JPS5968372A - Fluoran derivative, its preparation and recording medium utilizing its derivative - Google Patents
Fluoran derivative, its preparation and recording medium utilizing its derivativeInfo
- Publication number
- JPS5968372A JPS5968372A JP57178145A JP17814582A JPS5968372A JP S5968372 A JPS5968372 A JP S5968372A JP 57178145 A JP57178145 A JP 57178145A JP 17814582 A JP17814582 A JP 17814582A JP S5968372 A JPS5968372 A JP S5968372A
- Authority
- JP
- Japan
- Prior art keywords
- derivative
- fluoran
- acid
- color
- formula
- 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
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- YKRHZYMTIOUCBR-UHFFFAOYSA-N 5-(cyclohexylamino)naphthalen-1-ol Chemical class C1=CC=C2C(O)=CC=CC2=C1NC1CCCCC1 YKRHZYMTIOUCBR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 238000004040 coloring Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims 1
- 239000000981 basic dye Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 28
- 239000000463 material Substances 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 26
- 239000000123 paper Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002775 capsule Substances 0.000 description 8
- 238000001454 recorded image Methods 0.000 description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- -1 attapulgide Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product 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
- 239000005457 ice water Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin 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
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 241000978776 Senegalia senegal Species 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012752 auxiliary agent Substances 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
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 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
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 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
- 239000002985 plastic film Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-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
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- WHTZQYDVDPHTAM-UHFFFAOYSA-N 2,2,2-tribromo-1-phenylethanone Chemical compound BrC(Br)(Br)C(=O)C1=CC=CC=C1 WHTZQYDVDPHTAM-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
- SSGBXVPTFUOGFO-UHFFFAOYSA-N 2-(tribromomethyl)pyridine Chemical compound BrC(Br)(Br)C1=CC=CC=N1 SSGBXVPTFUOGFO-UHFFFAOYSA-N 0.000 description 1
- KWVDRAXPOZQNKU-UHFFFAOYSA-N 2-[1-(2-hydroxyphenyl)butyl]phenol Chemical group C=1C=CC=C(O)C=1C(CCC)C1=CC=CC=C1O KWVDRAXPOZQNKU-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- SMNNDVUKAKPGDD-UHFFFAOYSA-N 2-butylbenzoic acid Chemical group CCCCC1=CC=CC=C1C(O)=O SMNNDVUKAKPGDD-UHFFFAOYSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical class ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-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
- GMOYUTKNPLBTMT-UHFFFAOYSA-N 2-phenylmethoxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OCC1=CC=CC=C1 GMOYUTKNPLBTMT-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-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
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- IHYOYFVKBXZDJE-UHFFFAOYSA-N 4-benzyl-3-hydroxynaphthalene-2-carboxylic acid Chemical compound OC=1C(C(=O)O)=CC2=CC=CC=C2C=1CC1=CC=CC=C1 IHYOYFVKBXZDJE-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
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 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
- 101001077535 Emericella nidulans (strain FGSC A4 / ATCC 38163 / CBS 112.46 / NRRL 194 / M139) Nicotinate hydroxylase hnxS Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- 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 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002585 base Substances 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- JFIOVJDNOJYLKP-UHFFFAOYSA-N bithionol Chemical compound OC1=C(Cl)C=C(Cl)C=C1SC1=CC(Cl)=CC(Cl)=C1O JFIOVJDNOJYLKP-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000006840 diphenylmethane group Chemical class 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229960000304 folic acid Drugs 0.000 description 1
- 235000019152 folic acid Nutrition 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- PFAHQYGACXSZLL-UHFFFAOYSA-N hexylbenzene Chemical compound [CH2]CCCCCC1=CC=CC=C1 PFAHQYGACXSZLL-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium 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
- 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
- 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 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LTEQMZWBSYACLV-UHFFFAOYSA-N n-hexyl benzene Natural products CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002223 polystyrene 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
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 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
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- VZUBRRXYUOJBRS-UHFFFAOYSA-N trichloromethylsulfonylbenzene Chemical compound ClC(Cl)(Cl)S(=O)(=O)C1=CC=CC=C1 VZUBRRXYUOJBRS-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（３）
本発明は感圧記録シート、感熱記録シート、通電感熱記
録シート、感光性記録シートなどの記録体に用いられる
発色物質として有用なフルオラン誘導体およびその製造
方法、さらにその誘導体を用しり：記録体に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (3) The present invention relates to a fluorane derivative useful as a color-forming substance used in recording materials such as pressure-sensitive recording sheets, heat-sensitive recording sheets, current-carrying heat-sensitive recording sheets, and photosensitive recording sheets, and a method for producing the same; Furthermore, the use of its derivatives relates to recording materials.
従来、無色ないし淡色の塩基性染料と有機ないし無機の
電子受容性物質との呈色反応を利用し、圧力、熱、電気
、光などのエネルギーの媒介によって伝達される情報を
記録する方式には各種の方式が提案されでおり、例えば
近藤、岩崎、紙パ技協誌３０巻４１１〜４２１頁、４６
３〜４７０頁（１９７６年）に記載されているよ・）な
感圧複写シー］・、感熱記録シー１、通電感熱記録シー
ト、超音波記録シーＩ・、電子線記録シート、静電記録
シー）・、感光性記録シートさらには感光性印刷材、タ
イプリボン、ボールペンインキ、クレヨン、スタンプイ
ンキなどへの応用まで非常に沢山の方式が提案されてい
る。Conventionally, there has been no method to record information transmitted through energy media such as pressure, heat, electricity, or light, using a color reaction between a colorless or light-colored basic dye and an organic or inorganic electron-accepting substance. Various methods have been proposed; for example, Kondo, Iwasaki, Paper Paper Technology Association Journal, Vol. 30, pp. 411-421, 46.
3-470 (1976) Pressure-sensitive copy sheet], Thermal recording sheet 1, Electrical thermal recording sheet, Ultrasonic recording sheet I, Electron beam recording sheet, Electrostatic recording sheet ), a large number of methods have been proposed for application to photosensitive recording sheets, photosensitive printing materials, type ribbons, ballpoint pen inks, crayons, stamp inks, etc.
