JP2008200918A - Thermosensitive recording element - Google Patents
Thermosensitive recording element Download PDFInfo
- Publication number
- JP2008200918A JP2008200918A JP2007037419A JP2007037419A JP2008200918A JP 2008200918 A JP2008200918 A JP 2008200918A JP 2007037419 A JP2007037419 A JP 2007037419A JP 2007037419 A JP2007037419 A JP 2007037419A JP 2008200918 A JP2008200918 A JP 2008200918A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- methyl
- protective layer
- modified polyvinyl
- heat
- 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- Withdrawn
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 53
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 53
- -1 aromatic monocarboxylic acid Chemical class 0.000 claims abstract description 38
- 239000011241 protective layer Substances 0.000 claims abstract description 37
- 239000010410 layer Substances 0.000 claims abstract description 24
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 4
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000001678 irradiating effect Effects 0.000 abstract description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 49
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000000975 dye Substances 0.000 description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000001747 Potassium fumarate Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 3
- 239000004299 sodium benzoate Substances 0.000 description 3
- 235000010234 sodium benzoate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- MTMKZABGIQJAEX-UHFFFAOYSA-N 4,4'-sulfonylbis[2-(prop-2-en-1-yl)phenol] Chemical compound C1=C(CC=C)C(O)=CC=C1S(=O)(=O)C1=CC=C(O)C(CC=C)=C1 MTMKZABGIQJAEX-UHFFFAOYSA-N 0.000 description 2
- ZTILAOCGFRDHBH-UHFFFAOYSA-N 4-(4-propan-2-yloxyphenyl)sulfonylphenol Chemical compound C1=CC(OC(C)C)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 ZTILAOCGFRDHBH-UHFFFAOYSA-N 0.000 description 2
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 description 2
- WZUKKIPWIPZMAS-UHFFFAOYSA-K Ammonium alum Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZUKKIPWIPZMAS-UHFFFAOYSA-K 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006216 polyvinyl aromatic Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001454 recorded image Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BIQGQLXQLYTHRA-UHFFFAOYSA-N (2-phenylnaphthalen-1-yl) hydrogen carbonate Chemical compound C1=CC2=CC=CC=C2C(OC(=O)O)=C1C1=CC=CC=C1 BIQGQLXQLYTHRA-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- 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
- LJSLYKNKVQMIJY-UHFFFAOYSA-N 1,4-diethoxynaphthalene Chemical compound C1=CC=C2C(OCC)=CC=C(OCC)C2=C1 LJSLYKNKVQMIJY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ODLXMYFBEHWJFT-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethenoxy]benzene Chemical group CC1=CC=CC(OC=COC=2C=C(C)C=CC=2)=C1 ODLXMYFBEHWJFT-UHFFFAOYSA-N 0.000 description 1
- OAGNKYSIOSDNIG-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound CC1=CC=CC(OCCOC=2C=C(C)C=CC=2)=C1 OAGNKYSIOSDNIG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WQYFETFRIRDUPJ-UHFFFAOYSA-N 2-[2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]sulfanyl-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(SC=2C(=CC=C(C=2)C(C)(C)CC(C)(C)C)O)=C1 WQYFETFRIRDUPJ-UHFFFAOYSA-N 0.000 description 1
- APOJPPIKGSIVIG-UHFFFAOYSA-N 2-[2-hydroxy-6-(2,4,4-trimethylpentan-2-yl)phenyl]sulfanyl-3-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC(O)=C1SC1=C(O)C=CC=C1C(C)(C)CC(C)(C)C APOJPPIKGSIVIG-UHFFFAOYSA-N 0.000 description 1
- YAZSBRQTAHVVGE-UHFFFAOYSA-N 2-aminobenzenesulfonamide Chemical class NC1=CC=CC=C1S(N)(=O)=O YAZSBRQTAHVVGE-UHFFFAOYSA-N 0.000 description 1
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 description 1
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-UHFFFAOYSA-N 0.000 description 1
- WXWMNIHSZVPJOL-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfonyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1S(=O)(=O)C1=CC(C(C)(C)C)=C(O)C=C1C WXWMNIHSZVPJOL-UHFFFAOYSA-N 0.000 description 1
- ZMYXVVLVLCQKQN-UHFFFAOYSA-N 3',6,6'-tris(diethylamino)spiro[2-benzofuran-3,9'-fluorene]-1-one Chemical compound C12=CC=C(N(CC)CC)C=C2C2=CC(N(CC)CC)=CC=C2C21OC(=O)C1=CC(N(CC)CC)=CC=C21 ZMYXVVLVLCQKQN-UHFFFAOYSA-N 0.000 description 1
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- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- KZQFPRKQBWRRHQ-UHFFFAOYSA-N phenyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CC=C1 KZQFPRKQBWRRHQ-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 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
- 150000003751 zinc Chemical class 0.000 description 1
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
この発明は、耐水性、耐溶剤性に優れ、発色感度が良好な感熱記録体に関する。 The present invention relates to a heat-sensitive recording material excellent in water resistance and solvent resistance and having good color development sensitivity.
一般に、感熱記録体は通常無色ないし淡色の電子供与性ロイコ染料とフェノ−ル性化合物等の電子受容性顕色剤とを、それぞれ微細な粒子に磨砕分散した後、両者を混合し、バインダ−、充填剤、感度向上剤、滑剤及びその他の助剤を添加して得られた塗液を、紙、合成紙、フィルム、プラスチック等の支持体に塗工したものであり、サ−マルヘッド、ホットスタンプ、熱ペン、レ−ザ−光等の加熱による瞬時の化学反応により発色し、記録画像が得られる。感熱記録体は、ファクシミリ、コンピュ−タ−の端末プリンタ−、自動券売機、計測用レコ−ダ−等に広く使用されており、その用途の多様化に伴い、高いレベルの画像部及び白紙部の保存性が求められている。しかし、感熱記録層に含まれる電子供与性ロイコ染料及び電子受容性顕色剤は、各種溶剤に容易に溶解するため、感熱記録体の白紙部に水性インキペンや油性インキペン等のインキ、接着剤等に触れると容易に発色する問題や、画像部に可塑剤などの薬品が付着した場合に発色濃度が低下する問題がある。
また近年においては、各種チケット用、レシート用、ラベル用、銀行のＡＴＭ用、ガスや電気の検針用、車馬券等の金券用などにも感熱記録体の用途が拡大してきており、これまで問題視されていなかったような特性が要求され始めている。例えば、屋外で使用に耐えることができる品質、具体的には、雨などの水分や湿気、日光、真夏の車内の高温状態などの環境下における画像部及び白紙部の保存性が必要とされてきている。
これらの要求品質を満たすために、感熱記録層上に保護層を設け、この保護層が、カルボキシ変性ポリビニルアルコール、ポリアミドエピクロロヒドリン及びポリエチレンイミンを含有する感熱記録体（特許文献１）、カルボキシ変性ポリビニルアルコールとブチルナフタレンスルホン酸塩を含有する感熱記録体（特許文献２）、カルボキシ変性ポリビニルアルコールとステアリン酸亜鉛を含有し、これを加熱して架橋させた感熱記録体（特許文献３）、カルボキシ変性ポリビニルアルコールと架橋剤としてポリアミドエポキシ樹脂を含有する感熱記録体（特許文献４）、カルボキシ変性ポリビニルアルコールと架橋剤としてメラミン−ホルムアルデヒド樹脂を含有する感熱記録体（特許文献５）、カルボキシ変性ポリビニルアルコールと架橋剤としてヒドラジド化合物を含有する感熱記録体（特許文献６）などが開発されている。
In general, a heat-sensitive recording medium is usually a colorless or light-colored electron-donating leuco dye and an electron-accepting developer such as a phenolic compound, which are ground and dispersed in fine particles, and then mixed together. -, A coating liquid obtained by adding a filler, a sensitivity improver, a lubricant and other auxiliary agents to a support such as paper, synthetic paper, film, plastic, thermal head, Color is generated by an instantaneous chemical reaction by heating such as hot stamping, thermal pen, laser light, etc., and a recorded image is obtained. Thermosensitive recording media are widely used in facsimiles, computer terminal printers, automatic ticket vending machines, measuring recorders, etc., and with the diversification of their uses, high-level image portions and blank paper portions. Storability is required. However, since the electron-donating leuco dye and the electron-accepting developer contained in the heat-sensitive recording layer are easily dissolved in various solvents, inks such as water-based ink pens and oil-based ink pens, adhesives, etc. There is a problem that a color is easily developed when touched, and a color density is lowered when a chemical such as a plasticizer adheres to the image area.
