JPS63120760A - Fluorene compound and recording material obtained by using the same - Google Patents
Fluorene compound and recording material obtained by using the sameInfo
- Publication number
- JPS63120760A JPS63120760A JP61266603A JP26660386A JPS63120760A JP S63120760 A JPS63120760 A JP S63120760A JP 61266603 A JP61266603 A JP 61266603A JP 26660386 A JP26660386 A JP 26660386A JP S63120760 A JPS63120760 A JP S63120760A
- Authority
- JP
- Japan
- Prior art keywords
- fluorene compound
- color
- formula
- recording material
- paper
- 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
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 20
- -1 Fluorene compound Chemical class 0.000 title claims description 34
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000011161 development Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003094 microcapsule Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 description 4
- 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 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000011981 development test Methods 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- JJXVDRYFBGDXOU-UHFFFAOYSA-N dimethyl 4-hydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=C(O)C=C1C(=O)OC JJXVDRYFBGDXOU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YKPAABNCNAGAAJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)propane Chemical compound C=1C=C(O)C=CC=1C(CC)C1=CC=C(O)C=C1 YKPAABNCNAGAAJ-UHFFFAOYSA-N 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-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
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical class C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- LKWSCLZNBWZMTI-UHFFFAOYSA-N dibenzyl 4-hydroxybenzene-1,2-dicarboxylate Chemical compound C=1C=CC=CC=1COC(=O)C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 LKWSCLZNBWZMTI-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000001951 dura mater Anatomy 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000000314 lubricant Substances 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Color Printing (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規なフルオレン化合物及びそれを従来の技術
電子供与性発色剤を用いる記録材料としては感圧複写紙
、感熱記録紙、４＋転写記鎌紙など種々の形態のものが
知られている。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel fluorene compound and its use in conventional techniques.Recording materials using electron-donating coloring agents include pressure-sensitive copying paper, heat-sensitive recording paper, and 4+ transfer recording paper. Various forms such as these are known.
感圧、感熱記録材料は一般的にはほぼ無色の電子供与性
発色剤と、その発色剤を接触特発色せしめ着色像を形成
しうる呈色剤との間の化学反応を利用したものである。Pressure-sensitive and heat-sensitive recording materials generally utilize a chemical reaction between an almost colorless electron-donating coloring agent and a coloring agent that causes the coloring agent to develop a special color upon contact and form a colored image. .
これらの記録材料は他の記録材料１例えば電子写真や静
電記録材料に比べ現像、定着などの煩雑な処理を施すこ
となく比較的簡単な装置で短時間に記録が得られること
等から各方面に利用されている。そしてこのような記録
材料に用いられる電子供与性発色剤としては、トリフェ
ニルメタン系の染料やフルオラン系の染料等が主に使用
されている。Compared to other recording materials such as electrophotographic and electrostatic recording materials, these recording materials are widely used in various fields because they can produce records in a short time using relatively simple equipment without the need for complicated processes such as development and fixing. It is used for. As electron-donating color formers used in such recording materials, triphenylmethane dyes, fluoran dyes, and the like are mainly used.
一方光学文字読取装置やラベルバーコード読取装置にお
いてはその光源として発光ダイオードや半導体レーザー
を用いた光波長７００ ｎｍ 以上の光源が一般的に使
用されるようになってきた。On the other hand, in optical character reading devices and label barcode reading devices, light sources with light wavelengths of 700 nm or more using light emitting diodes or semiconductor lasers have come to be commonly used.
ところが上記のトリフェニルメタン系の染料やフルオラ
ン系の染料は可視光による読み取りを指向したものであ
り７００ ｎｍ 以上の近赤外領域の光吸収がほとんど
ないため、前記の読取装置ではその発色読取りが不可能
である。However, the triphenylmethane-based dyes and fluorane-based dyes mentioned above are intended for reading using visible light and have almost no light absorption in the near-infrared region of 700 nm or more, so the above-mentioned reading devices cannot read their color. It's impossible.
このような情況から発色体の光吸収波長が７００ｎｍ
以上である電子供与性発色剤の開発が強く要望されて
いる。Under these circumstances, the light absorption wavelength of the coloring body is 700 nm.
There is a strong demand for the development of the above electron-donating color former.
従来近赤外領域の波長を吸収する電子供与性発色剤につ
いていくつかの提案がなされており、公知の文献として
例えば特公昭５８−５９４０１％開昭５９−１９９７５
７等がある。即ち特公昭５８−５９４０にはジビニル基
含有フタリド誘導体の使用が提案されている。しかしな
がら、この化合物を記録材料として用いた場合、呈色剤
と接触して発色した像は近赤外領域の光を吸収するけれ
ども１発色前でもかなりの近赤外領域の光を吸収するた
め発色像を光学文字読取装置で判読させた場合、誤読を
起こし読取精度が劣るという欠点を有する。Conventionally, several proposals have been made regarding electron-donating color formers that absorb wavelengths in the near-infrared region.