電子供与性発色物質（以下単に発色剤という）と電子受
容性顕色物質（以下単に顕色剤という）（４）
との呈色反応を利用したこれらの記録体においては、発
色剤の種類を選択することによって種々の色相を呈する
発色像が形成されるものであるが、近年、得られた発色
像からさらに複写を得たいといった目的のため黒色発色
像の得られる記録体の要望が強くなっている。この場合
、原理的には赤、青、黄、緑など異なった色相に発色す
る発色剤を混合することによって黒色発色像をｆＪるこ
とができるが、発色剤の種類により発色速度や光、温湿
度に対する堅牢性が異なるため最初発色した発色像がそ
の色調を維持し得ない欠点がある。従って、従来から単
一の発色剤で黒色発色像を得る研究が行なわれているが
、発色前の発色剤の安定性、発色速度、発色濃度、堅牢
性、色相あるいはコスト等の全てを満足し得る黒色発色
剤は未だ見出されておらず、結果として黒発色記録体も
必ずしも満足できるものではなかった。In these recording materials that utilize a color reaction between an electron-donating color-forming substance (hereinafter simply referred to as a color-forming agent) and an electron-accepting color-developing substance (hereinafter simply referred to as a color-forming agent) (4), the type of color-forming agent is determined. Colored images exhibiting various hues can be formed depending on the color selected, but in recent years there has been a strong demand for recording media that can produce black colored images for the purpose of making further copies of the obtained colored images. ing. In this case, in principle, it is possible to create a black colored image by mixing coloring agents that develop different hues such as red, blue, yellow, and green, but the coloring speed, light, and temperature depend on the type of coloring agent. Since the fastness to humidity is different, the color image that is initially developed cannot maintain its color tone. Therefore, research has been carried out to obtain black colored images using a single coloring agent, but it has not been possible to satisfy all of the requirements such as the stability of the coloring agent before coloring, coloring speed, coloring density, fastness, hue, and cost. A black color forming agent that can be obtained has not yet been found, and as a result, black color recording materials have not always been satisfactory.
しかるに本発明の下記一般式（１）で表わされるフルオ
ラン誘導体
（５）
〔式中Ｒ，，Ｒ２はＣＩ−Ｃ嘆のアルキル基を、Ｘはハ
ロケン原子を示し、ｎは０〜４の整数を示す。〕
ば無色ないし淡色の安定な化合物で顕色剤と接触すると
赤黒色、ｔｐ＝色ないし黒色の高濃度な色相に発色し、
この物質を用いて得られた記録像は日光に曝されても安
定して川明の色調を維持する特性を有するものであり、
かつ例えば感圧記録紙へ適用した場合には特に初期発色
性に優れた記録像が１ｑられ、又感熱記録紙に適用した
場合には地肌カブリが少なくしかも発色性に優れた記録
像が得られるものである。However, the fluoran derivative (5) of the present invention represented by the following general formula (1) [wherein R,, R2 represents an alkyl group such as CI-C, X represents a halogen atom, and n represents an integer of 0 to 4] show. ] It is a colorless or light-colored stable compound, and when it comes in contact with a color developer, it develops a highly concentrated hue of red-black, tp = color or black,
The recorded image obtained using this material has the property of stably maintaining its color tone even when exposed to sunlight,
For example, when applied to pressure-sensitive recording paper, a recorded image with particularly excellent initial color development is obtained, and when applied to heat-sensitive recording paper, a recorded image with less background fog and excellent color development is obtained. It is something.
而して、上記の如く優れた特性を有する本発明の一般式
（１）で表わされるフルオラン誘導体は（６）
主に次のような代表的な方法によって製造することがで
きる。即ち、下記に示すようにまずｒｎ−アミノフェノ
ール誘導体（ｒＶ）と無水フタル酸誘導体（Ｖ）を反応
させて２−（２−ヒドロキシ−４−アミン）ヘンジイル
安息香酸誘導体［１１）を合成する。Therefore, the fluoran derivative represented by the general formula (1) of the present invention having the excellent properties as described above (6) can be mainly produced by the following representative method. That is, as shown below, first, an rn-aminophenol derivative (rV) and a phthalic anhydride derivative (V) are reacted to synthesize a 2-(2-hydroxy-4-amine)hendiylbenzoic acid derivative [11].
ｔ Ｒｚ
Ｃ７；７〕ＣＶ３ Ｄｌ：）（Ｒ，、
Ｒ２、Ｘ、ｎは前述の意味を示す。）（ｑられた２〜（
２−ヒドロキシ−４−アミノ）ヘンジイル安息香酸誘導
体（ＩＩ）と５−シクロへキシルアミノ−Ｉ−ナフトー
ル誘導体（ＩＩＩ）を縮合させることによって一般式〔
１〕で表わされるフルオラン誘う１１体を製造すること
ができる。t Rz C7;7]CV3 Dl:)(R,,
R2, X, and n have the above meanings. )(qed 2～(
The general formula [
1] can be produced.
（７）
〔式中Ｒ，は水素原子またはＣ／〜ｃ２のアルキル基を
示し、Ｒ／、Ｒ２、Ｘ、ｎは前述の意味を示す。〕
２−（２−ヒドロキシ−４−アミノ）ヘンジイル安息香
酸誘導体ＮＪ）と５−シクロヘキシルアミノ−１−ナフ
トール誘導体［１１１）との縮合反応における縮合剤と
しては、硫酸；五酸化リン；リン酸；ポリリン酸；無水
塩化スズ、無水塩化亜鉛、無水塩化アルミニウム、無水
臭化スズ、無水臭化亜鉛、無水臭化アルミニウム、無水
臭化鉄などの（８）
無水金属ハロゲン化物；三塩化リン；三臭化リン；五塩
化リン；五臭化リン；無水玉フッ化ホウ素；フッ化水素
酸などのフリーデルタラット触媒が単独あるいは混合し
て使用される。なかでも溶媒をかねた硫酸がより好まし
く用いられる。また溶媒としては二硫化炭素、モノクロ
ルベンゼン、ジクロルベンゼン、トリクロルベンゼン、
ニトロベ〜ｌ
−グクトール
！誘導体のＲ３が０７−Ｃｚのアルキル基の場合、目的
とするフルオラン誘導体の前駆体である下記一般式［Ｖ
Ｉ）で表わされるトリフェニルメタ（９）
この場合は得られた１−リフェニルメタン誘導体を必要
に応じて濾別し水酸化ナトリウム、水酸化カリウム等の
アルカリ性物質によって系のＰ Ｈを９゜５〜Ｉ２にし
、５０〜１００ °ｃに加温することによって目的とす
るフルオラン誘導体を得ることができる。なお、」二記
の水性媒体中にアセトン、ベンゼン、トルエン、キシレ
ン等の有機溶媒を併用すると収率が効果的に高められる
。とりわけベンゼン、トルエン、キシレン等の疎水性有
機溶媒は副反応の生成を防止し好ましい反応条件を与え
るためより好ましく用いられる。(7) [In the formula, R represents a hydrogen atom or a C/ to C2 alkyl group, and R/, R2, X, and n have the above-mentioned meanings. ] As a condensing agent in the condensation reaction of 2-(2-hydroxy-4-amino)hendiylbenzoic acid derivative NJ) and 5-cyclohexylamino-1-naphthol derivative [111), sulfuric acid; phosphorus pentoxide; phosphoric acid; Polyphosphoric acid; anhydrous tin chloride, anhydrous zinc chloride, anhydrous aluminum chloride, anhydrous tin bromide, anhydrous zinc bromide, anhydrous aluminum bromide, anhydrous iron bromide, etc. (8) Anhydrous metal halide; phosphorus trichloride; Free delta rat catalysts such as phosphorus chloride; phosphorus pentachloride; phosphorus pentabromide; anhydrous boron fluoride; and hydrofluoric acid are used alone or in combination. Among these, sulfuric acid which also serves as a solvent is more preferably used. In addition, as a solvent, carbon disulfide, monochlorobenzene, dichlorobenzene, trichlorobenzene,
Nitrobe~l-guktol! When R3 of the derivative is an alkyl group of 07-Cz, the following general formula [V
Triphenylmethane (9) represented by I) In this case, the obtained 1-liphenylmethane derivative is filtered if necessary, and the pH of the system is reduced to 9° with an alkaline substance such as sodium hydroxide or potassium hydroxide. The target fluorane derivative can be obtained by adjusting the temperature to 5 to I2 and heating to 50 to 100°C. Furthermore, if an organic solvent such as acetone, benzene, toluene, or xylene is used in combination with the aqueous medium described in Section 2, the yield can be effectively increased. In particular, hydrophobic organic solvents such as benzene, toluene, and xylene are more preferably used because they prevent the formation of side reactions and provide preferable reaction conditions.