In recent years, the use of thermal recording media has been expanded to various tickets, receipts, labels, bank ATMs, gas and electricity meter readings, and car tickets, etc. Characteristics that were not seen are beginning to be demanded. For example, quality that can withstand use outdoors, specifically, moisture and moisture such as rain, sunlight, storage conditions of the image portion and the blank paper portion in an environment such as a high temperature inside a car in the summer has been required. ing.
In order to satisfy these required qualities, a protective layer is provided on the thermosensitive recording layer, and this protective layer contains a thermosensitive recording material containing carboxy-modified polyvinyl alcohol, polyamide epichlorohydrin and polyethyleneimine (Patent Document 1), carboxy. A heat-sensitive recording material containing a modified polyvinyl alcohol and butylnaphthalene sulfonate (Patent Document 2), a heat-sensitive recording material containing a carboxy-modified polyvinyl alcohol and zinc stearate and crosslinked by heating (Patent Document 3), Thermal recording material containing carboxy-modified polyvinyl alcohol and polyamide epoxy resin as a crosslinking agent (Patent Document 4), Thermal recording material containing carboxy-modified polyvinyl alcohol and melamine-formaldehyde resin as a crosslinking agent (Patent Document 5), carboxy-modified polyvinyl Alcohol and rack Heat-sensitive recording material containing a hydrazide compound and (Patent Document 6) have been developed as agents.
感熱記録体の耐可塑剤性や耐ヘッドカス性を向上させるために、ポリビニルアルコールを含有する保護層を設けることはよく行われている。しかし、通常ポリビニルアルコールから成る保護層には十分な耐水性がないため、カルボキシ変性ポリビニルアルコールを用いたり（特許文献１〜３など）、カルボキシ変性ポリビニルアルコールと各種架橋剤を併用して架橋させる方法が行なわれている（特許文献４〜６など）。しかし、これらの感熱記録体においても、金券用途に用いられている感熱紙に求められている極めて高い耐水性や印字走行適性（耐ヘッドカス性）については十分とはいえない。
更に、ポリビニルアルコールの耐水化の他の方法としては、ポリビニルアルコールに非常に高エネルギー（１０３〜１０５ｅＶ程度）の電子線を照射することでポリビニルアルコールを架橋させて耐水化する方法があるが、電子線のエネルギーによって感熱記録体が発色してしまう。一方、紫外線レベルのエネルギー（１〜１０ｅＶ程度）では、ポリビニルアルコールの十分に架橋が進行しない。そのため、ポリビニルアルコールに不飽和二重結合など非常に反応性の高い官能基を付加することが必要となるが、塗料の安定性などの問題を生じる。このため、感熱記録体を製造するに当たって、紫外線あるいは電子線によるポリビニルアルコールの架橋は用いられていないのが現状である。
そこで、本発明は、紫外線により架橋することのできる保護層を有し、耐水性と印字走行性に優れた感熱記録体を提供することを課題とする。
In order to improve the plasticizer resistance and the head residue resistance of the heat-sensitive recording material, it is often performed to provide a protective layer containing polyvinyl alcohol. However, since the protective layer usually made of polyvinyl alcohol does not have sufficient water resistance, carboxy-modified polyvinyl alcohol is used (such as Patent Documents 1 to 3), or carboxy-modified polyvinyl alcohol and various crosslinking agents are used in combination. (Patent Documents 4 to 6 etc.). However, even in these thermal recording media, it cannot be said that the extremely high water resistance and print running suitability (head-cass resistance) required for thermal paper used for vouchers are sufficient.
Furthermore, as another method for making polyvinyl alcohol water resistant, there is a method for making polyvinyl alcohol cross-linked by irradiating polyvinyl alcohol with an electron beam of very high energy (about 10 3 to 10 5 eV). However, the thermal recording material is colored by the energy of the electron beam. On the other hand, at an ultraviolet level energy (about 1 to 10 eV), the crosslinking of polyvinyl alcohol does not proceed sufficiently. For this reason, it is necessary to add a highly reactive functional group such as an unsaturated double bond to polyvinyl alcohol, but this causes problems such as coating stability. For this reason, in the production of thermosensitive recording materials, the present situation is that crosslinking of polyvinyl alcohol by ultraviolet rays or electron beams is not used.
Therefore, an object of the present invention is to provide a heat-sensitive recording material having a protective layer that can be crosslinked by ultraviolet rays and having excellent water resistance and printing runnability.
本発明者らは鋭意検討の結果、保護層にカルボキシ変性ポリビニルアルコールと芳香族モノカルボン酸又はその誘導体を含有させ、これを紫外線を用いて架橋させることにより、上記課題を解決することができることを見出し、本発明を完成させるに至った。
即ち、本発明は、支持体上に、順に、無色ないし淡色の電子供与性ロイコ染料及び電子受容性顕色剤を含有する感熱記録層及び保護層を設けた感熱記録体であって、該保護層がカルボキシ変性ポリビニルアルコール及び芳香族モノカルボン酸又はその誘導体を含有し、該保護層が紫外線処理された感熱記録体である。
As a result of intensive studies, the present inventors have found that the protective layer can contain carboxy-modified polyvinyl alcohol and aromatic monocarboxylic acid or a derivative thereof, and can be solved using ultraviolet rays to solve the above problem. The headline and the present invention have been completed.
That is, the present invention is a heat-sensitive recording material provided with a heat-sensitive recording layer and a protective layer containing, in order, a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on the support, The layer contains a carboxy-modified polyvinyl alcohol and an aromatic monocarboxylic acid or a derivative thereof, and the protective layer is a heat-sensitive recording material treated with an ultraviolet ray.
本発明によれば、極めて高い耐水性、印字走行性（耐ヘッドカス性）に優れた感熱記録体を得ることができる。 According to the present invention, it is possible to obtain a heat-sensitive recording material excellent in extremely high water resistance and printing running property (head residue resistance).
本発明の感熱記録体は、後記の実施例で明らかにされるように、優れた耐水性等の性質を示すが、そのメカニズムは以下のように考えられる。
保護層にカルボキシ変性ポリビニルアルコールと芳香族モノカルボン酸又はその誘導体を共存させて、紫外線を照射すると、保護層中のカルボキシ変性ポリビニルアルコールの水酸基とカルボキシル基とが反応して、エステル結合を形成する。この架橋反応において、芳香族モノカルボン酸は一種の光増感剤（光増幅剤）のような役割を果たし、外部からの紫外線エネルギーをカルボキシ変性ポリビニルアルコールへ効率的に伝えると考えられる。
The heat-sensitive recording material of the present invention exhibits excellent properties such as water resistance, as will be clarified in the examples described later, and the mechanism is considered as follows.
When the protective layer is made to coexist with carboxy-modified polyvinyl alcohol and aromatic monocarboxylic acid or a derivative thereof and irradiated with ultraviolet rays, the hydroxyl group and carboxyl group of carboxy-modified polyvinyl alcohol in the protective layer react to form an ester bond. . In this cross-linking reaction, it is considered that the aromatic monocarboxylic acid plays a role as a kind of photosensitizer (light amplifying agent), and efficiently transmits external ultraviolet energy to carboxy-modified polyvinyl alcohol.
本発明で使用されるカルボキシ変性ポリビニルアルコールは、ポリビニルアルコールとフマル酸、無水フタル酸、無水メリト酸、無水イタコン酸などの多価カルボン酸との反応物、又はこれらの反応物のエステル化物、さらに酢酸ビニルとマレイン酸、フマル酸、イタコン酸、クロトン酸、アクリル酸、メタアクリル酸などのエチレン性不飽和ジカルボン酸との共重合物の鹸化物として得られる。具体的には例えば特開昭５３−９１９９５号公報の実施例１もしくは４に例示されている製造方法が挙げられる。また、カルボキシ変性ポリビニルアルコールの鹸化度は７２〜１００ｍｏｌ％であることが好ましく、重合度は５００〜２４００、より好ましくは１０００〜２０００である。 The carboxy-modified polyvinyl alcohol used in the present invention is a reaction product of polyvinyl alcohol and a polycarboxylic acid such as fumaric acid, phthalic anhydride, mellitic anhydride, itaconic anhydride, or an esterified product of these reactants. It can be obtained as a saponified product of a copolymer of vinyl acetate and an ethylenically unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid or methacrylic acid. Specifically, for example, the production method exemplified in Example 1 or 4 of JP-A-53-91995 can be mentioned. Moreover, it is preferable that the saponification degree of carboxy modified polyvinyl alcohol is 72-100 mol%, and a polymerization degree is 500-2400, More preferably, it is 1000-2000.
