JP4459074B2 - Thermal recording material - Google Patents
Thermal recording material Download PDFInfo
- Publication number
- JP4459074B2 JP4459074B2 JP2005021172A JP2005021172A JP4459074B2 JP 4459074 B2 JP4459074 B2 JP 4459074B2 JP 2005021172 A JP2005021172 A JP 2005021172A JP 2005021172 A JP2005021172 A JP 2005021172A JP 4459074 B2 JP4459074 B2 JP 4459074B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyvinyl alcohol
- undercoat layer
- parts
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 41
- 229920005989 resin Polymers 0.000 claims description 93
- 239000011347 resin Substances 0.000 claims description 93
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 60
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 60
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 46
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 28
- 229920000768 polyamine Polymers 0.000 claims description 20
- 239000005995 Aluminium silicate Substances 0.000 claims description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims description 16
- 150000001408 amides Chemical class 0.000 claims description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 16
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- 239000000049 pigment Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000004640 Melamine resin Substances 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 69
- 238000000576 coating method Methods 0.000 description 54
- 239000007788 liquid Substances 0.000 description 52
- 239000011248 coating agent Substances 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- -1 malachite green lactone Chemical class 0.000 description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 23
- 230000035945 sensitivity Effects 0.000 description 19
- 239000000975 dye Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000003431 cross linking reagent Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000004952 Polyamide Substances 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 229940015043 glyoxal Drugs 0.000 description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000007127 saponification reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 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
- 239000002245 particle Substances 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 238000001454 recorded image Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 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
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-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
- 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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003277 amino group Chemical group 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
- 125000002091 cationic group Chemical group 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
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000010419 fine particle Substances 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
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 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
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 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
- 150000002989 phenols Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 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
- JQPWJEGBJABCDA-UHFFFAOYSA-N 1-[4-[1-(4-pyrrolidin-1-ylphenyl)ethenyl]phenyl]pyrrolidine Chemical group C=1C=C(N2CCCC2)C=CC=1C(=C)C(C=C1)=CC=C1N1CCCC1 JQPWJEGBJABCDA-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
- QWQJPPOEEGYTIW-UHFFFAOYSA-N 1-fluoro-1-phenylhydrazine Chemical compound NN(F)C1=CC=CC=C1 QWQJPPOEEGYTIW-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
- 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
- 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 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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-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
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-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
- MDTCOHCLYIIHEY-UHFFFAOYSA-N 2-hydroxy-4-[2-(4-methoxyphenoxy)ethoxy]benzoic acid Chemical compound C1=CC(OC)=CC=C1OCCOC1=CC=C(C(O)=O)C(O)=C1 MDTCOHCLYIIHEY-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-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
- GPJAXNFFHOCRGM-UHFFFAOYSA-N 3',6,6'-tris(diethylamino)spiro[2-benzofuran-3,9'-fluorene]-1-one;3',6,6'-tris(dimethylamino)spiro[2-benzofuran-3,9'-fluorene]-1-one Chemical compound C12=CC=C(N(C)C)C=C2C2=CC(N(C)C)=CC=C2C21OC(=O)C1=CC(N(C)C)=CC=C21.C12=CC=C(N(CC)CC)C=C2C2=CC(N(CC)CC)=CC=C2C21OC(=O)C1=CC(N(CC)CC)=CC=C21 GPJAXNFFHOCRGM-UHFFFAOYSA-N 0.000 description 1
- IBDQOLXTHOIVSO-UHFFFAOYSA-N 3,3-bis(1-ethyl-2-methylindol-3-yl)-2-benzofuran-1-one;7-[4-(2-cyclohexylethylamino)-2-methoxyphenyl]-7-(1-ethyl-2-methylindol-3-yl)furo[3,4-b]pyridin-5-one Chemical compound C1=CC=C2C(C3(C4=CC=CC=C4C(=O)O3)C3=C(C)N(C4=CC=CC=C43)CC)=C(C)N(CC)C2=C1.C12=CC=CC=C2N(CC)C(C)=C1C1(C2=NC=CC=C2C(=O)O1)C(C(=C1)OC)=CC=C1NCCC1CCCCC1 IBDQOLXTHOIVSO-UHFFFAOYSA-N 0.000 description 1
- ABJAMKKUHBSXDS-UHFFFAOYSA-N 3,3-bis(6-amino-1,4-dimethylcyclohexa-2,4-dien-1-yl)-2-benzofuran-1-one Chemical compound C1=CC(C)=CC(N)C1(C)C1(C2(C)C(C=C(C)C=C2)N)C2=CC=CC=C2C(=O)O1 ABJAMKKUHBSXDS-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
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- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- BRNPAEUKZMBRLQ-UHFFFAOYSA-N octadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 BRNPAEUKZMBRLQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 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
- 150000003013 phosphoric acid derivatives Chemical class 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 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
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- LOZZZCPSUGHCMI-UHFFFAOYSA-L zinc;2-carboxy-5-(octoxycarbonylamino)phenolate;dihydrate Chemical compound O.O.[Zn+2].CCCCCCCCOC(=O)NC1=CC=C(C(O)=O)C([O-])=C1.CCCCCCCCOC(=O)NC1=CC=C(C(O)=O)C([O-])=C1 LOZZZCPSUGHCMI-UHFFFAOYSA-L 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)
Description
本発明は、記録感度、画質、耐水性、印字走行性（ヘッドカス、スティック）に優れた感熱記録体に関するものである。 The present invention relates to a heat-sensitive recording material excellent in recording sensitivity, image quality, water resistance, and print runnability (head residue, stick).
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ール性化合物など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、バインダー、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料を、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、サーマルヘッド、ホットスタンプ、熱ペン、レーザー光など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、コンピューターの端末プリンター、自動券売機、計測用レコーダーなどに広範囲に使用されている。近年、記録装置の多様化や高性能化の進展に伴って高速印字および高速の画像形成も可能となってきており、感熱記録体の記録感度に対してより優れた品質が求められている。また、用途の多様化に伴い、低濃度から高濃度にいたるいずれの領域においても、高画質の記録画像が得られることも求められている。 In general, a heat-sensitive recording material 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 into fine particles, and then mixed together to form a binder, a filling Coatings obtained by adding additives, sensitivity improvers, lubricants and other auxiliaries to substrates such as paper, synthetic paper, film, and plastic. Thermal heads, hot stamps, thermal pens Color is developed by an instantaneous chemical reaction by heating with laser light or the like, and a recorded image is obtained. Thermal recording media are widely used in facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, and the like. In recent years, with the diversification of recording apparatuses and the progress of high performance, high-speed printing and high-speed image formation have become possible, and higher quality is required for the recording sensitivity of the thermal recording medium. Further, with the diversification of applications, it is also required to obtain a high-quality recorded image in any region from low density to high density.