かくして得られる本発明の一般式（１）で表わされるフ
ルオラン誘導体は前述の如く優れた特性を有する無色な
いし淡色の塩基性染料であり、特に顕色剤との呈色反応
を利用する各種の記録体に用いて極めて優れた効果を発
揮するものである。The fluoran derivative represented by the general formula (1) of the present invention obtained in this way is a colorless to light-colored basic dye having excellent properties as described above, and is particularly suitable for various types of recording using a color reaction with a color developer. It has extremely excellent effects when used on the body.
ここで用いられる顕色剤は記録体の種類に応じて適宜選
択されるものであるが、圧力、熱、電気エネルギーの媒
介によってフルオラン誘導体と顕色剤を接触せしめる、
例えば感圧記録体、感熱記録（１０）
体、通電感熱記録体、超音波記録体、静電記録体、タイ
プリボン、ボールペンインキ、クレヨンなどの記録体に
おいてはブレンステッドまたはルイス酸として作用する
物質が好ましく用いられる。具体的には例えば酸性白土
、活性白土、アタパルガイド、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、タルクなどの無機顕色
剤、シュウ酸、マレイン酸、酒石酸、クエン酸、コハク
酸、ステアリン酸などの脂肪族カルボン酸、安息香酸、
パラターシャリブチル安息香酸、フタル酸、没食子酸、
サリチル酸、３−イソブロビルザリチル酸、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
−ジ−ターシャリブチルサリチル酸、３−メチル−５−
ベンジルサリチル酸、３−フェニル−５−（α、α−ジ
メヂルヘンジル）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−ナフトエ酸など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、（１１）
４．４’−−イソプロピリデンビス（２−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’−イソプロピリチンビス
（２，６−ジクロロフェノール）、４．４’−イソプロ
ピリデンビス（２−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−タージャリブデ
ルフェノール）、４．４’−セカンダリーブヂリデンジ
フェノール、４．４′−シクロへキシリデンビスフェノ
ール、４．４′−シクロへキシリデンビス（２−メチル
フェノール）、４−ターシャリブチルフェノール、４−
フェニルフェノール、４−ヒ）ロキンジフエノキシド、
α−ナフトール、β−ナフトール、メチル−４−ヒドロ
キシヘンゾエート、ヘンシル−４−ヒトロキシヘンゾエ
ート、２．２′−チオビス（４，６−ジクロロフェノー
ル）、４−クーシャリ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−ター（１２）
シャリブチルフェノール）、２．２’−ジヒドロキシジ
フェニールなどのフェノール性化合物、パラ−フェニル
フェノール−ホルマリン樹脂、パラ−ブチルフェノール
−アセチレン樹脂などのフェノール樹脂の如き有機顕色
剤さらにはこれら有機顕色剤と例えば亜鉛、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、ニッケルなどの多価金属との塩、塩化水素、臭化水
素、沃化水素、ホウ酸、ケイ酸、リン酸、硫酸、硝酸、
過塩素酸の如き無機酸、およびアルミニウム、亜鉛、ニ
ッケル、スズ、チタン、ホウ素などのハロゲン化物など
が挙げられる。The color developer used here is appropriately selected depending on the type of recording medium, but the fluoran derivative and the color developer are brought into contact with each other through pressure, heat, or electrical energy.
For example, substances that act as Brønsted or Lewis acids in recording media such as pressure-sensitive recording media, thermosensitive recording media (10), electrically conductive thermosensitive recording media, ultrasonic recording media, electrostatic recording media, type ribbons, ballpoint pen inks, and crayons. is preferably used. Specifically, for example, acid clay, activated clay, attapulgide, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, inorganic color developer such as talc, oxalic acid, maleic acid, tartaric acid, citric acid. acids, aliphatic carboxylic acids such as succinic acid, stearic acid, benzoic acid,
paratertiary butylbenzoic acid, phthalic acid, gallic acid,
Salicylic acid, 3-isobrobylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3.5
-di-tert-butylsalicylic acid, 3-methyl-5-
Aromatic carboxylic acids such as benzylsalicylic acid, 3-phenyl-5-(α,α-dimedylhenzyl)salicylic acid, 3.5-di(α-methylbenzyl)salicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, 4.4'
-isopropylidene diphenol, (11) 4.4'--isopropylidene bis(2-chlorophenol), 4.4'-isopropylidene bis(2,6-dibromophenol), 4.4'-isopropyritine bis (2,6-dichlorophenol), 4,4'-isopropylidene bis(2-methylphenol), 4,4'-isopropylidene bis(2,6-dimethylphenol),
4.4'-isopropylidene bis(2-terjalibdelphenol), 4.4'-secondary butylidene diphenol, 4.4'-cyclohexylidene bisphenol, 4.4'-cyclohexylidene bis( 2-methylphenol), 4-tert-butylphenol, 4-
phenylphenol, 4-hy)loquine diphenoxide,
α-naphthol, β-naphthol, methyl-4-hydroxyhenzoate, hensyl-4-hydroxyhenzoate, 2,2'-thiobis(4,6-dichlorophenol), 4-cushalioctylcatechol, 2゜2 ′−
Phenolic compounds such as methylenebis(4-chlorophenol), 2,2'-methylenebis(4-methyl-6-ter(12)shabutylphenol), 2,2'-dihydroxydiphenyl, para-phenylphenol-formalin resin , organic color developers such as phenolic resins such as para-butylphenol-acetylene resins, and salts of these organic color developers with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, etc. Hydrogen chloride, hydrogen bromide, hydrogen iodide, boric acid, silicic acid, phosphoric acid, sulfuric acid, nitric acid,
Examples include inorganic acids such as perchloric acid, and halides such as aluminum, zinc, nickel, tin, titanium, and boron.