本発明で使用される芳香族モノカルボン酸は、ベンゼン環などの芳香環にカルボキシル基を付した化合物をいい、好ましくは安息香酸を挙げることができる。
この誘導体としては金属塩、エステル、アミド、イミド、アンモニウム塩、サフファイト、酸無水物などが挙げられるが、金属塩や各種エステルが好ましい。
金属塩の金属種としては、ナトリウム、カリウム、マグネシウム、カルシウム、アルミニウム、亜鉛、ニッケル、銅、鉄、コバルト等が挙げられる、
このほか、例えば、安息香酸の誘導体として、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸ブチル、安息香酸アミル、安息香酸ヘキシル、安息香酸アミド、安息香酸アンモニウム、安息香酸イミド、安息香酸サルファイト、安息香酸フェニル、安息香酸アセチル等を挙げることができる。
これらの中で、安息香酸ナトリウムなどの水溶性である安息香酸の誘導体が好ましい。
The aromatic monocarboxylic acid used in the present invention refers to a compound having a carboxyl group attached to an aromatic ring such as a benzene ring, preferably benzoic acid.
Examples of this derivative include metal salts, esters, amides, imides, ammonium salts, sulphites, and acid anhydrides, and metal salts and various esters are preferable.
Examples of the metal species of the metal salt include sodium, potassium, magnesium, calcium, aluminum, zinc, nickel, copper, iron, cobalt and the like.
In addition, for example, as derivatives of benzoic acid, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl benzoate, benzoic acid amide, ammonium benzoate, benzoic acid imide, salicyl benzoate Phyto, phenyl benzoate, acetyl benzoate and the like can be mentioned.
Of these, water-soluble benzoic acid derivatives such as sodium benzoate are preferred.
本発明に用いられる芳香族モノカルボン酸又はその誘導体の含有量は、カルボキシ変性ポリビニルアルコール１００重量部に対してそれぞれ０．１〜３０重量部であることが好ましく、より好ましくは０．５〜１５重量部である。含有量が少なすぎると架橋反応が不十分となり良好な耐水性が得られず、多すぎると塗膜内の残存比率が増加し耐水性に悪影響を与えるためである。また、光架橋反応は酸性下で反応がより効率的に進むため、保護層塗料はｐＨ４．０〜６．０に調整することが好ましい。ｐＨを下げすぎると塗料粘度の上昇や塗料の固化等の問題が生じ塗工することが困難になるためである。
本発明の感熱記録体の保護層に架橋剤を添加することは耐水性の点から望ましい。架橋剤としては、グリオキザール、メチロールメラミン、メラミンホルムアルデヒド系樹脂、メラミン尿素系樹脂、ポリアミンエピクロロヒドリン系樹脂、ポリアミドエピクロロヒドリン系樹脂、過硫酸カリウム、過硫酸アンモニウム、過硫酸ソーダ、塩化第二鉄、塩化マグネシウム、ホウ砂、ホウ酸、ミョウバン、塩化アンモニウム、ポリアミン樹脂、ポリアミド樹脂などを例示することができ、単独あるいは２種類以上を併用することが可能である。なお、保護層にポリアミンエピクロロヒドリン系樹脂あるいはポリアミドエピクロロヒドリン系樹脂を使用した場合、感熱記録層にもポリアミンエピクロロヒドリン系樹脂あるいはポリアミドエピクロロヒドリン系樹脂を含有させることは、保護層と感熱記録層の密着性の点から好ましい。
本発明の感熱記録体の保護層において、顔料を添加することも可能である。添加できる顔料としては、シリカ、炭酸カルシウム、カオリン、焼成カオリン、ケイソウ土、タルク、酸化チタン、水酸化アルミニウムなどの無機又は有機充填剤などが挙げられ、単独あるいは２種類以上併用することが可能であり、保護層中の顔料及びバインダーの含有量は、顔料１００重量部に対しバインダーは固形分で０〜３００重量部程度である。
The content of the aromatic monocarboxylic acid or derivative thereof used in the present invention is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts per 100 parts by weight of carboxy-modified polyvinyl alcohol. Parts by weight. If the content is too small, the crosslinking reaction is insufficient and good water resistance cannot be obtained. If the content is too large, the residual ratio in the coating film increases and adversely affects the water resistance. In addition, since the photocrosslinking reaction proceeds more efficiently under acidic conditions, the protective layer coating is preferably adjusted to pH 4.0 to 6.0. This is because if the pH is lowered too much, problems such as an increase in the viscosity of the paint and solidification of the paint occur and it becomes difficult to perform coating.
It is desirable from the viewpoint of water resistance to add a crosslinking agent to the protective layer of the heat-sensitive recording material of the present invention. Cross-linking agents include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, secondary chloride Examples thereof include iron, magnesium chloride, borax, boric acid, alum, ammonium chloride, polyamine resin, polyamide resin and the like, and these can be used alone or in combination of two or more. When a polyamine epichlorohydrin resin or a polyamide epichlorohydrin resin is used for the protective layer, it is possible that the thermosensitive recording layer contains a polyamine epichlorohydrin resin or a polyamide epichlorohydrin resin. From the viewpoint of adhesion between the protective layer and the heat-sensitive recording layer, it is preferable.
In the protective layer of the heat-sensitive recording material of the present invention, a pigment can be added. Examples of pigments that can be added include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide, and these can be used alone or in combination of two or more. The content of the pigment and binder in the protective layer is about 0 to 300 parts by weight in solid content of the binder with respect to 100 parts by weight of the pigment.
本発明においては、感熱記録層上に上記保護層を設けた感熱記録体の保護層を紫外線処理する。紫外線を照射することで保護層中のカルボキシ変性ポリビニルアルコールが架橋し、感熱記録体は良好な耐水性を示すと考えられる。
紫外線は、メタルハライド、高圧水銀ランプなどの紫外線ランプを使用し、積算光量が１０ｍ〜５００ｍＪ程度になるように照射することが好ましい。１０ｍＪ未満ではＰＶＡの架橋反応が不十分であり、５００ｍＪを超えると紫外線ランプの熱により感熱紙が発色することがあるためである。
In the present invention, the protective layer of the heat-sensitive recording material provided with the protective layer on the heat-sensitive recording layer is treated with ultraviolet rays. It is considered that the carboxy-modified polyvinyl alcohol in the protective layer is cross-linked by irradiating with ultraviolet rays, and the heat-sensitive recording material exhibits good water resistance.
It is preferable to irradiate the ultraviolet rays using an ultraviolet lamp such as a metal halide or a high-pressure mercury lamp so that the integrated light quantity is about 10 m to 500 mJ. If it is less than 10 mJ, the crosslinking reaction of PVA is insufficient, and if it exceeds 500 mJ, the thermal paper may be colored by the heat of the ultraviolet lamp.
本発明の感熱記録層に含有する電子供与性ロイコ染料としては従来の感圧あるいは感熱記録紙分野で公知のものは全て使用可能であり、特に制限されるものではないが、トリフェニルメタン系化合物、フルオラン系化合物、フルオレン系、ジビニル系化合物等が好ましい。以下に代表的な無色ないし淡色の染料（染料前駆体）の具体例を示す。また、これらの染料前駆体は単独又は２種以上混合して使用してもよい。
<トリフェニルメタン系ロイコ染料>
３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジメチルアミノフタリド〔別名クリスタルバイオレットラクトン〕； ３，３−ビス（ｐ−ジメチルアミノフェニル）フタリド〔別名マラカイトグリーンラクトン〕
As the electron-donating leuco dye contained in the heat-sensitive recording layer of the present invention, any of those known in the conventional pressure-sensitive or heat-sensitive recording paper field can be used, and is not particularly limited. Fluoran compounds, fluorene compounds, divinyl compounds and the like are preferable. Specific examples of typical colorless or light-colored dyes (dye precursors) are shown below. These dye precursors may be used alone or in combination of two or more.
