリチ
ル酸の亜鉛塩
実施例１３：４−（４−フェニルチオブチルオキシ）サ
リチル酸の亜鉛塩
実施例１４：４−（２−ｐ−メチルフェニルチオエトキ
シ）サリチル酸の亜鉛塩
実施例１５：４−（４−ｐ−クロルフェニルチオブトキ
シ）サリチル酸の亜鉛塩
実施例１６：４−（２−ｐ−メトキシフェニルチオエト
キシ）サリチル酸の亜鉛塩
実施例１７：４−（２−ｐ−ビフェニルチオエトキシ）
サリチル酸の亜鉛塩
実施例１８ ： ５−（２−フェニルチオエトキシ）サ
リチル酸の亜鉛塩
実施例１９：４−（２−フェニルチオエトキシ）サリチ
ル酸のカルシウム塩
実施例２０：４−（２−フェニルチオエトキシ）サリチ
ル酸のマグネシウム塩
実施例２１：４−（２−フェニルチオエトキシ）サリチ
ル酸のアルミニウム塩
実施例２２
実施例５のＢ液調製において、水１１０部の代わりに、
酸化亜鉛３０部と水８０部を用いた以外は実施例５と同
様にして感熱記録紙を得た。Example 6: 4-(4-phenylthiobutyloxy) salicylic acid Example 7: 4-(2-p-methylphenylthioethoxy) salicylic acid Example 4jA18: 4-(4-p-chlorophenylthiobutoxy) salicylic acid Example 9:4-(2-p-methoxyphenylthioethoxy)salicylic acidExample 101-(2-p-biphenylthioethoxy)salicylic acidExample 11:5-(2-phenylthioethoxy)salicylic acidExample 12:4-( Zinc salt of 2-phenylthioethoxy) salicylic acid Example 13: Zinc salt of 4-(4-phenylthiobutyloxy) salicylic acid Example 14: Zinc salt of 4-(2-p-methylphenylthioethoxy) salicylic acid 15: Zinc salt of 4-(4-p-chlorophenylthiobutoxy) salicylic acid Example 16: Zinc salt of 4-(2-p-methoxyphenylthioethoxy) salicylic acid Example 17: 4-(2-p-biphenyl thioethoxy)
Zinc salt of salicylic acid Example 18: Zinc salt of 5-(2-phenylthioethoxy) salicylic acid Example 19: Calcium salt of 4-(2-phenylthioethoxy) salicylic acid Example 20: 4-(2-phenylthioethoxy) ) Magnesium salt of salicylic acid Example 21: Aluminum salt of 4-(2-phenylthioethoxy) salicylic acid Example 22 In the preparation of solution B of Example 5, instead of 110 parts of water,
A thermosensitive recording paper was obtained in the same manner as in Example 5 except that 30 parts of zinc oxide and 80 parts of water were used.
実施例２３〜３３
実施例２２のＢ液調製において、４−（２−フェニルチ
オエトキシ）サリチル酸の代わりに、下記の化合物を用
いた以外は実施例２２と同様にして１１種類の感熱記録
紙を得た。Examples 23 to 33 Eleven types of thermal recording paper were prepared in the same manner as in Example 22, except that the following compound was used instead of 4-(2-phenylthioethoxy)salicylic acid in the preparation of liquid B in Example 22. Obtained.
