EP0525535A1 - Thermoreactive recording material with improved stability - Google Patents
Thermoreactive recording material with improved stability Download PDFInfo
- Publication number
- EP0525535A1 EP0525535A1 EP92112199A EP92112199A EP0525535A1 EP 0525535 A1 EP0525535 A1 EP 0525535A1 EP 92112199 A EP92112199 A EP 92112199A EP 92112199 A EP92112199 A EP 92112199A EP 0525535 A1 EP0525535 A1 EP 0525535A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methyl
- recording materials
- weight
- formula
- butylene
- 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.)
- Withdrawn
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- -1 modified bisphenol carboxylic acid Chemical class 0.000 claims description 60
- 239000006185 dispersion Substances 0.000 claims description 46
- 239000000123 paper Substances 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 239000012876 carrier material Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 239000003086 colorant Substances 0.000 claims description 11
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 11
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- 239000000203 mixture Substances 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 239000011111 cardboard Substances 0.000 claims description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
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- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- 239000011701 zinc Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 3
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- 238000009499 grossing Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 2
- XAAILNNJDMIMON-UHFFFAOYSA-N 2'-anilino-6'-(dibutylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CCCC)CCCC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 XAAILNNJDMIMON-UHFFFAOYSA-N 0.000 description 2
- GQWCEMIEJPSMHV-UHFFFAOYSA-N 2,2-bis(4-hydroxy-3-methylphenyl)propanoic acid Chemical compound C1=C(O)C(C)=CC(C(C)(C(O)=O)C=2C=C(C)C(O)=CC=2)=C1 GQWCEMIEJPSMHV-UHFFFAOYSA-N 0.000 description 2
- SCBGJZIOPNAEMH-UHFFFAOYSA-N 2,2-bis(4-hydroxyphenyl)acetic acid Chemical compound C=1C=C(O)C=CC=1C(C(=O)O)C1=CC=C(O)C=C1 SCBGJZIOPNAEMH-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 2
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-UHFFFAOYSA-N 0.000 description 2
- ZDRSNHRWLQQICP-UHFFFAOYSA-N 2-tert-butyl-4-[2-(3-tert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 ZDRSNHRWLQQICP-UHFFFAOYSA-N 0.000 description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PGAAZCXJMPDCHO-UHFFFAOYSA-N 3-(4-chloro-2-hydroxy-5-methylphenyl)-3-[4-(dimethylamino)-2-methoxyphenyl]-2-benzofuran-1-one Chemical compound COC1=CC(N(C)C)=CC=C1C1(C=2C(=CC(Cl)=C(C)C=2)O)C2=CC=CC=C2C(=O)O1 PGAAZCXJMPDCHO-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 2
- NOMXFWAANLCUKA-UHFFFAOYSA-N 4-[2-[2-(4-hydroxyphenyl)sulfanylethoxy]ethylsulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SCCOCCSC1=CC=C(O)C=C1 NOMXFWAANLCUKA-UHFFFAOYSA-N 0.000 description 2
- QBZPUSKHVURBGP-UHFFFAOYSA-N 4-[2-[2-(4-hydroxyphenyl)sulfanylethoxymethoxy]ethylsulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SCCOCOCCSC1=CC=C(O)C=C1 QBZPUSKHVURBGP-UHFFFAOYSA-N 0.000 description 2
- LKWGELSXCONAIO-UHFFFAOYSA-N 4-[2-hydroxy-3-(4-hydroxyphenyl)sulfanylpropyl]sulfanylphenol Chemical compound C=1C=C(O)C=CC=1SCC(O)CSC1=CC=C(O)C=C1 LKWGELSXCONAIO-UHFFFAOYSA-N 0.000 description 2
- FBEZGURIIDZGTJ-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)sulfanylpropylsulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SCCCSC1=CC=C(O)C=C1 FBEZGURIIDZGTJ-UHFFFAOYSA-N 0.000 description 2
- MGFRAVRBCSPOHR-UHFFFAOYSA-N 4-[4-(4-hydroxyphenyl)sulfanylbutylsulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SCCCCSC1=CC=C(O)C=C1 MGFRAVRBCSPOHR-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- KGYNGVVNFRUOOZ-UHFFFAOYSA-N 5-chloro-2-hydroxy-n-phenylbenzamide Chemical compound OC1=CC=C(Cl)C=C1C(=O)NC1=CC=CC=C1 KGYNGVVNFRUOOZ-UHFFFAOYSA-N 0.000 description 2
- KCBLOCLSUSTAMW-UHFFFAOYSA-N 6-chloro-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(Cl)C=C2C(=O)O1 KCBLOCLSUSTAMW-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 2
- CMHMMKSPYOOVGI-UHFFFAOYSA-N Isopropylparaben Chemical compound CC(C)OC(=O)C1=CC=C(O)C=C1 CMHMMKSPYOOVGI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical class 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
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- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- XAUGWFWQVYXATQ-UHFFFAOYSA-N n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1 XAUGWFWQVYXATQ-UHFFFAOYSA-N 0.000 description 2
- BRNPAEUKZMBRLQ-UHFFFAOYSA-N octadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 BRNPAEUKZMBRLQ-UHFFFAOYSA-N 0.000 description 2
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- WKEDVNSFRWHDNR-UHFFFAOYSA-N salicylanilide Chemical compound OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 WKEDVNSFRWHDNR-UHFFFAOYSA-N 0.000 description 2
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- 150000003751 zinc Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- 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
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- PKRSYEPBQPFNRB-UHFFFAOYSA-N 2-phenoxybenzoic acid Chemical class OC(=O)C1=CC=CC=C1OC1=CC=CC=C1 PKRSYEPBQPFNRB-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 description 1
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyloxyacetoaldehyde Natural products CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 1
- 239000003613 bile acid Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 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
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- OIVQLSUKOZNNCT-UHFFFAOYSA-N dibenzyl benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC=2C=CC=CC=2)=CC=1C(=O)OCC1=CC=CC=C1 OIVQLSUKOZNNCT-UHFFFAOYSA-N 0.000 description 1
- IWGFEQWCMAADJZ-UHFFFAOYSA-N dibenzyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 IWGFEQWCMAADJZ-UHFFFAOYSA-N 0.000 description 1
- ZYZXGWGQYNTGAU-UHFFFAOYSA-N dibenzyl oxalate Chemical compound C=1C=CC=CC=1COC(=O)C(=O)OCC1=CC=CC=C1 ZYZXGWGQYNTGAU-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 235000010386 dodecyl gallate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass 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
- 238000007646 gravure printing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 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
- 239000003550 marker Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- JZCLWFULJLDXDT-UHFFFAOYSA-N methyl 4,4-bis(4-hydroxyphenyl)pentanoate Chemical compound C=1C=C(O)C=CC=1C(C)(CCC(=O)OC)C1=CC=C(O)C=C1 JZCLWFULJLDXDT-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- WHSXTWFYRGOBGO-UHFFFAOYSA-N o-cresotic acid Natural products CC1=CC=CC(C(O)=O)=C1O WHSXTWFYRGOBGO-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- NRPKURNSADTHLJ-UHFFFAOYSA-N octyl gallate Chemical compound CCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 NRPKURNSADTHLJ-UHFFFAOYSA-N 0.000 description 1
- 235000010387 octyl gallate Nutrition 0.000 description 1
- 239000000574 octyl gallate Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- B41M5/26—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
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
Definitions
- the present invention relates to thermoreactive recording material containing carrier material, dye formers, salts of carboxylic acids and optionally acidic developers.
- Dispersions b) and c) can optionally be prepared as a common dispersion. It is also not possible to mix these individual dispersions, but to apply them successively to a carrier material.
- the carrier material can be used as such or in pretreated, e.g. pre-coated form.
- a pre-coating can condition the substrate in any way, e.g. with regard to smoothness, absorbency and / or reflectivity.
- thermoactive layer images or information are generated by color formation using thermal energy, for example by means of a thermal head.
- thermal energy for example by means of a thermal head.
- Such systems include described in JP-OSs 57-191 089, 58-205 793, 58-205 795, 58-209 592, 58-211 494, 58-098 285, 58-289 591.58-211 493 and 59- 9092, and DE-OS 3 242 262, EP-OS 173 232 and US-PS 4 713 364.
- Such heat sensitive recording materials can e.g. as thermal papers in printers of computers, in ticket machines, in label printers, in pens of medical measuring instruments, for example, and in facsimile machines (thermofax devices).
- a major disadvantage of the known heat-sensitive recording materials is the poor stability of the images against fats and plasticizers.
- thermosensitive layer Stability against such influences is particularly important with food labels, medical information storage and information received by facsimile.
- the images and information in the thermosensitive layer fade or almost completely disappear over time.
- coating the thermosensitive layer with certain materials (see, for example, DE-OS 3 828 731 and GB-OS 2 122 363), the fading or disappearance of the images and information can be delayed or prevented, but this overlaying increases the sensitivity of the thermosensitive recording material reduced so much that in high-speed fax machines they need thermal papers with higher sensitivity, can no longer be used or can only be used with a high loss of intensity of the images and information.
- subsequent coating is a cost-intensive process.
- JP-OS 58-005 288, JP-OS 59-209 192 and JP-OS 57-045 093 describe bisphenol carboxylic acids and their esters as developers which are said to contribute to improving the fat and plasticizer stability of thermosensitive recording material. However, their effect is either weak or associated with inadequate storage stability, which leads to a strong graying of the otherwise mostly white thermosensitive recording materials.
- U.S. Patent 3,565,848 describes salts of modified bisphenol carboxylic acids which serve to improve the stability of phenolic resins used in molding compositions, molds and abrasive materials (e.g. grindstones).
- EP-OS 0 218 810, EP-OS 0 271 081 and DE-OS 2 724 107 describe the use of metal salts of substituted salicylic acids in recording materials.
- the disadvantage here is that when used in thermosensitive layers, the degree of whiteness is poor, combined with a very poor storage stability.
- an oxide or, preferably, a hydroxide of the desired polyvalent metal in a stoichiometric ratio with the free bisphenol carboxylic acid in aqueous solution, optionally together with a water-miscible cosolvent, is heated and a salt of a modified bisphenol carboxylic acid of the formula (I ) receive.
- salts of modified bisphenolcarboxylic acids of the formula (I) in which the OH groups are either in the para or in the ortho and para position to the R 2 -CR 3 -COOM group and R 1 in are meta and / or in the ortho position to the R 2 -CR 3 -COOM grouping.
- OH is particularly preferably in the para and R 1 in the meta position to the R 2 -CR 3 -COOM grouping.
- thermoreactive recording materials can be used in thermoreactive recording materials according to the invention, as are obtained in the production processes described above, that is to say, for example, with purities of 70 to 100% by weight and optionally containing crystal water.
- thermoreactive recording material may be any, as a color developer conventional electron acceptors or acids when heat inducing color formation of the leuco dye, such as polyphenols, Hydroxydiphenylsulfone, Hydroxydiphenylsulfoxide, hydroxybenzoic acid, esters of bile acids, Hydroxydiphenylsulfide, Hydroxydiphenyldisulfide, salicylic acids, their esters or amides, Hydroxynaphthalinklaren, their esters or amides, bis (hydroxyphenylthio) dioxaalkanes, bis (hydroxyphenylthio) oxaalkanes and bis (hydroxyphenyl) alkanes.