There is a 7th grade. That is, Japanese Patent Publication No. 58-5940 proposes the use of divinyl group-containing phthalide derivatives. However, when this compound is used as a recording material, the image that develops when it comes into contact with a coloring agent absorbs light in the near-infrared region, but even before one color develops, it absorbs a considerable amount of light in the near-infrared region, so the color develops. When the image is read by an optical character reading device, it has the disadvantage that reading errors occur and the reading accuracy is poor.
又特開昭５９−１９９７５７には式（ｎ）で示されるフ
ルオレン化合物
が記載されており、その発色画像は近赤外領域に吸収が
ある。Further, JP-A-59-199757 describes a fluorene compound represented by formula (n), and its colored image has absorption in the near-infrared region.
しかし式（Ｉｆ）の発色画像は画像の安定性、特に耐光
堅牢度に劣るという欠点を有し、かつ感熱記録紙に用い
た場合１発色感度が悪いという欠点を有する。また感圧
複写紙に用いた場合には１式（ｎ）の化合物がアルキル
ナフタリン等の溶剤に溶解しにくいため高鎖度のマイク
ロカプセルを作り難く。However, the colored image of formula (If) has the drawback of poor image stability, particularly light fastness, and also has the drawback of poor color development sensitivity when used on thermosensitive recording paper. Furthermore, when used in pressure-sensitive copying paper, the compound of Formula 1 (n) is difficult to dissolve in solvents such as alkylnaphthalene, making it difficult to form microcapsules with a high chain degree.
コントラストの強い発色画像を得にくいという欠点を有
する。It has the disadvantage that it is difficult to obtain colored images with strong contrast.
発明が解決しようとする問題点
アルキルナフタリン等の溶剤に溶解しゃすくかつ発色感
度１発色濃度１発色像の堅牢度等にすぐれ読取精度のた
がい近赤外領域に吸収を有する発色剤の開発が望まれて
いる。Problems to be Solved by the Invention It is desirable to develop a color forming agent that is soluble in a solvent such as alkylnaphthalene, has excellent color development sensitivity, color density, fastness of color image, etc., and has absorption in the near-infrared region with reading accuracy. It is rare.
問題点を解決する為の手段
本発明者らは前記したような問題点を解決すべく鋭意研
究を重ねた結果本発明に到ったものである。即ち本発明
は
一般式ＣＩ）
（式中・Ｒ１，Ｒ２・Ｒ３，Ｒ４，Ｒ５およびＲ６は各
々炭素数１〜４のアルキル基又はアリル基を、又は水素
、メチル又はハロゲンを表す。但しＸが水素の時はＲ１
，Ｒ２，ＲＳ、 Ｒ４，Ｒ５およびＲ６のうち少なくと
も一つはアリル基を表す）
で表されるフルオレン化合物及びこれを用いた記録材料
を提供する。Means for Solving the Problems The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result they have arrived at the present invention. That is, the present invention relates to the general formula CI) (wherein R1, R2, R3, R4, R5 and R6 each represent an alkyl group or an allyl group having 1 to 4 carbon atoms, or hydrogen, methyl or halogen, provided that X is R1 for hydrogen
, R2, RS, at least one of R4, R5 and R6 represents an allyl group) and a recording material using the same.
本発明の一般式（１）で表されるフルオレン化合物は新
規であり、それ自体は実質的に無色の結晶で近赤外領域
に吸収を有しないが、酸性白土、フェノール樹脂、フェ
ノール性化合物などの酸性物質と接触することにより、
青色から緑色に発色し。The fluorene compound represented by the general formula (1) of the present invention is new, and it is a substantially colorless crystal and has no absorption in the near-infrared region, but it is compatible with acid clay, phenolic resins, phenolic compounds, etc. By contact with acidic substances,
The color changes from blue to green.
７００ ｎ１ｌｌ〜１．０００ ｎｍ付近の近赤外領域
に吸収を有しかつ前記したような欠点を改良した記録材
料を与えるものである。すなわち一般式ＣＩ）で表され
る化合物による発色画像は耐光堅牢度にすぐれ、感熱記
録紙に用いた場合、地肌の白色度が優れ誤読取りがなく
１発色速度がすぐれるため高感度の記録材料を得ること
が出来る。又１発色画像の耐水性、耐湿熱性等の諸堅牢
度にも優れる。The present invention provides a recording material which has absorption in the near-infrared region around 700 nm to 1.000 nm and which has improved the above-mentioned drawbacks. In other words, the colored image produced by the compound represented by the general formula CI) has excellent light fastness, and when used in heat-sensitive recording paper, it is a highly sensitive recording material because the whiteness of the background is excellent, there is no misreading, and the color development speed is excellent. can be obtained. Furthermore, it is excellent in various fastness properties such as water resistance and heat and humidity resistance for single-color images.