これらの要求を満たす方法として、スーパーカレンダーなどにより感熱記録層表面の平滑度を高めることが一般的に行われているが、必ずしも満足すべき画質が得られなくなってきている。また、高画質を得るためには下塗層の塗工均一性が重要であることが知られており、特許文献１ではスーパーカレンダーにより下塗層の平滑性を向上することが提案されているが、カレンダー圧によって下塗層の多孔性が損なわれ断熱性を失い感度が低下してしまう。さらに、ドット再現性に優れた感熱記録材料を提供するために、特許文献２および３では第一中間層、第二中間層を積層する方法が提案されているが、工程が複雑になるなど製造上不利である。さらには、感度を向上させるために、下塗層中に無機顔料よりも熱伝導率の低い有機微粒子を含有させる特許文献４や空気の断熱性を加味するため中空粒子を含有させる特許文献５が提案されている。しかし、これらの方法は、感度の向上に効果は見られるが、ヘッドカスの付着やスティックなどによる印字障害が発生しやすく不十分な技術であった。 As a method for satisfying these requirements, it is generally performed to increase the smoothness of the surface of the heat-sensitive recording layer by using a super calender or the like, but satisfactory image quality has not necessarily been obtained. In addition, it is known that the coating uniformity of the undercoat layer is important for obtaining high image quality, and Patent Document 1 proposes to improve the smoothness of the undercoat layer by a super calendar. However, the calender pressure impairs the porosity of the undercoat layer and loses heat insulation, resulting in a decrease in sensitivity. Furthermore, in order to provide a heat-sensitive recording material having excellent dot reproducibility, Patent Documents 2 and 3 propose a method of laminating the first intermediate layer and the second intermediate layer. It is disadvantageous. Furthermore, in order to improve the sensitivity, there are Patent Document 4 in which organic fine particles having lower thermal conductivity than the inorganic pigment are contained in the undercoat layer and Patent Document 5 in which hollow particles are incorporated in order to add heat insulation to the air. Proposed. However, although these methods are effective in improving the sensitivity, they are insufficient techniques that are liable to cause a printing failure due to adhesion of a head residue or a stick.
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、車馬券など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、このため、感熱記録体に対して従来では問題になっていなかった耐水性のような厳しい特性が要求され始めている。これらの用途の場合、屋外で使用されることが多く、雨などの水分や湿気などによって記録部の判読が困難とならないよう、従来に比べて過酷な環境下での使用に耐える品質性能が必要となる。
そこで、本発明は、記録感度および画質、耐水性に優れ、さらには印字走行性（ヘッドカス、スティック）の良好な感熱記録体を提供することを課題とする。 SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-sensitive recording material that has excellent recording sensitivity, image quality, and water resistance, and also has good print running properties (head residue, stick).
本発明者らは鋭意検討の結果、カルボキシル基含有樹脂とエピクロロヒドリン系樹脂を含有した下塗り層を設けることで上記課題を解決することを見出し、本発明を完成するに至った。
即ち、本発明は、支持体上に顔料とバインダーとを主成分とする下塗り層、無色ないし淡色の電子供与性ロイコ染料および電子受容性顕色剤とを主成分として含有する感熱記録層を設けた感熱記録体において、該下塗り層がカルボキシル基含有樹脂、特にカルボキシ変性ポリビニルアルコールとエピクロロヒドリン系樹脂と、メラミン系樹脂または変性ポリアミン／アミド系樹脂を含有することを特徴とする感熱記録体とすることにより、課題を解決するものである。
As a result of intensive studies, the present inventors have found that the above problems can be solved by providing an undercoat layer containing a carboxyl group-containing resin and an epichlorohydrin-based resin, and have completed the present invention.
That is, the present invention provides an undercoat layer comprising a pigment and a binder as main components on a support, and a thermosensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer as main components. A heat-sensitive recording material, wherein the undercoat layer contains a carboxyl group-containing resin, particularly a carboxy-modified polyvinyl alcohol and an epichlorohydrin resin, and a melamine resin or a modified polyamine / amide resin. By doing so, the problem is solved.
本発明によれば、記録感度および画質、耐水性に優れ、さらには印字走行性（ヘッドカス、スティック）の良好な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 that is excellent in recording sensitivity, image quality, and water resistance, and also has good print running properties (head residue, stick).
本発明は、カルボキシル基含有樹脂とエピクロロヒドリン系樹脂とを含有した下塗り層を設けることによって、優れた記録感度および画質、耐水性、さらには印字走行性（ヘッドカス、スティック）の良好な感熱記録体を得ることができる。
本発明において、下塗層に含有されるカルボキシル基含有樹脂とは、カルボキシル基を有するバインダーである。例えば、メタクリル酸、メタクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシプロピル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチル、メタクリル酸ターシャーリーブチルアミノエチル、メタクリル酸グリシジル、メタクリル酸テトラヒドロフリフリルなどのカルボキシル基を有する一官能性アクリルモノマーを含む樹脂、酸化でんぷん、カルボキシメチルセルロース、ポリビニルアルコールにカルボキシル基を導入したカルボキシ変性ポリビニルアルコールなどが挙げられ、単独あるいは２種類以上を組み合わせて用いることができる。また、上記カルボキシル基含有樹脂と併用できるバインダーとして、デンプンおよび変性デンプン、ポリビニルアルコールおよび変性ポリビニルアルコール、メチルセルロース、カルボキシメチルセルロース等の水溶性高分子やスチレン・ブタジエン共重合体、アクリル酸系共重合体等の合成樹脂エマルジョン等が挙げられる。
なお、目標とする品質に合わせて、カルボキシル基含有樹脂と併用するバインダーの組み合わせは任意に選択することができ、配合量は適宜調整することが可能である。
In the present invention, by providing an undercoat layer containing a carboxyl group-containing resin and an epichlorohydrin-based resin, excellent recording sensitivity and image quality, water resistance, and good heat sensitivity of printing runability (head residue, stick) are provided. A record can be obtained.
In the present invention, the carboxyl group-containing resin contained in the undercoat layer is a binder having a carboxyl group. For example, carboxyl such as methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Examples thereof include a resin containing a monofunctional acrylic monomer having a group, oxidized starch, carboxymethyl cellulose, carboxy-modified polyvinyl alcohol in which a carboxyl group is introduced into polyvinyl alcohol, and the like. These can be used alone or in combination of two or more. In addition, as binders that can be used in combination with the carboxyl group-containing resin, water-soluble polymers such as starch and modified starch, polyvinyl alcohol and modified polyvinyl alcohol, methylcellulose, carboxymethylcellulose, styrene / butadiene copolymers, acrylic acid copolymers, etc. And synthetic resin emulsions.
In addition, according to target quality, the combination of the binder used together with carboxyl group-containing resin can be selected arbitrarily, and a compounding quantity can be adjusted suitably.
本発明において、カルボキシル基含有樹脂として、耐熱性、耐溶剤性が優れているカルボキシ変性ポリビニルアルコールを用いるのが好ましい。
カルボキシ変性ポリビニルアルコールは、水溶性高分子に反応性を高める目的でカルボキシル基を導入したものであり、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、あるい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号公報などに例示されている製造方法が挙げられる。
本発明の下塗り層において、カルボキシル基含有樹脂としてカルボキシ変性ポリビニルアルコールを用いた場合、塗料の保水性や塗工層強度の点から、カルボキシ変性ポリビニルアルコールの重合度は１５００以上、鹸化度は８５％以上が好ましい。また、塗液の流動性を改善する効果のあるカルボキシ変性ポリビニルアルコールの含有量としては、顔料１００重量部に対して０．５〜１０重量部含有することが好ましく、より好ましくは顔料１００重量部に対して１〜５重量部である。カルボキシ変性ポリビニルアルコールの含有量が少なすぎるとその作用が十分に発揮されず、多すぎると塗液粘度が高くなり高濃度塗工が困難となってしまう。塗液の濃度を下げた場合、同じ塗布量を得るためには塗液を多量に塗工しなければならず、乾燥負荷も増大し好ましくない。
また、カルボキシ変性ポリビニルアルコールは、低ハーキュレス粘度（回転力（シェア）がかかっている状態での流動性が高く、シェアの低いところでは不動化しやすい特性）であること、保水性が高い特性を有している。このため、カルボキシ変性ポリビニルアルコールを含有した塗料を塗工した場合、塗工時には塗料は滑らかに延びるが塗工後は直ちに不動化し易く、支持体へのバインダーの浸透を抑えることができるため、均質で凹凸のない下塗り層が形成される。つまり、下塗り層にカルボキシ変性ポリビニルアルコールを含有させることにより、優れた記録感度および画質である感熱記録体を得ることができる。
In the present invention, it is preferable to use carboxy-modified polyvinyl alcohol having excellent heat resistance and solvent resistance as the carboxyl group-containing resin.