<Triphenylmethane leuco dye>
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone); 3,3-bis (p-dimethylaminophenyl) phthalide (also known as malachite green lactone)
<フルオラン系ロイコ染料>
３−ジエチルアミノ−６−メチルフルオラン； ３−ジエチルアミノ−６−メチル−７−アニリノフルオラン； ３−ジエチルアミノ−６−メチル−７−（ｏ，ｐ−ジメチルアニリノ）フルオラン； ３−ジエチルアミノ−６−メチル−７−クロロフルオラン； ３−ジエチルアミノ−６−メチル−７−（ｍ−トリフルオロメチルアニリノ）フルオラン； ３−ジエチルアミノ−６−メチル−７−（ｏ−クロロアニリノ）フルオラン； ３−ジエチルアミノ−６−メチル−７−（ｐ−クロロアニリノ）フルオラン； ３−ジエチルアミノ−６−メチル−７−（ｏ−フルオロアニリノ）フルオラン； ３−ジエチルアミノ−６−メチル−７−（ｍ−メチルアニリノ）フルオラン； ３−ジエチルアミノ−６−メチル−７−ｎ−オクチルアニリノフルオラン； ３−ジエチルアミノ−６−メチル−７−ｎ−オクチルアミノフルオラン； ３−ジエチルアミノ−６−メチル−７−ベンジルアミノフルオラン； ３−ジエチルアミノ−６−メチル−７−ジベンジルアミノフルオラン； ３−ジエチルアミノ−６−クロロ−７−メチルフルオラン； ３−ジエチルアミノ−６−クロロ−７−アニリノフルオラン； ３−ジエチルアミノ−６−クロロ−７−ｐ−メチルアニリノフルオラン； ３−ジエチルアミノ−６−エトキシエチル−７−アニリノフルオラン； ３−ジエチルアミノ−７−メチルフルオラン； ３−ジエチルアミノ−７−クロロフルオラン； ３−ジエチルアミノ−７−（ｍ−トリフルオロメチルアニリノ）フルオラン； ３−ジエチルアミノ−７−（ｏ−クロロアニリノ）フルオラン； ３−ジエチルアミノ−７−（ｐ−クロロアニリノ）フルオラン； ３−ジエチルアミノ−７−（ｏ−フルオロアニリノ）フルオラン； ３−ジエチルアミノ−ベンゾ〔ａ〕フルオラン； ３−ジエチルアミノ−ベンゾ〔ｃ〕フルオラン； ３−ジブチルアミノ−６−メチル−フルオラン； ３−ジブチルアミノ−６−メチル−７−アニリノフルオラン； ３−ジブチルアミノ−６−メチル−７−（ｏ，ｐ−ジメチルアニリノ）フルオラン； ３−ジブチルアミノ−６−メチル−７−（ｏ−クロロアニリノ）フルオラン； ３−ジブチルアミノ−６−メチル−７−（ｐ−クロロアニリノ）フルオラン； ３−ジブチルアミノ−６−メチル−７−（ｏ−フルオロアニリノ）フルオラン； ３−ジブチルアミノ−６−メチル−７−（ｍ−トリフルオロメチルアニリノ）フルオラン； ３−ジブチルアミノ−６−メチル−クロロフルオラン； ３−ジブチルアミノ−６−エトキシエチル−７−アニリノフルオラン； ３−ジブチルアミノ−６−クロロ−７−アニリノフルオラン； ３−ジブチルアミノ−６−メチル−７−ｐ−メチルアニリノフルオラン； ３−ジブチルアミノ−７−（ｏ−クロロアニリノ）フルオラン； ３−ジブチルアミノ−７−（ｏ−フルオロアニリノ）フルオラン； ３−ジ−ｎ−ペンチルアミノ−６−メチル−７−アニリノフルオラン； ３−ジ−ｎ−ペンチルアミノ−６−メチル−７−（ｐ−クロロアニリノ）ルオラン； ３−ジ−ｎ−ペンチルアミノ−７−（ｍ−トリフルオロメチルアニリノ）フルオラン； ３−ジ−ｎ−ペンチルアミノ−６−クロロ−７−アニリノフルオラン； ３−ジ−ｎ−ペンチルアミノ−７−（ｐ−クロロアニリノ）フルオラン； ３−ピロリジノ−６−メチル−７−アニリノフルオラン； ３−ピペリジノ−６−メチル−７−アニリノフルオラン； ３−（Ｎ−メチル−Ｎ−プロピルアミノ）−６−メチル−７−アニリノフルオラン； ３−（Ｎ−メチル−Ｎ−シクロヘキシルアミノ）−６−メチル−７−アニリノフルオラン； ３−（Ｎ−エチル−Ｎ−シクロヘキシルアミノ）−６−メチル−７−アニリノフルオラン； ３−（Ｎ−エチル−Ｎ−キシルアミノ）−６−メチル−７−（ｐ−クロロアニリノ）フルオラン； ３−（Ｎ−エチル−ｐ−トルイディノ）−６−メチル−７−アニリノフルオラン； ３−（Ｎ−エチル−Ｎ−イソアミルアミノ）−６−メチル−７−アニリノフルオラン； ３−（Ｎ−エチル−Ｎ−イソアミルアミノ）−６−クロロ−７−アニリノフルオラン； ３−（Ｎ−エチル−Ｎ−テトラヒドロフルフリルアミノ）−６−メチル−７−アニリノフルオラン； ３−（Ｎ−エチル−Ｎ−イソブチルアミノ）−６−メチル−７−アニリノフルオラン； ３−（Ｎ−エチル−Ｎ−エトキシプロピルアミノ）−６−メチル−７−アニリノフルオラン； ３−シクロヘキシルアミノ−６−クロロフルオラン； ２−（４−オキサヘキシル）−３−ジメチルアミノ−６−メチル−７−アニリノフルオラン； ２−（４−オキサヘキシル）−３−ジエチルアミノ−６−メチル−７−アニリノフルオラン； ２−（４−オキサヘキシル）−３−ジプロピルアミノ−６−メチル−７−アニリノフルオラン； ２−メチル−６−ｐ−（ｐ−ジメチルアミノフェニル）アミノアニリノフルオラン； ２−メトキシ−６−ｐ−（ｐ−ジメチルアミノフェニル）アミノアニリノフルオラン； ２−クロロ−３−メチル−６−ｐ−（ｐ−フェニルアミノフェニル）アミノアニリノフルオラン； ２−クロロ−６−ｐ−（ｐ−ジメチルアミノフェニル）アミノアニリノフルオラン； ２−ニトロ−６−ｐ−（ｐ−ジエチルアミノフェニル）アミノアニリノフルオラン； ２−アミノ−６−ｐ−（ｐ−ジエチルアミノフェニル）アミノアニリノフルオラン； ２−ジエチルアミノ−６−ｐ−（ｐ−ジエチルアミノフェニル）アミノアニリノフルオラン； ２−フェニル−６−メチル−６−ｐ−（ｐ−フェニルアミノフェニル）アミノアニリノフルオラン； ２−ベンジル−６−ｐ−（ｐ−フェニルアミノフェニル）アミノアニリノフルオラン； ２−ヒドロキシ−６−ｐ−（ｐ−フェニルアミノフェニル）アミノアニリノフルオラン； ３−メチル−６−ｐ−（ｐ−ジメチルアミノフェニル）アミノアニリノフルオラン； ３−ジエチルアミノ−６−ｐ−（ｐ−ジエチルアミノフェニル）アミノアニリノフルオラン； ３−ジエチルアミノ−６−ｐ−（ｐ−ジブチルアミノフェニル）アミノアニリノフルオラン； ２，４−ジメチル−６−〔（４−ジメチルアミノ）アニリノ〕−フルオラン
<Fluoran leuco dye>
3-diethylamino-6-methylfluorane; 3-diethylamino-6-methyl-7-anilinofluorane; 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane; 3-diethylamino- 6-methyl-7-chlorofluorane; 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane; 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane; Diethylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane; 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane 3-diethylamino-6-methyl-7-n-octylanilinofluorane; 3-diethylamino-6-methyl-7-n-octylaminofluorane; 3-diethylamino-6-methyl-7-benzylaminofluorane; 3-diethylamino-6-methyl-7-dibenzylaminofluorane; 3-diethylamino-6-chloro-7-anilinofluorane; 3-diethylamino-6-chloro-7-p-methylanilinofluorane; 3-diethylamino-6 3-Ethoxyethyl-7-anilinofluorane; 3-diethylamino-7-methylfluorane; 3-diethylamino-7-chlorofluorane; 3-diethylamino-7- (m-trifluoromethylanilino) fluorane; Diethylamino-7- (o-chloroanilino) fluorane; 3-diethyla 3-diethylamino-7- (o-fluoroanilino) fluorane; 3-diethylamino-benzo [a] fluorane; 3-diethylamino-benzo [c] fluorane; 3-dibutylamino -6-methyl-fluorane; 3-dibutylamino-6-methyl-7-anilinofluorane; 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluorane; 3-dibutylamino- 6-methyl-7- (o-chloroanilino) fluorane; 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluorane 3-dibutylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane 3-dibutylamino-6-methyl-chlorofluorane; 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane; 3-dibutylamino-6-chloro-7-anilinofluorane; 3-dibutylamino -6-methyl-7-p-methylanilinofluorane; 3-dibutylamino-7- (o-chloroanilino) fluorane; 3-dibutylamino-7- (o-fluoroanilino) fluorane; 3-di-n -Pentylamino-6-methyl-7-anilinofluorane; 3-di-n-pentylamino-6-methyl-7- (p-chloroanilino) luolane; 3-di-n-pentylamino-7- (m -Trifluoromethylanilino) fluoran; 3-di-n-pentylamino-6-chloro-7-anilinofluoran; 3-di-n-pentyla 3-pyrrolidino-6-methyl-7-anilinofluorane; 3-piperidino-6-methyl-7-anilinofluorane; 3- (N-methyl-N- Propylamino) -6-methyl-7-anilinofluorane; 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-cyclohexylamino) ) -6-Methyl-7-anilinofluorane; 3- (N-ethyl-N-xylamino) -6-methyl-7- (p-chloroanilino) fluorane; 3- (N-ethyl-p-toludino)- 6-methyl-7-anilinofluorane; 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-isoamyl) Mino) -6-chloro-7-anilinofluorane; 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-isobutyl) Amino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluorane; 3-cyclohexylamino-6-chlorofluorane; 2- (4-oxahexyl) -3-dimethylamino-6-methyl-7-anilinofluorane; 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluorane; 2 -(4-oxahexyl) -3-dipropylamino-6-methyl-7-anilinofluorane; 2-methyl-6-p- (p-dimethylaminophenyl) aminoanily 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane; Chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 2-nitro-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 2-amino-6-p- (p- 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 2-phenyl-6-methyl-6-p- (p-phenylaminophenyl) aminoani Linofluorane; 2-benzyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane; 3-hydroxy-6-p- (p-phenylaminophenyl) aminoanilinofluorane; 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 3-diethylamino-6-p- ( p-diethylaminophenyl) aminoanilinofluorane; 3-diethylamino-6-p- (p-dibutylaminophenyl) aminoanilinofluorane; 2,4-dimethyl-6-[(4-dimethylamino) anilino]- Fluoran
<フルオレン系ロイコ染料>