又、感圧複写紙として用いた場合には一般式ＣＩ）の化
合物がアル中ルナフタレン等の溶剤に溶解し易いため、
コントラストの強い発色画像が得られる。In addition, when used as pressure-sensitive copying paper, the compound of general formula CI) is easily dissolved in solvents such as lunaphthalene in alcohol.
A colored image with strong contrast can be obtained.
したがって、一般式ＣＩ）で表されるフルオレン化合物
は近赤外領域に吸収を有する電子供与性発色剤として幅
広い用途を有するものである。Therefore, the fluorene compound represented by the general formula CI) has a wide range of uses as an electron-donating color former having absorption in the near-infrared region.
本発明の一般式ＣＩ）で表されるフルオレン化合物は例
えば次のようにして製造される。The fluorene compound represented by the general formula CI) of the present invention is produced, for example, as follows.
（１） 一般式ＣＩ［［）
Ｃ式中、 Ｒ１、Ｒ２，Ｒ３，ｕ４＋Ｒ５，Ｒ６及Ｕ
ｘハ前記と同じ意味を表す）
で表される化合物を無機酸中、好ましくは硫酸中−５〜
１０℃でジアゾ化し１次いで１０℃〜１３０℃で数時間
ないし数十時間攪拌して閉環させる。(1) General formula CI[[] In the C formula, R1, R2, R3, u4+R5, R6 and U
x represents the same meaning as above) in an inorganic acid, preferably in sulfuric acid.
Diazotization is carried out at 10°C, followed by stirring at 10°C to 130°C for several hours to several tens of hours to effect ring closure.
尚銅粉あるいは銅化合物の存在下に閉環させることが収
率向上に有効である。Furthermore, ring closure in the presence of copper powder or a copper compound is effective for improving the yield.
次いで反応生成物をアルカリ中和し、析出物を公知の方
法で溶剤精製することにより、一般式ＣＩ）で表される
フルオレン化合物が実質的に無色の結晶として得られる
。Next, the reaction product is neutralized with an alkali, and the precipitate is purified with a solvent by a known method to obtain a fluorene compound represented by the general formula CI) as substantially colorless crystals.
（２） 一般式（ＩＶ）
、ぐ＼６
（式中、 Ｒｔ 、ｕ２ｒＲ５１Ｒ４ｔＲｓ ＋Ｒ６及
ヒＸハ前記と同じ意味を表す。）
で表される化合物を例えば・〜ロゲン化アルミニウムを
触媒として４０〜２００℃好ましくは８０℃〜１５０℃
で撹拌して閉環させる。尚、尿素等のカルボニル化合物
の存在下に閉環させることが収率向上に有効である。(2) A compound represented by the general formula (IV) (where Rt, u2rR51R4tRs +R6 and H °C preferably 80 °C to 150 °C
Stir with to close the ring. Note that ring closure in the presence of a carbonyl compound such as urea is effective in improving the yield.
次いで反応生成物を水中に投入し析出物を公知の方法で
溶剤精製することにより、一般式ＣＩ）で表されるフル
オレン化合物が実質的に無色の結晶として得られる。Next, the reaction product is poured into water and the precipitate is purified with a solvent by a known method to obtain a fluorene compound represented by the general formula CI) as substantially colorless crystals.
本発明のフルオレン化合物は従来のトリフェニルメタン
系染料やフルオラン染料と同様に、感圧複写紙や、感熱
記碌紙、熱転写型記録紙等の記録材料の電子供与性発色
剤として使用することが出来る。又、従来のトリフェニ
ルメタン系染料やフルオラン系染料と併用して使用する
ことも出来る。The fluorene compound of the present invention, like conventional triphenylmethane dyes and fluorane dyes, can be used as an electron-donating coloring agent for recording materials such as pressure-sensitive copying paper, thermal recording paper, and thermal transfer recording paper. I can do it. It can also be used in combination with conventional triphenylmethane dyes and fluoran dyes.
本発明のフルオレン化合物を用いて感圧複写紙を得るに
は、先ず、フルオレン化合物溶解油のマイクロカプセル
を調製する。この場合マイクロカプセルの調製は、例え
ば、米国特許第２８００４５７号に記載されているよう
な方法で、ゼラチン等の樹脂を硬化させた外殻壁中に１
−４％のフルオレン化合物を溶解したジイソプロピルナ
７タレン系やターフェニル系の油を包蔵させることによ
って行なうことが出来る。マイクロカプセルの粒径は通
常５μｍ 前後である。このマイクロカプセルをバイン
ダーを用いて紙やプラスチックフィルム等の支・特休上
に支持させて、呈色剤としての電子受容性化合物層を有
する呈色剤シートと重ね、タイプライタ−１筆圧等で加
圧してマイクロカプセルを破壊し、フルオレン化合物と
呈色剤とを接触させることによって、呈色剤シート上に
発色画像を得ることができる。In order to obtain pressure-sensitive copying paper using the fluorene compound of the present invention, first, microcapsules of a fluorene compound-dissolved oil are prepared. In this case, the microcapsules can be prepared by, for example, using a method as described in US Pat.