Carboxy-modified polyvinyl alcohol is a water-soluble polymer having a carboxyl group introduced for the purpose of enhancing reactivity. Polyvinyl alcohol and polyvalent carboxylic acids such as fumaric acid, phthalic anhydride, melitonic anhydride, and itaconic anhydride Or saponification of copolymers of vinyl acetate with ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid and methacrylic acid It is obtained as a product. Specific examples include the production methods exemplified in JP-A-53-91995.
In the undercoat layer of the present invention, when carboxy-modified polyvinyl alcohol is used as the carboxyl group-containing resin, the polymerization degree of the carboxy-modified polyvinyl alcohol is 1500 or more and the saponification degree is 85% from the viewpoint of water retention and coating layer strength. The above is preferable. In addition, the content of the carboxy-modified polyvinyl alcohol having an effect of improving the fluidity of the coating liquid is preferably 0.5 to 10 parts by weight, more preferably 100 parts by weight of the pigment with respect to 100 parts by weight of the pigment. 1 to 5 parts by weight based on the weight. If the content of the carboxy-modified polyvinyl alcohol is too small, the effect is not sufficiently exhibited. If the content is too large, the viscosity of the coating solution becomes high and high concentration coating becomes difficult. When the concentration of the coating liquid is lowered, in order to obtain the same coating amount, a large amount of the coating liquid must be applied, which increases the drying load, which is not preferable.
In addition, carboxy-modified polyvinyl alcohol has a low hercules viscosity (high fluidity in a state where rotational force (share) is applied, and is easily immobilized at a low share) and high water retention. is doing. For this reason, when a paint containing carboxy-modified polyvinyl alcohol is applied, the paint extends smoothly at the time of application, but it is easy to immobilize immediately after application, and the penetration of the binder into the support can be suppressed. As a result, an undercoat layer without irregularities is formed. That is, by including carboxy-modified polyvinyl alcohol in the undercoat layer, a heat-sensitive recording material having excellent recording sensitivity and image quality can be obtained.
本発明では下塗層に含有されたカルボキシル基含有樹脂の架橋剤としてエピクロロヒドリン系樹脂を用いることで優れた品質が得られる。
本発明に使用されるエピクロロヒドリン系樹脂の具体例としては、ポリアミドエピクロロヒドリン樹脂、ポリアミンエピクロロヒドリン樹脂などを挙げることができ、単独又は併用することもできる。また、エピクロロヒドリン系樹脂の主鎖に存在するアミンとしては第１級から第４級までのものを使用することができ、特に制限はない。さらに、カチオン化度および分子量は、耐水性が良好なことから、カチオン化度５ｍｅｑ／ｇ・Ｓｏｌｉｄ以下（ｐＨ７での測定値）、分子量５０万以上が好ましい。具体例としては、スミレーズレジン６５０（３０）（住友化学社製）、スミレーズレジン６７５Ａ（住友化学社製）、スミレーズレジン６６１５（住友化学社製）、ＷＳ４００２（星光ＰＭＣ社製）、ＷＳ４０２０（星光ＰＭＣ社製）、ＷＳ４０２４（星光ＰＭＣ社製）、ＷＳ４０４６（星光ＰＭＣ社製）、ＷＳ４０１０（星光ＰＭＣ社製）、ＣＰ８９７０（星光ＰＭＣ社製）などが挙げられる。
本発明に用いられるエピクロロヒドリン系樹脂の含有比率としては、カルボキシル基含有樹脂１００重量部に対して１〜１００重量部含有させることが好ましく、より好ましくはカルボキシル基含有樹脂１００重量部に対して５〜１００重量部であることが望ましい。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、多すぎると塗液の粘度増加やゲル化により操業性の問題が生じてしまうので好ましくない。
In the present invention, excellent quality can be obtained by using an epichlorohydrin resin as a crosslinking agent for the carboxyl group-containing resin contained in the undercoat layer.
Specific examples of the epichlorohydrin resin used in the present invention include polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, and the like, and they can be used alone or in combination. Moreover, as an amine which exists in the principal chain of an epichlorohydrin-type resin, the thing from a primary to a quaternary can be used, and there is no restriction | limiting in particular. Further, the degree of cationization and molecular weight are preferably water cation resistance, so that the degree of cationization is 5 meq / g · Solid (measured value at pH 7) and the molecular weight is 500,000 or more. Specific examples include Sumire's Resin 650 (30) (manufactured by Sumitomo Chemical), Sumire's Resin 675A (manufactured by Sumitomo Chemical), Sumire's Resin 6615 (manufactured by Sumitomo Chemical), WS4002 (manufactured by Seiko PMC), WS4020. (Made by Starlight PMC), WS4024 (made by Starlight PMC), WS4046 (made by Starlight PMC), WS4010 (made by Starlight PMC), CP8970 (made by Starlight PMC), and the like.
The content ratio of the epichlorohydrin resin used in the present invention is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin, more preferably 100 parts by weight of the carboxyl group-containing resin. 5 to 100 parts by weight is desirable. If the content is too small, the crosslinking reaction becomes insufficient and good water resistance cannot be obtained. If the content is too large, problems of operability occur due to increased viscosity of the coating liquid or gelation, which is not preferable.
本発明において、エピクロロヒドリン系樹脂を含有させることによって優れた効果が発現する理由について、カルボキシル基含有樹脂にカルボキシ変性ポリビニルアルコールを使用した場合を例にして説明する。
本発明で用いられるエピクロロヒドリン系樹脂は多反応性官能基を有する架橋剤であり、エピクロロヒドリン系樹脂のアミンあるいはアミド部分がカルボキシ変性ポリビニルアルコールのカルボキシ基と架橋反応した際に網目構造を形成する。このため、カルボキシ変性ポリビニルアルコールとエピクロロヒドリン系樹脂を含有させた下塗り層は断熱効果の高いポーラスな層になり、電子供与性ロイコ染料と電子受容性顕色剤との発色反応においてサーマルヘッドからの熱を有効に使用できるため感度、画質が向上するものと推測される。また、サーマルヘッドからの熱で塗工層中の耐熱性の低い材料が溶融してしまい発生するヘッドカスやスティックの問題においても、ポーラスな下塗層の空隙に溶融物が吸着されることで溶融物の発生を抑制するため優れた印字走行性が得られたと推測される。
In the present invention, the reason why an excellent effect is manifested by containing an epichlorohydrin resin will be described with reference to the case where carboxy-modified polyvinyl alcohol is used as the carboxyl group-containing resin.
The epichlorohydrin resin used in the present invention is a cross-linking agent having a polyreactive functional group. When the amine or amide part of the epichlorohydrin resin cross-links with the carboxy group of carboxy-modified polyvinyl alcohol, a network is formed. Form a structure. For this reason, the undercoat layer containing carboxy-modified polyvinyl alcohol and epichlorohydrin resin becomes a porous layer having a high heat insulating effect, and in the color reaction between the electron donating leuco dye and the electron accepting developer, the thermal head It is estimated that the sensitivity and image quality are improved because the heat from the water can be used effectively. Also, in the problem of head debris and sticks that occur due to the heat from the thermal head melting the low heat-resistant material in the coating layer, the melt is adsorbed by the pores in the porous undercoat layer. It is presumed that excellent printing runnability was obtained in order to suppress the generation of objects.