実施例２３：４−（４−フェニルチオブチルオキシ）サ
リチル酸
実施例２４：４−（２−ｐ−メチルフェニルチオエトキ
シ）サリチル酸
実施例２５：４−（４−ｐ−クロルフェニルチオブトキ
シ）サリチル酸
実施例２６：４−（２−ｐ−メトキシフェニルチオエト
キシ）サリチル酸
実ｍ例２７：４− （２−ｐ−ビフェニルチオエトキシ
）サリチル酸
実施例２８：４−Ｃ２−フェニルチオエトキシ）サリチ
ル酸の亜鉛塩
実施例２９： ４− （４−ｐ−クロルフェニルチオブ
トキシ）サリチル酸の亜鉛塩
実施例３０：４−（２−ｐ−ビフェニルチオエトキシ）
サリチル酸の亜鉛塩
実施例３１：４−（２−フェニルチオエトキシ）サリチ
ル酸のカルシウム塩
実施例３２：４−Ｃ２−フェニルチオエトキシ）サリチ
ル酸のマグネシウム塩
実施例３３：４−（２−フェニルチオエトキシ）サリチ
ル酸のアルミニウム塩
実施例３４〜３６
実施例２２のＢ漆調製において、酸化亜鉛の代わりに下
記の化合物を用いた以外は、実施例２２と同様にして３
種類の感熱記録紙を得た。Example 23: 4-(4-phenylthiobutyloxy)salicylic acidExample 24: 4-(2-p-methylphenylthioethoxy)salicylic acidExample 25: 4-(4-p-chlorophenylthiobutoxy)salicylic acid Example 26: 4-(2-p-methoxyphenylthioethoxy)salicylic acid Example 27: 4-(2-p-biphenylthioethoxy)salicylic acid Example 28: Zinc salt implementation of 4-C2-phenylthioethoxy)salicylic acid Example 29: Zinc salt of 4-(4-p-chlorophenylthiobutoxy)salicylic acid Example 30: 4-(2-p-biphenylthioethoxy)
Zinc salt of salicylic acid Example 31: Calcium salt of 4-(2-phenylthioethoxy) salicylic acid Example 32: Magnesium salt of 4-C2-phenylthioethoxy) salicylic acid Example 33: 4-(2-phenylthioethoxy) Aluminum salt of salicylic acid Examples 34 to 36 Example 3 was prepared in the same manner as in Example 22, except that the following compound was used instead of zinc oxide in the preparation of B lacquer in Example 22.
Various types of thermal recording paper were obtained.
実施例３４：炭酸カルシウム
実施例３５：酸化マグネシウム
実施例３６：酸化アルミニウム
比較例１〜３
実施例５のＢｆｉ調製において、４−（２−フェニルチ
オエトキシ）サリチル酸の代わりに、下記の化合物を用
いた以外は実施例５と同様にして３種類の感熱記録紙を
得た。Example 34: Calcium carbonate Example 35: Magnesium oxide Example 36: Aluminum oxide Comparative Examples 1 to 3 In the Bfi preparation of Example 5, the following compound was used instead of 4-(2-phenylthioethoxy)salicylic acid. Three types of thermal recording paper were obtained in the same manner as in Example 5 except that
比較例１：４．４’−イソプロピリデンジフェノール
比較例２； ４．４’−シクロへキシリデンビスフェノ
ール
比較例３；ｐ−クロロ安息香酸の亜鉛塩かくして得られ
た３５種類の感熱記録紙を感熱ファクシミリ（日立ＨＩ
ＦＡＸ−７００型）を使用して記録し、その発色濃度を
マクベス濃度計（ＲＤ−９１４型）にて測定し、その結
果を第１表に示した。Comparative example 1: 4.4'-isopropylidene diphenol Comparative example 2; 4.4'-cyclohexylidene bisphenol Comparative example 3: Zinc salt of p-chlorobenzoic acid The 35 types of heat-sensitive recording paper thus obtained were Thermal facsimile (Hitachi HI)
The color density was measured using a Macbeth densitometer (model RD-914), and the results are shown in Table 1.
又、記録後の感熱記録紙を６０°Ｃの高温乾燥条件下に
２０時間放置後、及び４０°Ｃ１９０％ＲＨの高湿度条
件下に２０時間放置後、それぞれの記録像の発色濃度を
再度マクベス濃度計にて測定し、記録像の耐熱性および
耐湿性を評価し、その結果を第１表に記載した。In addition, after leaving the thermal recording paper after recording under a high temperature drying condition of 60°C for 20 hours, and after leaving it under a high humidity condition of 40°C and 190% RH for 20 hours, the color density of each recorded image was checked again using Macbeth. The heat resistance and moisture resistance of the recorded image were evaluated using a densitometer, and the results are shown in Table 1.