３，６，６'−トリス（ジメチルアミノ）スピロ〔フルオレン−９，３'−フタリド〕； ３，６，６'−トリス（ジエチルアミノ）スピロ〔フルオレン−９，３'−フタリド〕
<ジビニル系ロイコ染料>
３，３−ビス−〔２−（ｐ−ジメチルアミノフェニル）−２−（ｐ−メトキシフェニル）エテニル〕−４，５，６，７−テトラブロモフタリド； ３，３−ビス−〔２−（ｐ−ジメチルアミノフェニル）−２−（ｐ−メトキシフェニル）エテニル〕−４，５，６，７−テトラクロロフタリド； ３，３−ビス−〔１，１−ビス（４−ピロリジノフェニル）エチレン−２−イル〕−４，５，６，７−テトラブロモフタリド； ３，３−ビス−〔１−（４−メトキシフェニル）−１−（４−ピロリジノフェニル）エチレン−２−イル〕−４，５，６，７−テトラクロロフタリド
<Fluorene leuco dye>
3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′-phthalide]; 3,6,6′-tris (diethylamino) spiro [fluorene-9,3′-phthalide]
<Divinyl leuco dye>
3,3-bis- [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide; 3,3-bis- [2- (P-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide; 3,3-bis- [1,1-bis (4-pyrrolidinophenyl) ) Ethylene-2-yl] -4,5,6,7-tetrabromophthalide; 3,3-bis- [1- (4-methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene-2- Yl] -4,5,6,7-tetrachlorophthalide
<その他>
３−（４−ジエチルアミノ−２−エトキシフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド； ３−（４−ジエチルアミノ−２−エトキシフェニル）−３−（１−オクチル−２−メチルインドール−３−イル）−４−アザフタリド； ３−（４−シクロヘキシルエチルアミノ−２−メトキシフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド； ３，３−ビス（１−エチル−２−メチルインドール−３−イル）フタリド； ３，６−ビス（ジエチルアミノ）フルオラン−γ−（３'−ニトロ）アニリノラクタム； ３，６−ビス（ジエチルアミノ）フルオラン−γ−（４'−ニトロ）アニリノラクタム； １，１−ビス−〔２'，２'，２''，２''−テトラキス−（ｐ−ジメチルアミノフェニル）−エテニル〕−２，２−ジニトリルエタン； １，１−ビス−〔２'，２'，２''，２''−テトラキス−（ｐ−ジメチルアミノフェニル）−エテニル〕−２−β−ナフトイルエタン； １，１−ビス−〔２'，２'，２''，２''−テトラキス−（ｐ−ジメチルアミノフェニル）−エテニル〕−２，２−ジアセチルエタン； ビス−〔２，２，２'，２'−テトラキス−（ｐ−ジメチルアミノフェニル）−エテニル〕−メチルマロン酸ジメチルエステル等があげられる。
<Others>
3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide; 3- (4-diethylamino-2-ethoxyphenyl) -3- ( 1-octyl-2-methylindol-3-yl) -4-azaphthalide; 3- (4-cyclohexylethylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl)- 4-Azaphthalide; 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide; 3,6-bis (diethylamino) fluorane-γ- (3′-nitro) anilinolactam; -Bis (diethylamino) fluorane-γ- (4'-nitro) anilinolactam; 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p-dimethyla Nophenyl) -ethenyl] -2,2-dinitrileethane; 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2- β-naphthoylethane; 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,2-diacetylethane; bis- [2, 2,2 ′, 2′-tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester and the like.
本発明で用いられる電子受容性顕色剤は、ビス-（3-アリル-4-ヒドロキシフェニル）スルホンであるが、必要に応じて、従来の感圧あるいは感熱記録紙の分野で公知のものを併用することができる。併用できる電子受容性顕色剤として、例えば、活性白土、アタパルジャイト、コロイダルシリカ、珪酸アルミニウムなどの無機酸性物質、４，４'−イソプロピリデンジフェノール、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、２，２−ビス（４−ヒドロキシフェニル）−４−メチルペンタン、４，４'−ジヒドロキシジフェニルスルフィド、ヒドロキノンモノベンジルエーテル、４−ヒドロキシ安息香酸ベンジル、４，４'−ジヒドロキシジフェニルスルホン、２，４'−ジヒドロキシジフェニルスルホン、４−ヒドロキシ−４'−イソプロポキシジフェニルスルホン、４−ヒドロキシ−４'−ｎ−プロポキシジフェニルスルホン、ビス（３−アリル−４−ヒドロキシフェニル）スルホン、４−ヒドロキシ−４'−メチルジフェニルスルホン、４−ヒドロキシフェニル−４'−ベンジルオキシフェニルスルホン、３，４−ジヒドロキシフェニル−４'−メチルフェニルスルホン、特開平８−５９６０３号公報記載のアミノベンゼンスルホンアミド誘導体、ビス（４−ヒドロキシフェニルチオエトキシ）メタン、１，５−ジ（４−ヒドロキシフェニルチオ）−３−オキサペンタン、ビス（ｐ−ヒドロキシフェニル）酢酸ブチル、ビス（ｐ−ヒドロキシフェニル）酢酸メチル、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、１，４−ビス［α−メチル−α−（４'−ヒドロキシフェニル）エチル］ベンゼン、１，３−ビス［α−メチル−α−（４'−ヒドロキシフェニル）エチル］ベンゼン、ジ（４−ヒドロキシ−３−メチルフェニル）スルフィド、２，２'−チオビス（３−tert−オクチルフェノール）、２，２'−チオビス（４−tert−オクチルフェノール）、国際公開ＷＯ９７／１６４２０号に記載のジフェニルスルホン架橋型化合物等のフェノール性化合物、国際公開ＷＯ０２／０８１２２９号あるいは特開２００２−３０１８７３号公報記載の化合物、またＮ，Ｎ'−ジ−ｍ−クロロフェニルチオウレア等のチオ尿素化合物、ｐ−クロロ安息香酸、没食子酸ステアリル、ビス［４−（ｎ−オクチルオキシカルボニルアミノ）サリチル酸亜鉛］２水和物、４−［２−（ｐ−メトキシフェノキシ）エチルオキシ］サリチル酸、４−［３−（ｐ−トリルスルホニル）プロピルオキシ］サリチル酸、５−［ｐ−（２−ｐ−メトキシフェノキシエトキシ）クミル］サリチル酸の芳香族カルボン酸、及びこれらの芳香族カルボン酸の亜鉛、マグネシウム、アルミニウム、カルシウム、チタン、マンガン、スズ、ニッケル等の多価金属塩との塩、さらにはチオシアン酸亜鉛のアンチピリン錯体、テレフタルアルデヒド酸と他の芳香族カルボン酸との複合亜鉛塩等が挙げられる。これらの顕色剤は、単独又は２種以上混合して使用することもできる。国際公開ＷＯ９７／１６４２０号に記載のジフェニルスルホン架橋型化合物は、日本曹達（株）製商品名Ｄ−９０として入手可能である。また、国際公開ＷＯ０２／０８１２２９号等に記載の化合物は、日本曹達（株）製商品名Ｄ−１０２、Ｄ−１００として入手可能である。この他、特開平１０−２５８５７７号公報記載の高級脂肪酸金属複塩や多価ヒドロキシ芳香族化合物などの金属キレート型発色成分を含有することもできる。 The electron-accepting developer used in the present invention is bis- (3-allyl-4-hydroxyphenyl) sulfone, but if necessary, a known one in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used. Can be used together. Examples of electron-accepting developers that can be used in combination include inorganic acidic substances such as activated clay, attapulgite, colloidal silica, and aluminum silicate, 4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane. 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4′-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4′-dihydroxydiphenyl sulfone, 2, 4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-n-propoxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4 '-Methyldiphenyls Ruhon, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, aminobenzenesulfonamide derivatives described in JP-A-8-59603, bis (4-hydroxyphenyl) Thioethoxy) methane, 1,5-di (4-hydroxyphenylthio) -3-oxapentane, butyl bis (p-hydroxyphenyl) acetate, methyl bis (p-hydroxyphenyl) acetate, 1,1-bis (4 -Hydroxyphenyl) -1-phenylethane, 1,4-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,3-bis [α-methyl-α- (4′-hydroxy) Phenyl) ethyl] benzene, di (4-hydroxy-3-methylphenyl) sulfide, 2,2′-thiobis (3-tert-octylphenol), 2,2′-thiobis (4-tert-octylphenol), phenolic compounds such as diphenylsulfone bridged compounds described in WO97 / 16420, WO02 / 081229 or special No. 2002-301873, thiourea compounds such as N, N′-di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, bis [4- (n-octyloxycarbonylamino) Zinc salicylate] dihydrate, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxy) Phenoxyethoxy) cumyl] salicylic acid aromatic carboxylic acids and their aromatics Salts of carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, and also antipyrine complexes of zinc thiocyanate, composites of terephthalaldehyde acid with other aromatic carboxylic acids A zinc salt etc. are mentioned. These developers can be used alone or in combination of two or more. The diphenylsulfone cross-linking compound described in International Publication No. WO97 / 16420 is available as trade name D-90 manufactured by Nippon Soda Co., Ltd. Moreover, the compound as described in international publication WO02 / 081229 etc. is available as Nippon Soda Co., Ltd. brand name D-102 and D-100. In addition, a metal chelate color-developing component such as a higher fatty acid metal double salt and a polyvalent hydroxyaromatic compound described in JP-A-10-258577 can also be contained.