一方、一般的な架橋剤であるグリオキザールは２反応性官能基であり、カルボキシ変性ポリビニルアルコールの水酸基と架橋反応はするものの、網目構造は形成しないため、下塗り層にエピクロロヒドリン系樹脂を含有させた場合と比較して、感度、画質、印字走行性などが劣ると結果になったと推測される。
また、グリオキザールとカルボキシ変性ポリビニルアルコールの反応性より、エピクロロヒドリン系樹脂とカルボキシ変性ポリビニルアルコールの反応性の方が高いため、優れた耐水性が発現すると推測される。
本発明において、エピクロロヒドリン系樹脂はｐＨが６．０以上で良好な架橋反応が起こるアルカリ硬化型の樹脂であるため、エピクロロヒドリン系樹脂を含有した下塗層塗液のｐＨは６．０以上にすることが好ましい。
On the other hand, glyoxal, which is a general cross-linking agent, is a bi-reactive functional group and crosslinks with the hydroxyl group of carboxy-modified polyvinyl alcohol, but does not form a network structure, so it contains an epichlorohydrin resin in the undercoat layer. It is presumed that the result is inferior in sensitivity, image quality, printing runnability, and the like as compared with the case where it is applied.
Moreover, since the reactivity of epichlorohydrin resin and carboxy modified polyvinyl alcohol is higher than the reactivity of glyoxal and carboxy modified polyvinyl alcohol, it is estimated that excellent water resistance is developed.
In the present invention, epichlorohydrin resin is an alkali curable resin that undergoes a good crosslinking reaction at a pH of 6.0 or higher, and therefore the pH of the undercoat layer coating solution containing epichlorohydrin resin is It is preferable to make it 6.0 or more.
また、本発明においてエピクロロヒドリン系樹脂を添加する際は、ｐＨを６．５〜１０に調整することで凝集物の発生しない下塗層塗液を得ることができる。
一般にエピクロロヒドリン系樹脂の水溶液は水溶液中に遊離しているアミンを水溶液中に留めるために塩酸や硫酸で酸性にしている。このため、エピクロロヒドリン系樹脂のアミノ基は−ＮＨ３ ＋で存在しているため、表面がマイナスに帯電している顔料に対して凝集を起こしやすい。一方、本発明のように、エピクロロヒドリン系樹脂の水溶液のｐＨを中性からアルカリ性領域にすることで、エピクロロヒドリン系樹脂のアミノ基は−ＮＨ２の状態、つまりイオン的にニュートラルな状態なり、顔料に対して凝集を起こしにくくなっていると考えられる。このため、下塗層中において、エピクロロヒドリン系樹脂とバインダーが均一に架橋反応することにより、強固な下塗層となり、優れた耐水性が得られると共に、よりポーラスな塗工層が得られると考えられる。また、エピクロロヒドリン系樹脂の水溶液のｐＨを６．５以上にすることで炭酸カルシウムなどの顔料の溶解を抑制できる。
エピクロロヒドリン系樹脂のｐＨ調整剤としては、水に溶解した際にアルカリ性を示すものであれば何れも使用することが可能であるが、水酸化ナトリウム及び水酸化カルシウムなどの水酸化物、珪酸ナトリウム等の珪酸塩、炭酸ナトリウム、炭酸カリウム、及び炭酸水素ナトリウムなどの炭酸塩並びに炭酸水素塩、リン酸ナトリウム及びリン酸水素二ナトリウムなどのリン酸塩並びにリン酸水素塩などの、水溶性アルカリ性塩類の水溶液や、アンモニア水などを例示することができる。
In addition, when an epichlorohydrin resin is added in the present invention, an undercoat layer coating solution in which no aggregate is generated can be obtained by adjusting the pH to 6.5 to 10.
In general, an aqueous solution of epichlorohydrin resin is acidified with hydrochloric acid or sulfuric acid in order to keep the amine released in the aqueous solution in the aqueous solution. For this reason, the amino group of the epichlorohydrin-based resin exists as —NH 3 + , and thus easily aggregates with respect to a pigment whose surface is negatively charged. On the other hand, as in the present invention, the pH of the aqueous solution of the epichlorohydrin resin is changed from neutral to alkaline, so that the amino group of the epichlorohydrin resin is in the -NH 2 state, that is, ionically neutral. Thus, it is considered that the pigment is less likely to aggregate. For this reason, in the undercoat layer, the epichlorohydrin-based resin and the binder are uniformly cross-linked to form a strong undercoat layer that provides excellent water resistance and a more porous coating layer. It is thought that. Moreover, dissolution of pigments, such as calcium carbonate, can be suppressed by making pH of the aqueous solution of epichlorohydrin resin 6.5 or more.
As the pH adjuster of the epichlorohydrin-based resin, any can be used as long as it shows alkalinity when dissolved in water, but hydroxides such as sodium hydroxide and calcium hydroxide, Water-soluble, such as silicates such as sodium silicate, carbonates such as sodium carbonate, potassium carbonate, and sodium hydrogen carbonate, and phosphates such as hydrogen carbonate, sodium phosphate and disodium hydrogen phosphate, and hydrogen phosphate Examples include aqueous solutions of alkaline salts and aqueous ammonia.
本発明において、下塗層に含有される顔料としては、（焼成）クレー、（焼成）カオリン、炭酸カルシウム、酸化アルミニウム、酸化チタン、炭酸マグネシウム、無定形シリカ、珪酸アルミニウム、珪酸マグネシウム、珪酸カルシウムなどが挙げられる。特に、吸油量（ＪＩＳ Ｋ ５１０１法に基づく）が８０ｃｃ／１００ｇ〜１２０ｃｃ／１００ｇの焼成カオリンを用い場合、充分な断熱効果が与えられ、バインダーが顔料に多量に吸収されることがないため、均一な塗工層が形成される。この結果、高い記録感度と優れた画質のバランスのとれた感熱記録体を得ることができる。
しかしながら、形状が扁平である焼成カオリンを用いた場合、紡錘形、立方形、球形の炭酸カルシウムなどに比べて塗料の流動性に劣る傾向があり、また焼成されていることから表面にシラノールのＯＨ基（水酸基）が存在しないため、水との結合性が弱くなり保水性が低い塗料になる。
これに対しては、本発明では、高い保水性を有するカルボキシ変性ポリビニルアルコールの添加、あるいは炭酸カルシウムの併用により、焼成クレーを用いた場合の塗料適性（保水性、流動性）を改善することが望ましい。
なお、炭酸カルシウムの添加量は全顔料に対する含有比率が３０％以下となるように用いることが望ましい。この範囲で炭酸カルシウムを含有することにより、塗料の流動性が良好になり、均一な塗工層が形成されて画質が向上すると考えられる。一方、含有量が３０％より多い場合は、発色感度が低くなる傾向があるため好ましくない。
In the present invention, the pigment contained in the undercoat layer includes (fired) clay, (fired) kaolin, calcium carbonate, aluminum oxide, titanium oxide, magnesium carbonate, amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, and the like. Is mentioned. In particular, when calcined kaolin having an oil absorption amount (based on the JIS K 5101 method) of 80 cc / 100 g to 120 cc / 100 g is used, a sufficient heat insulating effect is given, and the binder is not absorbed in a large amount by the pigment. A simple coating layer is formed. As a result, it is possible to obtain a thermal recording material in which high recording sensitivity and excellent image quality are balanced.
However, when calcined kaolin having a flat shape is used, the fluidity of the paint tends to be inferior to that of spindle-shaped, cubic, or spherical calcium carbonate. Since (hydroxyl group) does not exist, the binding property with water becomes weak and the paint has low water retention.
