CN101687424B - 热敏记录体 - Google Patents
热敏记录体 Download PDFInfo
- Publication number
- CN101687424B CN101687424B CN2008800237908A CN200880023790A CN101687424B CN 101687424 B CN101687424 B CN 101687424B CN 2008800237908 A CN2008800237908 A CN 2008800237908A CN 200880023790 A CN200880023790 A CN 200880023790A CN 101687424 B CN101687424 B CN 101687424B
- Authority
- CN
- China
- Prior art keywords
- resin
- recording body
- thermosensitive recording
- fluorane
- methyl
- 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.)
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- 229920005989 resin Polymers 0.000 claims abstract description 84
- 239000011347 resin Substances 0.000 claims abstract description 84
- 229920000768 polyamine Polymers 0.000 claims abstract description 38
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 26
- 150000001408 amides Chemical class 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims description 50
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 33
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 32
- 229920002647 polyamide Polymers 0.000 claims description 15
- 239000004952 Polyamide Substances 0.000 claims description 14
- 239000011241 protective layer Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 230000035945 sensitivity Effects 0.000 abstract description 16
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 55
- 239000007788 liquid Substances 0.000 description 47
- -1 described above Chemical compound 0.000 description 34
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 32
- 229940068984 polyvinyl alcohol Drugs 0.000 description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 29
- 239000000975 dye Substances 0.000 description 25
- 239000000126 substance Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 22
- 230000000873 masking effect Effects 0.000 description 20
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 17
- QWQJPPOEEGYTIW-UHFFFAOYSA-N 1-fluoro-1-phenylhydrazine Chemical compound NN(F)C1=CC=CC=C1 QWQJPPOEEGYTIW-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 7
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- 239000000463 material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229940015043 glyoxal Drugs 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- 229920002396 Polyurea Polymers 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- MDQRDWAGHRLBPA-UHFFFAOYSA-N fluoroamine Chemical compound FN MDQRDWAGHRLBPA-UHFFFAOYSA-N 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000009877 rendering Methods 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 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