また、電子線記録体、感光性記録体の場合には電子綿や
光によって塩化水素、臭化水素、沃化水素の如きハロゲ
ン化水素、カルボン酸、スルホン酸、フェノール類など
を生じる例えば、四臭化炭素、α、α、α−トリブロモ
アセトフェノン、ヘキサクロロエタン、ヨードホルム、
２−トリブロモメチルピリジン、トリクロロメチルスル
ホニルベンゼンの如き有機ハロゲン化合物、０−キノン
シア（１３）
シト系化合物、光Ｉ’ｒｉｅｓ転移を起１ようなカルボ
ン酸又はスルホン酸のフェノールエステル類などが好ま
しく用いられる。In addition, in the case of electron beam recording materials and photosensitive recording materials, hydrogen halides such as hydrogen chloride, hydrogen bromide, hydrogen iodide, carboxylic acids, sulfonic acids, phenols, etc. are generated by electron beams or light. Carbon bromide, α, α, α-tribromoacetophenone, hexachloroethane, iodoform,
Preferably used are organic halogen compounds such as 2-tribromomethylpyridine and trichloromethylsulfonylbenzene, 0-quinonesia(13)cyto compounds, and phenolic esters of carboxylic or sulfonic acids that cause photoI'ries rearrangement. It will be done.
かかる顕色剤と本発明の一般式（１）で表わされるフル
オラン誘導体を用いた各種の代表的な記録体について、
以下にさらに具体的に説明する。Regarding various typical recording materials using such a color developer and the fluoran derivative represented by the general formula (1) of the present invention,
This will be explained in more detail 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
゜７３帆４５６号、同２，７３０，４５７号、同３，４
１８．２５０号、同３，９２４，０２７号、同４，０１
０，０３８号などに記載されているように種々の形態の
ものがあり、本発明のフルオラン誘導体はこれら各種の
形態の感圧記録体に適用出来るものである。Pressure-sensitive recording bodies are disclosed, for example, in U.S. Pat. No. 2,505,470;
No. 2,505,471, No. 2,505,489, No. 2,548,366, No. 2,712,507, No. 2
゜73 sail number 456, same number 2,730,457, same number 3,4
No. 18.250, No. 3,924,027, No. 4,01
As described in No. 0,038, there are various types of fluorane derivatives, and the fluorane derivative of the present invention can be applied to these various types of pressure-sensitive recording media.
一般的には本発明のフルオラン誘導体を単独又は混合し
、さらに必要に応じてトリフェニルメタンラクトン類、
スピロピラン類、フルオラン類、ジフェニルメタン類、
ロイコメチレンブルー類などの塩基性染料とともにアル
キル化ナフタレン、アルキル化ジフェニル、アルキル化
ジフェニルツク（１４）
ン、アルキル化ターフェニルなどの合成油、木綿油、ヒ
マシ油などの植物油、動物油、鉱物油或いはこれらの混
合物などからなる溶媒に熔解し、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法などの各種カプセル
製造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
脂コーテツド紙などの支持体上に塗布することによって
本発明の感圧記録体は製造される。勿論、支持体の片面
に上記分ｌＩ（！液を塗布した所謂上用シート、支持体
の片面に顕色剤を主体とする顕色剤塗液を塗布し、反対
面に上記分散液を塗布した所謂牛用シート、さらには支
持体の同一面に上記カプセルと顕色剤が混在する塗液を
塗布するか、カプセル分散液を塗布した」二に顕色剤塗
液を塗布するなどして、同一面に上記カプセルと顕色剤
を共存させた所謂単体複写シートなど各種の形態が含ま
れることは前述のとおりである。なお、フルオラン誘導
体の使用量は所望の塗布量、感圧記録体の形態、（１５
）
カプセルの製法、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
して適宜選択すればよい。いずれにしろ本発明の一般式
（１）で表わされるフルオラン誘導体を従来の各種感圧
記録体の塩基性染料として使用することにより、耐光性
に優れた記録像を形成することができる感圧記録体が得
られるものである。Generally, the fluoran derivatives of the present invention are used alone or in combination, and if necessary, triphenylmethane lactones,
Spiropyrans, fluorans, diphenylmethanes,
Along with basic dyes such as leucomethylene blue, synthetic oils such as alkylated naphthalene, alkylated diphenyl, alkylated diphenyl chloride (14), alkylated terphenyl, vegetable oils such as cotton oil and castor oil, animal oils, mineral oils, or these A dispersion prepared by dissolving this in a solvent such as a mixture of The pressure-sensitive recording material of the present invention is manufactured by applying the dispersion liquid dispersed in a binder onto a support such as paper, plastic sheet, resin-coated paper, or the like. Of course, one side of the support is coated with the above-mentioned lI (! liquid), and one side of the support is coated with a color developer coating liquid mainly consisting of a color developer, and the other side is coated with the above dispersion. A coating solution containing a mixture of the above capsules and a color developer is applied to the so-called cow sheet, and furthermore, a coating solution containing a mixture of the above capsules and a color developer is applied, or a developer coating solution is applied to a capsule dispersion. As mentioned above, various forms are included, such as a so-called stand-alone copying sheet in which the capsule and color developer coexist on the same surface.The amount of the fluoran derivative used depends on the desired coating amount and the pressure-sensitive recording material. form, (15
) It varies depending on various conditions such as the capsule manufacturing method, the composition of the coating liquid including various auxiliary agents, and the coating method, so it may be selected appropriately according to the conditions. In any case, by using the fluoran derivative represented by the general formula (1) of the present invention as a basic dye in various conventional pressure-sensitive recording materials, it is possible to form recorded images with excellent light resistance. It's what the body gets.