On the other hand, in the present invention, by adding carboxy-modified polyvinyl alcohol having high water retention or using calcium carbonate in combination, the suitability of paint (water retention, fluidity) when using baked clay can be improved. desirable.
In addition, it is desirable to use the added amount of calcium carbonate so that the content ratio to the total pigment is 30% or less. By containing calcium carbonate in this range, it is considered that the fluidity of the coating is improved, a uniform coating layer is formed, and the image quality is improved. On the other hand, when the content is more than 30%, the color development sensitivity tends to be low, which is not preferable.
本発明の下塗層においてはエピクロロヒドリン系樹脂と併用し、第二の架橋剤としてメラミン系樹脂または変性ポリアミン／アミド系樹脂を含有させることによって、さらに優れた記録感度および画質、耐水性、さらには印字走行性（ヘッドカス、スティック）の良好な感熱記録体を得ることができる。
本発明において、第二の架橋剤に使用されるメラミン系樹脂としては、メラミンホルムアルデヒド樹脂、メラミン尿素樹脂などを挙げることができ、具体例としてはスミレーズレジン６１３−ｓ（住友化学社製）などが挙げられる。
本発明おいて、第二の架橋剤に使用される変性ポリアミン／アミド系樹脂としては、一般的に印刷適性向上剤と呼ばれるものであり、ポリアミド尿素系樹脂やポリエチレンイミンなどのポリアルキレンポリアミンなどが挙げられる。具体例としてはスミレーズレジン３０２（住友化学社製）、スミレーズレジン７１２（住友化学社製）、スミレーズレジン７０３（住友化学社製）、スミレーズレジン６３６（住友化学社製）、スミレーズレジンＳＰＩ−１００（住友化学社製）、スミレーズレジンＳＰＩ−１０２Ａ（住友化学社製）、スミレーズレジンＳＰＩ−１０６Ｎ（住友化学社製）、スミレーズレジンＳＰＩ−２０３（５０）（住友化学社製）、スミレーズレジンＳＰＩ−１９８（住友化学社製）、プリンティブＡ−７００（旭化成社製）、プリンティブＡ−６００（旭化成社製）、ＰＡ６５００（星光ＰＭＣ社製）、ＰＡ６５０４（星光ＰＭＣ社製）、ＰＡ６６３４（星光ＰＭＣ社製）、ＰＡ６６３８（星光ＰＭＣ社製）、ＰＡ６６４０（星光ＰＭＣ社製）、ＰＡ６６４４（星光ＰＭＣ社製）、ＰＡ６６４６（星光ＰＭＣ社製）、ＰＡ６６５４（星光ＰＭＣ社製）、ＰＡ６７０２（星光ＰＭＣ社製）、ＰＡ６７０４（星光ＰＭＣ社製）、ＣＰ８９９４（星光ＰＭＣ社製）などが挙げられる。
In the undercoat layer of the present invention, by using together with epichlorohydrin resin and containing melamine resin or modified polyamine / amide resin as the second crosslinking agent, further excellent recording sensitivity and image quality, water resistance In addition, it is possible to obtain a heat-sensitive recording material having good print running properties (head residue, stick).
In the present invention, examples of the melamine resin used for the second cross-linking agent include melamine formaldehyde resin and melamine urea resin, and specific examples include Sumire Resin 613-s (manufactured by Sumitomo Chemical Co., Ltd.). Is mentioned.
In the present invention, the modified polyamine / amide resin used for the second cross-linking agent is generally called a printability improver, and polyalkylene polyamines such as polyamide urea resins and polyethyleneimine are used. Can be mentioned. Specific examples include Sumire's Resin 302 (manufactured by Sumitomo Chemical), Sumire's Resin 712 (manufactured by Sumitomo Chemical), Sumire's Resin 703 (manufactured by Sumitomo Chemical), Sumire's Resin 636 (manufactured by Sumitomo Chemical), Sumire's. Resin SPI-100 (manufactured by Sumitomo Chemical), Sumire Resin SPI-102A (manufactured by Sumitomo Chemical), Sumire Resin SPI-106N (manufactured by Sumitomo Chemical), Sumire Resin SPI-203 (50) (Sumitomo Chemical) Manufactured), Sumirez resin SPI-198 (manufactured by Sumitomo Chemical Co., Ltd.), printable A-700 (manufactured by Asahi Kasei Co., Ltd.), printable A-600 (manufactured by Asahi Kasei Co., Ltd.), PA6500 (manufactured by Seiko PMC), PA6504 (starlight PMC) PA6664 (manufactured by Seiko PMC), PA6638 (manufactured by Seiko PMC), PA6640 (manufactured by Seiko PMC), PA 644 (manufactured by Starlight PMC), PA6646 (manufactured by Starlight PMC), PA6654 (manufactured by Starlight PMC), PA6702 (manufactured by Starlight PMC), PA6704 (manufactured by Starlight PMC), CP8994 (manufactured by Starlight PMC), etc. It is done.
本発明において、第二の架橋剤として用いられるメラミン系樹脂または変性ポリアミン／アミド系樹脂の含有比率としてはエピクロロヒドリン系樹脂と同様に、カルボキシル基含有樹脂１００重量部に対してそれぞれ１〜１００重量部含有させることが好ましく、より好ましくはカルボキシル基含有樹脂１００重量部に対して５〜１００重量部であることが望ましい。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、多すぎると塗液の粘度増加やゲル化により操業性の問題が生じてしまうので好ましくない。
本発明において、第二の架橋剤を添加することにより優れた効果が得られる理由について、カルボキシル基含有樹脂にカルボキシ変性ポリビニルアルコールを使用した場合を例にして説明する。
第二の架橋剤としてメラミン系樹脂を用いた場合、第一の反応としてカルボキシル基と水酸基を有しているカルボキシ変性ポリビニルアルコールに対して、架橋剤であるエピクロロヒドリン系樹脂のアミンあるいはアミド部分などとカルボキシ変性ポリビニルアルコールのカルボキシル基、メラミン系樹脂とカルボキシ変性ポリビニルアルコールの水酸基の架橋反応が起こる。次に第二の反応として、第一の反応でメラミン系樹脂とカルボキシ変性ポリビニルアルコールが架橋反応することにより、メラミン系樹脂に電子的な偏りが生じるため、メラミン系樹脂の官能基あるいは特定部位の反応性が高くなり、もう一方の架橋剤であるエピクロロヒドリン系樹脂のアミンあるいはアミドなどの部分と反応が起こる。この第一および第二の反応により、カルボキシ変性ポリビニルアルコール、エピクロロヒドリン系樹脂、メラミン系樹脂の三者間のより強固な三次元的分子間架橋構造を形成し、よりポーラスな下塗層をとなるため、優れた耐水性、発色性、画質、印字走行性（ヘッドカス、スティック）が得られると推測される。
In the present invention, the content ratio of the melamine resin or modified polyamine / amide resin used as the second crosslinking agent is 1 to 100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin, as in the case of the epichlorohydrin resin. The content is preferably 100 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin. If the content is too small, the crosslinking reaction becomes insufficient and good water resistance cannot be obtained. If the content is too large, problems of operability occur due to increased viscosity of the coating liquid or gelation, which is not preferable.
In the present invention, the reason why an excellent effect can be obtained by adding the second cross-linking agent will be described with reference to a case where carboxy-modified polyvinyl alcohol is used for the carboxyl group-containing resin.