- conventional electron acceptors or acids when heat inducing color formation of the leuco dye such as polyphenols, Hydroxydiphenylsulfone, Hydroxydiphenylsulfoxide, hydroxybenzoic acid, esters of bile acids, Hydroxydiphenylsulfide
- the salts of modified bisphenol carboxylic acids of the formula (I) to be used according to the invention also have certain developer properties. In special cases, the addition of a special color developer may therefore not be necessary.
- thermoreactive recording materials according to the invention contain, in addition to colorants, color developers and salts of modified bisphenolcarboxylic acids, so-called sensitizers. These can be customary heat-fusible substances which are able to accelerate the color development speed and / or to intensify the color formation.
- sensitizers can have, for example, a melting point in the range from 70 to 140.degree. C., preferably from 70 to 130.degree. C. and in particular from 75 to 120.degree.
- Diphenylsulfones, benzyldiphenyls, phenylsalicylic acid esters, terephthalic acid diesters, isophthalic acid diesters and waxes see also JP-OS'en 57-191 089, 58-98 285, 58-205 793, 58-205 795, 58-209 591, 58-209 592, 58 -211 493, 58-211 494 and 59-9092.
- Thermoreactive recording materials according to the invention can optionally also contain binders and / or other customary additives.
- the binders can be, for example, partially or completely saponified polyvinyl acetate, hydroxyethyl cellulose, gum arabic, starch, polyvinylpyrrolidone or casein, and the other additives can be, for example, fillers, surface-active agents, antioxidants and / or defoamers.
- suitable fillers are fine powders of inorganic compounds such as calcium carbonate, calcium sulfate, silicon dioxide, titanium oxide, barium sulfate, talc, and surface-treated silicon dioxide, and fine powders of organic compounds such as urea, formaldehyde resins, styrene-methacrylic acid copolymers, polystyrene resins and polyacrylic copolymers (see, for example, DE- OS 3 715 724).
- inorganic compounds such as calcium carbonate, calcium sulfate, silicon dioxide, titanium oxide, barium sulfate, talc, and surface-treated silicon dioxide
- organic compounds such as urea, formaldehyde resins, styrene-methacrylic acid copolymers, polystyrene resins and polyacrylic copolymers
- Thermoreactive recording materials according to the invention can contain a wide variety of carrier materials.
- any paper that can be used untreated or pretreated can be used.
- pretreated papers can be pre-treated act coated papers, wherein the coating can serve, for example, for the purpose of applying fillers and / or for influencing the thermal conductivity.
- Such pre-treatments may have been carried out on one or both sides of the paper.
- the paper can also have been calendered or smoothed on one or both sides in the paper machine.
- thermoreactive recording materials for example, papers with a basis weight of 20 to 200 g / m 2 , preferably 30 to 100 g / m 2, are suitable. Any films can also be used as carrier materials for thermoreactive recording materials according to the invention.
- Preferred foils are those which are usually used as carrier materials for overhead projection or other presentation systems.
- cardboard and cardboard can also be used as the carrier material, which, if appropriate, can be coated, and / or pretreated as described for the paper as carrier material.
- Thermoreactive recording materials according to the invention can contain, for example, 0.1 to 40% by weight of modified bisphenol carboxylic acids of the formula (I) in the coating (i.e. without taking into account the carrier material). This amount is preferably 1 to 30% by weight, particularly preferably 5 to 25% by weight.
- the coating may further contain, for example, 1 to 20% by weight of color donor.
- the amount of colorant is preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight.
- the coating can also contain, for example, 0 to 30% by weight of color developer. Amounts of 5 to 25% by weight, in particular those of 10 to 20% by weight, are preferred.
- the coating may contain sensitizers, for example in an amount of 0 to 30% by weight, preferably 5 to 25% by weight, in particular 10 to 20% by weight.
- Binder and conventional additives can be contained in the coating, for example, in an amount of 5 to 80% by weight, 20 to 70% by weight, in particular 30 to 60% by weight, being preferred. The sum of all components of the coating is 100% by weight.
- Thermo-reactive recording materials according to the invention can be produced, for example, by first preparing starting dispersions, namely a colorant dispersion, a dispersion which contains at least one salt of a modified bisphenol carboxylic acid of the formula (I) and a developer dispersion.
- the starting dispersions can be mixed and then with a suitable device, e.g. a doctor blade, on a carrier material, e.g. on a plastic film or paper.
- Binder and other additives can optionally be added to one, more or all of the starting dispersions or to the mixture of these dispersions. One can also proceed in such a way that individual starting dispersions or any different mixtures of starting dispersions are applied in succession to a carrier material.
- Thermoactive recording materials according to the invention are preferably produced as follows (parts are parts by weight):
- 5 to 95 parts of one or more colorants are in 250 parts of an aqueous polyvinyl acetate solution, which consists of 0.1 to 30 parts, preferably 1 to 20 parts, particularly preferably 2 to 15 parts partially saponified polyvinyl acetate and 92 parts of water, stirred in and milled (for example with a sand mill) until the average particle size of the colorant particles is 3 ⁇ m or less.
- an aqueous polyvinyl acetate solution which consists of 0.1 to 30 parts, preferably 1 to 20 parts, particularly preferably 2 to 15 parts partially saponified polyvinyl acetate and 92 parts of water, stirred in and milled (for example with a sand mill) until the average particle size of the colorant particles is 3 ⁇ m or less.
- 1 to 50 parts of one or more color developers preferably 5 to 30 parts, particularly preferably 10 to 20 parts and 10 to 100 parts of a sensitizer, preferably 20 to 80 parts, particularly preferably 35 to 60 parts and 10 to 100 parts of one or more fillers , preferably 15 to 70 parts, particularly preferably 20 to 50 parts, are stirred into 272 parts of an aqueous polyvinyl acetate solution which consists of 0.1 to 20 parts, preferably 1.5 to 10 parts of partially saponified polyvinyl acetate and 98 parts of water, and are ground for as long as possible (eg with a sand mill) until the average particle size of all solid particles is 3 ⁇ m or less.
- 5 to 50 parts of one or more salts of modified bisphenol carboxylic acids of the formula (I) are preferred 10 to 45 parts, particularly preferably 20 to 35 parts, are stirred into 70 parts of an aqueous polyvinyl acetate solution which consists of 0.1 to 30 parts, preferably 1 to 20 parts, particularly preferably 2 to 15 parts of partially saponified polyvinyl acetate and 66 parts of water, and so on grind long (eg with a sand mill) until the average particle size is 3 ⁇ m or less.
- 120 to 40 parts preferably 100 to 50 parts, particularly preferably 80 to 60 parts of developer dispersion are mixed with 20 to 0.5 parts, preferably 15 to 3 parts, particularly preferably 10 to 5 parts of colorant dispersion and 40 to 0.5 parts, preferably 30 to 5 parts, particularly preferably 20 to 10 parts of bisphenol carboxylic acid salt dispersion stirred together and adjusted to a pH of 6 to 14, preferably 7 to 11, particularly preferably 7.5 to 9.5 with dilute sodium hydroxide solution.
- thermoactive recording material e.g., thermoactive recording material according to the invention
- the coating color is applied by means of a wire doctor knife to a paper surface in an amount which corresponds to a coating weight of 2 to 15 g / m 2 , preferably 5 to 12 g / m 2 , particularly preferably 7.5 to 10.5 g / m 2 .
- the coated paper is preferably calendered.
- thermoactive recording materials in the following examples was carried out according to the following measurement methods:
- the plasticizer stability was determined by first printing an area of 4x4 cm with different screen density in black in a thermal printer (Sharp CE 700 P) with maximum energy.
- the whiteness was determined as% remission (large value corresponds to high whiteness), the undesired discoloration of the unprinted paper after storage at 60 ° C. was calculated as% absorption from the remission (as explained under c.) (Large value corresponds to dark paper).
- the sensitivity was determined by printing an area of 5.5 ⁇ 0.8 cm with a head voltage of 26 V and variable burning times using a TP 104 thermal printer (Geminus, Germany). The optical density of these areas was determined using a RD 917 Macbeth densitometer. A thermal paper is the more sensitive, the bigger the differences in the optical densities with short and longer burning times.
- the salts of modified bisphenol carboxylic acids to be used according to the invention are also suitable as developers and / or additives in carbon-free copying systems.
- Recording materials according to the invention have a stabilization of the color even with a long storage time, good light stability and excellent stability towards water, plasticizers, fats and ingredients of text marker pens.
- Example 1 Preparation of a salt to be used according to the invention
- Example 2 Preparation of a salt to be used according to the invention
- Example 3 (Production of a recording material without bisphenol carboxylic acid salt - not according to the invention)
- Example 4 (Production of a Recording Material According to the Invention)
- Dispersions 1 and 2 were prepared as described in Example 3. 30 g of the Mg salt of 4,4-bis (4-hydroxyphenyl) pentanoic acid were stirred into 70 g of a 10% by weight polyvinyl acetate solution (made from Mowiol @ 8/88) and then as in Example 3 described ground to an average particle size of 2.6 ⁇ m (- dispersion 3). 72 parts of the dispersion, 2.7 parts of the dispersion 1 and 14 parts of the dispersion 3 were mixed, the pH of the mixture was adjusted to 9 and the surface of a base paper with a basis weight of 70 g / m 2 was coated using a wire doctor. The application weight was 10.1 g / m 2 . The smoothing was carried out analogously to Example 3.
- Example 5 (Production of a recording material without bisphenol carboxylic acid salt - not according to the invention)
- Example 3 was repeated. Before smoothing the coated paper, a second coating was carried out using a mixture of 100 parts of 10% by weight polyvinyl acetate solution (made from Mowiol @ 4/98), 20 parts of calcium carbonate, 10 parts of a polyethylene wax emulsion (Luba-print @ 499 , LP Bader und Co. GmbH Chem. Fabrik, Rottweil, Germany) and 55 parts of water.
- the application weight of the second layer was 6 g / m 2. Finally, smoothing was carried out analogously to Example 3.
- Example 6 (Production of a recording material with bisphenol carboxylic acid as additive - not according to the invention)
- Example 7 (Production of a recording material according to the invention without developer)
- Example 3 The procedure was as in Example 3, but the dispersion 2 was prepared using an appropriate amount of the salt mentioned in Example 4 instead of bisphenol A.
- Example 8 (Production of a recording material with the salt of a salicylic acid - not according to the invention)
- Example 4 The procedure was as in Example 4, but the dispersion 3 was prepared using an appropriate amount of the zinc salt of 3-methylsalicylic acid instead of the Mg salt used in Example 4.
- Example 18 (Production of a recording material with the ester of a bisphenol carboxylic acid as additive - not according to the invention)
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)
- Paints Or Removers (AREA)
- Paper (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft thermoreaktives Aufzeichnungsmaterial enthaltend Trägermaterial, Farbstoffbildner, Salze von Carbonsäuren und gegebenenfalls saure Entwickler.The present invention relates to thermoreactive recording material containing carrier material, dye formers, salts of carboxylic acids and optionally acidic developers.