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 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 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 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
- 230000000007 visual effect Effects 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000586 desensitisation Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-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
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 239000004576 sand Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- LSYZRUOXXOTVAV-UHFFFAOYSA-N (3-chlorophenyl)thiourea Chemical compound NC(=S)NC1=CC=CC(Cl)=C1 LSYZRUOXXOTVAV-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
- ZBUCIAUZAGKZOS-UHFFFAOYSA-N 1-ethenoxy-3-methylbenzene Chemical compound CC1=CC=CC(OC=C)=C1 ZBUCIAUZAGKZOS-UHFFFAOYSA-N 0.000 description 1
- JWMKUKRBNODZFA-UHFFFAOYSA-N 1-ethoxy-2-methylbenzene Chemical compound CCOC1=CC=CC=C1C JWMKUKRBNODZFA-UHFFFAOYSA-N 0.000 description 1
- 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 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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-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
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-UHFFFAOYSA-N 0.000 description 1
- GPBLVTFWNRNYKR-UHFFFAOYSA-N 3-(1-ethyl-2-methylindol-3-yl)-3h-2-benzofuran-1-one Chemical class C12=CC=CC=C2N(CC)C(C)=C1C1C2=CC=CC=C2C(=O)O1 GPBLVTFWNRNYKR-UHFFFAOYSA-N 0.000 description 1
- VHSOMXOOWFXZSD-UHFFFAOYSA-N 3-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC(O)=C1 VHSOMXOOWFXZSD-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- IBNFPRMKLZDANU-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)sulfanyl-2-methylphenol Chemical compound C1=C(O)C(C)=CC(SC=2C=C(C)C(O)=CC=2)=C1 IBNFPRMKLZDANU-UHFFFAOYSA-N 0.000 description 1
- JKYWRCFCKIREMM-UHFFFAOYSA-N 4-butyl-2-cyclohexyl-5-methylphenol Chemical compound C1=C(C)C(CCCC)=CC(C2CCCCC2)=C1O JKYWRCFCKIREMM-UHFFFAOYSA-N 0.000 description 1
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
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- 241000692870 Inachis io Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 229920000877 Melamine resin Polymers 0.000 description 1