This can be done by incorporating diisopropylna-7talene or terphenyl oil in which -4% of a fluorene compound is dissolved. The particle size of microcapsules is usually around 5 μm. These microcapsules are supported on a support such as paper or plastic film using a binder, and layered with a coloring agent sheet having an electron-accepting compound layer as a coloring agent. By applying pressure to destroy the microcapsules and bringing the fluorene compound into contact with the coloring agent, a colored image can be obtained on the coloring agent sheet.
本発明のフルオレン化合物を用いて感熱記録材料を得る
には１式ＣＩ）のフルオレン化合物と呈色剤を別個に結
合剤を含む分散媒中で平均粒径が０．５〜３μとなる様
に分散化した後混合し、必要に応じて増感剤や充填剤等
の添加剤を加えて紙。To obtain a heat-sensitive recording material using the fluorene compound of the present invention, the fluorene compound of formula 1 CI) and a coloring agent are separately mixed in a dispersion medium containing a binder so that the average particle size is 0.5 to 3μ. After dispersion, mix and add additives such as sensitizers and fillers as necessary to make paper.
樹脂膜等の支持体上に塗布、乾燥して作成する。It is created by coating on a support such as a resin film and drying it.
なお前記において呈色剤の具体例としては。In the above, specific examples of the coloring agent are as follows.
Ｐ−オクチルフェノール、Ｐ−ｔθｒ七−ブチルフェノ
ール、Ｐ−フェニールフェノール、１，１−ビス（ｐ−
ヒドロキシフェニル）プロパン、２，２−ビスーＣＰ−
ヒドロキシフェニル）−／／ロパン、１，１−（ビス−
（Ｐ−ヒドロキシフェニル）−シクロヘキシル、４．４
’−スルホニルジフェノール、ビス−（３−７！Ｊルー
４−ヒドロキシフェニル）スルホン等のフェノール性化
合物Ｐ−ヒドロキシ安息香酸ベンジル、Ｐ−ヒドロキシ
安息香酸エテル。P-octylphenol, P-tθr7-butylphenol, P-phenylphenol, 1,1-bis(p-
hydroxyphenyl)propane, 2,2-bis-CP-
hydroxyphenyl)-//lopane, 1,1-(bis-
(P-hydroxyphenyl)-cyclohexyl, 4.4
Phenolic compounds such as '-sulfonyldiphenol, bis-(3-7!J-4-hydroxyphenyl)sulfone, benzyl P-hydroxybenzoate, ether P-hydroxybenzoate.
４−ヒドロキシフタル酸ジベンジル、４−ヒドロキシフ
タル酸ジメチル、５−ヒドロキシインフタル酸エチル、
３，５−ジーｔａｒｔ−ブチルサリチル酸。Dibenzyl 4-hydroxyphthalate, dimethyl 4-hydroxyphthalate, ethyl 5-hydroxyinphthalate,
3,5-di-tart-butylsalicylic acid.
５．５−ジ−α−メチルベンジルサリチル酸等の芳香族
カルボン酸誘導体及びカルボン酸に於てはその多価金属
塩が挙げられる。Examples of aromatic carboxylic acid derivatives such as 5.5-di-α-methylbenzylsalicylic acid and polyvalent metal salts thereof include carboxylic acids.
又結合剤の具体例としては、メチルセルロース。A specific example of the binder is methyl cellulose.
メトキシセルロース、ヒドロキシエチルセルロース、カ
ルボキシメチル七ルロース、ポリビニルアルコール、カ
ルボキシ基変性ポリビニルアルコール、ポリビニルピロ
リドン、ポリアクリルアミド、ポリアクリル酸、デンプ
ン及びその誘導体、カゼイン、ゼラチン、スチレン、無
水マレイン酸共重合体のアルカリ塩、イン（又はジイソ
）ブチレン−無水マレイン酸共重合体のアルカリ塩等の
水溶性のもの或いはポリ酢酸ビニル、塩化ビニル／酢威
ビニル共重合体、ポリスチレン、ポリアクリル酸エステ
ル、ポリウレタン、スチレン／ブタジェン／アクリル酸
系共重合体等の非水溶性エマルジョンが用いられる。Methoxycellulose, hydroxyethylcellulose, carboxymethyl heptalulose, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, starch and its derivatives, casein, gelatin, styrene, alkaline salts of maleic anhydride copolymers , water-soluble ones such as alkaline salts of in(or diiso)butylene-maleic anhydride copolymer, polyvinyl acetate, vinyl chloride/vinyl acetate copolymer, polystyrene, polyacrylic acid ester, polyurethane, styrene/butadiene /A water-insoluble emulsion such as an acrylic acid copolymer is used.