Es ist bekannt thermoreaktive Aufzeichnungsmaterialien herzustellen, indem man zunächst folgende wäßrige Dispersionen herstellt:
- a) eine Dispersion, die mindestens einen farblosen oder schwach gefärbten Farbstoffbildner enthält,
- b) eine Dispersion, die mindestens einen sauren Entwickler enthält und gegebenenfalls
- c) eine Dispersion, die mindestens einen Sensibilisator und gegebenenfalls weitere Zusatzstoffe enthält, diese Dispersionen mischt, das Dispersionsgemisch auf ein Trägermaterial aufträgt, z.B. auf Papier oder Kunststoffolie und trocknet.
- a) a dispersion which contains at least one colorless or slightly colored dye former,
- b) a dispersion which contains at least one acidic developer and optionally
- c) a dispersion which contains at least one sensitizer and optionally other additives, mixes these dispersions, applies the dispersion mixture to a carrier material, for example on paper or plastic film, and dries.
Die Dispersionen b) und c) können gegebenenfalls als eine gemeinsame Dispersion hergestellt werden. Man kann diese einzelnen Dispersionen auch nicht mischen, sondern nacheinander auf ein Trägermaterial auftragen.Dispersions b) and c) can optionally be prepared as a common dispersion. It is also not possible to mix these individual dispersions, but to apply them successively to a carrier material.
Das Trägermaterial kann als solches oder in vorbehandelter, z.B. vorbeschichteter Form zum Einsatz gelangen. Eine solche Vorbeschichtung kann das Trägermaterial in beliebiger Weise konditionieren, z.B. hinsichtlich Glätte, Saugfähigkeit und/oder Reflexionsvermögen.The carrier material can be used as such or in pretreated, e.g. pre-coated form. Such a pre-coating can condition the substrate in any way, e.g. with regard to smoothness, absorbency and / or reflectivity.
In der thermoaktiven Schicht werden mit Hilfe thermischer Energie, beispielsweise durch einen Thermokopf, Bilder oder Informationen durch Farbbildung erzeugt. Solche Systeme sind u.a. beschrieben in den JP-OS'en 57-191 089, 58-205 793, 58-205 795, 58-209 592, 58-211 494, 58-098 285, 58-289 591,58-211 493 und 59-9092, sowie DE-OS 3 242 262, EP-OS 173 232 und US-PS 4 713 364.In the thermoactive layer, images or information are generated by color formation using thermal energy, for example by means of a thermal head. Such systems include described in JP-OSs 57-191 089, 58-205 793, 58-205 795, 58-209 592, 58-211 494, 58-098 285, 58-289 591.58-211 493 and 59- 9092, and DE-OS 3 242 262, EP-OS 173 232 and US-PS 4 713 364.
Solche wärmeempfindlichen Aufzeichnungsmaterialien können z.B. als Thermopapiere in Druckern von Computern, in Fahrkartenautomaten, in Etikettendruckern, in Schreibern von beispielsweise medizinischen Meßinstrumenten und in Fernkopierern (Thermofaxgeräte) angewendet werden.Such heat sensitive recording materials can e.g. as thermal papers in printers of computers, in ticket machines, in label printers, in pens of medical measuring instruments, for example, and in facsimile machines (thermofax devices).
Ein großer Nachteil der bekannten wärmeempfindlichen Aufzeichnungsmaterialien ist die mangelnde Stabilität der erzeugten Bilder gegen Fette und Weichmacher.A major disadvantage of the known heat-sensitive recording materials is the poor stability of the images against fats and plasticizers.
Die Stabilität gegen solche Einflüsse ist besonders wichtig bei Etiketten für Lebensmittel, beim Aufbewahren medizinischer Informationen und bei Informationen, die über einen Fernkopierer empfangen worden sind. Beispielsweise bei Kontakt mit Fetten oder Weichmachern, wie sie in Kunststoffhüllen enthalten sein können, in denen entsprechende Ausdrucke sortiert und gelagert werden, verblassen die Bilder und Informationen in der thermosensitiven Schicht oder verschwinden im Lauf der Zeit nahezu ganz. Zwar kann durch Beschichten der thermosensitiven Schicht mit bestimmten Materialien (siehe z.B. DE-OS 3 828 731 und GB-OS 2 122 363) das Verblassen oder Verschwinden der Bilder und Informationen verzögert oder verhindert werden, jedoch wird durch diese Überschichtung die Sensitivität des thermosensitiven Aufzeichnungsmaterials so stark gesenkt, daß sie in schnell laufenden Fernkopierern die Thermopapiere mit höherer Sensitivität benötigen, nicht mehr oder nur unter hohem Intensitätsverlust der Bilder und Informationen verwendet werden können. Außerdem ist eine nachträgliche Beschichtung ein kostenintensiver Prozeß.Stability against such influences is particularly important with food labels, medical information storage and information received by facsimile. For example, in the event of contact with greases or plasticizers, such as those that can be contained in plastic sleeves, in which appropriate printouts are sorted and stored, the images and information in the thermosensitive layer fade or almost completely disappear over time. Although coating the thermosensitive layer with certain materials (see, for example, DE-OS 3 828 731 and GB-OS 2 122 363), the fading or disappearance of the images and information can be delayed or prevented, but this overlaying increases the sensitivity of the thermosensitive recording material reduced so much that in high-speed fax machines they need thermal papers with higher sensitivity, can no longer be used or can only be used with a high loss of intensity of the images and information. In addition, subsequent coating is a cost-intensive process.
In JP-OS 58-005 288, JP-OS 59-209 192 und JP-OS 57-045 093 werden Bisphenolcarbonsäuren und deren Ester als Entwickler beschrieben, die zur Verbesserung der Fett- und Weichmacherstabilität von thermosensitivem Aufzeichnungsmaterial beitragen sollen. Deren Wirkung ist jedoch entweder schwach oder verbunden mit einer mangelhaften Lagerstabilität, die zu einer starken Vergrauung der sonst meist weißen thermosensitiven Aufzeichnungsmaterialien führt.JP-OS 58-005 288, JP-OS 59-209 192 and JP-OS 57-045 093 describe bisphenol carboxylic acids and their esters as developers which are said to contribute to improving the fat and plasticizer stability of thermosensitive recording material. However, their effect is either weak or associated with inadequate storage stability, which leads to a strong graying of the otherwise mostly white thermosensitive recording materials.
In der US-PS 3 565 848 sind Salze modifizierter Bisphenolcarbonsäuren beschrieben, die dazu dienen, die Stabilität von Phenolharzen zu verbessern, die in Formmassen, Gußformen und abrasiven Materialien (z.B. Schleifsteinen) eingesetzt werden. Die EP-OS 0 218 810, die EP-OS 0 271 081 und DE-OS 2 724 107 beschreiben die Verwendung von Metallsalzen substituierter Salicylsäuren in Aufzeichnungsmaterialien. Nachteilig hierbei ist, daß bei deren Verwendung in thermosensitiven Schichten der Weißgrad mangelhaft ist, verbunden mit einer sehr schlechten Lagerstabilität.U.S. Patent 3,565,848 describes salts of modified bisphenol carboxylic acids which serve to improve the stability of phenolic resins used in molding compositions, molds and abrasive materials (e.g. grindstones). EP-OS 0 218 810, EP-OS 0 271 081 and DE-OS 2 724 107 describe the use of metal salts of substituted salicylic acids in recording materials. The disadvantage here is that when used in thermosensitive layers, the degree of whiteness is poor, combined with a very poor storage stability.
Es besteht daher ein Bedürfnis nach einem wärmeempfindlichen Aufzeichnungsmaterial mit hoher thermischer Sensitivität und guter Stabilität gegen Fette und Weichmacher bei gleichzeitig hohem Weißgrad und guter Lagerstabilität.There is therefore a need for a heat-sensitive recording material with high thermal sensitivity and good stability against fats and plasticizers with a high degree of whiteness and good storage stability.
Es wurden nun thermoreaktive Aufzeichnungsmaterialien gefunden, die dadurch gekennzeichnet sind, daß sie wenigstens ein Salz einer modifizierten Bisphenolcarbonsäure der Formel (I) enthalten
in der
- R1 jeweils unabhängig voneinander für C1- bis Cs-Alkoxy, C1- bis C6-Alkyl, C3- bis C6-Cycloalkyl oder Phenyl steht,
- R2 für Wasserstoff, C1- bis C6-Alkyl oder Phenyl steht,
- R3 für C1- bis Cs-Alkylen oder eine direkte Bindung steht,
- m jeweils unabhängig voneinander für eins oder zwei steht,
- n jeweils unabhängig voneinander für null, eins oder zwei steht und
- M für ein Äquivalent eines mehrwertigen Metallions steht, beispielsweise für ein Äquivalent von Mg2+, Zn2+, Ca2+, Al3+, B3+, Pb2+ oder Ti4+.
in the
- R 1 each independently represents C 1 to C s alkoxy, C 1 to C 6 alkyl, C 3 to C 6 cycloalkyl or phenyl,
- R 2 represents hydrogen, C 1 to C 6 alkyl or phenyl,
- R 3 represents C 1 to Cs alkylene or a direct bond,
- m each independently represents one or two,
- n each independently stands for zero, one or two and
- M represents an equivalent of a polyvalent metal ion, for example an equivalent of Mg 2+ , Zn 2+ , Ca 2+ , Al 3+ , B 3+ , Pb 2+ or Ti 4+ .
Beispiele für Verbindungen der Formel (I) sind solche, bei denen
- R1 jeweils unabhängig voneinander für Ethoxy, Methoxy, i-Propoxy, Butoxy, Pentoxy, Methyl, Ethyl, Propyl, Butyl, i-Propyl, Pentyl, Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl oder Phenyl steht,
- R2 für Wasserstoff, Methyl, Ethyl, Propyl, Butyl, 2-Propyl, 1-Pentyl, 2-Pentyl, 1-Hexyl, i-Butyl oder Phenyl steht,
- R3 für Methylen, 1,1-Ethylen, 1,2-Ethylen, 1,1-Propylen, 1,2-Propylen, 1,3-Propylen, 2,2-Propylen, 1,1-Butylen, 1,2-Butylen, 1,3-Butylen, 1,4-Butylen, 2,2-Butylen, 2,3-Butylen oder eine direkte Bindung steht und
- m, n und M die oben angegebene Bedeutung haben.
- R 1 each independently represents ethoxy, methoxy, i-propoxy, butoxy, pentoxy, methyl, ethyl, propyl, butyl, i-propyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl,
- R 2 represents hydrogen, methyl, ethyl, propyl, butyl, 2-propyl, 1-pentyl, 2-pentyl, 1-hexyl, i-butyl or phenyl,
- R 3 for methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 2,2-propylene, 1,1-butylene, 1,2 -Butylene, 1,3-butylene, 1,4-butylene, 2,2-butylene, 2,3-butylene or a direct bond and
- m, n and M have the meaning given above.
Bevorzugt sind Verbindungen der Formel (I), bei denen
- R1 jeweils unabhängig voneinander für Ethoxy, Methoxy, i-Propoxy, Butoxy, Pentoxy, Methyl, Ethyl, Propyl, Butyl, i-Propyl, Pentyl, Cyclopropyl, Cyclopentyl, Cyclohexyl oder Phenyl steht,
- R2 für Wasserstoff, Methyl, Ethyl, Propyl, Butyl, 2-Propyl, Pentyl, Hexyl, i-Butyl oder Phenyl steht,
- R3 für Methylen, 1,1-Ethylen, 1,2-Ethylen, 1,1-Propylen, 1,2-Propylen, 1,3-Propylen, 1,1-Butylen, 1,2-Butylen, 1,3-Butylen, 1,4-Butylen, 2,2-Butylen, 2,3-Butylen oder eine direkte Bindung steht, und
- M für ein Äquivalent von Mg2+, Zn2+, Ca2+, Al3+, B3+ oder Pb2+ steht und
- m und n die oben angegebenen Bedeutungen haben.