When a melamine-based resin is used as the second crosslinking agent, the amine or amide of the epichlorohydrin-based resin that is the crosslinking agent is used as the first reaction with respect to the carboxy-modified polyvinyl alcohol having a carboxyl group and a hydroxyl group. The cross-linking reaction of the carboxyl group of the carboxy-modified polyvinyl alcohol and the hydroxyl group of the melamine resin and the carboxy-modified polyvinyl alcohol occurs. Next, as the second reaction, the melamine resin and the carboxy-modified polyvinyl alcohol undergo a cross-linking reaction in the first reaction, resulting in an electronic bias in the melamine resin. The reactivity becomes high, and a reaction occurs with the amine or amide portion of the epichlorohydrin resin which is the other crosslinking agent. By this first and second reaction, a stronger three-dimensional intermolecular cross-linking structure between carboxy-modified polyvinyl alcohol, epichlorohydrin resin, and melamine resin is formed, and a more porous subbing layer Therefore, it is presumed that excellent water resistance, color developability, image quality, and print runnability (head residue, stick) can be obtained.
第二の架橋剤として変性ポリアミン／アミド系樹脂を用いた場合、カルボキシ変性ポリビニルアルコールのカルボキシル基と、架橋剤であるエピクロロヒドリン系樹脂のアミンあるいはアミド部分が、架橋反応を引き起こし一次的な耐水化を発現する。次に、変性ポリアミン／アミド系樹脂の親水性部位とカルボキシ変性ポリビニルアルコールとエピクロロヒドリン系樹脂で形成された親水性のある架橋部位が引き合うため、この架橋部位は変性ポリアミン／アミド系樹脂の疎水基を外側にして包まれた状態、つまり親水性のある架橋部位が疎水性基で水から保護された状態となり、二次的な耐水化が発現する。このため、より強固な耐水性が得られると推測される。また、変性ポリアミン／ポリアミド系樹脂の親水性部位がカルボキシ変性ポリビニルアルコールの水酸基に引き付けられ、カルボキシ変性ポリビニルアルコールが変性ポリアミン／アミド系樹脂の疎水基を外側にして包まれた状態になるとともに、変性ポリアミン／アミド系樹脂のカチオン性部位がカルボキシ変性ポリビニルアルコールのカルボキシル基と一種の架橋反応していることも、高い耐水化が発現している一因であると考えられる。また、カルボキシ変性ポリビニルアルコールとエピクロロヒドリン系樹脂の架橋反応により三次元的な構造を有していること、カチオン性である変性ポリアミン／アミド系樹脂がアニオン性の顔料に対して分散効果を発揮するため、よりポーラスな下塗層になると推測される。
このような理由から、本発明の下塗層においてはエピクロロヒドリン系樹脂と併用し、第二の架橋剤としてメラミン系樹脂または変性ポリアミン／アミド系樹脂を含有させることによって、より優れた感度および画質、耐水性と印字走行性（ヘッドカス、スティック）が得られたと考えられる。
When a modified polyamine / amide resin is used as the second crosslinking agent, the carboxyl group of the carboxy-modified polyvinyl alcohol and the amine or amide moiety of the epichlorohydrin resin that is the crosslinking agent cause a crosslinking reaction, which is a primary Expresses water resistance. Next, since the hydrophilic site of the modified polyamine / amide resin and the hydrophilic crosslinked site formed of carboxy-modified polyvinyl alcohol and epichlorohydrin resin are attracted, this crosslinked site is the same as that of the modified polyamine / amide resin. A state in which the hydrophobic group is encapsulated, that is, a hydrophilic cross-linked site is protected from water by the hydrophobic group, and secondary water resistance is exhibited. For this reason, it is estimated that stronger water resistance is obtained. In addition, the hydrophilic part of the modified polyamine / polyamide resin is attracted to the hydroxyl group of the carboxy-modified polyvinyl alcohol, and the carboxy-modified polyvinyl alcohol is encased with the hydrophobic group of the modified polyamine / amide resin on the outside. The cationic site of the polyamine / amide-based resin reacts with the carboxyl group of the carboxy-modified polyvinyl alcohol as a kind of cross-linking reaction. In addition, it has a three-dimensional structure due to the crosslinking reaction of carboxy-modified polyvinyl alcohol and epichlorohydrin resin, and the modified polyamine / amide resin that is cationic has a dispersion effect on anionic pigments. In order to exert, it is estimated that it becomes a more porous undercoat layer.
For this reason, in the undercoat layer of the present invention, a combination of epichlorohydrin resin and a melamine resin or a modified polyamine / amide resin as the second crosslinking agent can be used to improve the sensitivity. In addition, it is considered that image quality, water resistance, and print running properties (head residue, stick) were obtained.
本発明において、下塗り層の塗布量は１〜１５ｇ／ｍ２程度で、通常の塗工機を用いて紙、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、不織布などの適当な材質の支持体上に塗布することによって容易に行われる。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。塗工方法としてはエアーナイフ法、ブレード法、グラビア法、ロールコーター法、カーテン法などの既知の塗布方法をいずれも利用してよいが、高濃度の塗工が可能で塗液が支持体に浸透しにくく、均一な層構成が形成されることからブレード塗工によって下塗層を形成することが好ましい。 In the present invention, the coating amount of the undercoat layer is about 1 to 15 g / m 2 , and a suitable material such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, and non-woven fabric using a normal coating machine. It is easily performed by coating on the support. Moreover, you may use the composite sheet which combined these as a support body. As a coating method, any known coating method such as an air knife method, a blade method, a gravure method, a roll coater method, or a curtain method may be used, but high concentration coating is possible and the coating liquid is applied to the support. It is preferable that the undercoat layer is formed by blade coating because it does not easily penetrate and a uniform layer structure is formed.
次に、本発明で使用される各種材料を例示するが、バインダーや架橋剤、顔料などは上記課題に対する所望の効果を阻害しない範囲で下塗層にも使用でき、また下塗層のみならず感熱記録層などをはじめとする必要に応じて設けられた各塗工層にも使用することができる。
本発明で使用するバインダーとしては、重合度が２００〜１９００の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、ポリスチロースおよ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。
Next, various materials used in the present invention are exemplified, but binders, cross-linking agents, pigments and the like can be used for the undercoat layer as long as they do not impair the desired effects on the above-mentioned problems. It can also be used for each coating layer provided as required, including a heat-sensitive recording layer.
As the binder used in the present invention, fully saponified polyvinyl alcohol having a polymerization degree of 200 to 1900, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, Butyral modified polyvinyl alcohol, 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 ethyl cellulose, acetyl Cellulose derivatives such as cellulose, casein, arabic gum, oxidized starch, etherified starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylate, polyvinyl butyral, polystyrose and their Examples include copolymers, polyamide resins, silicone resins, petroleum resins, terpene resins, ketone resins, and coumaro resins. 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.
本発明でエピクロロヒドリン系樹脂と併用できる架橋剤としては、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、ポリアミド尿素系樹脂、ポリアルキレンポリアミン、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または有機充填剤などが挙げられる。下塗層中に用いる顔料としては発色感度と画質のバランスなどを考慮した場合、焼成カオリンが好ましい。
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などの脂肪酸金属塩、ワックス類、シリコーン樹脂類などが挙げられる。
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ベンゾ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。
Examples of the crosslinking agent that can be used in combination with epichlorohydrin resin in the present invention include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, polyamide urea resin, poly Examples include alkylene polyamine, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, 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. As the pigment used in the undercoat layer, calcined kaolin is preferable in consideration of the balance between color development sensitivity and image quality.
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.