更に増感剤の具体例としては、動植物性ワックス、ポリ
エチレンワックス、合成ワックスなどのワックス類や高
級脂肪酸、高級脂肪酸アミド、高級脂肪酸金属塩、芳香
族アミンのアセチル化物。Specific examples of sensitizers include waxes such as animal and vegetable waxes, polyethylene waxes, and synthetic waxes, higher fatty acids, higher fatty acid amides, higher fatty acid metal salts, and acetylated products of aromatic amines.
芳香族エーテル化合物、ビフェニル誘導体等常温で固体
であり８０℃以上の融点を有するものが好ましい。Those that are solid at room temperature and have a melting point of 80°C or higher, such as aromatic ether compounds and biphenyl derivatives, are preferred.
更に充填剤の具体例としては、炭酸カルシウム。Further, a specific example of the filler is calcium carbonate.
炭酸マグネシワム、酸化マグネシウム、シリカ、ホワイ
トカーボン、メルク、クレー、アルミナ。Magnesium carbonate, magnesium oxide, silica, white carbon, Merck, clay, alumina.
水酸化マグネシウム、水酸化アルミニウム、酸化アルミ
ニウム、硫酸バリウム、ポリスチレン樹脂。Magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, polystyrene resin.
尿素−ホルマリン樹脂等があげられる。Examples include urea-formalin resin.
その他系加物質として、ステアリン酸唾鉛、ステアリン
酸カルシウム、ステアリン酸アルミニウム等の滑剤、各
種の界面活性剤、消泡剤等が必要に応じて加えられる。Other additives such as lubricants such as lead stearate, calcium stearate, and aluminum stearate, various surfactants, and antifoaming agents may be added as necessary.
フルオレン化合物と呈色剤の比は通常乾燥重量比で１：
１乃至１：１０で用いられ、その塗布量は乾燥重量が５
〜１５？／−好ましくは８〜１２９と
／ｒｔ？である。又、必要に応じて感熱記録層１支持体
の間に中間層を設けたり、感熱記録層上にオーバーコー
ト層を設けてもよい。The ratio of fluorene compound to coloring agent is usually 1:1 by dry weight.
It is used at a ratio of 1 to 1:10, and the application amount is 5% by dry weight.
~15? /-preferably 8-129 and /rt? It is. Further, if necessary, an intermediate layer may be provided between the heat-sensitive recording layer 1 and the support, or an overcoat layer may be provided on the heat-sensitive recording layer.
このようにしてえた感熱記録材料をサーマルヘッド等で
加熱し、フルオレン化合物と呈色剤を溶融接触させるこ
とにより１発色画像を得ることができる。A one-color image can be obtained by heating the heat-sensitive recording material thus obtained with a thermal head or the like to bring the fluorene compound and the coloring agent into melt contact.
本発明の式（１）のフルオレン化合物は熱転写型記録材
料を得る為の発色剤としても使用出来る。The fluorene compound of formula (1) of the present invention can also be used as a coloring agent for obtaining a thermal transfer type recording material.
本発明のフルオレン化合物を用いて熱転写型記録材料を
得るには、フルオレン化合物を支持体に支持させて感熱
転写シートを作成し、呈色剤を支持体に支持させて受容
シートを作成する。転写シートと受容シートを重ね、転
写シートの表面から加熱すると受容シート上に発色画像
が得られる。To obtain a thermal transfer recording material using the fluorene compound of the present invention, a thermal transfer sheet is prepared by supporting the fluorene compound on a support, and a receptor sheet is prepared by supporting a coloring agent on the support. When a transfer sheet and a receiving sheet are placed one on top of the other and heated from the surface of the transfer sheet, a colored image is obtained on the receiving sheet.
本発明の前記式ＣＩ）のフルオレン化合物は、殊にその
優れた近赤外光吸収特性を利用して、光学文字読取装置
や、ラベルバーコード読取装置等の記＠読取り用の記録
材料における発色剤として利用することができる。The fluorene compound of the formula CI) of the present invention utilizes its excellent near-infrared light absorption property to produce color in recording materials for reading such as optical character reading devices and label barcode reading devices. It can be used as a drug.
なお１本発明のフルオレン化合物を感熱記録型ラベルシ
ートに使用する場合、支持体の一方の面に本発明のフル
オレン化合物と呈色剤を含む感熱発色層を設け、支持体
の他方の面に接着剤層を介してハクリ台紙を設けた構造
のものにすればよく。Note that 1. When the fluorene compound of the present invention is used in a heat-sensitive recording label sheet, a heat-sensitive coloring layer containing the fluorene compound of the present invention and a coloring agent is provided on one side of the support, and is adhered to the other side of the support. It is sufficient to use a structure in which a peeler mount is provided through the agent layer.