- PFIMJZLHTUKTPH-UHFFFAOYSA-N OC1=CC=C([S])C=C1 Chemical compound OC1=CC=C([S])C=C1 PFIMJZLHTUKTPH-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 241000276498 Pollachius virens Species 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供显色灵敏度、耐水性、耐增塑剂性、保存性(耐背景显色性)优良的环境友好的热敏记录体。所述热敏记录体在支撑体上设有含有无色或浅色的碱性无色染料和与该碱性无色染料反应而显色的显色剂作为主成分的热敏记录层,其特征在于,在所述热敏记录层中含有含羧基树脂、表氯醇系树脂和聚胺/酰胺系树脂。该热敏记录体适用于以低外加能量进行打印的使用法。
Description
技术领域
本发明涉及利用无色或浅色的供电子性无色染料和受电子性显色剂的反应的热敏记录体,特别涉及即使在手持终端用纸、配送传票等以低外加能量进行打印的情况下也可得到高显色灵敏度的热敏记录体。
背景技术
具有以无色或浅色的供电子性隐色染料(以下,称为染料)、染料以及在加热时反应而显色的受电子性显色剂(以下,称为显色剂)为主成分的热敏记录层的热敏记录体已广泛实用化。向该热敏记录体的记录使用内藏有热敏头的热敏打印机等。该热敏记录方式与以往已实用化的其他记录方式相比,由于在记录时没有噪音、无需显影定影、免维护、机器比较廉价、小型、得到的显色非常鲜明这样的特征,而广泛用于传真、计算机用打印机、自动售票机,测量用记录器、手持终端等中。
尤其是对于在室外使用的手持终端等中使用的热敏记录体而言,要求对雨水等的耐水性。另外,要求即使在节电打印机、高速打印机(打印和图像形成)的低外加能量下仍可得到高显色灵敏度的热敏记录体。
另一方面,为了提高热敏记录体的耐水性,进行在热敏记录层上设置含有聚乙烯醇等粘合剂的保护层(防护层)的操作,已知尤其是在保护层中含有含羧基树脂、表氯醇系树脂和聚胺/酰胺系树脂的情况下,显示出优良的耐水性、打印运转性(专利文献1)。
但是,当在热敏记录层上设置保护层时,由于热敏头的热不直接传导至热敏记录层,因此存在在低外加能量下无法得到足够的显色灵敏度这样的问题。
因此,为了兼顾显色灵敏度和耐水性,进行不设置保护层而在热敏记录层中含有羧基改性聚乙烯醇作为粘合剂的操作(专利文献2、3)、配合聚乙烯醇和乙二醛的操作(专利文献4)等。
但是,含羧基树脂具有降低灵敏度的作用,对聚乙烯醇等水溶性树脂赋予优良的耐水性的乙二醛是被PRTR法第1种指定物质所指定的物质,担心其对环境产生恶劣影响等,在热敏记录层中含有这样的粘合剂是存在问题的。
专利文献1:WO2006/075467
专利文献2:日本专利第3501308号
专利文献3:日本特开平6-155916
专利文献4:日本特开平6-270547
发明内容
对于热敏记录体,要求提高显色灵敏度、即使不设置保护层也提高耐水性等的膜性能、以及对环境没有恶劣影响等。
因此,本发明的课题在于提供显色灵敏度、耐水性、耐增塑剂性、保存性(耐背景显色性)优良的且环境友好的热敏记录体。
本发明人等发现,通过使热敏记录层中含有含羧基树脂、表氯醇系树脂和聚胺/酰胺系树脂能够解决上述课题,从而完成了本发明。
明确了对于设有该热敏记录层的热敏记录体,即使以低外加能量进行打印的情况下,其应答性也特别优异。
即,本发明是一种热敏记录体,在支撑体上设有含有无色或浅色的碱性无色染料和与该碱性无色染料反应而显色的显色剂作为主成分的热敏记录层,其特征在于,在该热敏记录层中含有含羧基树脂、表氯醇系树脂和聚胺/酰胺系树脂。
另外,本发明是一种热敏记录体,是以0.1~0.3mj/dot的外加能量进行打印的热敏打印机用的热敏记录体。
进而,本发明是一种经打印的热敏记录体的制法,包括对热敏记录体以0.1~0.3mj/dot的外加能量进行打印。
根据本发明,可以得到显色灵敏度、耐水性、保存性(背景显色性)优良的且环境友好的热敏记录体。
本发明的热敏记录体即使在用手持终端打印机等以低外加能量进行打印的情况下,其显色灵敏度也特别优异。
另外,与设有保护层的热敏记录体(专利文献1)相比,虽然具有同等的膜性能,却能以少的打印能量进行同等的打印,因此能够谋求打印机的耗电量的减少,尤其是在用使用电池的手持终端打印机等进行打印的情况下,能够长时间使用等,其优点突出。
具体实施方式
本发明的构成的热敏记录体显示优良效果的原理可以认为如下。
在本发明的热敏记录体的热敏记录层中,含羧基树脂的羧基与作为交联剂的表氯醇系树脂的胺或酰胺部分发生交联反应,从而显现出耐水性。然后,由于聚胺/酰胺系树脂的亲水性部位与由含羧基树脂和表氯醇系树脂形成的具有亲水性的交联部位相互吸引,因此该交联部位成为将聚胺/酰胺系树脂的疏水基置于外侧而被包围的状态,即,具有亲水性的交联部位成为被疏水性基团保护而远离水的状态,显现出进一步的耐水性。
尤其是含羧基树脂如羧基改性聚乙烯醇等这样具有羟基时,聚胺/聚酰胺系树脂的亲水性部位被含羧基树脂的羟基吸引,含羧基树脂成为将聚胺/酰胺系树脂的疏水基置于外侧而被包围的状态,同时,聚胺/酰胺系树脂的阳离子性部位与含羧基树脂的羧基发生一种交联反应,这也可以认为是得到高耐水性的原因之一。
另外,热敏记录层中含有的乙二醛、表氯醇系树脂等酸性物质有时阻碍染料与显色剂的反应。因此,当热敏记录层中含有酸性物质时,在低外加能量下无法得到足够的显色灵敏度,在长期保存时发生背景显色这样的问题,但在像本发明这样配合表氯醇系树脂和聚胺/酰胺系树脂时,如上述说明那样,表氯醇系树脂成为被聚胺/酰胺系树脂包围的状态,对表氯醇系树脂的染料或者显色剂的影响减小。因此,可以得到优良的保存性和显色灵敏度。
进而,本发明的热敏记录体的热敏记录层具有由含羧基树脂与表氯醇系树脂的交联反应形成的三维结构,作为阳离子性的聚氨基/酰胺系树脂对热敏记录层中配合的阴离子性颜料发挥分散效果,因此可以认为,与现有技术相比成为多孔层。因此,在高温条件下产生的涂敷层中的耐热性低的材料的熔融物,被吸附于保护层中的空隙中,所以具有优良的打印走行性(耐头部废物性)。