- R 1 each independently represents ethoxy, methoxy, i-propoxy, butoxy, pentoxy, methyl, ethyl, propyl, butyl, i-propyl, pentyl, cyclopropyl, cyclopentyl, cyclohexyl or phenyl,
- R 2 represents hydrogen, methyl, ethyl, propyl, butyl, 2-propyl, pentyl, hexyl, i-butyl or phenyl,
- R 3 for methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 1,1-butylene, 1,2-butylene, 1,3 -Butylene, 1,4-butylene, 2,2-butylene, 2,3-butylene or a direct bond, and
- M represents an equivalent of Mg 2+ , Zn 2+ , Ca 2+ , Al 3+ , B 3+ or Pb 2+ and
- m and n have the meanings given above.
Besonders bevorzugt sind Verbindungen der Formel (I), bei denen
- R1 jeweils unabhängig voneinander für Ethoxy, Methoxy, i-Propoxy, Butoxy, Methyl, Ethyl, Propyl, Butyl, i-Propyl, Pentyl, Cyclopentyl, Cyclohexyl oder Phenyl steht,
- R2 für Wasserstoff, Methyl, Ethyl, Propyl, Butyl, 2-Propyl, Pentyl, Hexyl oder Phenyl steht,
- R3 für Methylen, 1,1-Ethylen, 1,2-Ethylen, 1,1-Propylen, 1,2-Propylen, 1,3-Propylen, 1,1-Butylen, 1,2-Butylen, 1,3-Butylen, 1,4-Butylen, 2,2-Butylen, oder eine direkte Bindung steht,
- m für eins steht,
- M für ein Äquivalent von Mg2+, Zn2+ oder Ca2+ steht und
- n die oben angegebene Bedeutung hat.
- R 1 each independently represents ethoxy, methoxy, i-propoxy, butoxy, methyl, ethyl, propyl, butyl, i-propyl, pentyl, cyclopentyl, cyclohexyl or phenyl,
- R 2 represents hydrogen, methyl, ethyl, propyl, butyl, 2-propyl, pentyl, hexyl or phenyl,
- R 3 for methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 1,1-butylene, 1,2-butylene, 1,3 -Butylene, 1,4-butylene, 2,2-butylene, or a direct bond,
- m stands for one,
- M stands for an equivalent of Mg 2+ , Zn 2+ or Ca 2+ and
- n has the meaning given above.
Bevorzugt sind symmetrisch aufgebaute Salze von modifizierten Bisphenolcarbonsäuren der Formel (I), d.h. solche Verbindungen der Formel (I), bei denen beide Reste R1 gleich sind, beide Zahlen m gleich sind, beide Zahlen n gleich sind und die OH- und R, -Gruppen sich an den beiden aromatischen Ringen in den gleichen Positionen befinden.Preference is given to symmetrically structured salts of modified bisphenol carboxylic acids of the formula (I), ie those compounds of the formula (I) in which both radicals R 1 are identical, both numbers m are identical, both numbers n are identical and the OH and R, Groups are in the same positions on the two aromatic rings.
Weiterhin bevorzugt sind Verbindungen der Formel (I), in welchen
- R1 für Wasserstoff, Methyl oder tert.-Butyl steht,
- R2 für Wasserstoff oder Methyl steht,
- R3 für C1- bis C3-Alkylen oder für eine direkte Bindung steht,
- m für eins steht,
- n für null oder eins steht und
- M für ein Äquivalent von Mg2+, Zn2+, Ca2+ oder Pb2+, besonders bevorzugt von Mg2+, Zn2+ oder Ca2 steht.
- R 1 represents hydrogen, methyl or tert-butyl,
- R 2 represents hydrogen or methyl,
- R 3 represents C 1 to C 3 alkylene or a direct bond,
- m stands for one,
- n stands for zero or one and
- M represents an equivalent of Mg 2+ , Zn 2+ , Ca 2+ or Pb 2+ , particularly preferably of Mg 2+ , Zn 2+ or Ca2.
Die Salze der Bisphenolcarbonsäuren der Formel (I) können nach an sich bekannten Verfahren aus den entsprechenden freien Bisphenolcarbonsäuren (Formel (I) mit M = Wasserstoff) hergestellt werden, die ihrerseits durch Kondensation des entsprechenden Phenols der Formel (II)
in der
- Ri, m und n die bei Formel (I) angegebene Bedeutung haben,
- mit der entsprechenden Oxocarbonsäure der Formel (III)
in der R2 und R3 die bei Formel (I) angegebene Bedeutung haben, zugänglich sind (vergleiche beispielsweise J. Org. Chem. 23, 1005 (1958); J. Org. Chem. 24, 1949 (1951); J. Org. Chem. 27, 455 (1962) und JACS 76, 4465 (1954)). Die freie Bisphenolcarbonsäure (Formel (I), M = Wasserstoff) kann mit einer wäßrigen Base, z.B. einer wäßrigen Lösung von Alkalihydroxid, -carbonat oder -hydrogencarbonat zu dem entsprechenden Alkalisalz (Formel (I), M = Alkali) umgesetzt und aus einer wäßrigen Lösung davon durch Zusatz eines löslichen Salzes des gewünschten mehrwertigen Metalls ein Salz der modifizierten Bisphenolcarbonsäure der Formel (I) ausgefällt und isoliert werden.
in the
- Ri, m and n have the meaning given for formula (I),
- with the corresponding oxocarboxylic acid of the formula (III)
in which R 2 and R 3 have the meaning given for formula (I), are accessible (see, for example, J. Org. Chem. 23, 1005 (1958); J. Org. Chem. 24, 1949 (1951); J. Org. Chem. 27, 455 (1962) and JACS 76, 4465 (1954)). The free bisphenol carboxylic acid (formula (I), M = hydrogen) can be reacted with an aqueous base, for example an aqueous solution of alkali metal hydroxide, carbonate or hydrogen carbonate, to give the corresponding alkali metal salt (formula (I), M = alkali) and from an aqueous Solution thereof by adding a soluble salt of the desired polyvalent metal, a salt of the modified bisphenol carboxylic acid of the formula (I) is precipitated and isolated.
Nach einem anderen Verfahren kann man ein Oxid oder, bevorzugt, ein Hydroxid des gewünschten mehrwertigen Metalls im stöchiometrischen Verhältnis mit der freien Bisphenolcarbonsäure in wäßriger Lösung, gegebenenfalls zusammen mit einem mit Wasser mischbaren Cosolvens, erhitzen und so ein Salz einer modifizierten Bisphenolcarbonsäure der Formel (I) erhalten.According to another process, an oxide or, preferably, a hydroxide of the desired polyvalent metal in a stoichiometric ratio with the free bisphenol carboxylic acid in aqueous solution, optionally together with a water-miscible cosolvent, is heated and a salt of a modified bisphenol carboxylic acid of the formula (I ) receive.
Für erfindungsgemäße Aufzeichnungsmaterialien sind auch solche Salze von modifizierten Bisphenolcarbonsäuren der Formel (I) bevorzugt, bei denen sich die OH-Gruppen entweder in para- oder in ortho-und para-Stellung zur R2-C-R3-COOM-Gruppierung und R1 in meta- und/oder in ortho-Stellung zur R2-C-R3-COOM-Gruppierung befinden. Besonders bevorzugt befindet sich OH in para- und R1 in meta-Stellung zur R2-C-R3-COOM-Gruppierung.For recording materials according to the invention, preference is also given to salts of modified bisphenolcarboxylic acids of the formula (I) in which the OH groups are either in the para or in the ortho and para position to the R 2 -CR 3 -COOM group and R 1 in are meta and / or in the ortho position to the R 2 -CR 3 -COOM grouping. OH is particularly preferably in the para and R 1 in the meta position to the R 2 -CR 3 -COOM grouping.
Die Salze modifizierter Bisphenolcarbonsäuren der Formel (I) können in erfindungsgemäße thermoreaktive Aufzeichnungsmaterialien eingesetzt werden, wie sie bei den oben beschriebenen Herstellungsverfahren anfallen, also beispielsweise mit Reinheiten von 70 bis 100 Gew.-% und gegebenenfalls Kristallwaser enthaltend.The salts of modified bisphenol carboxylic acids of the formula (I) can be used in thermoreactive recording materials according to the invention, as are obtained in the production processes described above, that is to say, for example, with purities of 70 to 100% by weight and optionally containing crystal water.
Erfindungsgemäße thermoreaktive Aufzeichnungsmaterialien können beliebige, als Farbgeber übliche Leukofarbstoffe enthalten. Bevorzugt sind Leukofarbstoffe vom Triphenylmethan-, Fluoran-, Phenothiazin-, Auramin-, Spiropyran- und Indolinophthalid-Typ, die jeweils allein oder in Kombination angewendet werden können. Beispiele für solche Farbgeber sind:
- 3,3-Bis-(p-dimethylaminophenyl)-6-dimethylaminophthalid (= Kristallviolettlacton), 3,3-Bis-(p-dimethylaminophenyl)-6-chlorphthalid, 3-Cyclohexylamino-6-chlorfluoran, 3-Dimethylamino-5,7-dimethylfluoran, 3-Diethylamino-7-methyl-fluoran, 3-(N-p-Tolyl-N-ethylamino)-6-methyl-7-anilinofluoran, 2-[3,6-Bis-(diethylamino)-9-(o-chloranilino)-xanthylbenzoesäurelactam],3-N-Methyl-N-cyclohexyl-amino-6-methyl-7-anilinofluoran, 3-Diethylamino-6-methyl-7-anilinofluoran, 3-(N,N-Diethylamino)-5-methyl-7-(N,N-dibenzylami- no)-fluoran, 6'-Chlor-8'-methoxy-benzoindolino-spiropyran, 3-(2'-Hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)-phthalid, 3-(2'-Methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chlor-5'-methylphenyl)-phthalid, 3-(N-Ethyl-N-tetrahydrofurfuryl)-amino-6-methyl-7-anilinofluoran, 3-N-Ethyl-N-(2-ethoxypropyl)-amino-6-methyl-7-anilinofluoran, 3-(N-Methyl-N-isopropyl)-amino-6-methyl-7-anilinofluoran, 3-Morpholino-7-(N-propyl-trifluormethylanilino)-fluoran, 3-Diethylamino-5-cblor-7-(N-benzyl-trifluormethylanili- i-no)-fluoran, 3-(N-Ethyl-p-toluidino)-7-(a-phenylethylamino)-fluoran, 3-Diethylamino-7-(o-methoxycarbonylp- henylamino)-fluoran, 3-Diethylamino-5-methyl-7-(a-phenylethylamino)-fluoran, 3-Diethylamino-7-piperidino- fluoran, 3-Dibutylamino-6-methyl-7-anilinofluoran, 3,6-Bis-(dimethylanino)-fluorenspiro(9,3')-6-dimethylamino- naphthalid, 3-(N-Benzyl-N-cyclohexylamino)-5,6-benzo-7-naphthylamino-4'-bromfluoran, 3-Diethylamino-6-chlor-7-anilinofluoran, 3-N-Methyl-N-isopropyl-6-methyl-7-anilinofluoran, 3-N-Ethyl-N-amyl-6-methyl-7-anilinofluoran und 3-Diethylamino-6-methyl-7-(2',4'-dimethylanilino)-fluoran.