また、この場合、必要に応じ画像安定性を高めるために
１発色感熱層上に保護層を設けることもできる。Further, in this case, a protective layer may be provided on the one-color heat-sensitive layer in order to improve image stability, if necessary.
実施例 以下実施例により本発明を更に詳細に説明する。Example The present invention will be explained in more detail with reference to Examples below.
実施例１
３．６−ビス（ジメチルアミノ）フルオレンスピロ−（
９，３’） −５’−メチル−６′−ジメチルアミノフ
タリドの製法
ｓ、ｓ−ヒス（バラジメチルアミノフェール）−５−メ
チル−６−ジメチルアミノフタリド５６０部を金物に添
加し、１４０−１４５℃で２０時間反応させた。Example 1 3.6-bis(dimethylamino)fluorene spiro-(
9,3') -Production method of 5'-methyl-6'-dimethylaminophthalide s. Add 560 parts of s-his(baladimethylaminophel)-5-methyl-6-dimethylaminophthalide to the hardware, The reaction was carried out at 140-145°C for 20 hours.
次いで反応物を５００部の氷水に投入し析出物をトルエ
ン−メタノール中で精製することにより。Next, the reaction product was poured into 500 parts of ice water, and the precipitate was purified in toluene-methanol.
３．６−１：’ス（ジメチルアミノ）フルオレンスピロ
−（９，３’） −５’−メチル−６′−ジメチルアミ
ノフタリド４．０１を得た。3.6-1:'S(dimethylamino)fluorene spiro-(9,3')-5'-methyl-6'-dimethylaminophthalide 4.01 was obtained.
ｍＰ、２３Ｂ−２４１℃。mP, 23B-241°C.
実施例２
３−ジメチルアミノ−６−ジアリルアミノフルオレンス
ピロ−（９，３’） −６’−ジメチルアミノフタリド
の製法
。く＼。ヨ
３−（２−アミノ−４−ジアリルアミノフェニル）−５
−（４−ジメチルアミノフェニル）−６−シメチルアミ
ノフタリド５．０部を８０％硫酸６０部中に溶解し、０
℃に冷却する。Example 2 Method for producing 3-dimethylamino-6-diallylaminofluorene spiro-(9,3')-6'-dimethylaminophthalide. Ku\. 3-(2-amino-4-diallylaminophenyl)-5
5.0 parts of -(4-dimethylaminophenyl)-6-dimethylaminophthalide was dissolved in 60 parts of 80% sulfuric acid, and
Cool to ℃.
次いでこれに亜硝酸ナトリウム０．８６部を一５〜５℃
に保ちながら徐々に添加する。同温度で２時間撹拌して
ジアゾ化を完了する。このジアゾ化液を、８０％硫酸１
０部、銅粉０．１部を３５℃−４０℃に保りた液中に徐
々に添加し、添加後１時間３５℃−４０℃に保った後８
０℃に３時間加熱して閉環を完了させた。次いで氷水中
に投入し中和後析出物をトルエン−メタノール中で精製
すること、ζより３−ジメチルアミノ−６−ジアリルア
ミノフルオレンスピロ−（９１５’ ） −６’−ジメ
チルアミノフタリド３・９１を得た。Next, add 0.86 parts of sodium nitrite to this at -5 to 5°C.
Add gradually while maintaining The diazotization was completed by stirring at the same temperature for 2 hours. This diazotized solution was mixed with 80% sulfuric acid.
0 part and 0.1 part of copper powder were gradually added to the solution kept at 35°C-40°C, and kept at 35°C-40°C for 1 hour after addition.
Heating to 0° C. for 3 hours completed ring closure. Then, the precipitate was neutralized in ice water and purified in toluene-methanol to give 3-dimethylamino-6-diallylaminofluorene spiro-(915')-6'-dimethylaminophthalide 3.91 from ζ. I got it.
ｍｐ、２０３−２０５℃
実施例５〜１２
実施例１又は同２に準じて表１に表されるフルオレン化
合物を合成しその融点を測定した。mp, 203-205°C Examples 5 to 12 Fluorene compounds shown in Table 1 were synthesized according to Example 1 or 2, and their melting points were measured.
実施例１３ 感熱記録紙の製造
下記組成物より成る混合物を各々別々にサンドグライン
ダーを用いて平均粒径が１〜３μになる様に粉砕１分散
化して（Ａ）〜〔Ｃ〕液を調製した。Example 13 Production of thermal recording paper Mixtures consisting of the following compositions were separately ground and dispersed using a sand grinder so that the average particle size was 1 to 3 μm to prepare liquids (A) to [C]. .