另外,虽然含羧基树脂具有降低灵敏度的作用,但可以认为,通过含羧基树脂和表氯醇系树脂的交联反应这样的作用被削弱。
作为本发明的热敏记录层中使用的含羧基树脂,可以例示甲基丙烯酸、甲基丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基丙基、甲基丙烯酸二甲基氨基乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸四氢糠酯等具有羧基的含有单官能性丙烯酸单体的树脂、酸化淀粉、羧基甲基纤维素、在聚乙烯醇中引入了羧基的羧基改性聚乙烯醇等,特别优选使用耐热性、耐增塑剂性优异的羧基改性聚乙烯醇。
本发明中使用的羧基改性聚乙烯醇可以作为以下化合物而得到:聚乙烯醇与富马酸、邻苯二甲酸酐、苯六甲酸酐、衣康酸酐等多元羧酸的反应物;或者这些反应物的酯化物;以及乙酸乙烯酯与马来酸、富马酸、衣康酸、巴豆酸、丙烯酸、甲基丙烯酸等乙烯性不饱和二羧酸的共聚物的皂化物。具体可以举出例如日本特开昭53-91995号公报的实施例1或4中例示的制造方法。另外,羧基改性聚乙烯醇的皂化度优选为72~100mol%,聚合度为500~2400,更优选1000~2000。
另外,可以在不损害所需性能的范围并用下述粘合剂。即,可以例示出聚合度为200~1900的完全皂化聚乙烯醇、部分皂化聚乙烯醇、乙酰乙酰化聚乙烯醇、羧基改性聚乙烯醇、酰胺改性聚乙烯醇、磺酸改性聚乙烯醇、缩丁醛改性聚乙烯醇、烯烃改性聚乙烯醇、腈改性聚乙烯醇、吡咯烷酮改性聚乙烯醇、硅酮改性聚乙烯醇、其他改性聚乙烯醇、羟乙基纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素、苯乙烯-马来酸酐共聚物、苯乙烯-丁二烯共聚物以及乙基纤维素、乙酰纤维素之类的纤维素衍生物、酪蛋白、阿拉伯胶、酸化淀粉、醚化淀粉、双醛淀粉、酯化淀粉、聚氯乙烯、聚乙酸乙烯酯、聚丙烯酰胺、聚丙烯酸酯、聚乙烯基缩丁醛、聚苯乙烯(Polystyrols)及它们的共聚物、聚酰胺树脂、硅酮树脂、石油树脂、萜烯树脂、酮树脂、香豆酮树脂等。这些高分子物质除了可溶解在水、醇、酮类、酯类、烃等溶剂中使用以外,也可以在水或其他介质中呈乳化或分散成糊状的状态下使用,也可以根据所要求的品质而并用。
作为本发明中可以使用的表氯醇系树脂的具体例,可以举出聚酰胺表氯醇树脂、聚胺表氯醇树脂等,也可以单独使用或并用。另外,作为表氯醇系树脂的主链中存在的胺,可以使用伯胺乃至季胺,没有特殊限制。进而,对于阳离子化度和分子量,从耐水性良好出发,优选阳离子化度为5meq/g·固体以下(pH7时的测定值)、分子量为50万以上。作为具体例,可以举出SUMIREZRESIN650(30)、SUMIREZRESIN675A、SUM1REZRESIN6615(以上住友化学公司制);WS4002、WS4020、WS4024、WS4030、WS4046、WS4010、CP8970(以上,星光PMC公司制)等。
另外,作为聚胺/酰胺系树脂,可以举出聚酰胺脲系树脂、聚亚烷基聚胺树脂、聚亚烷基聚酰胺树脂、聚胺聚脲系树脂、改性聚胺树脂、改性聚酰胺树脂、聚亚烷基聚胺脲福尔马林树脂、聚亚烷基聚胺聚酰胺聚脲树脂等,作为具体例,可以举出SUMIREZRESIN302(住友化学公司制:聚胺聚脲树脂)、SUMIREZRESIN712(住友化学公司制:聚胺聚脲树脂)、SUMIREZRESIN703(住友化学公司制:聚胺聚脲系树脂)、SUMIREZRESIN636(住友化学公司制:聚胺聚脲系树脂)、SUMIREZRESIN SPI-100(住友化学公司制:改性聚胺树脂)、SUMIREZRESIN SPI-102A(住友化学公司制:改性聚胺树脂)、SUMIREZRESIN SPI-106N(住友化学公司制:改性聚酰胺树脂)、SUMIREZRESIN SPI-203(50)(住友化学公司制)、SUMIREZRESIN SPI-198(住友化学公司制)、PRINTIVE A-700(旭化成公司制),PRINTIVE A-600(旭化成公司制)、PA6500、PA6504、PA6634、PA6638、PA6640、PA6644、PA6646、PA6654、PA6702、PA6704(以上,星光PMC公司制:聚亚烷基聚胺聚酰胺聚脲树脂)、CP8994(星光PMC公司制:聚乙烯亚胺树脂)等,没有特殊限制,可以将它们单独使用或使用2种以上,从显色灵敏度方面出发,较理想的是使用聚胺系树脂(聚亚烷基聚胺树脂、聚胺聚脲系树脂、改性聚胺树脂、聚亚烷基聚胺脲福尔马林树脂、聚亚烷基聚胺聚酰胺聚脲树脂)。
作为含羧基树脂的配合量,相对于热敏记录层中的颜料100重量份,优选配合1~80重量份,更优选10~60重量份。过少则涂敷层强度、耐水性不足,过多则易发生灵敏度降低。
本发明中使用的表氯醇系树脂和聚胺/酰胺系树脂的含量,相对于含羧基树脂100重量份优选分别为1~100重量份,更优选5~50重量份。含量过少则交联反应变得不充分,无法得到良好的耐水性,过多则由于涂液的粘度增加、凝胶化而产生操作性的问题。
另外,在热敏记录层涂料的制备中,从涂料的稳定性方面出发,优选在配合有含羧基树脂的体系中以聚胺/酰胺系树脂、表氯醇系树脂的顺序配合。
作为本发明中使用的供电子性隐色染料,以往在压敏或热敏记录纸领域公知的供电子性隐色染料均可使用,没有特别限制,优选三苯基甲烷系化合物、荧烷系化合物、芴系、二乙烯基系化合物等。以下示出代表性的无色或浅色的染料(染料前体)的具体例。另外,这些染料前体可以单独使用或2种以上混合使用。
<三苯基甲烷系隐色染料>
3,3-双(对二甲基氨基苯基)-6-二甲基氨基苯酞[别名结晶紫内酯];3,3-双(对二甲基氨基苯基)苯酞[别名孔雀绿内酯]。
<荧烷系隐色染料>