本発明の感熱記録体に使用する増感剤は従来公知の増感剤を併用することができる。かかる増感剤としては、ステアリン酸アミド、パルミチン酸アミド等の脂肪酸アマイド、エチレンビスアミド、モンタン酸ワックス、ポリエチレンワックス、１，２−ジ−（３−メチルフェノキシ）エタン、ｐ−ベンジルビフェニル、β−ベンジルオキシナフタレン、４−ビフェニル−ｐ−トリルエーテル、ｍ−ターフェニル、１，２−ジフェノキシエタン、シュウ酸ジベンジル、シュウ酸ジ（ｐ−クロロベンジル）、シュウ酸ジ（ｐ−メチルベンジル）、テレフタル酸ジベンジル、ｐ−ベンジルオキシ安息香酸ベンジル、ジ−ｐ−トリルカーボネート、フェニル−α−ナフチルカーボネート、１，４−ジエトキシナフタレン、１−ヒドロキシ−２−ナフトエ酸フェニルエステル、ｏ−キシレン−ビス−（フェニルエーテル）、４−（ｍ−メチルフェノキシメチル）ビフェニル、４，４'−エチレンジオキシ−ビス−安息香酸ジベンジルエステル、ジベンゾイルオキシメタン、１，２−ジ（３−メチルフェノキシ）エチレン、ビス［２−（４−メトキシ−フェノキシ）エチル］エーテル、ｐ−ニトロ安息香酸メチル、ｐ−トルエンスルホン酸フェニルなどを例示することができるが、特にこれらに制限されるものではない。これらの増感剤は、単独又は２種以上混合して使用してもよい。 A conventionally known sensitizer can be used in combination with the sensitizer used in the heat-sensitive recording material of the present invention. Examples of such sensitizers include fatty acid amides such as stearamide and palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di- (3-methylphenoxy) ethane, p-benzylbiphenyl, β- Benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, di (p-methylbenzyl) oxalate, Dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, o-xylene-bis -(Phenyl ether), 4- (m-methyl) Ruphenoxymethyl) biphenyl, 4,4′-ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, 1,2-di (3-methylphenoxy) ethylene, bis [2- (4-methoxy- Examples thereof include, but are not limited to, phenoxy) ethyl] ether, methyl p-nitrobenzoate, phenyl p-toluenesulfonate, and the like. These sensitizers may be used alone or in combination of two or more.
本発明の感熱記録体に使用する電子供与性ロイコ染料、電子受容性顕色剤、その他の各種成分の種類及び量は要求される性能及び記録適性に従って決定され、特に限定されるものではないが、通常、電子供与性ロイコ染料１部に対して電子受容性顕色剤０．５〜１０部、増感剤０．５〜１０部程度が使用される。 The types and amounts of the electron-donating leuco dye, electron-accepting developer, and other various components used in the heat-sensitive recording material of the present invention are determined according to the required performance and recording suitability, and are not particularly limited. Usually, about 0.5 to 10 parts of an electron accepting developer and about 0.5 to 10 parts of a sensitizer are used with respect to 1 part of the electron donating leuco dye.
本発明で使用するバインダーとしては、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、アセトアセチル化ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、アマイド変性ポリビニルアルコール、スルホン酸変性ポリビニルアルコール、ブチラール変性ポリビニルアルコール、オレフィン変性ポリビニルアルコール、ニトリル変性ポリビニルアルコール、ピロリドン変性ポリビニルアルコール、シリコーン変性ポリビニルアルコール、その他の変性ポリビニルアルコール、ヒドロキシエチルセルロース、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、スチレン−無水マレイン酸共重合体、スチレン−ブタジエン共重合体並びにエチルセルロース、アセチルセルロースのようなセルロース誘導体、カゼイン、アラビヤゴム、酸化澱粉、エーテル化澱粉、ジアルデヒド澱粉、エステル化澱粉、ポリ塩化ビニル、ポリ酢酸ビニル、ポリアクリルアミド、ポリアクリル酸エステル、ポリビニルブチラール、ポリスチロース及びそれらの共重合体、ポリアミド樹脂、シリコーン樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、クマロ樹脂などを例示することができる。これらの高分子物質は水、アルコール、ケトン類、エステル類、炭化水素などの溶剤に溶かして使用するほか、水又は他の媒体中に乳化又はペースト状に分散した状態で使用し、要求品質に応じて併用することも出来る。 The binder used in the present invention includes fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, and olefin-modified. Polyvinyl alcohol, nitrile modified polyvinyl alcohol, pyrrolidone modified polyvinyl alcohol, silicone modified polyvinyl alcohol, other modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer and Cellulose like ethyl cellulose, acetyl cellulose Derivatives, casein, arabic gum, oxidized starch, etherified starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic ester, polyvinyl butyral, polystyrose and copolymers thereof, Examples thereof include polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin, and coumaro resin. These polymer substances are used by dissolving them in solvents such as water, alcohol, ketones, esters, hydrocarbons, etc., and are used in the state of being emulsified or pasted in water or other media to achieve the required quality. It can also be used in combination.
本発明で使用する架橋剤としては、グリオキザール、メチロールメラミン、メラミンホルムアルデヒド樹脂、メラミン尿素樹脂、ポリアミンエピクロロヒドリン樹脂、ポリアミドエピクロロヒドリン樹脂、過硫酸カリウム、過硫酸アンモニウム、過硫酸ソーダ、塩化第二鉄、塩化マグネシウム、ホウ砂、ホウ酸、ミョウバン、塩化アンモニウムなどを例示することができる。
本発明で使用する顔料としては、シリカ、炭酸カルシウム、カオリン、焼成カオリン、ケイソウ土、タルク、酸化チタン、水酸化アルミニウムなどの無機又は有機充填剤などが挙げられる。
本発明で使用する滑剤としては、ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸金属塩、ワックス類、シリコーン樹脂類などが挙げられる。
Examples of the crosslinking agent used in the present invention include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, chloride chloride Examples include ferric iron, magnesium chloride, borax, boric acid, alum, ammonium chloride and the like.
Examples of the pigment used in the present invention include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide.
Examples of the lubricant used in the present invention include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, and silicone resins.