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-based and benzotriazole-based ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
本発明で使用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または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 used in the present invention, those known in the conventional pressure-sensitive or heat-sensitive recording paper field can be used, and are not particularly limited, but include triphenylmethane compounds, fluorane compounds. 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
<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 3-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 -Methylfluorane 3-diethylamino-6-chloro-7-anilinofluorane 3-diethylamino-6-chloro-7-p-methylanilinofluorane 3-diethylamino-6-ethoxyethyl-7-anilinofluorane
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-diethylamino-7-methylfluorane 3-diethylamino-7-chlorofluorane 3-diethylamino-7- (m-trifluoromethylanilino) fluorane 3-diethylamino-7- (o-chloroanilino) fluorane 3-diethylamino- 7- (p-chloroanilino) fluorane 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) fluoran 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−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）フルオラン
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-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) fluorane 3-di-n-pentylamino-7- (m-trifluoromethylanilino) fluorane 3-di-n-pentylamino-6-chloro -7-anilinofluorane 3-di-n-pentylamino-7- (p-chloroanilino) fluorane 3-pyrrolidino-6-methyl -7-anilinofluorane 3-piperidino-6-methyl-7-anilinofluorane
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
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-Toluidino) -6-methyl-7-anilinofluorane 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane 3- (N-ethyl-N-isoamylamino) -6-chloro-7-anilinofluorane 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane 3- (N-ethyl-N-isobutane) Ruamino) -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-oxa (Hexyl) -3-dipropylamino-6-methyl-7-anilinofluorane
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
2-Methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluorane 2-chloro-3-methyl-6- p- (p-phenylaminophenyl) aminoanilinofluoran 2-chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluoran 2-nitro-6-p- (p-diethylaminophenyl) aminoani Linofluorane 2-amino-6-p- (p-diethylaminophenyl) aminoanilinofluorane 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane 2-phenyl-6-methyl-6 -P- (p-phenylaminophenyl) aminoanilinofluorane 2-benzyl-6-p- (p-fe Ruaminophenyl) aminoanilinofluorane 2-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] -fluorane
＜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
<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 3,6-bis (diethylamino) Fluorane-γ- (4′-nitro) anilinolactam 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -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
本発明で用いられる電子受容性顕色剤としては、従来の感圧あるいは感熱記録紙の分野で公知のものはすべて使用可能であり、特に制限されるものではないが、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、 As the electron-accepting developer used in the present invention, those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and are not particularly limited. For example, activated clay, attapulgite Inorganic acidic substances such as colloidal silica and aluminum silicate, 4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 4,4′-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4′-dihydroxydiphenyl sulfone, 2,4′-dihydroxydiphenyl sulfone, 4-hydroxy-4′-isopropoxy Diphenylsulfone, 4-hydroxy-4'-n-propyl Poxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4′-methyldiphenylsulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4 ′ -Methylphenylsulfone, aminobenzenesulfonamide derivatives described in JP-A-8-59603, bis (4-hydroxyphenylthioethoxy) methane, 1,5-di (4-hydroxyphenylthio) -3-oxapentane, bis (P-hydroxyphenyl) butyl 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−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、およ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、単独または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ＮＫＫ−３９５、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。 1,3-bis [α-methyl-α- (4′-hydroxyphenyl) 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 cross-linking compounds described in International Publication WO97 / 16420, and the like described in International Publication WO02 / 081229 or JP2002-301873A Compounds, and thiourea compounds such as N, N′-di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, zinc bis [4- (n-octyloxycarbonylamino) salicylate] dihydrate, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- (p-to Rusulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid aromatic carboxylic acid, and zinc, magnesium, aluminum, calcium, titanium, manganese of these aromatic carboxylic acids , Salts with polyvalent metal salts such as tin and nickel, antipyrine complexes of zinc thiocyanate, and complex zinc salts of terephthalaldehyde acid with other aromatic carboxylic acids. 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 NKK-395 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としては、従来公知の増感剤を使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などの脂肪酸アマイド、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、単独または２種以上混合して使用してもよい。 As the sensitizer used in the heat-sensitive recording material of the present invention, a conventionally known sensitizer can be used. 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-me Tilphenoxymethyl) 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。
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。
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.
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、バインダーおよび目的に応じて各種の添加材料を加えて塗液とする。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。
本発明の感熱記録体はさらに、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。
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. The means for applying is not particularly limited, and can be applied in accordance with a well-known conventional technique. For example, various coaters such as an air knife coater, a rod blade coater, a vent blade coater, a bevel blade coater, a roll coater, and a curtain coater are provided. An off-machine coating machine or an 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 .
The heat-sensitive recording material of the present invention can be further provided with a backcoat layer on the surface opposite to the heat-sensitive recording layer of the support to correct the curl. 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.
以下に本発明の感熱記録体を実施例によって説明する。尚、説明中、部及び％はそれぞれ重量部及び重量％を示す。各種溶液、分散液、あるいは塗液を以下のように調製した。
［参考例１］
下記配合からなる配合物を攪拌分散して、下塗層塗液を調製した。
Ｕ液（下塗層塗液）
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
＜吸油量９０ｃｃ／１００ｇ＞） 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
カルボキシ変性ポリビニルアルコール
（クラレ社製商品名：ＫＬ−１１８＜重合度：約１７００、
鹸化度：９５〜９９モル％、酢酸ナトリウム：３％以下＞）１０％水溶液
３０部
ポリアミドエピクロロヒドリン樹脂
（星光ＰＭＣ社製商品名：ＷＳ４０２０、固形分２５％＜カチオン化度：２．７、分子量：２２０万、４級アミン＞） ４．０部
水 １６０部
The thermosensitive recording material of the present invention will be described below with reference to examples. In the description, parts and% indicate parts by weight and% by weight, respectively. Various solutions, dispersions, or coating solutions were prepared as follows.
[ Reference Example 1]
A composition comprising the following composition was stirred and dispersed to prepare an undercoat layer coating solution.
U solution (undercoat layer coating solution)
Baked kaolin (trade name: Ensilex 90, manufactured by Engelhard)
<Oil absorption amount 90 cc / 100 g>) 100 parts Styrene-butadiene copolymer latex (solid content 48%) 40 parts Carboxy-modified polyvinyl alcohol (trade name: KL-118 manufactured by Kuraray Co., Ltd .: degree of polymerization: about 1700,
Degree of saponification: 95-99 mol%, sodium acetate: 3% or less>) 10% aqueous solution
30 parts Polyamide epichlorohydrin resin (trade name: WS4020 manufactured by Seiko PMC Co., Ltd., solid content 25% <degree of cationization: 2.7, molecular weight: 2.2 million, quaternary amine>) 4.0 parts water 160 parts
次いで、下塗層塗液を支持体（６０ｇ／ｍ２の基紙）の片面に塗布した後、乾燥を行ない、塗布量１０ｇ／ｍ２の下塗層塗工紙を得た。
下記配合の顕色剤分散液（Ａ液）、ロイコ染料分散液（Ｂ液）、および増感剤分散液（Ｃ液）を、それぞれ別々にサンドグラインダーで平均粒子径０．５ミクロンになるまで湿式磨砕を行なった。
Ａ液（顕色剤分散液）
４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン ６．０部
ポリビニルアルコール１０％水溶液 １８．８部
水 １１．２部
Ｂ液（ロイコ染料分散液）
３−ジブチルアミノ−６−メチル−７−アニリノフルオラン（ＯＤＢ−２）
３．０部
ポリビニルアルコール１０％水溶液 ６．９部
水 ３．９部
Ｃ液（増感剤分散液）
シュウ酸ジベンジル ６．０部
ポリビニルアルコール１０％水溶液 １８．８部
水 １１．２部
Next, the undercoat layer coating solution was applied to one side of a support (60 g / m 2 base paper) and then dried to obtain an undercoat layer coated paper having a coating amount of 10 g / m 2 .