3-二乙基氨基-6-甲基荧烷;3-二乙基氨基-6-甲基-7-苯氨基荧烷;3-二乙基氨基-6-甲基-7-(邻,对-二甲基苯氨基)荧烷;3-二乙基氨基-6-甲基-7-氯荧烷;3-二乙基氨基-6-甲基-7-(间三氟甲基苯氨基)荧烷;3-二乙基氨基-6-甲基-7-(邻氯苯氨基)荧烷;3-二乙基氨基-6-甲基-7-(对氯苯氨基)荧烷;3-二乙基氨基-6-甲基-7-(邻氟苯氨基)荧烷;3-二乙基氨基-6-甲基-7-(间甲基苯氨基)荧烷;3-二乙基氨基-6-甲基-7-正辛基苯氨基荧烷;3-二乙基氨基-6-甲基-7-正辛基氨基荧烷;3-二乙基氨基-6-甲基-7-苄基氨基荧烷;3-二乙基氨基-6-甲基-7-二苄基氨基荧烷;3-二乙基氨基-6-氯-7-甲基荧烷;3-二乙基氨基-6-氯-7-苯氨基荧烷;3-二乙基氨基-6-氯-7-对甲基苯氨基荧烷;3-二乙基氨基-6-乙氧基乙基-7-苯氨基荧烷;3-二乙基氨基-7-甲基荧烷;3-二乙基氨基-7-氯荧烷;3-二乙基氨基-7-(间三氟甲基苯氨基)荧烷;3-二乙基氨基-7-(邻氯苯氨基)荧烷;3-二乙基氨基-7-(对氯苯氨基)荧烷;3-二乙基氨基-7-(邻氟苯氨基)荧烷;3-二乙基氨基-苯并[a]荧烷;3-二乙基氨基-苯并[c]荧烷;3-二丁基氨基-6-甲基-荧烷;3-二丁基氨基-6-甲基-7-苯氨基荧烷;3-二丁基氨基-6-甲基-7-(邻、对-二甲基苯氨基)荧烷;3-二丁基氨基-6-甲基-7-(邻氯苯氨基)荧烷;3-二丁基氨基-6-甲基-7-(对氯苯氨基)荧烷;3-二丁基氨基-6-甲基-7-(邻氟苯氨基)荧烷;3-二丁基氨基-6-甲基-7-(间三氟甲基苯氨基)荧烷;3-二丁基氨基-6-甲基-氯荧烷;3-二丁基氨基-6-乙氧基乙基-7-苯氨基荧烷;3-二丁基氨基-6-氯-7-苯氨基荧烷;3-二丁基氨基-6-甲基-7-对甲基苯氨基荧烷;3-二丁基氨基-7-(邻氯苯氨基)荧烷;3-二丁基氨基-7-(邻氟苯氨基)荧烷;3-二正戊基氨基-6-甲基-7-苯氨基荧烷;3-二正戊基氨基-6-甲基-7-(对氯苯氨基)荧烷;3-二正戊基氨基-7-(间三氟甲基苯氨基)荧烷;3-二正戊基氨基-6-氯-7-苯氨基荧烷;3-二正戊基氨基-7-(对氯苯氨基)荧烷;3-吡咯烷基-6-甲基-7-苯氨基荧烷;3-哌啶子基-6-甲基-7-苯氨基荧烷;3-(N-甲基-N-丙基氨基)-6-甲基-7-苯氨基荧烷;3-(N-甲基-N-环己基氨基)-6-甲基-7-苯氨基荧烷;3-(N-乙基-N-环己基氨基)-6-甲基-7-苯氨基荧烷;3-(N-乙基-N-二甲苯氨基)-6-甲基-7-(对氯苯氨基)荧烷;3-(N-乙基-对甲苯氨基)-6-甲基-7-苯氨基荧烷;3-(N-乙基-N-异戊基氨基)-6-甲基-7-苯氨基荧烷;3-(N-乙基-N-异戊基氨基)-6-氯-7-苯氨基荧烷;3-(N-乙基-N-四氢糠基氨基)-6-甲基-7-苯氨基荧烷;3-(N-乙基-N-异丁基氨基)-6-甲基-7-苯氨基荧烷;3-(N-乙基-N-乙氧基丙基氨基)-6-甲基-7-苯氨基荧烷;3-环己基氨基-6-氯荧烷;2-(4-氧己基)-3-二甲基氨基-6-甲基-7-苯氨基荧烷;2-(4-氧己基)-3-二乙基氨基-6-甲基-7-苯氨基荧烷;2-(4-氧己基)-3-二丙基氨基-6-甲基-7-苯氨基荧烷;2-甲基-6-对(对二甲基氨基苯基)氨基苯氨基荧烷;2-甲氧基-6-对(对二甲基氨基苯基)氨基苯氨基荧烷;2-氯-3-甲基-6-对(对苯基氨基苯基)氨基苯氨基荧烷;2-氯-6-对(对二甲基氨基苯基)氨基苯氨基荧烷;2-硝基-6-对(对二乙基氨基苯基)氨基苯氨基荧烷;2-氨基-6-对(对二乙基氨基苯基)氨基苯氨基荧烷;2-二乙基氨基-6-对(对二乙基氨基苯基)氨基苯氨基荧烷;2-苯基-6-甲基-6-对(对苯基氨基苯基)氨基苯氨基荧烷;2-苄基-6-对(对苯基氨基苯基)氨基苯氨基荧烷;2-羟基-6-对(对苯基氨基苯基)氨基苯氨基荧烷;3-甲基-6-对(对二甲基氨基苯基)氨基苯氨基荧烷;3-二乙基氨基-6-对(对二乙基氨基苯基)氨基苯氨基荧烷;3-二乙基氨基-6-对(对二丁基氨基苯基)氨基苯氨基荧烷;2,4-二甲基-6-[(4-二甲基氨基)苯氨基]-荧烷
<芴系隐色染料>
3,6,6’-三(二甲基氨基)螺[芴-9,3′-苯酞];3,6,6’-三(二乙基氨基)螺[芴-9,3′-苯酞]
<二乙烯基系隐色染料>
3,3-双-[2-(对二甲基氨基苯基)-2-(对甲氧基苯基)酯]-4,5,6,7-四溴苯酞;3,3-双-[2-(对二甲基氨基苯基)-2-(对甲氧基苯基)酯]-4,5,6,7-四氯苯酞;3,3-双-[1,1-双(4-吡咯烷基苯基)亚乙基-2-基]-4,5,6,7-四溴苯酞;3,3-双-[1-(4-甲氧基苯基)-1-(4-吡咯烷基苯基)亚乙基-2-基]-4,5,6,7-四氯苯酞
<其他>
3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞;3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-辛基-2-甲基吲哚-3-基)-4-氮杂苯酞;3-(4-环己基乙基氨基-2-甲氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞;3,3-双(1-乙基-2-甲基吲哚-3-基)苯酞;3,6-双(二乙基氨基)荧烷-γ-(3′-硝基)苯氨基内酰胺;3,6-双(二乙基氨基)荧烷-γ-(4′-硝基)苯氨基内酰胺;1,1-双-[2’,2’,2”,2”-四(对二甲基氨基苯基)-酯]-2,2-二腈乙烷;1,1-双-[2’,2’,2”,2”-四(对二甲基氨基苯基)-酯]-2-β-萘甲酰基乙烷;1,1-双-[2’,2’,2”,2”-四(对二甲基氨基苯基)-酯]-2,2-二乙酰乙烷;双-[2,2,2’,2’-四(对二甲基氨基苯基)-酯]-甲基丙二酸二甲酯