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−４３８
３０号、同４９−６９号、同４９−７０号、同５２−２
０１４２号などに記載されているように種々の形態のも
のがあり、本発明のフルオラン誘導体はこれら各種の形
態の感熱記録体に適用でき、しかも単に本発明のフルオ
ラン誘導体を染料として用いるのみで前述の如く優れた
性質を有する記録像を呈する感熱記録体が得られるもの
である。一般的にはバインダーを熔解または分散した媒
体中に本発明のフルオラン誘導体と顕色剤の微粒子を分
散させて得られる塗液を紙、（１６）
プラスチックフィルム、合成紙さらには織布シート、成
形物などの適当な支持体上に塗布することによって本発
明の感熱記録体は製造される。記録層中のフルオラン誘
導体を主体とする塩基性染料と顕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重量部の顕色剤が用
いられる。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-438
No. 30, No. 49-69, No. 49-70, No. 52-2
As described in No. 0142, etc., there are various forms of the fluoran derivative, and the fluoran derivative of the present invention can be applied to these various forms of heat-sensitive recording materials.Moreover, by simply using the fluoran derivative of the present invention as a dye, A heat-sensitive recording material exhibiting a recorded image having excellent properties as described above can be obtained. In general, a coating liquid obtained by dispersing the fluoran derivative of the present invention and fine particles of a color developer in a medium in which a binder is melted or dispersed is used for paper, (16) plastic films, synthetic papers, woven fabric sheets, and molding. The heat-sensitive recording material of the present invention is produced by coating it on a suitable support such as a material. The ratio of the basic dye mainly consisting of a fluoran derivative and the color developer used in the recording layer is not particularly limited, but is generally 1 part by weight of the dye.
~50 parts by weight, preferably 2 to 10 parts by weight of color developer are used.
また、発色能の改良、記録層表面の艶消し、筆記性の改
良などを目的として、多価金属の酸化物、水酸化物、炭
酸化物等の無機金属化合物や無機顔料を一般に顕色剤１
重量部に対し０．１〜５重量部、好ましくは０．２〜２
重量部併用することができ、さらに例えば分散剤、紫外
線吸収剤、熱可融性物質、消泡剤、螢光染料、着色染料
などの各種助剤を必要に応じて適宜併用できる。In addition, inorganic metal compounds such as oxides, hydroxides, and carbonates of polyvalent metals and inorganic pigments are generally used as color developers for the purpose of improving color development, matting the surface of the recording layer, and improving writing properties.
0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight
Parts by weight can be used in combination, and various auxiliary agents such as dispersants, ultraviolet absorbers, thermofusible substances, antifoaming agents, fluorescent dyes, and coloring dyes can be used in combination as necessary.
本発明の感熱記録体は上述の如く、一般にフルオラン誘
導体と顕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フルオラン誘導体と顕色
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（１７）
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。その他塗液の調製方法、塗布方法などについて
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２〜１２ｇ／イ程度塗布される。なお、バインダー
としては例えばデンプン類、セルｌコース類、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゛１クリル酸塩などが適宜選択して用いられる。As mentioned above, the heat-sensitive recording material of the present invention is generally manufactured by applying a coating liquid in which fine particles of a fluoran derivative and a color developer are dispersed to a support, but the fluoran derivative and the color developer are each dispersed separately. It is also possible to overcoat the two types of coating liquids on the support (17), and it is of course also possible to manufacture by impregnation or rolling. There are no particular limitations on the preparation method or coating method of the coating solution, and the amount of coating is generally about 2 to 12 g/I in terms of dry weight. Examples of the binder include starches, cellulose, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salt, styrene-butadiene copolymer emulsion, and vinegar-vinyl maleic anhydride copolymer salt. , poly(1-acrylate), etc. are appropriately selected and used.
１ｆｆｉ電感熱記録体は例えば特開昭４９−１１３４４
号、同５０−４８９３０号などに記載の方法によって製
造される。一般に、導電物質、本発明のフルオラン誘導
体を主体とする塩基性染料および顕色剤をバインダーと
共に分散した塗液を紙などの支持体に塗布するが、支持
体に導電物質を塗布して導電層を形成し、その上に染料
、顕色剤およびバインダーを分散した塗液を塗布するこ
とによって本発明の通電感熱記録体は製造される。なお
、染料と顕色剤が共に７０−１２０′ｃといった好ま（
１８）
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。1ffi electric thermosensitive recording material is disclosed in, for example, Japanese Patent Application Laid-Open No. 49-11344.
No. 50-48930. Generally, a coating liquid in which a conductive substance, a basic dye mainly composed of the fluoran derivative of the present invention, and a color developer are dispersed together with a binder is applied to a support such as paper. The current-carrying heat-sensitive recording material of the present invention is produced by forming a coating material and applying thereon a coating liquid in which a dye, a color developer, and a binder are dispersed. In addition, both the dye and the color developer are preferably 70-120'c (
18) If the material does not melt in the desired temperature range, sensitivity to Joule heat can be adjusted by using an appropriate thermofusible substance in combination.
感光性記録体は本発明のフルオラン誘導体を用い例えば
特公昭３Ｂ−２４１８８号、同４５−１０５５０号、同
４５−１３２５８号、同４９−２０４号、同４９−６２
１２号、同４９−２８４４９号、特開昭４７−３１６１
５号、同４Ｂ−３２５３２号、同４９−９２２７号、同
４９−１３５６１７号、同５０−８０１２０号、同５０
−８７３１７号、同５０−１２６２２８号などに記載の
方法によって製造される。The photosensitive recording material uses the fluoran derivative of the present invention, for example, Japanese Patent Publications No. 3B-24188, No. 45-10550, No. 45-13258, No. 49-204, No. 49-62.
No. 12, No. 49-28449, JP-A No. 47-3161
No. 5, No. 4B-32532, No. 49-9227, No. 49-135617, No. 50-80120, No. 50
-87317, No. 50-126228, etc.
その他超音波記録体（仏画特許第２１２０９２２号）、
電子線記録体（ベルギー特許第７９５９９８６号）、静
電記録体（特公昭４９−３９３２号）、感光性印刷材（
特開昭４８−１２１０４号）、捺印用材（特公昭４７−
１０７６６号）、タイプリボン（特開昭４９−３７１３
号）、ボールペンインキ（特開昭４８−８３９２４号）
、クレヨン（米国特許第３７６９０４５号）など各種の
（１９）
記録体については、従来の塩基性染料に替えて本発明の
フルオラン誘導体を使用し、それぞれの特許に記載され
た方法によって製造することができる。Other ultrasonic recording bodies (French Painting Patent No. 2120922),
Electron beam recording material (Belgium Patent No. 7959986), electrostatic recording material (Special Publication No. 1973-3932), photosensitive printing material (
JP-A-48-12104), stamping material (JP-A-1973-12104)
10766), Type Ribbon (JP-A-49-3713
No.), ballpoint pen ink (JP-A-48-83924)
Various types of (19) recording media, such as crayons (U.S. Pat. No. 3,769,045), can be manufactured by using the fluoran derivatives of the present invention in place of conventional basic dyes and by the methods described in the respective patents. can.