- 3,3-bis- (p-dimethylaminophenyl) -6-dimethylaminophthalide (= crystal violet lactone), 3,3-bis- (p-dimethylaminophenyl) -6-chlorophthalide, 3-cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5, 7-dimethylfluoran, 3-diethylamino-7-methyl-fluoran, 3- (Np-tolyl-N-ethylamino) -6-methyl-7-anilinofluoran, 2- [3,6-bis- (diethylamino) -9- ( o-chloroanilino) xanthylbenzoic acid lactam], 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) - 5-methyl-7- (N, N-dibenzylamino) -fluorane, 6'-chloro-8'-methoxy-benzoindolino-spiropyran, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2nd '-methoxy-5'-nitrophenyl) phthalide, 3- (2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hydroxy-4'-chloro-5'-methylphenyl) phthalide, 3- ( N-ethyl-N-tetrahydrofurfuryl) amino-6-methyl-7-anilinofluoran, 3-N-ethyl-N- (2-ethoxypropyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl- N-isopropyl) amino-6-methyl-7-anilinofluoran, 3- Morpholino-7- (N-propyl-trifluoromethylanilino) -fluorane, 3-diethylamino-5-cblor-7- (N-benzyl-trifluoromethylanili- i-no) -fluorane, 3- (N-ethyl-p-toluidino) - 7- (a-phenylethylamino) -fluorane, 3-diethylamino-7- (o-methoxycarbonylphenylamino) -fluorane, 3-diethylamino-5-methyl-7- (a-phenylethylamino) -fluorane, 3-diethylamino-7- piperidino-fluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3,6-bis (dimethylanino) -fluorenspiro (9,3 ') - 6-dimethylamino-naphthalide, 3- (N-benzyl-N-cyclohexylamino ) -5,6-benzo-7-naphthylamino-4'-bromofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-N-methyl-N-isopropyl-6-methyl-7-anilinofluorane, 3-N -Ethyl-N-amyl-6-methyl-7-anilinofluorane and 3-diethylamino-6-methyl-7- (2 ', 4'-dimethylanilino) fluorine.
Als Farbenentwickler können erfindungsgemäße thermoreaktive Aufzeichnungsmaterialien beliebige, als Farbenentwickler übliche Elektronenakzeptoren oder Säuren bei Wärmezufuhr die Farbbildung des Leukofarbstoffs induzieren, wie Polyphenole, Hydroxydiphenylsulfone, Hydroxydiphenylsulfoxide, Hydroxybenzoesäureester, Ester der Gallensäuren, Hydroxydiphenylsulfide, Hydroxydiphenyldisulfide, Salicylsäuren, deren Ester oder Amide, Hydroxynaphthalinsäuren, deren Ester oder Amide, Bis-(hydroxyphenylthio)-dioxaalkane, Bis-(hydroxyphenylthio)-oxaalkaneund Bis-(hydroxyphenyl)-alkane.As a color developer thermoreactive recording material according to the invention may be any, as a color developer conventional electron acceptors or acids when heat inducing color formation of the leuco dye, such as polyphenols, Hydroxydiphenylsulfone, Hydroxydiphenylsulfoxide, hydroxybenzoic acid, esters of bile acids, Hydroxydiphenylsulfide, Hydroxydiphenyldisulfide, salicylic acids, their esters or amides, Hydroxynaphthalinsäuren, their esters or amides, bis (hydroxyphenylthio) dioxaalkanes, bis (hydroxyphenylthio) oxaalkanes and bis (hydroxyphenyl) alkanes.
Beispiele für solche Farbentwickler sind:
- 4,4'-Isopropylidenbisphenol, 4,4'-Isopropylidenbis(o-methylphenol), 4,4'-sek.-Butylidenbisphenol, 4,4'-Isopropylidenbis(2-tert.-butylphenol), 4,4'-Cyclohexylidendiphenol, 4,4'-Isopropylidenbis(2-chlorphenol), 2,2'-Methylenbis(4-methyl-6-tert.-butylphenol), 2,2'-Methylenbis(4-ethyl-6-tert.-butylphenol), 4,4'-Butylidenbis(6-tert.-butyl-2-methyl)-phenol, 1,1,3-Tris(2-methyl-4-hydroxy-5-tert.-butylpheny1)-butan, 4,4'-Thiobis(6-tert.-butyl-2-methyl)-phenol, Bis(p-hydroxyphenyl)-sulfon, 4-Isopropoxy-4'-hydroxydiphenylsulfon, 4-Benzyloxy-4'-hydroxydiphenylsulfon, Bis(p-hydroxyphenyl)-sulfoxid, Isopropyl-p-hydroxybenzoat, Benzyl-p-hydroxybenzoat, Stearylgallat, Laurylgallat, Octylgallat, 1,7-Bis(4-hydroxyphenylthio)-3,5-dioxaheptan, 1,5-Bis(4-hydrox- yphenylthio)-3-oxapentan, 1,3-Bis(4-hydroxyphenylthio)-propan, 1,3-Bis(4-hydroxyphenylthio)-2-hydroxypropan, N,N'-Diphenylthioharnstoff,N,N'-Di(m-chlorphenyl)-thioharnstoff, Salicylanilid, 5-Chlor-salicylanilid, 2-Hydroxy-3-naphthoesäure, 2-Hydroxy-1-naphthoesäure, 1-Hydroxy-2-naphthoesäure, Bis(4-hydroxyphenyl)-benzylacetat, 3,4-Dihydroxyphenyl-4'-methylphenylsulfon, 1,7-Bis-(4-hydroxyphenylthio)-3-dioxaheptan, 1,5-Bis-(4-hydroxyphenylthio)-3-oxapentan und 1,4-Bis-(4-hydroxyphenylthio)-butan.
- 4,4'-isopropylidenebisphenol, 4,4'-isopropylidenebis (o-methylphenol), 4,4'-sec-butylidenebisphenol, 4,4'-isopropylidenebis (2-tert-butylphenol), 4,4'-cyclohexylidenediphenol , 4,4'-isopropylidenebis (2-chlorophenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) , 4,4'-butylidenebis (6-tert-butyl-2-methyl) phenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylpheny1) butane, 4, 4'-thiobis (6-tert-butyl-2-methyl) phenol, bis (p-hydroxyphenyl) sulfone, 4-isopropoxy-4'-hydroxydiphenyl sulfone, 4-benzyloxy-4'-hydroxydiphenyl sulfone, bis (p- hydroxyphenyl) sulfoxide, isopropyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, stearyl gallate, lauryl gallate, octyl gallate, 1,7-bis (4-hydroxyphenylthio) -3,5-dioxaheptane, 1,5-bis (4-hydrox- yphenylthio) -3-oxapentane, 1,3-bis (4-hydroxyphenylthio) propane, 1,3-bis (4-hydroxyphenylthio) -2-hydroxypropane, N, N'-diphenylthiourea, N, N'-di (m -chlorophenyl) -thiourea, salicylanilide, 5-chloro-salicylanilide, 2-hydroxy-3-naphthoic acid, 2-hydro xy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, bis (4-hydroxyphenyl) benzyl acetate, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 1,7-bis (4-hydroxyphenylthio) -3-dioxaheptane, 1,5-bis (4-hydroxyphenylthio) -3-oxapentane and 1,4-bis (4-hydroxyphenylthio) butane.
Die erfindungsgemäß einzusetzenden Salze modifizierter Bisphenolcarbonsäuren der Formel (I) haben auch gewisse Entwicklereigenschaften. In speziellen Fällen kann deshalb gegebenenfalls auf den Zusatz eines besonderen Farbentwicklers verzichtet werden.The salts of modified bisphenol carboxylic acids of the formula (I) to be used according to the invention also have certain developer properties. In special cases, the addition of a special color developer may therefore not be necessary.
Vorzugsweise, jedoch nicht zwingend, enthalten erfindungsgemäße thermoreaktive Aufzeichnungsmaterialien neben Farbgebern, Farbentwicklern und Salzen von modifizierten Bisphenolcarbonsäuren zusätzlich sogenannte Sensibilisatoren. Hierbei kann es sich um übliche wärmeschmelzbare Substanzen handeln, die in der Lage sind, die Farbentwicklungsgeschwindigkeit zu beschleunigen und/oder die Farbbildung zu verstärken. Solche Sensibilisatoren können beispielsweise einen Schmelzpunkt im Bereich 70 bis 140°C, vorzugsweise 70 bis 130°C und insbesondere 75 bis 120°C aufweisen und beispielsweise aus folgenden Substanzklassen stammen: aromatische Sulfonamide, Carbonamide, Anilide, p-Hydroxybenzoesäureester,p-Hydroxyterephthalsäureester, Diphenylsulfone, Benzyldiphenyle, Phenylsalicylsäureester, Terephthalsäurediester, Isophthalsäurediester und Wachse (siehe auch JP-OS'en 57-191 089, 58-98 285, 58-205 793, 58-205 795, 58-209 591, 58-209 592, 58-211 493, 58-211 494 und 59-9092.Preferably, but not necessarily, thermoreactive recording materials according to the invention contain, in addition to colorants, color developers and salts of modified bisphenolcarboxylic acids, so-called sensitizers. These can be customary heat-fusible substances which are able to accelerate the color development speed and / or to intensify the color formation. Such sensitizers can have, for example, a melting point in the range from 70 to 140.degree. C., preferably from 70 to 130.degree. C. and in particular from 75 to 120.degree. Diphenylsulfones, benzyldiphenyls, phenylsalicylic acid esters, terephthalic acid diesters, isophthalic acid diesters and waxes (see also JP-OS'en 57-191 089, 58-98 285, 58-205 793, 58-205 795, 58-209 591, 58-209 592, 58 -211 493, 58-211 494 and 59-9092.
Beispiele für Sensibilisatoren sind:
- Stearylamid, Benzolsulfonsäureanilid, p-Benzylbiphenyl, Dibenzyloxalat, Dimethylterephthalat, 1- und 2-Benzyloxynaphthalin, Ethylenglykol-m-tolylether, Diphenylcarbonat, Terephthalsäuredibenzylester, Isophthalsäuredibenzylester, m-Terphenyl, 1,2-Diphenoxyethan, Benzyl-p-hydroxybenzoat und Bis-(2-(4-methoxy)-phenyloxyethyl)-ether.
- Stearylamide, benzenesulfonic acid anilide, p-benzylbiphenyl, dibenzyl oxalate, dimethyl terephthalate, 1- and 2-benzyloxynaphthalene, ethylene glycol m-tolyl ether, diphenyl carbonate, terephthalic acid dibenzyl ester, isophthalic acid dibenzyl ester, m-terphenyl-benzene, 1,2-terphenylane, 1,2-benzophenyl, 1,2-benzophenyl 2- (4-methoxy) phenyloxyethyl) ether.