次いで〔Ａ〕液：〔Ｂ〕液：〔Ｃ〕液を６：４７：４７
の割゛合で混合して感熱発色層形成液を調製し坪量約５
０ｙ／ゴの上質紙表面に乾燥固形分が１０ｐ／ＦＦ／と
なる様に塗布乾燥し、本発明の感熱記録材料（感熱記録
紙）を得た。Next, [A] solution: [B] solution: [C] solution at 6:47:47
A heat-sensitive coloring layer forming solution was prepared by mixing in the proportions of
It was coated and dried on the surface of a high quality paper of 0y/G to give a dry solid content of 10p/FF/FF to obtain a heat-sensitive recording material (heat-sensitive recording paper) of the present invention.
実施例１４ 感熱記録紙の製造
実施例１３で用いた実施例１のフルオレン化合物の代り
に実施例２で合成したフルオレン化合物を用いた以外は
実施例１３と同様にして感熱記録紙を用いた。Example 14 Production of thermal recording paper A thermal recording paper was used in the same manner as in Example 13, except that the fluorene compound synthesized in Example 2 was used in place of the fluorene compound of Example 1 used in Example 13.
比較例１〜３
実施例１３で用いた実施例１のフルオレン化合物の代り
に表２の比較例１〜３に示すロイコ染料を用いた以外は
実施例１５と同様にして比較用の感熱記録紙を得た。Comparative Examples 1 to 3 Comparative thermal recording paper was prepared in the same manner as in Example 15, except that the leuco dyes shown in Comparative Examples 1 to 3 in Table 2 were used instead of the fluorene compound of Example 1 used in Example 13. I got it.
以上のようにして得た本発明並びに比較用の感熱記録紙
を用いて発色試験及び堅牢度試験を実施した。A color development test and a fastness test were carried out using the heat-sensitive recording paper of the present invention and a comparative heat-sensitive recording paper obtained as described above.
結果を表２に示す。The results are shown in Table 2.
（１） 発色試験 ローゼアスター試験機を用いて８０℃。(1) Color development test 80°C using a Roseaster tester.
９０℃ｓ １４０℃５秒間記録紙を押圧し１発色濃度を
マクベス濃度計ＲＤ−９１４で測定した。The recording paper was pressed for 5 seconds at 90°C and 140°C, and the density of one color was measured using a Macbeth densitometer RD-914.
（２） 堅牢度試験 １４０℃５秒で発色させた感熱紙を用いて試験した。(2) Fastness test The test was conducted using thermal paper that was colored at 140°C for 5 seconds.
耐水性二 発色させた感熱紙を１ｔの水に１５時間浸漬
した後の濃度を測定し１式％式％（）
を用いて計算した。値が高い程良い。Water Resistance 2 The color-developed thermal paper was immersed in 1 ton of water for 15 hours, and then the density was measured and calculated using the formula % (%). The higher the value, the better.
耐湿性： ６０℃飽和水蒸気圧下に２４時間放置した後
の濃度を測定し１式
％式％（）
を用いて計算した。値が高い程良い。Moisture resistance: The concentration was measured after being left under saturated water vapor pressure at 60°C for 24 hours, and calculated using the formula % (%). The higher the value, the better.
耐光性２ １０，０００ルツクスで１週間照射した後の
濃度を測定し１式
％式％（）
を用いて計算した。値が高い程良い。Light resistance 2 The concentration was measured after irradiation at 10,000 lux for one week and calculated using the formula % (%). The higher the value, the better.
（３） 吸収波長領域、地肌発色性
吸収波長領域： １４０℃５秒で発色させた発色部の反
射スペクトルを測定した。(3) Absorption wavelength region, background coloration absorption wavelength region: The reflection spectrum of the colored area was measured at 140° C. for 5 seconds.
地肌発色性： 感熱記録紙調製直後の着色（゛発色）の
度合（マクベス濃度計ＲＤ−９１４で測定）
表２の結果より１本発明のフルオレン化合物は吸収波長
領域が７００〜１，０００ｎｍ 付近の近赤外領域まで
吸収があり１発色感度、堅牢度にすぐれていることが明
きらかである。Background coloring property: Degree of coloring ('coloring') immediately after preparing thermal recording paper (measured with a Macbeth densitometer RD-914) From the results in Table 2, 1. The fluorene compound of the present invention has an absorption wavelength range of around 700 to 1,000 nm. It is clear that it absorbs up to the near infrared region and has excellent color development sensitivity and fastness.