以下に実施例を挙げて本発明をさらに具体的に説明する
が、本発明の要旨をこえない限り、これらに限定される
ものではない。また、実施例中の部および％は特に断ら
ない限り、それぞれ重量部、重量％を表わす。The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto unless it goes beyond the gist of the present invention. Further, parts and % in the examples represent parts by weight and % by weight, respectively, unless otherwise specified.
〔実施例１〕
２−（２−ヒドロキン−４−ジメチルアミノ）へソイル
安息ｆ’ＭＯ，０１１Ｅ−ルと５−シクロへキシルアミ
ノ−１−ナフトール−メチルエーテル０゜０１０モルと
を１５ｍβの濃硫酸中で室温下２４時間反応させた。得
られた反応物を１００ｍρの氷水中に注加し室温下２０
％の水酸化ナトリウム水溶液を加えてＰＨＩＩとした後
、トルエン５０ｍ１２を加え８５℃で３時間加温した。[Example 1] 2-(2-Hydroquine-4-dimethylamino)hexylbenzene f'MO,011E- and 0.010 mol of 5-cyclohexylamino-1-naphthol-methyl ether were dissolved in 15 mβ of concentrated sulfuric acid. The mixture was reacted for 24 hours at room temperature. The obtained reaction product was poured into ice water of 100mρ and heated at room temperature for 20 minutes.
% aqueous sodium hydroxide solution was added to prepare PHII, 50 ml of toluene was added and heated at 85° C. for 3 hours.
次いでトルエン層を分取し、トルエンを減圧留去した後
でエチルアルコールによって再結晶し、３−シクロへ（
２０）
キシルアミノ−８−ジメチルアミノベンゾＣＣ）フルオ
ランを無色針状晶として得た。なお、収率５３％、ｍ、
ｐ、 ： １８５〜１８９°Ｃ、シリカゲル上で赤黒
色に発色した。Next, the toluene layer was separated, toluene was distilled off under reduced pressure, and then recrystallized from ethyl alcohol to form 3-cyclo(
20) Xylamino-8-dimethylaminobenzoCC) fluoran was obtained as colorless needles. In addition, yield 53%, m,
p: Developed red-black color on silica gel at 185-189°C.
〔実施例２〕
２−（２−ヒドロキシ−４−ジエチルアミノ）ベンゾイ
ル安息香ＭＯ，０１モルと５−シクロヘキシルアミノ−
１−ナノトール０．０１モルとを１０ｍＡＣ）濃硫酸中
で室温下１７時間反応させた。得られた反応物を１００
ｍｊ！の氷水中に注加し室温下２０％の水酸化ナトリウ
ム水溶液を加えてＰ Ｈ９とした後、生成した沈澱を濾
過、水洗、乾燥した。次いでベンゼンにより再結晶をし
、３−シクロヘキシルアミノ−８−ジエチルアミノベン
ゾ〔Ｃ〕フルオランを無色の結晶として得た。なお、収
率８５％、ｍ、ｐ、：１６９〜１７２℃、シリカゲル上
で赤黒色に発色した。[Example 2] 2-(2-hydroxy-4-diethylamino)benzoylbenzoic acid MO, 01 mol and 5-cyclohexylamino-
0.01 mol of 1-nanotol was reacted with 0.01 mol of 1-nanotoll in 10 mAC) concentrated sulfuric acid at room temperature for 17 hours. The obtained reaction product was 100
mj! The mixture was poured into ice water and adjusted to pH 9 by adding a 20% aqueous sodium hydroxide solution at room temperature, and the resulting precipitate was filtered, washed with water, and dried. Then, recrystallization was performed from benzene to obtain 3-cyclohexylamino-8-diethylaminobenzo[C]fluoran as colorless crystals. Note that the yield was 85%, m, p,: 169 to 172°C, and a red-black color developed on silica gel.
〔実施例３〕
２−（２−ヒドロキシ−４−ジブチルアミノ）ベンゾイ
ル−３，４，５，６−テトラクロル安息（２１）
香酸０．０１モルと５−シクロへキシルアミノ−１−ナ
フトール−エチルエーテル０．０１モルとを１０ ｍ
ｊ＋の濃硫酸中で室温下２４時間反応させた。[Example 3] 2-(2-hydroxy-4-dibutylamino)benzoyl-3,4,5,6-tetrachlorobenzoate (21) 0.01 mol of folic acid and 5-cyclohexylamino-1-naphthol-ethyl 0.01 mole of ether and 10 m
The reaction was carried out in concentrated sulfuric acid of J+ at room temperature for 24 hours.
得られた反応物を１００ｍρの氷水中に注加し室温下２
０％の水酸化ナトリウム水溶液を加えてＰＩｌｌｌとし
、アセトン３０ｒｒ＋ｊ！を加えた後３時間還流した。The obtained reaction product was poured into ice water of 100 mρ and heated at room temperature for 2 hours.
Add 0% sodium hydroxide aqueous solution to make PIll, and add acetone 30rr+j! was added, and the mixture was refluxed for 3 hours.
次いでアセトンを除去し、得られた結晶状の沈澱を濾別
後水洗し、さらにイソプロピルアルコールで再結晶して
、３−シクロへキシルアミノ−８−ジブチルアミノ−３
’、４’、５’。Next, acetone was removed, and the obtained crystalline precipitate was filtered, washed with water, and further recrystallized from isopropyl alcohol to obtain 3-cyclohexylamino-8-dibutylamino-3.
', 4', 5'.
６′−テトラクロル安息ゾＣＣ）フルオランを無色針状
晶として得た。なお、収率７１％、ｍ、ｐ。6'-TetrachlorobenzoCC) fluoran was obtained as colorless needles. Note that the yield was 71%, m, p.
＝１７３〜１７９℃、シリカゲル上で黒色に発色した。=173-179°C, developed black color on silica gel.
〔実施例４〕
実施例２で得られた３−シクロヘキシルアミノ−８−ジ
エチルアミノベンゾＣＣ）フルオランを用いて下記の方
法で感熱記録紙を製造した。[Example 4] A thermosensitive recording paper was produced using the 3-cyclohexylamino-8-diethylaminobenzo CC) fluoran obtained in Example 2 in the following manner.