作为本发明中使用的显色剂,以往在压敏或热敏记录纸领域公知的显色剂均可使用,没有特别限制,例如可以举出活性白土、凹凸棒土(attapulgite)、胶体二氧化硅、硅酸铝等无机酸性物质、4,4’-异亚丙基二苯酚、1,1-双(4-羟基苯基)环己烷、2,2-双(4-羟基苯基)-4-甲基戊烷、4,4’-二羟基二苯基硫醚、氢醌单苄基醚、4-羟基苯甲酸苄酯、4,4’-二羟基二苯砜、2,4’-二羟基二苯砜、4-羟基-4’-异丙氧基二苯砜、4-羟基-4’-正丙氧基二苯砜、双(3-烯丙基-4-羟基苯基)砜、4-羟基-4,-甲基二苯砜、4-羟基苯基-4’-苄氧基苯基砜、3,4-二羟基苯基-4’-甲基苯基砜、日本特开平8-59603号公报记载的氨基苯磺酰胺衍生物、双(4-羟基苯基硫乙氧基)甲烷、1,5-二(4-羟基苯基硫)-3-氧杂戊烷、双(对羟基苯基)乙酸丁酯、双(对羟基苯基)乙酸甲酯、1,1-双(4-羟基苯基)-1-苯基乙烷、1,4-双[α-甲基-α-(4’-羟基苯基)乙基]苯、1,3-双[α-甲基-α-(4’-羟基苯基)乙基]苯、二(4-羟基-3-甲基苯基)硫醚、2,2,-硫代双(3-叔辛基苯酚)、2,2’-硫代双(4-叔辛基苯酚)、国际公开WO97/16420号中记载的二苯砜交联型化合物等酚性化合物、国际公开WO02/081229号或日本特开2002-301873号公报记载的化合物、或者N,N’-二间氯苯基硫脲等硫脲化合物、对氯苯甲酸、没食子酸十八烷基酯、双[4-(正辛氧基羰基氨基)水杨酸锌]二水合物、4-[2-(对甲氧基苯氧基)乙氧基]水杨酸、4-[3-(对甲苯磺酰基)丙氧基]水杨酸、5-[对(2-对甲氧基苯氧基乙氧基)枯基]水杨酸的芳香族羧酸、这些芳香族羧酸与锌、镁、铝、钙、钛、锰、锡、镍等多价金属的盐、以及硫氰酸锌的安替比林配合物、对苯二甲醛酸与其他芳香族羧酸的复合锌盐等。这些显色剂可以单独使用或2种以上混合使用。国际公开WO97/16420号中记载的二苯砜交联型化合物可以购得日本曹达公司制商品名D-90。另外,国际公开WO02/081229号等中记载的化合物可以购得日本曹达公司制商品名D-102、D-100。此外,还可以含有日本特开平10-258577号公报记载的高级脂肪酸金属复盐、多元羟基芳香族化合物等金属螯合物型显色成分。
作为本发明的热敏记录体中使用的增感剂,可以使用以往公知的增感剂。作为该增感剂,可以例示硬脂酸酰胺、棕榈酸酰胺等脂肪酸酰胺、亚乙基双酰胺、褐煤酸蜡、聚乙烯蜡、1,2-二-(3-甲基苯氧基)乙烷、对苄基联苯、β-苄氧基萘、4-联苯-对甲苯基醚、间三联苯、1,2-二苯氧基乙烷、乙二酸二苄酯、乙二酸二(对氯苄基)酯、乙二酸二(对甲基苄基)酯、对苯二甲酸二苄酯、对苄氧基苯甲酸苄酯、二对甲苯基碳酸酯、苯基-α-萘基碳酸酯、1,4-二乙氧基萘、1-羟基-2-萘酸苯酯、邻二甲苯-双-(苯基醚)、4-(间甲基苯氧基甲基)联苯、4,4’-亚乙基二氧-双-苯甲酸二苄酯、二苯甲酰氧基甲烷、1,2-二(3-甲基苯氧基)乙烯、双[2-(4-甲氧基-苯氧基)乙基]醚、对硝基苯甲酸甲酯、对甲苯磺酸苯酯等,没有特别限制。这些增感剂可以单独使用或2种以上混合使用。
本发明的热敏记录层中,除了染料、显色剂、含羧基树脂、表氯醇系树脂、聚胺/酰胺系树脂以外,可以使用颜料、润滑剂、稳定剂、交联剂等
作为本发明中使用的颜料,可以举出二氧化硅、碳酸钙、高岭土、煅烧高岭土、硅藻土、滑石、氧化钛、氢氧化铝等无机或有机填充剂等。
作为本发明中使用的润滑剂,可以举出硬脂酸锌、硬脂酸钙等脂肪酸金属盐、蜡类、硅酮树脂类等。
另外,本发明中,在不损害对上述课题的所需效果的范围,还可以进一步根据需要并用聚亚胺系树脂、羟甲基密胺、密胺甲醛树脂、过硫酸钾、过硫酸铵、过硫酸钠、氯化铁、氯化镁、硼砂、硼酸、明矾、氯化铵等作为交联剂,还可以添加4,4′-丁叉基(6-叔丁基-3-甲基苯酚)、2,2′-二叔丁基-5,5′-二甲基-4,4′-磺酰基二苯酚、1,1,3-三(2-甲基-4-羟基-5-环己基苯基)丁烷、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷等作为显示记录图像的耐油性效果等的图像稳定剂。
除此以外还可以使用二苯甲酮系和三唑系的紫外线吸收剂、分散剂、消泡剂、抗氧化剂、荧光染料等。
本发明热敏记录体中使用的供电子性隐色染料、受电子性显色剂、其他各种成分的种类和用量可根据所要求的性能和记录适应性来决定,没有特殊限制,通常,相对于供电子性隐色染料1份,可使用受电子性显色剂0.5~10份、增感剂0.5~10份、颜料0.5~10份左右。
通过将上述组成的涂液涂布在纸、再生纸、合成纸、膜、塑料膜、发泡塑料膜、无纺布等任意的支撑体上,即可得到目标热敏记录体。并且也可以使用将它们组合而成的复合片用作支撑体。
供电子性隐色染料、受电子性显色剂以及根椐需要添加的材料,通过球磨机、超微磨碎机、砂磨机等粉碎机或适当的乳化装置微粒化至数微米以下的粒径,加入粘合剂和根据目的的各种添加材料,制成涂液。涂布方法没有特殊限定,可采用周知的惯用技术来进行涂布,例如可适当选择使用具备气刀涂布机、辊刀式涂布机、挠性刮刀涂布机、锥刀式涂布机、辊涂机、淋幕涂布机、喷涂机等各种涂布机的离线(off machine)涂敷机或在线(on machine)涂敷机。热敏记录层的涂布量没有特殊限定,通常按干燥重量计为2~12g/m2的范围。
本发明的热敏记录体,为了提高显色灵敏度,较理想的是进一步在热敏记录层下方设置含有填料的高分子物质等底涂层,从与热敏记录层的密合性方面出发,较理想的是含有选自含羧基树脂、表氯醇系树脂、聚胺/酰胺系树脂中的至少一种成分。
另外,还可以在支撑体的与热敏记录层相反的面上设置背涂层,来矫正卷曲。另外,在各层的涂敷后,也可以根据需要适当附加施加利用超级轧光机进行的平滑化处理等热敏记录体领域中各种公知的技术。