実施例１５ 感圧複写紙の製造
実施例、２で得られたフルオレン化合物３部をジイソプ
ロピルナフタレン９８部に５０℃で溶解し、この温度で
アラビアゴム２０部と水１６０部の溶液を加えて乳化す
る。これに酸処理を施したゼラチン２０部と水１６０部
を加え、酢酸でｐＨを５とする。次に水５００部を加え
コアセルベーションを進行させ、ジインプロピルナフタ
レンの油滴のまわりにゼラチン−アラビアゴムの濃厚液
状膜を形成させ、ｐＨを４．４とした後、５７％ホルマ
リン溶液４部を加え、硬膜を形成させる。次にこの系を
１０℃に冷却し、希水酸化ナトリウム水溶液を加えｐＨ
を９とし数時間放置することでカプセル化を進行させる
。このカプセル化液を平均型１４ｏｐ／ｒｒ？の紙に乾
燥固形分が５１／ｄとなるように塗布し乾燥し上葉シー
トを得る。こうしテ得り上葉シートをパラフェニールフ
ェノール−ホルムアルデヒド重合体を顕色剤とする顕色
シートと重ね合わせ筆圧あるいはタイプライタ−の印字
の圧力を加えると緑色に発色した。この複写像は７００
〜１，０００ｎｌｎ 付近の近赤外領域までの吸収が
あり、かつ、耐水性、耐光性にすぐれていた。Example 15 Production of pressure-sensitive copying paper 3 parts of the fluorene compound obtained in Example 2 was dissolved in 98 parts of diisopropylnaphthalene at 50°C, and at this temperature a solution of 20 parts of gum arabic and 160 parts of water was added to emulsify. do. 20 parts of acid-treated gelatin and 160 parts of water are added to this, and the pH is adjusted to 5 with acetic acid. Next, 500 parts of water was added to allow coacervation to proceed, forming a thick gelatin-gum arabic liquid film around the diimpropylnaphthalene oil droplets, and adjusting the pH to 4.4, followed by 4 parts of a 57% formalin solution. is added to form a dura mater. Next, this system was cooled to 10°C, and a dilute aqueous sodium hydroxide solution was added to adjust the pH.
is set to 9 and allowed to stand for several hours to allow encapsulation to proceed. This encapsulation liquid has an average type of 14 op/rr? It is coated on paper so that the dry solid content is 51/d and dried to obtain an upper sheet. The resulting upper sheet was superimposed on a color developer sheet containing paraphenylphenol-formaldehyde polymer as a color developer, and when writing pressure or typewriter printing pressure was applied, a green color developed. This copy image is 700
It had absorption in the near-infrared region around ~1,000 nln, and had excellent water resistance and light resistance.
発明の効果
発色感度１発色濃度にすぐれ、その発色画像が近赤外線
吸収特性にすぐれたフルオレン化合物がえられた。又こ
の発色画像の耐水、耐光堅牢度がすぐれている。Effects of the Invention A fluorene compound with excellent color development sensitivity 1 color density and a color image with excellent near-infrared absorption characteristics was obtained. Moreover, this colored image has excellent water resistance and light fastness.
Claims (1)
びＲ＿６は各各炭素数１〜４のアルキル基又はアリル基
を、Ｘは水素、メチル又はハロゲンを表す。但しＸが水
素の時は、Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿５お
よびＲ＿６のうち少なくとも一つはアリル基を表す） で表されるフルオレン化合物。 ２、一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿５およ
びＲ＿６は各各炭素数１〜４のアルキル基又はアリル基
を、Ｘは水素、メチル又はハロゲンを表す。但しＸが水
素の時はＲ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿５およ
びＲ＿６のうち少なくとも一つはアリル基を表す）で表
されるフルオレン化合物を用いたことを特徴とする記録
材料。[Claims] 1. General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1, R_2, R_3, R_4, R_5 and R_6 each have 1 to 4 carbon atoms. an alkyl group or an allyl group, and X represents hydrogen, methyl, or halogen; however, when Fluorene compound. 2. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1, R_2, R_3, R_4, R_5 and R_6 each represent an alkyl group or allyl group having 1 to 4 carbon atoms. , X represents hydrogen, methyl or halogen.However, when X is hydrogen, at least one of R_1, R_2, R_3, R_4, R_5 and R_6 represents an allyl group) was used. Recording material featuring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61266603A JPS63120760A (en) | 1986-11-11 | 1986-11-11 | Fluorene compound and recording material obtained by using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61266603A JPS63120760A (en) | 1986-11-11 | 1986-11-11 | Fluorene compound and recording material obtained by using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63120760A true JPS63120760A (en) | 1988-05-25 |
Family
ID=17433104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61266603A Pending JPS63120760A (en) | 1986-11-11 | 1986-11-11 | Fluorene compound and recording material obtained by using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63120760A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7903422B2 (en) | 2004-12-15 | 2011-03-08 | Nec Corporation | Mobile terminal device and method for radiating heat therefrom |
-
1986
- 1986-11-11 JP JP61266603A patent/JPS63120760A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7903422B2 (en) | 2004-12-15 | 2011-03-08 | Nec Corporation | Mobile terminal device and method for radiating heat therefrom |
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