さらに、耐薬品性を評価するために、記録後の感熱記録
紙の発色面に塩化ビニルフィルムを重ねて室温で２０時
間放置した場合（耐可塑剤性）、発色面にエタノールを
塗布した場合（耐アルコール性）、及び発色面に綿実油
を塗布した場合（耐油性）のそれぞれについて、白紙部
のカブリおよび記録像の褪色の度合を評価し、その結果
を第１表に示した。Furthermore, in order to evaluate chemical resistance, a vinyl chloride film was layered on the colored side of thermal recording paper after recording and left at room temperature for 20 hours (plasticizer resistance), and when ethanol was applied to the colored side ( The degree of fog in the blank area and the degree of fading of the recorded image was evaluated for each case (alcohol resistance) and when cottonseed oil was applied to the coloring surface (oil resistance), and the results are shown in Table 1.
「効果」
第１表の結果から明らかな如く、本発明による記録材料
は、発色濃度が高く、記録像の保存性、特に薬品による
発色部の褪色及び地肌カブリのない優れた記録材料であ
った。"Effect" As is clear from the results in Table 1, the recording material according to the present invention had a high color density and was an excellent recording material in terms of storage stability of the recorded image, especially without fading of the colored part due to chemicals and without background fogging. .
Claims (4)
と接触して呈色し得る呈色剤との反応を利用した記録材
料において、呈色剤として下記一般式〔 I 〕で表され
るサリチル酸誘導体又はその多価金属塩の少なくとも一
種を用いたことを特徴とする記録材料。 ▲数式、化学式、表等があります▼〔 I 〕 〔式中、Ａｒは置換基を有してもよいフェニル基、置換
基を有してもよいナフチル基、又は置換基を有してもよ
い複素芳香環基を示し、Ｒはエーテル結合、エステル結
合又はアミド結合を有してもよいアルキレン基、エーテ
ル結合、エステル結合又はアミド結合を有してもよいシ
クロアルキレン基、又はエーテル結合、エステル結合又
はアミド結合を有してもよいアラルキレン基を示す。ま
た、Ｘは水素原子、アルキル基、シクロアルキル基、ア
ルケニル基、アラルキル基、アリール基、アルコキシル
基、アリールオキシ基、ニトロ基、又はハロゲン原子を
示し、ｍは１〜３の整数を示す。〕(1) In a recording material that utilizes the reaction between a colorless or light-colored basic dye and a coloring agent that can change color when it comes into contact with the basic dye, the coloring agent is represented by the following general formula [I]. A recording material characterized in that it uses at least one salicylic acid derivative or a polyvalent metal salt thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, Ar is a phenyl group that may have a substituent, a naphthyl group that may have a substituent, or a naphthyl group that may have a substituent. Represents a heteroaromatic ring group, R is an alkylene group that may have an ether bond, an ester bond, or an amide bond, a cycloalkylene group that may have an ether bond, an ester bond, or an amide bond, or an ether bond, an ester bond or an aralkylene group which may have an amide bond. Further, X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, an aryloxy group, a nitro group, or a halogen atom, and m represents an integer of 1 to 3. ]
ル酸誘導体又はその多価金属塩の少なくとも一種と金属
化合物を併用した請求項（１）記載の記録材料。(2) The recording material according to claim (1), in which at least one salicylic acid derivative represented by the general formula [I] or a polyvalent metal salt thereof and a metal compound are used together as a coloring agent.
２）記載の記録材料。(3) Claim (1) or (
2) Recording materials described.
２）記載の記録材料。(4) Claim (1) or (
2) Recording materials described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1104831A JPH02281992A (en) | 1989-04-24 | 1989-04-24 | Recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1104831A JPH02281992A (en) | 1989-04-24 | 1989-04-24 | Recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02281992A true JPH02281992A (en) | 1990-11-19 |
Family
ID=14391322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1104831A Pending JPH02281992A (en) | 1989-04-24 | 1989-04-24 | Recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02281992A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05147351A (en) * | 1991-11-28 | 1993-06-15 | Fuji Photo Film Co Ltd | Thermal recording material |
-
1989
- 1989-04-24 JP JP1104831A patent/JPH02281992A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05147351A (en) * | 1991-11-28 | 1993-06-15 | Fuji Photo Film Co Ltd | Thermal recording material |
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