Ａ波調製
実施例２のフルオラン誘導体 ５部（２２）
ステアリン酸アミド １部ヒドロ
キシエチルセルロースの２％水ｆａ ？（１２５部
ごの組成物をサントグラインダーで平均￥′ｌ′１．経
２ミクロンまでわ）砕した。Fluoran derivative of A-wave preparation example 2 5 parts (22) Stearic acid amide 1 part 2% water fa of hydroxyethyl cellulose ? (Every 125 parts of the composition was ground to an average size of ¥'l'1.2 microns using a sand grinder).
Ｂ波調製
４．４′−イソプロピリデンジフェノール５０部
ステアリン酸アミド １０部ヒドロ
キシエチルセルロースの２％水熔液２５０宮（；
この組成物をサンドグラインダーで平均粒１￥２ミクロ
ンまで粉砕した。B wave preparation 4. 4'-Isopropylidene diphenol 50 parts Stearic acid amide 10 parts 2% hydroxyethyl cellulose in water 250 parts (This composition was ground to an average particle size of 1.2 microns with a sand grinder.
Ｃｌｌ開開
Ａ液 ６２部Ｂ液
３１部超敬粒子状無水シリカ（商
品名サイロイド２４４、富士デヴイソン化学社製）
２５部スチレン−無水マレイン酸共市合体塩の２０％
水ン容ン夜 １７
５部（２３）
ステアリン酸亜鉛 ５部水
１００部
上記の割合で混合して塗液とした。Cll opening liquid A 62 parts liquid B
31 parts ultra-particle anhydrous silica (trade name Thyroid 244, manufactured by Fuji Davison Chemical Co., Ltd.)
25 parts styrene-maleic anhydride co-merchandising salt 20%
water night 17
5 parts (23) Zinc stearate 5 parts Water
100 parts were mixed at the above ratio to prepare a coating liquid.
痔られた塗液を５０ｇ／ポの原紙上に乾燥塗布量が６
ｇ ／ ｍとなるように塗−１−シて感熱記録紙を得た
。１厚られた記録紙は地肌カフリがなく良々ｒな白紙外
観を有し、これを４ ｋｇ ／ ｃＩｌの圧力で１２５
゛Ｃ０）熱板に５秒ｍ）押圧したところ遍い川魚に発色
した。この発色像は耐光性に優れており日光に曝しても
変色したり消失することは無かった。The dry coating amount is 6 on the base paper of 50g/po.
A heat-sensitive recording paper was obtained by coating the sample to give a coating weight of 1-1 g/m. The 1-thick recording paper has a good blank appearance with no background cuffing, and is heated to 125 cm at a pressure of 4 kg/cIl.
゛C0) When pressed for 5 seconds on a hot plate, color developed all over the river fish. This colored image had excellent light resistance and did not discolor or disappear even when exposed to sunlight.
なお、ト実施例の感熱記録ＩＦ、を炭酸カスレーザー（
出力１〜′ ビーム径１５０μ）により、走査速度ｆ）
７ｍ ” ｓＰｃの円筒走査型記録試験機で記録し一二
七ごろ、＋ｎ＋ Ｊｉ度の川魚を呈する記録像が得られ
た。It should be noted that the thermal recording IF of Example 1 was used with a carbon dioxide gas laser (
Output 1~' beam diameter 150μ), scanning speed f)
Recording was performed using a 7 m'' sPc cylindrical scanning recording tester, and around 127, a recorded image showing a +n+ Ji degree river fish was obtained.
Ｃ実施例５）
実施例２で得られたフルＡラン誘導体５部をイソプロピ
ル化ナフタし２１００部にｆｇ解し、等電点８のビグス
キンゼラヂン２５部とアラビアゴム２５部を熔解した３
５０部の温水（５０’ｃン中に（２４）
添加し乳化分散した。この乳化液に１０００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２５％水溶液ＩＯ部を加えカプ
セルを硬化した。このカプセル含有塗液を４５ｇ／ｒｄ
の原紙の片面に乾燥重量が５ｇ／ｒＫとなるよう塗工し
、裏面には水２００部に３．５−ジー（α−メヂルヘン
ジル）サリチル酸の亜鉛塩２０部、カオリンｓ ｏ ｑ
＋＋、スヂレンーブタジエン共重合体エマルジョン（５
０％固形分）３０部を分散した顕色剤塗液を乾燥重量が
５ｇ／−となるよう塗工して感圧記録紙（中用紙）を得
た。C Example 5) 5 parts of the full A run derivative obtained in Example 2 was dissolved in isopropylated naphtha to 2100 parts, and 25 parts of bigskin geladine with an isoelectric point of 8 and 25 parts of gum arabic were melted.
50 parts of warm water (24) was added to 50 cm and emulsified and dispersed. 1000 parts of warm water was added to this emulsion, the pH was adjusted to 4 with acetic acid, and the mixture was cooled to 10°C.
IO parts of a 25% aqueous solution of gel taraldehyde was added to harden the capsules. 45g/rd of this capsule-containing coating liquid
One side of the base paper was coated with a dry weight of 5 g/rK, and the other side was coated with 200 parts of water, 20 parts of zinc salt of 3.5-G (α-medylhenzyl) salicylic acid, and kaolin SOQ.
++, styrene-butadiene copolymer emulsion (5
A pressure-sensitive recording paper (inside paper) was obtained by applying a color developer coating liquid containing 30 parts of 0% solids dispersed therein to a dry weight of 5 g/-.
カプセル塗布面と顕色剤塗布面が相対向するように数枚
重ね筆記、加圧したところ即色剤塗布面に緑黒色の発色
像が得られた。この発色像は発色初期より発色速度が早
く、印字初期より高濃度であり、かつ日光に曝しても変
色あるいは褪色は認められなかった。When several sheets were written and pressed so that the capsule-coated surface and the color developer-coated surface faced each other, a green-black colored image was obtained on the color fixing agent-coated surface. This colored image had a faster color development rate than the initial stage of color development, a higher density than the initial stage of printing, and no discoloration or fading was observed even when exposed to sunlight.
（実施例６〕
１％のポリビニルアルコール水溶液２００部に（２５）
ヨウ化第−銅２００部、１０％の亜硫酸ナトリウム水溶
液５部を加えサントグラインダーで平均粒径が２ミクロ
ンになるまで粉砕した。、これにポリアクリル酸エステ
ルエマルジョン８部、酸化チタン２０部を加え充分に分
散した１多、５０ｇ／ｍの厚紙に乾燥塗布量が７ｇ／ｎ
ｆとなるよう塗工した。(Example 6) 200 parts of cupric iodide (25) and 5 parts of a 10% sodium sulfite aqueous solution were added to 200 parts of a 1% polyvinyl alcohol aqueous solution and ground with a sand grinder until the average particle size was 2 microns. To this, 8 parts of polyacrylic acid ester emulsion and 20 parts of titanium oxide were added and thoroughly dispersed, and the dry coating amount was 7 g/n on 50 g/m cardboard.