Erfindungsgemäße thermoreaktive Aufzeichnungsmaterialien können gegebenenfalls außerdem Bindemittel und/oder sonstige übliche Zusätze enthalten. Bei den Bindemitteln kann es sich beispielsweise um teilweise oder vollständig verseiftes Polyvinylacetat, Hydroxyethylcellulose, Gummi arabicum, Stärke, Polyvinylpyrrolidon oder Kasein handeln, bei den sonstigen Zusätzen beispielsweise um Füllstoffe, oberflächenaktive Mittel, Antioxidantien und/oder Entschäumer.Thermoreactive recording materials according to the invention can optionally also contain binders and / or other customary additives. The binders can be, for example, partially or completely saponified polyvinyl acetate, hydroxyethyl cellulose, gum arabic, starch, polyvinylpyrrolidone or casein, and the other additives can be, for example, fillers, surface-active agents, antioxidants and / or defoamers.
Beispiele für geeignete Füllstoffe sind Feinpulver von anorganischen Verbindungen wie Calciumcarbonat, Calciumsulfat, Siliciumdioxid, Titanoxid, Bariumsulfat, Talkum, und oberflächenbehandeltes Siliciumdioxid, sowie Feinpulver von organischen Verbindungen wie Harnstoff, Formaldehydharze, Styrol-Methacrylsäure-Copolymere, Polystyrolharze und Polyacrylcopolymere (siehe z.B. DE-OS 3 715 724).Examples of suitable fillers are fine powders of inorganic compounds such as calcium carbonate, calcium sulfate, silicon dioxide, titanium oxide, barium sulfate, talc, and surface-treated silicon dioxide, and fine powders of organic compounds such as urea, formaldehyde resins, styrene-methacrylic acid copolymers, polystyrene resins and polyacrylic copolymers (see, for example, DE- OS 3 715 724).
Erfindungsgemäße thermoreaktive Aufzeichnungmaterialien können die verschiedensten Trägermaterialien enthalten. In Frage kommt beispielsweise beliebiges Papier, das unvorbehandelt oder vorbehandelt zum Einsatz gelangen kann. Bevorzugt sind Papiere wie sie üblicherweise zur Herstellung von Kopien auf Fernkopierern, Etiketten und Fahrkarten, zur Kennzeichnung von Fracht- und Gepäckstücken und für ähnliche Zwecke verwendet werden. Bei vorbehandelten Papieren kann es sich beispielsweise um vorbeschichtete Papiere handeln, wobei die Beschichtung beispielsweise zum Zwecke des Aufbringens von Füllstoffen und/oder zur Beeinflussung der Wärmeleitfähigkeit dienen kann. Derartige Vorbehandlungen können auf einer oder beiden Seiten des Papieres vorgenommen worden sein. Das Papier kann auch kalandriert oder ein- oder beidseitig in der Papiermaschine geglättet worden sein. Eine Seite des Papiers, vorzugsweise die Rückseite, kann gegebenenfalls auch mit Plastikmaterial, Gelatine, Klebstoff und/oder einer Release-Schicht versehen worden sein. Für erfindungsgemäße thermoreaktive Aufzeichnungsmaterialien sind beispielsweise Papiere mit einem Flächengewicht von 20 bis 200 g/m2, vorzugsweise 30 bis 100 g/m2 geeignet. Für erfindungsgemäße thermoreaktive Aufzeichnungsmaterialien können als Trägermaterialien auch beliebige Folien verwendet werden. Bevorzugt sind solche Folien, die üblicherweise als Trägermaterialien für die Overhead-Projektion oder sonstige Präsentationssysteme zum Einsatz gelangen. Weiterhin kann als Trägermaterial auch Pappe und Karton verwendet werden, die gegebenenfalls wie beim Papier als Trägermaterial beschrieben, beschichtet und/oder vorbehandelt sein können.Thermoreactive recording materials according to the invention can contain a wide variety of carrier materials. For example, any paper that can be used untreated or pretreated can be used. Preference is given to papers as are usually used for the production of copies on facsimile machines, labels and tickets, for the identification of cargo and luggage and for similar purposes. For example, pretreated papers can be pre-treated act coated papers, wherein the coating can serve, for example, for the purpose of applying fillers and / or for influencing the thermal conductivity. Such pre-treatments may have been carried out on one or both sides of the paper. The paper can also have been calendered or smoothed on one or both sides in the paper machine. One side of the paper, preferably the back, can optionally also have been provided with plastic material, gelatin, adhesive and / or a release layer. For thermoreactive recording materials according to the invention, for example, papers with a basis weight of 20 to 200 g / m 2 , preferably 30 to 100 g / m 2, are suitable. Any films can also be used as carrier materials for thermoreactive recording materials according to the invention. Preferred foils are those which are usually used as carrier materials for overhead projection or other presentation systems. Furthermore, cardboard and cardboard can also be used as the carrier material, which, if appropriate, can be coated, and / or pretreated as described for the paper as carrier material.
Erfindungsgemäße thermoreaktive Aufzeichnungsmaterialien können in der Beschichtung (d.h. ohne Berücksichtigung des Trägermaterials) beispielsweise 0,1 bis 40 Gew.-% modifizierte Bisphenolcarbonsäuren der Formel (I) enthalten. Bevorzugt beträgt diese Menge 1 bis 30 Gew.-%, besonders bevorzugt 5 bis 25 Gew.-%. Die Beschichtung kann weiterhin beispielsweise 1 bis 20 Gew.-% Farbgeber enthalten. Bevorzugt beträgt die Farbgeber-Menge 2 bis 15 Gew.-%, besonders bevorzugt 5 bis 10 Gew.-%. Die Beschichtung kann beispielsweise weiterhin 0 bis 30 Gew.-% Farbentwickler enthalten. Bevorzugt sind dabei Mengen von 5 bis 25 Gew.-%, insbesondere solche von 10 bis 20 Gew.-%. Weiterhin kann die Beschichtung Sensibilisatoren beispielsweise in einer Menge von 0 bis 30 Gew.-%, vorzugsweise 5 bis 25 Gew.-%, insbesondere 10 bis 20 Gew.-% enthalten. Bindemittel und übliche Zusätze können in der Beschichtung beispielsweise in einer Menge von 5 bis 80 Gew.-% enthalten sein, bevorzugt sind hier 20 bis 70 Gew.-%, insbesondere 30 bis 60 Gew.-%. Die Summe aller Bestandteile der Beschichtung ergibt 100 Gew.-%.Thermoreactive recording materials according to the invention can contain, for example, 0.1 to 40% by weight of modified bisphenol carboxylic acids of the formula (I) in the coating (i.e. without taking into account the carrier material). This amount is preferably 1 to 30% by weight, particularly preferably 5 to 25% by weight. The coating may further contain, for example, 1 to 20% by weight of color donor. The amount of colorant is preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight. The coating can also contain, for example, 0 to 30% by weight of color developer. Amounts of 5 to 25% by weight, in particular those of 10 to 20% by weight, are preferred. Furthermore, the coating may contain sensitizers, for example in an amount of 0 to 30% by weight, preferably 5 to 25% by weight, in particular 10 to 20% by weight. Binder and conventional additives can be contained in the coating, for example, in an amount of 5 to 80% by weight, 20 to 70% by weight, in particular 30 to 60% by weight, being preferred. The sum of all components of the coating is 100% by weight.
Erfindungsgemäße thermoreäktive Aufzeichnungsmaterialien können beispielsweise hergestellt werden, indem man zunächst Ausgangsdispersionen herstellt, nämlich eine Farbgeberdispersion, eine Dispersion, die wenigstens ein Salz einer modifizierten Bisphenolcarbonsäure der Formel (I) enthält und eine Entwicklerdispersion. Die Ausgangsdispersionen kann man mischen und dann mit einem geeigneten Gerät, z.B. einer Rakel, auf ein Trägermaterial, z.B. auf eine Kunststoffolie oder Papier, aufbringen.Thermo-reactive recording materials according to the invention can be produced, for example, by first preparing starting dispersions, namely a colorant dispersion, a dispersion which contains at least one salt of a modified bisphenol carboxylic acid of the formula (I) and a developer dispersion. The starting dispersions can be mixed and then with a suitable device, e.g. a doctor blade, on a carrier material, e.g. on a plastic film or paper.
Bindemittel und sonstige Zusätze kann man gegebenenfalls einer, mehreren oder allen der Ausgangsdispersionen oder dem Gemisch dieser Dispersionen zufügen. Man kann auch so verfahren, daß man einzelne Ausgangsdispersionen oder beliebige unterschiedliche Gemische von Ausgangsdispersionen nacheinander auf ein Trägermaterial aufbringt.Binder and other additives can optionally be added to one, more or all of the starting dispersions or to the mixture of these dispersions. One can also proceed in such a way that individual starting dispersions or any different mixtures of starting dispersions are applied in succession to a carrier material.
Nach dem Aufbringen einzelner oder aller Dispersionen schließt sich eine Trocknung an.After applying individual or all dispersions, drying follows.
Bevorzugt stellt man erfindungsgemäße thermoaktive Aufzeichnungsmaterialien wie folgt her (Teile sind Gewichtsteile):Thermoactive recording materials according to the invention are preferably produced as follows (parts are parts by weight):
5 bis 95 Teile eines oder mehrerer Farbgeber, bevorzugt 20 bis 75 Teile, besonders bevorzugt 40 bis 60 Teile werden in 250 Teilen einer wäßrigen Polyvinylacetatlösung, die aus 0,1 bis 30 Teilen, bevorzugt 1 bis 20 Teilen, besonders bevorzugt 2 bis 15 Teilen teilverseiftem Polyvinylacetat und 92 Teilen Wasser besteht, eingerührt und so lange gemahlen (z.B. mit einer Sandmühle) bis die mittlere Teilchengröße der Farbgeberpärtikel 3 um oder weniger beträgt.5 to 95 parts of one or more colorants, preferably 20 to 75 parts, particularly preferably 40 to 60 parts are in 250 parts of an aqueous polyvinyl acetate solution, which consists of 0.1 to 30 parts, preferably 1 to 20 parts, particularly preferably 2 to 15 parts partially saponified polyvinyl acetate and 92 parts of water, stirred in and milled (for example with a sand mill) until the average particle size of the colorant particles is 3 μm or less.
1 bis 50 Teile eines oder mehrerer Farbentwickler, bevorzugt 5 bis 30 Teile, besonders bevorzugt 10 bis 20 Teile und 10 bis 100 Teile eines Sensibilisators, bevorzugt 20 bis 80 Teile, besonders bevorzugt 35 bis 60 Teile sowie 10 bis 100 Teile eines oder mehrerer Füllstoffe, bevorzugt 15 bis 70 Teile, besonders bevorzugt 20 bis 50 Teile werden in 272 Teilen einer wäßrigen Polyvinylacetatlösung eingerührt, die aus 0,1 bis 20 Teilen, bevorzugt 1,5 bis 10 Teilen teilverseiftem Polyvinylacetat und 98 Teilen Wasser besteht, und so lange gemahlen (z.B. mit einer Sandmühle) bis die mittlere Teilchengröße aller festen Partikel 3 um oder weniger beträgt.1 to 50 parts of one or more color developers, preferably 5 to 30 parts, particularly preferably 10 to 20 parts and 10 to 100 parts of a sensitizer, preferably 20 to 80 parts, particularly preferably 35 to 60 parts and 10 to 100 parts of one or more fillers , preferably 15 to 70 parts, particularly preferably 20 to 50 parts, are stirred into 272 parts of an aqueous polyvinyl acetate solution which consists of 0.1 to 20 parts, preferably 1.5 to 10 parts of partially saponified polyvinyl acetate and 98 parts of water, and are ground for as long as possible (eg with a sand mill) until the average particle size of all solid particles is 3 µm or less.