また、本発明においては、上記課題に対する所望の効果を阻害しない範囲で、記録画像の耐油性効果などを示す画像安定剤として、４，４'−ブチリデン（６−ｔ−ブチル−３−メチルフェノール）、２，２'−ジ−ｔ−ブチル−５，５'−ジメチル−４，４'−スルホニルジフェノール、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−シクロヘキシルフェニル）ブタン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、４−ベンジルオキシ−４'−（２，３−エポキシ−２−メチルプロポキシ）ジフェニルスルホン等を添加することもできる。
このほかにベンゾフェノン系やトリアゾール系の紫外線吸収剤、分散剤、消泡剤、酸化防止剤、蛍光染料等を使用することができる。
上記組成からなる塗液を紙、再生紙、合成紙、フィルム、プラスチックフィルム、発泡プラスチックフィルム、不織布等任意の支持体に塗布することによって目的とする感熱記録体が得られる。またこれらを組み合わせた複合シートを支持体として使用してもよい。
Further, in the present invention, 4,4′-butylidene (6-tert-butyl-3-methylphenol) is used as an image stabilizer exhibiting an oil resistance effect of a recorded image and the like within a range that does not hinder a desired effect on the above problems. ), 2,2′-di-t-butyl-5,5′-dimethyl-4,4′-sulfonyldiphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) Butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 4-benzyloxy-4 ′-(2,3-epoxy-2-methylpropoxy) diphenyl sulfone, etc. Can also be added.
In addition, benzophenone and triazole ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
By applying the coating liquid having the above composition to any support such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, non-woven fabric, etc., the desired thermal recording material can be obtained. Moreover, you may use the composite sheet which combined these as a support body.
電子供与性ロイコ染料、電子受容性顕色剤並びに必要に応じて添加する材料は、ボールミル、アトライター、サンドグライダーなどの粉砕機あるいは適当な乳化装置によって数ミクロン以下の粒子径になるまで微粒化し、バインダー及び目的に応じて各種の添加材料を加えて塗液とする。この塗料に用いる溶媒としては水あるいはアルコール等を用いることができ、その固形分は２０〜４０％程度である。また、塗布する手段は特に限定されるものではなく、周知慣用技術に従って塗布することができ、例えばエアーナイフコーター、ロッドブレードコーター、ベントブレードコーター、ベベルブレードコーター、ロールコーター、カーテンコーターなど各種コーターを備えたオフマシン塗工機やオンマシン塗工機が適宜選択され使用される。感熱記録層の塗布量は特に限定されず、通常乾燥重量で２〜１２ｇ／ｍ２の範囲である。また、感熱記録層上に設ける保護層の塗布量は特に限定されず、通常１〜５ｇ／ｍ２の範囲である。 Electron-donating leuco dye, electron-accepting developer, and materials to be added as necessary are finely divided to a particle size of several microns or less by a pulverizer such as a ball mill, an attritor, or a sand glider, or an appropriate emulsifier. Depending on the binder and purpose, various additive materials are added to form a coating solution. Water or alcohol can be used as the solvent used in the paint, and its solid content is about 20 to 40%. Further, the means for applying is not particularly limited, and can be applied according to well-known conventional techniques. For example, various coaters such as an air knife coater, rod blade coater, vent blade coater, bevel blade coater, roll coater, curtain coater, etc. The provided off-machine coating machine or on-machine coating machine is appropriately selected and used. The coating amount of the heat-sensitive recording layer is not particularly limited and is usually in the range of 2 to 12 g / m 2 by dry weight. Further, the coating amount of the protective layer provided on the thermosensitive recording layer is not particularly limited, and is usually in the range of 1 to 5 g / m 2 .
本発明の感熱記録体はさらに、発色感度を高める目的で、填料を含有した高分子物質などの下塗層を感熱記録層の下に設けることもできる。また、支持体の感熱記録層とは反対面にバックコート層を設け、カールの矯正を図ることも可能である。また、各層の塗工後にスーパーカレンダーがけなどの平滑化処理を施すなど、感熱記録体分野における各種公知の技術を必要適宜付加することができる。 The heat-sensitive recording material of the present invention can further be provided with an undercoat layer such as a polymer material containing a filler under the heat-sensitive recording layer for the purpose of increasing the color development sensitivity. It is also possible to correct the curl by providing a backcoat layer on the opposite side of the support from the thermosensitive recording layer. Further, various known techniques in the heat-sensitive recording material field, such as supercalendering after the application of each layer, can be added as appropriate.
以下、実施例にて本発明を例証するが本発明を限定することを意図するものではない。
製造例１
[アンダーコート塗料の調整]
下記成分を攪拌分散しアンダーコート塗料を調整した。
焼成カオリン（エンゲルハード社製、商品名：アンシレックス９０） １００部
スチレン・ブタジエン共重合体ラテックス（固形分４８％） ４０部
完全鹸化ポリビニルアルコール（クラレ社製、商品名：ＰＶＡ１１７）１０％水溶液
３０部
水 １６０部
The following examples illustrate the invention but are not intended to limit the invention.
Production Example 1
[Adjustment of undercoat paint]
The following components were stirred and dispersed to prepare an undercoat paint.
Baked kaolin (manufactured by Engelhard, trade name: Ansilex 90) 100 parts Styrene / butadiene copolymer latex (solid content 48%) 40 parts Fully saponified polyvinyl alcohol (trade name: PVA117, manufactured by Kuraray Co., Ltd.) 10% aqueous solution
30 parts water 160 parts
[感熱発色層塗料の調整]
下記配合のロイコ染料分散液（Ａ液）、顕色剤分散液（Ｂ液）を、それぞれ別々にダイノーミルでそれぞれ平均粒子径０．８μｍ、１．１μｍになるまで湿式磨砕を行った。
<Ａ液>
３−ジブチルアミノ−６−メチル−７−アニリノフルオラン（山田化学社製：ＯＤＢ２） ４０部
完全ケン化型ポリビニルアルコール（クラレ社製：ＰＶＡ１１７）１０％水溶液
４０部
水 ２０部
<Ｂ液>
４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン（顕色剤、日本曹達社製：Ｄ８） １５部
ジフェニルスルホン（増感剤） ２５部
カルボキシ変成部分鹸化ポリビニルアルコール（クラレ社製ＰＶＡ−ＫＬ３１８）１０％水溶液 ４０部
ポリアミドエピクロロヒドリン樹脂（ＷＳ４０２０） ８部
水 ２０部
[Adjustment of thermal coloring layer coating]
The leuco dye dispersion (Liquid A) and developer dispersion (Liquid B) having the following composition were separately wet milled with a dyno mill until the average particle diameter was 0.8 μm and 1.1 μm, respectively.
<Liquid A>
40 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (Yamada Chemical Co., Ltd .: ODB2) 10% aqueous solution of completely saponified polyvinyl alcohol (Kuraray Co., Ltd .: PVA117)
40 parts water 20 parts
<Liquid B>
4-hydroxy-4'-isopropoxydiphenylsulfone (developer, Nippon Soda Co., Ltd .: D8) 15 parts diphenylsulfone (sensitizer) 25 parts carboxy-modified partially saponified polyvinyl alcohol (PVA-KL318, Kuraray) 10% Aqueous solution 40 parts Polyamide epichlorohydrin resin (WS4020) 8 parts Water 20 parts
<感熱発色層塗料>
Ａ液５０部、Ｂ液１２０部、珪酸（水澤化学社製、ミズカシルＰ５２７）２５部、カルボキシ変性ポリビニルアルコール１０％（クラレ社製、商品名：ＰＶＡ−ＫＬ３１８）５０部を混合し、さらに水２８０部を加えて攪拌し、感熱発色層塗料を調製した。
<Thermosensitive coloring layer paint>
50 parts of A liquid, 120 parts of B liquid, 25 parts of silicic acid (manufactured by Mizusawa Chemical Co., Ltd., Mizukasil P527), 50 parts of carboxy-modified polyvinyl alcohol 10% (manufactured by Kuraray Co., Ltd., trade name: PVA-KL318) are mixed, and water 280 is further mixed. Part was added and stirred to prepare a thermosensitive coloring layer coating.
［感熱記録体の作製］
６０ｇ／ｍ２の原紙に、アンダーコート塗料と感熱発色層塗料を乾燥後の塗布量がそれぞれ８．０ｇ／ｍ２、４．５ｇ／ｍ２となるようにブレードコーターで塗工し、感熱記録紙を得た。
[Preparation of thermal recording material]
Base paper of 60 g / m 2, was coated with a blade coater so undercoat paint and the heat-sensitive coloring layer coating the coating amount after drying of each 8.0 g / m 2, and 4.5 g / m 2, the heat-sensitive recording I got paper.