It was coated to give f.
この塗布層の１−に３−シクロへキンルアミノ−８−ジ
エチルアミノヘンヅＣＣ）フルオランの替りに実施例１
で得られた３−シクロへキンルアミノ−８ノメチルアミ
ノヘンゾＣＣ）フルオランを用いた以外は実施例４と同
様にして調製した感熱塗液を乾燥塗布量が５ｇ／＝とな
るよう塗工し、１１ＴＩ電堅舷ｄ己ｔｌ民をｉ尋た。Example 1 In place of 3-cyclohequinylamino-8-diethylaminohend CC) fluoran in 1- of this coating layer
A heat-sensitive coating liquid prepared in the same manner as in Example 4 except for using the 3-cyclohequinylamino-8nomethylaminohenzo CC) fluoran obtained in Example 4 was applied so that the dry coating amount was 5 g / =, 11 I asked the people on the TI electric board.
この記録紙を引圧１０ｇ、走査速度６３０１＊／ｓｅｃ
の円筒走査型記録試験機で記録したところ、濃厚な川魚
の記録像が１ηられた。この記録像は耐光性に優れてお
り、日光に曝しても変色したり、消色することはなかっ
た。This recording paper was pulled at a suction pressure of 10 g and a scanning speed of 6301*/sec.
When recording with a cylindrical scanning recording tester, a rich recorded image of river fish was recorded at 1η. This recorded image had excellent light resistance and did not change color or fade even when exposed to sunlight.
〔実施例７〕
実施例３で得られた３−シクロへキンルアミノ（２６）
−８−ジブチルアミノ−３／、 ４１． ５１． ６
Ｐ−テトラクロルーヘンゾ（Ｃ）フルオラン６ｇをクロ
ロホルム４９ｍｊ！に熔解し、これにポリスチレンのＩ
Ｏ％ヘンゼン溶液４０ｍ１ｌ、四臭化炭素５ｇを加えよ
く攪拌して調製した塗液を両面ポリエヂレンラミネート
紙に乾燥塗布量が５ｇ＃となるように暗所で塗工し感光
性記録シートを得た。[Example 7] 3-cyclohequinylamino(26)-8-dibutylamino-3/ obtained in Example 3, 41. 51. 6
6 g of P-tetrachlorhenzo(C) fluorane and 49 mj of chloroform! and polystyrene I to this.
A coating solution prepared by adding 40ml of O% Hensen's solution and 5g of carbon tetrabromide and stirring well was applied to double-sided polyethylene laminated paper in a dark place to a dry coating amount of 5g#, and a photosensitive recording sheet was prepared. Obtained.
これに２０Ｗの紫外燈８本で５ｃｍの距離から１０分間
照射発色させたところ赤黒色の発色像が得られた。この
後アセトン／ｎ−ヘキサン： ｌ ／ ５で洗藷して定
着した。発色像は日光に曝しても安定であった。When this was irradiated with eight 20 W ultraviolet lights from a distance of 5 cm for 10 minutes, a red-black colored image was obtained. Thereafter, it was fixed by washing with acetone/n-hexane: 1/5. The colored image was stable even when exposed to sunlight.
特許出願人 神崎製机株式会社 （２７）Patent applicant: Kanzaki Seiki Co., Ltd. (27)
Claims (1)
式中Ｒ，，ＲンはＣ／−Ｃ−ｆのアルキル基を、Ｘはハ
ロゲン原子を示し、ｎは０〜４の整数を示す。〕 （２）下記一般式（ＩＩ）で表わされる２−（２−ヒド
ロキシ−４−アミノ）ヘンジイル安息香酸ＭＭ導体と （１） （式中Ｒ１，Ｒ２はＣ７〜Ｃ４のアルキル基を、Ｘはハ
ロゲン原子を示し、ｎは０〜４の整数を示す。） 下記一般式（Ｉ［Ｉ）で表わされる５−シクロへキシル
アミノ−１−ナフトール誘導体 〔式中Ｒ３は水素原子又はＣ／〜ＣＺのアルキル基を示
す。〕 とを反応させることよりなる下記一般式Ｎ）で表わされ
るフルオラン誘導体の製造法。 （２） 〔式中Ｒ７、Ｒｚ、Ｘ、ｎは前述の意味を示す。〕（３
）下記一般式（１）で表わされるフルオラン銹〔式中Ｒ
／、Ｒ２はｃｙ〜Ｃダのアルキル基を、Ｘはハロゲン原
子を示し、ｎは０〜４の整数を示す。〕 の少なくとも一種を電子供与性発色物質として含有せし
めた記録体。[Claims] (II) Fluorane represented by the following general formula (1) [
In the formula, R,,Rn represents a C/-Cf alkyl group, X represents a halogen atom, and n represents an integer of 0 to 4. ] (2) 2-(2-hydroxy-4-amino)hendiylbenzoic acid MM conductor represented by the following general formula (II) and (1) (wherein R1 and R2 are C7 to C4 alkyl groups, and X is 5-cyclohexylamino-1-naphthol derivative represented by the following general formula (I [I], where R3 is a hydrogen atom or a C/~CZ Indicates an alkyl group. ] A method for producing a fluoran derivative represented by the following general formula N), which comprises reacting with: (2) [In the formula, R7, Rz, X, and n have the above-mentioned meanings. ](3
) Fluorane salt represented by the following general formula (1) [in the formula R
/, R2 represents an alkyl group of cy to Cda, X represents a halogen atom, and n represents an integer of 0 to 4. ] A recording medium containing at least one of the following as an electron-donating coloring substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57178145A JPS5968372A (en) | 1982-10-09 | 1982-10-09 | Fluoran derivative, its preparation and recording medium utilizing its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57178145A JPS5968372A (en) | 1982-10-09 | 1982-10-09 | Fluoran derivative, its preparation and recording medium utilizing its derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5968372A true JPS5968372A (en) | 1984-04-18 |
Family
ID=16043422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57178145A Pending JPS5968372A (en) | 1982-10-09 | 1982-10-09 | Fluoran derivative, its preparation and recording medium utilizing its derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5968372A (en) |
-
1982
- 1982-10-09 JP JP57178145A patent/JPS5968372A/en active Pending
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