5 bis 50 Teile eines oder mehrerer Salze modifizierter Bisphenolcarbonsäuren der Formel (I), bevorzugt 10 bis 45 Teile, besonders bevorzugt 20 bis 35 Teile werden in 70 Teilen einer wäßrigen Polyvinylacetatlösung eingerührt, die aus 0,1 bis 30 Teilen, bevorzugt 1 bis 20 Teilen, besonders bevorzugt 2 bis 15 Teilen teilverseiftem Polyvinylacetat und 66 Teilen Wasser besteht und so lange gemahlen (z.B. mit einer Sandmühle) bis die mittlere Teilchengröße 3 um oder weniger beträgt.5 to 50 parts of one or more salts of modified bisphenol carboxylic acids of the formula (I) are preferred 10 to 45 parts, particularly preferably 20 to 35 parts, are stirred into 70 parts of an aqueous polyvinyl acetate solution which consists of 0.1 to 30 parts, preferably 1 to 20 parts, particularly preferably 2 to 15 parts of partially saponified polyvinyl acetate and 66 parts of water, and so on grind long (eg with a sand mill) until the average particle size is 3 µm or less.
120 bis 40 Teile, bevorzugt 100 bis 50 Teile, besonders bevorzugt 80 bis 60 Teile Entwicklerdispersion werden mit 20 bis 0,5 Teilen, bevorzugt 15 bis 3 Teilen, besonders bevorzugt 10 bis 5 Teilen Farbgeberdispersion und 40 bis 0,5 Teilen, bevorzugt 30 bis 5 Teilen, besonders bevorzugt 20 bis 10 Teilen Bisphenolcarbonsäuresalz-Dispersion zusammengerührt und mit verdünnter Natronlauge auf einen pH-Wert von 6 bis 14, bevorzugt 7 bis 11, besonders bevorzugt 7,5 bis 9,5 eingestellt.120 to 40 parts, preferably 100 to 50 parts, particularly preferably 80 to 60 parts of developer dispersion are mixed with 20 to 0.5 parts, preferably 15 to 3 parts, particularly preferably 10 to 5 parts of colorant dispersion and 40 to 0.5 parts, preferably 30 to 5 parts, particularly preferably 20 to 10 parts of bisphenol carboxylic acid salt dispersion stirred together and adjusted to a pH of 6 to 14, preferably 7 to 11, particularly preferably 7.5 to 9.5 with dilute sodium hydroxide solution.
Die Streichfarbe wird mittels einer Drahtrakel auf eine Papieroberfläche in einer Menge aufgebracht, die einem Beschichtungsgewicht von 2 bis 15 g/m2, bevorzugt 5 bis 12 g/m2, besonders bevorzugt 7,5 bis 10,5 g/m2 entspricht.The coating color is applied by means of a wire doctor knife to a paper surface in an amount which corresponds to a coating weight of 2 to 15 g / m 2 , preferably 5 to 12 g / m 2 , particularly preferably 7.5 to 10.5 g / m 2 .
Nach dem Trocknen wird das beschichtete Papier vorzugsweise kalandriert.After drying, the coated paper is preferably calendered.
Die Beurteilung erfindungsgemäßer und nicht erfindungsgemäßer thermoaktiver Aufzeichnungsmaterialien in den nachfolgenden Beispielen wurde gemäß folgender Meßmethoden durchgeführt:The evaluation of inventive and non-inventive thermoactive recording materials in the following examples was carried out according to the following measurement methods:
In einem Thermoprinter (Sharp CE 700 P) wurde mit maximaler Energie eine Fläche von 4x0,9 cm vollschwarz gedruckt. Die optische Dichte dieser Meßfläche wurde mit einem Macbeth Densitometer RD 917 (Fa. Kollmorgen AG, Schweiz) bestimmt.In a thermal printer (Sharp CE 700 P), an area of 4x0.9 cm was printed completely black with maximum energy. The optical density of this measuring surface was determined using a Macbeth densitometer RD 917 (from Kollmorgen AG, Switzerland).
Es wurde zunächst die optische Dichte gemäß a. bestimmt. Auf die bedruckte Fläche wurde dann mit einem Tiefdruckgerät (Rastertiefe 150 #, Fa. Gockel, Deutschland) eine 20 gew.-%ige Lösung von Rizinusöl in Cyclohexan gedruckt. Nach 3 Stunden Lagerung des bedruckten Papiers bei 60 C wurde erneut die optische Dichte (analog a. gemessen und die verbliebene Intensität in Prozent wie folgt errechnet:
Die Weichmacherstabilität wurde bestimmt, indem zunächst in einem Thermoprinter (Sharp CE 700 P) mit maximaler Energie eine Fläche von 4x4 cm mit unterschiedlicher Rasterdichte in der Druckfläche schwarz gedruckt wurde.The plasticizer stability was determined by first printing an area of 4x4 cm with different screen density in black in a thermal printer (Sharp CE 700 P) with maximum energy.
Von dieser Fläche wurde die Absorption mit Hilfe eines Elrepho 44 381 (Fa. Carl Zeiss, Deutschland) bestimmt. Die Rückseite der bedruckten Fläche wurde auf eine Stahlplatte gelegt, die bedruckte Fläche mit einer PVC-Folie, die 30 Gew.-% Weichmacher (Dioctylphthalat) enthielt, bedeckt und mit einem Stahlblock der Größe 4x3x2,5 cm belastet. Das entsprach einem Druck von 20 g/cm2.The absorption of this area was determined using an Elrepho 44 381 (from Carl Zeiss, Germany). The back of the printed area was placed on a steel plate, the printed area was covered with a PVC film containing 30% by weight of plasticizer (dioctyl phthalate) and loaded with a steel block of size 4x3x2.5 cm. This corresponded to a pressure of 20 g / cm 2 .
Nach 24 Stunden Lagerung bei 50 ° C wurde von der bedruckten Fläche erneut die Absorption bestimmt und die verbliebene Intensität in Prozent wie folgt errechnet:
Der Weißgrad wurde als % Remission ermittelt (großer Wert entspricht großem Weißgrad), die unerwünschte Verfärbung des unbedruckten Papiers nach Lagerung bei 60 ° C wurde als % Absorption aus der Remission (wie unter c. ausgeführt) berechnet (großer Wert entspricht dunklem Papier).The whiteness was determined as% remission (large value corresponds to high whiteness), the undesired discoloration of the unprinted paper after storage at 60 ° C. was calculated as% absorption from the remission (as explained under c.) (Large value corresponds to dark paper).
Die Sensitivität wurde bestimmt, indem mit einem Thermoprintertestgerät TP 104 (Fa. Geminus, Deutschland) jeweils eine Fläche von 5,5x0,8 cm bei einer Kopfspannung von 26 V und variablen Brennzeiten vollschwarz gedruckt wurde. Von diesen Flächen wurde mit einem Macbeth-Densitometer RD 917 die optische Dichte bestimmt. Ein Thermopapier ist umso sensitiver, je größer die Unterschiede in den optischen Dichten bei kurzen und längeren Brennzeiten sind.The sensitivity was determined by printing an area of 5.5 × 0.8 cm with a head voltage of 26 V and variable burning times using a TP 104 thermal printer (Geminus, Germany). The optical density of these areas was determined using a RD 917 Macbeth densitometer. A thermal paper is the more sensitive, the bigger the differences in the optical densities with short and longer burning times.
Die erfindungsgemäß einzusetzenden Salze von modifizierten Bisphenolcarbonsäuren sind auch als Entwickler und/oder Additive in kohlefreien Durchschreibesystemen geeignet.The salts of modified bisphenol carboxylic acids to be used according to the invention are also suitable as developers and / or additives in carbon-free copying systems.
Erfindungsgemäße Aufzeichnungsmaterialien weisen eine Stabilisierung der Farbe auch bei längerer Lagerzeit, gute Lichtstabilitäten und ausgezeichnete Stäbilitäten gegenüber Wasser, Weichmachern, Fetten und Inhaltsstoffen von Textmarkierungsstiften auf.Recording materials according to the invention have a stabilization of the color even with a long storage time, good light stability and excellent stability towards water, plasticizers, fats and ingredients of text marker pens.
Im folgenden beziehen sich Teile und Prozente auf das Gewicht und entsprechende Mengen bedeuten gleiche Gewichtsmengen.In the following parts and percentages relate to the weight and corresponding amounts mean equal amounts of weight.
33,6 g (0,4 Mol) Natriumhydrogencarbonat wurden in 400 ml Wasser vorgelegt und portionsweise unter Rühren 97,7 g (0,4 Mol) 2,2-Bis-(4-hydroxyphenyl)-ethansäure zugegeben und noch 15 Minuten nachgerührt. Anschließend tropfte man eine Lösung von 27,2 g (0,2 Mol) Zinkchlorid in 100 ml Wasser hinzu und erhitzte auf 90 °C. Nach Einengen löste man den Rückstand in 100 ml Wasser, kühlte ab und saugte den gebildeten Niederschlag ab. Es wurden 78,1 g Zinksalz der 2,2-Bis-(4-hydroxyphenyl)-ethansäure erhalten.33.6 g (0.4 mol) of sodium hydrogen carbonate were placed in 400 ml of water and 97.7 g (0.4 mol) of 2,2-bis (4-hydroxyphenyl) ethanoic acid were added in portions with stirring and the mixture was stirred for a further 15 minutes . A solution of 27.2 g (0.2 mol) of zinc chloride in 100 ml of water was then added dropwise and the mixture was heated to 90.degree. After concentration, the residue was dissolved in 100 ml of water, cooled and the precipitate formed was filtered off with suction. 78.1 g of zinc salt of 2,2-bis (4-hydroxyphenyl) ethanoic acid were obtained.
Man erhitzte eine Suspension von 85,9 g (0,3 Mol) 2,2-Bis(4-hydroxy-3-methylphenyl)-propansäure und 6,05 g (0,15 Mol) Magnesiumoxid in 400 ml Wasser 1 Stunde lang auf 800 C, wobei die Reaktanten in Lösung gingen. Nach dem Einengen und Abkühlen wurden 79,2 g Magnesiumsalz der 2,2-Bis(4-hydroxy-3-methylphenyl)-propansäure isoliert.A suspension of 85.9 g (0.3 mol) of 2,2-bis (4-hydroxy-3-methylphenyl) propanoic acid and 6.05 g (0.15 mol) of magnesium oxide in 400 ml of water was heated for 1 hour to 800 C, with the reactants going into solution. After concentration and cooling, 79.2 g of magnesium salt of 2,2-bis (4-hydroxy-3-methylphenyl) propanoic acid were isolated.