可以采用公知的方法在本发明的热敏记录体上进行打印。通常,使来自具有发热电阻体的热敏头的热能量作用于热敏记录体而显色。通常,该热敏头被分时为多个记录块而被驱动控制,通过输送热敏记录纸,从而在热敏记录纸上打印所需的文字等。
本发明的热敏记录纸的特征在于,即使在以0.1~0.3mj/dot、特别是0.2~0.3mj/dot的低打印能量进行打印的情况下,也显示出良好的显色灵敏度。作为以这样的低打印能量进行打印的方式,有手持终端打印机、POS打印机、小型台式打印机等。此外,打印能量指给与热敏头的1个发热元件(1dot)的能量,采用(打印头部消费的电力)与(该电力被消费的时间)的乘积来表示。
实施例
以下,用实施例例证本发明,但并不意图限定本发明。
以下的实施例和比较例中,在支撑体的单面按顺序设置底涂层、热敏显色层和任选的保护层。
此外,说明中,份和%分别表示重量份和重量%。热敏记录体的各涂敷层中使用的涂料如下制备。
[底涂层涂料制备]
烧成高岭土(BASF公司制Ansilex 90) 90.0份
10%羧基改性聚乙烯醇溶液(KURARAY公司制:PVA-KL318) 10.0份
苯乙烯-丁二烯共聚物胶乳(固体成分50%) 10.0份
45%改性聚酰胺树脂(住友化学公司制:SUMIREZRESIN SPI-106N) 2.0份
25%聚酰胺表氯醇(SEIKO PMC公司制:WS4020) 1.3份
水 50.0份
将包含上述组成的混合物混合搅拌,制成底涂层涂料。
[热敏显色层涂料制备]
将下述A~C液分别用不同的砂磨机进行湿式磨碎,直至平均粒径达到约1μm。
A液(显色剂分散液)
4-羟基-4’-异丙氧基二苯砜(日本曹达公司制:D-8) 6.0份
聚乙烯醇 10%水溶液 5.0份
水 1.5份
B液(碱性无色染料分散液)
3-二丁基氨基-6-甲基-7-苯氨基荧烷(山本化成公司制:ODB-2) 6.0份
聚乙烯醇 10%水溶液 5.0份
水 1.5份
C液(增感剂分散液)
1,2双(2-甲基苯氧基)乙烷(三光公司制:KS232) 6.0份
聚乙烯醇10%水溶液 5.0份
水 1.5份
然后,按照下述比例将分散液混合,制成热敏显色层的涂液。
热敏显色层涂液1
A液(50%显色剂分散液) 30.0份
B液(50%碱性无色染料分散液) 15.0份
C液(50%增感剂分散液) 30.0份
25%二氧化硅分散液(水泽化学公司制:P527) 40.0份
10%羧基改性聚乙烯醇溶液(KURARAY公司制:PVA-KL318) 37.5份
45%改性聚酰胺树脂(住友化学公司制:SUMIREZRESIN SPI-106N) 2.5份
25%聚酰胺表氯醇(星光PMC公司制:WS4020) 5.0份
30%硬脂酸锌分散液(中京油脂公司制:Hydrin Z-7-30) 7.5份
热敏显色层涂液2
A液(50%显色剂分散液) 30.0份
B液(50%碱性无色染料分散液) 15.0份
C液(50%增感剂分散液) 30.0份
25%二氧化硅分散液(水泽化学公司制:P527) 40.0份
10%聚乙烯醇溶液(KURARAY公司制:PVA-117) 37.5份
40%乙二醛溶液(三井东压公司制) 5.0份
30%硬脂酸锌分散液(中京油脂公司制:Hydrin Z-7-30) 7.5份
热敏显色层涂液3
A液(50%显色剂分散液) 30.0份
B液(50%碱性无色染料分散液) 15.0份
C液(50%增感剂分散液) 30.0份
25%二氧化硅分散液(水泽化学公司制:P527) 40.0份
20%丙烯酸乳液溶液(三井化学制:Barrierstar B2000) 19.0份
40%乙二醛(三井束压公司制) 5.0份
30%硬脂酸锌分散液(中京油脂公司制:Hydrin Z-7-30) 7.5份
[保护层涂料制备]
然后,按照下述比例混合而制备保护层涂液。
50%氢氧化铝分散液(Martinsberg公司制:Martifin OL) 9.0份
10%羧基改性聚乙烯醇溶液(KURARAY公司制:PVA-KL318) 30.0份
30%硬脂酸锌分散液(中京油脂公司制:Hydrin Z-7-30) 2.0份
25%聚酰胺表氯醇(星光PMC公司制:WS4020) 4.0份
45%改性聚酰胺树脂(住友化学公司制:SUMIREZRESIN SPI-106N) 2.2份
[实施例1]
在克重47g/m2的优质纸(支撑体)上用绕线棒涂敷底涂层涂料,在保持于120℃的送风干燥器中干燥1分钟。由得到的衬纸的重量差求出的涂布量为8g/m2。在该衬纸上用绕线棒涂敷热敏层涂料1,在保持于60℃的送风干燥器中干燥2分钟,制作热敏记录体。由重量差求出的涂布量为5.1g/m2。
[实施例2]
代替热敏显色层涂液1的45%改性聚酰胺树脂而使用45%改性聚胺树脂(住友化学公司制:SUMIREZRESIN SPI-102A),与实施例1同样地制作热敏记录体。
[实施例3]
使热敏显色层涂液1的45%改性聚酰胺树脂(住友化学公司制:SUMIREZRESIN SPI-106N)为0.25份、并使25%聚酰胺表氯醇(星光PMC公司制:WS4020)为0.5份,除此以外与实施例1同样地制作热敏记录体。
[比较例1]
在热敏显色层涂液1中不配合45%改性聚酰胺树脂,与实施例1同样地制作热敏记录体。
[比较例2]
代替热敏显色层涂液1而使用热敏显色层涂液2,与实施例1同样地制作热敏记录体。
[比较例3]
代替热敏显色层涂液1而使用热敏显色层涂液3,与实施例1同样地制作热敏记录体。
[比较例4]
代替热敏显色层涂液1的10%羧基改性聚乙烯醇溶液(KURARAY公司制:PVA-KL318)而使用10%聚乙烯醇溶液(KURARAY公司制:PVA-117),除此以外与实施例1同样地制作热敏记录体。
[比较例5]
代替热敏显色层涂液1的25%聚酰胺表氯醇(星光PMC公司制:WS4020)而使用40%乙二醛溶液(三井东压公司制),除此以外与实施例1同样地制作热敏记录体。