[保護層塗料の調整]
下記の割合で混合して保護層塗量１〜４を調整した。
<保護層塗料１>
カルボキシル変性ポリビニルアルコール(クラレ社製、ＰＶＡ−ＫＬ３１８、重合度：１８００、ケン化度、９９ｍｏｌ％)１０％溶液 １００部
ポリアミドエピクロロヒドリン樹脂（星光ＰＭＣ社製、ＷＳ４０２０、固形分２５％、カチオン化度：２．７、分子量：２２０万、４級アミン） １０部
２０％安息香酸ナトリウム水溶液 １部
水酸化アルミニウム（マーティンスベルグ社製、マーティフィンＯＬ）５０％分散液
２０部
ステアリン酸亜鉛（中京油脂社製、商品名：ハイドリンＥ−３６６、固形分４０％）
５部
[Adjustment of protective coating]
The protective layer coating amount 1 to 4 was adjusted by mixing at the following ratio.
<Protective layer paint 1>
Carboxyl-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-KL318, polymerization degree: 1800, saponification degree, 99 mol%) 10% solution 100 parts polyamide epichlorohydrin resin (manufactured by Seiko PMC, WS4020, solid content 25%, cation Degree of conversion: 2.7, molecular weight: 2.2 million, quaternary amine) 10 parts 20% aqueous sodium benzoate solution 1 part Aluminum hydroxide (Martinsuf OL, Martinifol) 50% dispersion
20 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., trade name: Hydrin E-366, solid content 40%)
5 copies
<保護層塗料２>
カルボキシル変性ポリビニルアルコール（ＰＶＡ−ＫＬ３１８)１０％溶液 １００部
ポリアミドエピクロロヒドリン樹脂（ＷＳ４０２０） １０部
水酸化アルミニウム（マーティフィンＯＬ）５０％分散液 ２０部
ステアリン酸亜鉛（ハイドリンＥ−３６６） ５部
<Protective layer paint 2>
Carboxyl-modified polyvinyl alcohol (PVA-KL318) 10% solution 100 parts Polyamide epichlorohydrin resin (WS4020) 10 parts Aluminum hydroxide (Martyfin OL) 50% dispersion 20 parts Zinc stearate (hydrin E-366) 5 parts
<保護層塗料３>
完全鹸化ポリビニルアルコール(ＰＶＡ−１１７)１０％溶液 １００部
２０％安息香酸ナトリウム水溶液 １部
水酸化アルミニウム（マーティンスベルグ社製、マーティフィンＯＬ）５０％分散液
２０部
ステアリン酸亜鉛（中京油脂社製、商品名：ハイドリンＥ−３６６、固形分４０％）
５部
<Protective layer paint 3>
100% solution of fully saponified polyvinyl alcohol (PVA-117) 100 parts 20% aqueous solution of sodium benzoate 1 part Aluminum hydroxide (Martinfin OL, manufactured by Martinsberg) 50% dispersion
20 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., trade name: Hydrin E-366, solid content 40%)
5 copies
<保護層塗料４>
完全鹸化ポリビニルアルコール(ＰＶＡ−１１７)１０％溶液 １００部
水酸化アルミニウム（マーティンスベルグ社製、マーティフィンＯＬ）５０％分散液
２０部
ステアリン酸亜鉛（ハイドリンＥ−３６６） ５部
<Protective layer paint 4>
100% solution of fully saponified polyvinyl alcohol (PVA-117) 100 parts Aluminum hydroxide (Martin Fin OL, manufactured by Martinsberg) 50% dispersion
20 parts Zinc stearate (hydrin E-366) 5 parts
[実施例１]
上記の感熱記録体上に保護層塗料１を乾燥後の塗布量が２．５ｇ／ｍ２となるよう手塗りバーで塗工し、５０℃に保った送風乾燥機内で２分間乾燥した。乾燥後の水分量は７．５％であった。この手塗り紙にメタルハライドランプ（アイグラフィクス社製、波長２００ｎｍ〜４５０ｎｍ）にて１５０ｍＪの紫外線を照射し、２３℃、５０％環境下で２４時間調湿後ベック平滑度が１０００〜１５００秒になるようカレンダー処理を行い、実施例1の感熱記録体を作製した。
[Example 1]
The protective layer paint 1 was applied on the above heat-sensitive recording medium with a hand-painted bar so that the coating amount after drying was 2.5 g / m 2, and dried for 2 minutes in a blower drier maintained at 50 ° C. The moisture content after drying was 7.5%. This hand-coated paper was irradiated with 150 mJ of ultraviolet light using a metal halide lamp (produced by I-Graphics, wavelength 200 nm to 450 nm), and the humidity was adjusted for 24 hours at 23 ° C. in a 50% environment, resulting in a Beck smoothness of 1000 to 1500 seconds. Thus, a heat-sensitive recording material of Example 1 was produced.
［比較例１］
保護層塗料１の代わりに保護層塗料２を用いて、実施例１と同様にして感熱記録体を作製した。
［比較例２］
保護層塗料１の代わりに保護層塗料３を用いて、実施例１と同様にして感熱記録体を作製した。
［比較例３］
保護層塗料１の代わりに保護層塗料４を用いて、実施例１と同様にして感熱記録体を作製した。
[Comparative Example 1]
A thermal recording material was produced in the same manner as in Example 1 except that the protective layer coating 2 was used in place of the protective layer coating 1.
[Comparative Example 2]
A thermal recording material was produced in the same manner as in Example 1 except that the protective layer coating 3 was used in place of the protective layer coating 1.
[Comparative Example 3]
A thermal recording material was produced in the same manner as in Example 1 except that the protective layer coating 4 was used in place of the protective layer coating 1.
上記で得た感熱記録体に下記評価を行なった。
［印字濃度］
大倉社製感熱プリンタＴＨ−ＰMＤ、パターンＮＯ．８にて階調印字を行い、＃１４で得られた画像の印字濃度をマクベス濃度計ＲＤ９１８で測定した。数値が大きいほど発色濃度が優れている。
［耐水性１］
大倉社製感熱プリンタＴＨ−ＰＭＤ、パターンＮＯ．８にて市松印字を行い、発色部を水道水に２４時間浸し、自然乾燥した。試験前後の発色部濃度を測定し、残存率（＝試験後の発色濃度／試験前の発色濃度×１００（％））を算出した。残存率が高いほど耐水性能が優れている。
○：残存率が８５％以上
△：残存率が７０％以上
×：残存率が７０％未満
［耐水性２］
作成した感熱記録体を水道水に２４時間浸した後、表面を目視観察した。
○：変化は認められない
△：水泡が生じる
×：保護層が剥離又は溶ける
［耐ヘッドカス性］
イシダラベルプリンター：ＩＰ２１ＥＸにて２０００ｍ市松印字を行い、印字面及びサーマルヘッドについて目視評価を行った。
○：サーマルヘッドにカスの付着がなく２０００ｍ印字してもかすれがない。
△：印字かすれはないが、ヘッドカスが付着した。
×：ヘッドカス起因の印字かすれが発生した。
The following evaluation was performed on the heat-sensitive recording material obtained above.
[Print density]
Okura thermal printer TH-PMD, pattern NO. Gradation printing was performed at 8 and the print density of the image obtained at # 14 was measured with a Macbeth densitometer RD918. The larger the value, the better the color density.
[Water resistance 1]
Okura thermal printer TH-PMD, pattern NO. The checkerboard printing was performed at 8, and the colored portion was immersed in tap water for 24 hours and dried naturally. The color density before and after the test was measured, and the residual ratio (= color density after the test / color density before the test × 100 (%)) was calculated. The higher the residual rate, the better the water resistance.
○: Residual rate is 85% or more Δ: Residual rate is 70% or more ×: Residual rate is less than 70% [Water resistance 2]
The prepared thermal recording material was immersed in tap water for 24 hours, and then the surface was visually observed.
○: No change is observed Δ: Water bubbles are generated ×: The protective layer is peeled off or melted [Head residue resistance]
Ishida label printer: 2000m checkerboard printing was performed with IP21EX, and the print surface and the thermal head were visually evaluated.
○: No residue adhered to the thermal head, and no blurring occurs even after printing 2000 m.
Δ: Print was not faint, but head debris adhered.
×: Print blur due to head residue occurred.
評価結果を下表にまとめる。
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007037419A JP2008200918A (en) | 2007-02-19 | 2007-02-19 | Thermosensitive recording element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007037419A JP2008200918A (en) | 2007-02-19 | 2007-02-19 | Thermosensitive recording element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2008200918A true JP2008200918A (en) | 2008-09-04 |
Family
ID=39778907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007037419A Withdrawn JP2008200918A (en) | 2007-02-19 | 2007-02-19 | Thermosensitive recording element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2008200918A (en) |
-
2007
- 2007-02-19 JP JP2007037419A patent/JP2008200918A/en not_active Withdrawn
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20100511 |