50 g 2-(2-Chloranilino)-6-dibutylamino-fluoran wurden in 250 g einer 8 gew.-%igen Polyvinylacetat- Lösung (hergestellt mit Mowiol@ 8/88) eingerührt. Dann wurde die grobe Dispersion mit 1250 g Glasperlen (Durchmesser 1 mm) in einer Sandmühle gemahlen bis die mittlere Teilchengröße 2,5 um betrug (-Dispersion 1). 14 g Bisphenol A, 42 g Benzolsulfanilid und 35 g eines Acrylnitrilcopolymerisates als Füllstoff wurden in 272 g einer 2 gew.-%igen Polyvinylacetat-Lösung (hergestellt aus Mowiol@ 8/88) eingerührt und wie oben beschrieben in einer Sandmühle gemahlen bis eine mittlere Teilchengröße von 2,8 um erreicht war (- Dispersion 2). 72 Teile der Dispersion 2 und 7 Teile der Dispersion 1 wurden zusammengemischt, der pH-Wert auf 9 eingestellt und dann die Oberfläche eines Rohpapieres mit einem Flächengewicht von 70 g/m2 mit Hilfe einer Drahtrakel beschichtet. Das Auftragsgewicht betrug 8,8 g/m2. Das so erhaltene rauhe Papier wurde in einem Kalander mit einem Liniendruck von 80 kg/cm geglättet.50 g of 2- (2-chloroanilino) -6-dibutylamino-fluoran were stirred into 250 g of an 8% by weight polyvinyl acetate solution (prepared with Mowiol @ 8/88). Then the coarse dispersion was ground with 1250 g of glass beads (diameter 1 mm) in a sand mill until the average particle size was 2.5 μm (dispersion 1). 14 g bisphenol A, 42 g benzenesulfanilide and 35 g of an acrylonitrile copolymer as a filler were stirred into 272 g of a 2% by weight polyvinyl acetate solution (produced from Mowiol @ 8/88) and, as described above, ground in a sand mill until an average particle size of 2.8 μm was reached (- dispersion 2). 72 parts of dispersion 2 and 7 parts of dispersion 1 were mixed together, the pH was adjusted to 9 and then the surface of a base paper with a basis weight of 70 g / m 2 was coated using a wire knife. The application weight was 8.8 g / m 2 . The rough paper thus obtained was smoothed in a calender with a line pressure of 80 kg / cm.
Die Meßergebnisse der Beurteilung sind in den Tabellen 1 und 2 angegeben.The measurement results of the evaluation are shown in Tables 1 and 2.
Die Dispersionen 1 und 2 wurden wie in Beispiel 3 beschrieben hergestellt. 30 g des Mg-Salzes der 4,4-Bis-(4-hydroxyphenyl)-pentansäure wurden in 70 g einer 10 gew.-%igen Polyvinylacetat-Lösung (hergestellt aus Mowiol@ 8/88) eingerührt und dann wie in Beispiel 3 beschrieben auf eine mittlere Teilchengröße von 2,6 um gemahlen (- Dispersion 3). 72 Teile der Dispersion 2,7 Teile der Dispersion 1 und 14 Teile der Dispersion 3 wurden gemischt, der pH-Wert der Mischung auf 9 eingestellt und damit die Oberfläche eines Rohpapiers mit einem Flächengewicht von 70 g/m2 mit Hilfe einer Drahtrakel beschichtet. Das Auftragsgewicht betrug 10,1 g/m2. Die Glättung erfolgte analog Beispiel 3.Dispersions 1 and 2 were prepared as described in Example 3. 30 g of the Mg salt of 4,4-bis (4-hydroxyphenyl) pentanoic acid were stirred into 70 g of a 10% by weight polyvinyl acetate solution (made from Mowiol @ 8/88) and then as in Example 3 described ground to an average particle size of 2.6 µm (- dispersion 3). 72 parts of the dispersion, 2.7 parts of the dispersion 1 and 14 parts of the dispersion 3 were mixed, the pH of the mixture was adjusted to 9 and the surface of a base paper with a basis weight of 70 g / m 2 was coated using a wire doctor. The application weight was 10.1 g / m 2 . The smoothing was carried out analogously to Example 3.
Die Meßergebnisse der Beurteilung sind in den Tabellen 1 und 2 angegeben.The measurement results of the evaluation are shown in Tables 1 and 2.
Beispiel 3 wurde wiederholt. Vor dem Glätten des beschichteten Papiers wurde eine zweite Beschichtung vorgenommen mit einer Mischung aus 100 Teilen 10 gew.-%ige Polyvinylacetat-Lösung (hergestellt aus Mowiol@ 4/98), 20 Teilen Calciumcarbonat, 10 Teilen einer Polyethylenwachsemulsion (Luba-print@ 499, Fa. L.P. Bader und Co. GmbH Chem. Fabrik, Rottweil, Deutschland) und 55 Teilen Wasser.Example 3 was repeated. Before smoothing the coated paper, a second coating was carried out using a mixture of 100 parts of 10% by weight polyvinyl acetate solution (made from Mowiol @ 4/98), 20 parts of calcium carbonate, 10 parts of a polyethylene wax emulsion (Luba-print @ 499 , LP Bader und Co. GmbH Chem. Fabrik, Rottweil, Germany) and 55 parts of water.
Das Auftragsgewicht der zweiten Schicht betrug 6 g/m2. Abschließend wurde analog Beispiel 3 geglättet.The application weight of the second layer was 6 g / m 2. Finally, smoothing was carried out analogously to Example 3.
Die Meßergebnisse der Beurteilung sind in Tabelle 2 angegeben.The measurement results of the evaluation are shown in Table 2.
Die Herstellung erfolgte analog Beispiel 4, wobei die Dispersion 3 mit der entsprechenden Menge Bisphenolcarbonsäure (statt dem Magnesiumsalz aus Beispiel 4) hergestellt wurde.The preparation was carried out analogously to Example 4, dispersion 3 being prepared with the appropriate amount of bisphenol carboxylic acid (instead of the magnesium salt from Example 4).
Die Meßergebnisse der Beurteilung sind in Tabelle 1 angegeben.The measurement results of the evaluation are shown in Table 1.
Es wurde verfahren wie in Beispiel 3, jedoch wurde die Dispersion 2 unter Verwendung einer entsprechenden Menge des im Beispiel 4 genannten Salzes anstelle von Bisphenol A hergestellt.The procedure was as in Example 3, but the dispersion 2 was prepared using an appropriate amount of the salt mentioned in Example 4 instead of bisphenol A.
Die Meßergebnisse der Beurteilung sind in Tabelle 1 angegeben.The measurement results of the evaluation are shown in Table 1.
Es wurde verfahren wie in Beispiel 4, jedoch wurde die Dispersion 3 unter Verwendung einer entsprechenden Menge des Zinksalzes der 3-Methylsalicylsäure anstelle des in Beispiel 4 verwendeten Mg-Salzes hergestellt.The procedure was as in Example 4, but the dispersion 3 was prepared using an appropriate amount of the zinc salt of 3-methylsalicylic acid instead of the Mg salt used in Example 4.
Die Meßergebnisse der Beurteilung sind in Tabelle 1 angegeben.The measurement results of the evaluation are shown in Table 1.
Die Herstellungen erfolgten analog Beispiel 4, wobei jedoch die in Tabelle 3 angeführten Salze von modifizierten Bisphenolcarbonsäuren der Formel (I) in entsprechender Menge anstelle des in Beispiel 4 genannten Salzes eingesetzt wurden.The preparations were carried out analogously to Example 4, except that the salts of modified bisphenolcarboxylic acids of the formula (I) listed in Table 3 were used in an appropriate amount instead of the salt mentioned in Example 4.
Die Meßergebnisse der Beurteilung sind ebenfalls in der Tabelle 3 angegeben.The measurement results of the assessment are also shown in Table 3.
Die Herstellung erfolgte analog Beispiel 4, wobei jedoch statt des Mg-Salzes, eine entsprechende Menge 4,4-Bis(4-hydroxy-phenyl)-pentansäuremethylester eingesetzt wurde.The preparation was carried out analogously to Example 4, but using a corresponding amount of 4,4-bis (4-hydroxy-phenyl) pentanoic acid methyl ester instead of the Mg salt.
Die Meßergebnisse der Beurteilung sind in Tabelle 1 angegeben.
Claims (8)
in der
in the
m, n und M die in Anspruch 1 angegebenen Bedeutungen haben.2. Thermoreactive recording materials according to claim 1, characterized in that in formula (1)
m, n and M have the meanings given in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4125118 | 1991-07-30 | ||
| DE4125118A DE4125118A1 (en) | 1991-07-30 | 1991-07-30 | THERMOREACTIVE RECORDING MATERIAL WITH SPECIAL STABILITY |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0525535A1 true EP0525535A1 (en) | 1993-02-03 |
Family
ID=6437257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92112199A Withdrawn EP0525535A1 (en) | 1991-07-30 | 1992-07-17 | Thermoreactive recording material with improved stability |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5292712A (en) |
| EP (1) | EP0525535A1 (en) |
| JP (1) | JPH05193269A (en) |
| DE (1) | DE4125118A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2267578A (en) * | 1992-06-05 | 1993-12-08 | Bayer Ag | Thermosensitive recording material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10273315B2 (en) * | 2012-06-20 | 2019-04-30 | Chevron Phillips Chemical Company Lp | Methods for terminating olefin polymerizations |
| CN112095363A (en) * | 2019-11-04 | 2020-12-18 | 上海映通印刷包装有限公司 | Paper special for mark pen drawing |
-
1991
- 1991-07-30 DE DE4125118A patent/DE4125118A1/en not_active Withdrawn
-
1992
- 1992-07-17 EP EP92112199A patent/EP0525535A1/en not_active Withdrawn
- 1992-07-20 US US07/916,938 patent/US5292712A/en not_active Expired - Fee Related
- 1992-07-29 JP JP4220980A patent/JPH05193269A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 11, no. 218 (M-607)(2665) 15. Juli 1987 & JP-A-62 033 678 ( NIPPON SYNTHETIC CHEMISTRY INDUSTRIES K.K. ) 13. Februar 1987 * |
| PATENT ABSTRACTS OF JAPAN vol. 13, no. 593 (M-914)(3941) 27. Dezember 1989 & JP-A-01 249 385 ( NIPPON SYNTHETIC CHEMISTRY INDUSTRIES K.K. ) 4. Oktober 1989 * |
| PATENT ABSTRACTS OF JAPAN vol. 6, no. 117 (M-139)(995) 30. Juni 1982 & JP-A-57 045 093 ( MITSUI TOATSU KAGAKU K.K. ) 13. März 1982 * |
| PATENT ABSTRACTS OF JAPAN vol. 9, no. 80 (M-370)(1803) 10. April 1985 & JP-A-59 209 192 ( RICOH K.K. ) 27. November 1984 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2267578A (en) * | 1992-06-05 | 1993-12-08 | Bayer Ag | Thermosensitive recording material |
| US5439869A (en) * | 1992-06-05 | 1995-08-08 | Bayer Aktiengesellschaft | Thermoreactive recording material of particular stability |
| GB2267578B (en) * | 1992-06-05 | 1996-04-03 | Bayer Ag | Thermoreactive recording material of particular stability |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4125118A1 (en) | 1993-02-04 |
| JPH05193269A (en) | 1993-08-03 |
| US5292712A (en) | 1994-03-08 |
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