[比较例6]
在热敏显色层涂液1中,不使用45%改性聚酰胺树脂(住友化学公司制:SUMIREZRESIN SPI-106N)和25%聚酰胺表氯醇(星光PMC公司制:WS4020),除此以外与实施例1同样地制作热敏记录体。进而,在热敏显色层上用绕线棒涂敷上述保护层涂料,在保持于60℃的送风干燥器中干燥2分钟。由重量差求出的保护层的涂布量为3.0g/m2。
对于得到的热敏记录体进行下述评价。
<显色浓度>
使用热敏记录纸打印试验机(大仓电气公司制TH-PMD,安装有京瓷公司制热敏头),以0.23mJ/dot、0.35mJ/dot和0.41mJ/dot的外加能量进行打印,用Macbeth浓度计(RD-914)对打印份的显色浓度进行测定。
<耐背景显色性>
将热敏记录体在50℃、90%Rh放置24小时后,测定背景的Macbeth浓度。
<耐增塑剂性>
在纸筒上卷绕1层聚氯乙烯缠绕膜(三井东压制High Wrap KMA),在其上贴合通过上述打印机TH-PMD(0.23mj/dot)打印的热敏记录体,进而在其上卷绕3层聚氯乙烯缠绕膜,将得到的膜卷在23℃放置24小时后,测定打印部份的Macbeth浓度。
<湿润摩擦>
用手指沾上自来水摩擦热敏显色层涂液涂敷面50往复,按照以下基准目视评价涂敷层的剥离。
○:涂敷层完全没有剥离
△:涂敷层稍剥离
×:涂敷层整体剥离
<耐水粘连>
在热敏显色层涂液的涂敷面上滴下10ml自来水,在其上将记录层的涂敷面相对地重叠,施加10g/cm2的荷重并放置24小时后剥离,按照以下基准目视评价滴下了水的部分的涂敷层的剥离。
○:涂敷层完全没有剥离
△:涂敷层稍剥离
×:涂敷层整体剥离
<耐水胶粘>
将热敏记录体在水中浸渍3分钟,记录面以向内侧的方式对折,施加300g/cm2的载荷后,趁记录面湿润时剥离,在105℃显色2分钟,按照以下基准目视判断记录面的剥离程度。
○:记录面没有剥离
△:记录面稍见剥离
×:记录面的剥离多
将评价结果示于表1。表1的显色浓度栏的数字表示打印的试验机的外加能量。
由表1可知,本发明的热敏记录体显示出良好的显色浓度、保存性(耐背景显色性、耐增塑剂性)和耐水性,即使在以低外加能量(0.23mj/dot)进行打印的情况下,显色灵敏度也出色。
[表1]
Claims (6)
1.一种热敏记录体,
在支撑体上设有含无色或浅色的供电子性隐色染料和受电子性显色剂作为主成分的热敏记录层,其特征在于,
所述热敏记录层含有(a)含羧基树脂、(b)聚酰胺表氯醇树脂或聚胺表氯醇树脂和(c)聚胺/酰胺系树脂。
2.根据权利要求1所述的热敏记录体,其特征在于,
所述(a)含羧基树脂为羧基改性聚乙烯醇。
3.根据权利要求1或2所述的热敏记录体,其中,在热敏记录层上不设置保护层。
4.根据权利要求1或2所述的热敏记录体,其用于以0.1~0.3mj/dot的外加能量进行打印的热敏打印机。
5.经打印的热敏记录体的制法,包括对权利要求1或2所述的热敏记录体以0.1~0.3mj/dot的外加能量进行打印。
6.经打印的热敏记录体的制法,包括对权利要求3所述的热敏记录体以0.1~0.3mj/dot的外加能量进行打印。
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-
2008
- 2008-05-01 KR KR1020097023439A patent/KR20090128551A/ko not_active Application Discontinuation
- 2008-05-01 US US12/599,617 patent/US8283284B2/en active Active
- 2008-05-01 WO PCT/JP2008/058329 patent/WO2008139948A1/ja active Application Filing
- 2008-05-01 CN CN2008800237908A patent/CN101687424B/zh active Active
- 2008-05-01 JP JP2009514107A patent/JP5025029B2/ja active Active
- 2008-05-01 EP EP08752259A patent/EP2145771B1/en not_active Revoked
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CN101102903A (zh) * | 2005-01-13 | 2008-01-09 | 日本制纸株式会社 | 热敏记录体 |
Also Published As
Publication number | Publication date |
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US8283284B2 (en) | 2012-10-09 |
ATE522364T1 (de) | 2011-09-15 |
JP5025029B2 (ja) | 2012-09-12 |
EP2145771B1 (en) | 2011-08-31 |
CN101687424A (zh) | 2010-03-31 |
WO2008139948A1 (ja) | 2008-11-20 |
US20110105319A1 (en) | 2011-05-05 |
JPWO2008139948A1 (ja) | 2010-08-05 |
KR20090128551A (ko) | 2009-12-15 |
EP2145771A4 (en) | 2010-04-28 |
EP2145771A1 (en) | 2010-01-20 |
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