The developer dispersion liquid (A liquid), leuco dye dispersion liquid (B liquid), and sensitizer dispersion liquid (C liquid) having the following composition are each separately mixed with a sand grinder until the average particle diameter becomes 0.5 microns. Wet grinding was performed.
Liquid A (developer dispersion)
4-hydroxy-4'-isopropoxydiphenylsulfone 6.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts water 11.2 parts Liquid B (leuco dye dispersion)
3-Dibutylamino-6-methyl-7-anilinofluorane (ODB-2)
3.0 parts polyvinyl alcohol 10% aqueous solution 6.9 parts water 3.9 parts C liquid (sensitizer dispersion)
Dibenzyl oxalate 6.0 parts Polyvinyl alcohol 10% aqueous solution 18.8 parts Water 11.2 parts
次いで、下記の割合で分散液を混合して感熱記録層の塗液とした。
感熱記録層塗液
Ａ液（顕色剤分散液） ３６．０部
Ｂ液（ロイコ染料分散液） １３．８部
Ｃ液（増感剤分散液） ３６．０部
カオリンクレー（５０％分散液） １２．０部
完全ケン化型ポリビニルアルコール（クラレ社製商品名：ＰＶＡ−１１７）
１０％水溶液 １５部
グリオキザール４０％水溶液 １．５部
次いで、感熱記録層塗液を前記下塗層塗工紙の下塗層上に塗布量６．０ｇ／ｍ２となるように塗布した後、乾燥を行ない、このシートをスーパーカレンダーで平滑度が５００〜６００秒になるように処理して感熱記録体を得た。
Subsequently, the dispersion liquid was mixed at the following ratio to prepare a coating liquid for the heat-sensitive recording layer.
Thermal recording layer coating liquid A liquid (developer dispersion) 36.0 parts B liquid (leuco dye dispersion) 13.8 parts C liquid (sensitizer dispersion) 36.0 parts Kaolin clay (50% dispersion) 12.0 parts Completely saponified polyvinyl alcohol (trade name: PVA-117, manufactured by Kuraray Co., Ltd.)
10 parts aqueous solution 15 parts Glyoxal 40% aqueous solution 1.5 parts Next, after applying the thermosensitive recording layer coating liquid onto the undercoat layer of the undercoat layer-coated paper so as to have a coating amount of 6.0 g / m 2 , Drying was performed, and the sheet was processed with a super calendar so that the smoothness was 500 to 600 seconds to obtain a heat-sensitive recording material.
［参考例２］
参考例１のＵ液（下塗層塗液）に配合したカルボキシ変性ポリビニルアルコールを他のカルボキシ変性ポリビニルアルコール（クラレ社製商品名：ＫＬ−３１８＜重合度：約１７００、鹸化度：８５〜９０モル％、酢酸ナトリウム：３％以下＞）に変えた以外は参考例１と同様に感熱記録体を作製した。
［参考例３］
参考例１のＵ液（下塗層塗液）に配合したカルボキシ変性ポリビニルアルコールを他のカルボキシ変性ポリビニルアルコール（日本合成化学社製商品名：Ｔ３５０＜重合度：約１７００、鹸化度：９３〜９５モル％、酢酸ナトリウム：３％以下＞）に変えた以外は参考例１と同様に感熱記録体を作製した。
[ Reference Example 2 ]
The carboxy-modified polyvinyl alcohol blended in the U solution (undercoat layer coating solution) of Reference Example 1 was replaced with other carboxy-modified polyvinyl alcohol (trade name: KL-318 manufactured by Kuraray Co., Ltd .: degree of polymerization: about 1700, degree of saponification: 85-90. A thermosensitive recording material was prepared in the same manner as in Reference Example 1 except that mol% and sodium acetate: 3% or less were changed.
[ Reference Example 3]
Carboxy-modified polyvinyl alcohol blended in the U liquid (undercoat layer coating liquid) of Reference Example 1 was replaced with other carboxy-modified polyvinyl alcohol (trade name: T350 <polymerization degree: about 1700, saponification degree: 93 to 95 manufactured by Nippon Synthetic Chemical Co., Ltd.). A thermosensitive recording material was prepared in the same manner as in Reference Example 1 except that mol% and sodium acetate: 3% or less were changed.
［参考例４］
参考例１のＵ液（下塗層塗液）に配合したポリアミドエピクロロヒドリン樹脂４．０部をポリアミンエピクロロヒドリン樹脂（星光ＰＭＣ社製商品名：ＷＳ４０１０、固形分２０％＜カチオン化度：３．９、分子量：８０万、４級アミン＞）５．０部に変えた以外は参考例１と同様に感熱記録体を作製した。
［参考例５］
参考例１のＵ液（下塗層塗液）に配合したポリアミドエピクロロヒドリン樹脂４．０部を他のポリアミドエピクロロヒドリン樹脂（星光ＰＭＣ社製商品名：ＳＲＤ１５０、固形分５０％＜カチオン化度：６．７、分子量：４０万、４級アミン＞）２．０部に変えた以外は参考例１と同様に感熱記録体を作製した。
[ Reference Example 4]
4.0 parts of polyamide epichlorohydrin resin blended in the U liquid (undercoat layer coating liquid) of Reference Example 1 was added to polyamine epichlorohydrin resin (trade name: WS4010, manufactured by Seiko PMC Co., Ltd., solid content 20% <cationization). Degree: 3.9, molecular weight: 800,000, quaternary amine>) A heat-sensitive recording material was prepared in the same manner as in Reference Example 1 except that the amount was changed to 5.0 parts.
[ Reference Example 5]
4.0 parts of polyamide epichlorohydrin resin blended in the U liquid (undercoat layer coating liquid) of Reference Example 1 was replaced with another polyamide epichlorohydrin resin (trade name: SRD150, manufactured by Seiko PMC, solid content 50% < A heat-sensitive recording material was prepared in the same manner as in Reference Example 1 except that the degree of cationization was 6.7, the molecular weight was 400,000, and the quaternary amine>) 2.0 parts.
［参考例６］
参考例１のＵ液（下塗層塗液）に配合した焼成カオリン１００部をシリカ（水沢化学社製商品名：ミズカシルＰ−６０４＜吸油量：１３５ｃｃ／１００ｇ＞）１００部に変えた以外は参考例１と同様に感熱記録体を作製した。
［実施例１］
参考例１のＵ液（下塗層塗液）にメラミンホルムアルデヒド樹脂（住友化学社製商品名：スミレーズレジン６１３−ｓ、固形分６０％）１．６７部を加えた以外は参考例１と同様に感熱記録体を作製した。
[ Reference Example 6]
Except for changing 100 parts of calcined kaolin blended in the U liquid (undercoat layer coating liquid) of Reference Example 1 to 100 parts of silica (trade name: Mizukasil P-604 <oil absorption: 135 cc / 100 g>) manufactured by Mizusawa Chemical Co., Ltd. A heat-sensitive recording material was produced in the same manner as in Reference Example 1.
[Example 1 ]
Reference Example 1 except that 1.67 parts of melamine formaldehyde resin (trade name: Sumire Resin 613-s, solid content 60%) manufactured by Sumitomo Chemical Co., Ltd. was added to the U liquid (undercoat layer coating liquid) of Reference Example 1. Similarly, a heat-sensitive recording material was produced.
［実施例２］
参考例１のＵ液（下塗層塗液）に変性ポリアミン系樹脂（住友化学社製商品名：スミレーズレジンＳＰＩ−１０２Ａ、固形分４５％）２．２２部を加えた以外は参考例１と同様に感熱記録体を作製した。
［実施例３］
参考例１のＵ液（下塗層塗液）に変性ポリアミド系樹脂（住友化学社製商品名：スミレーズレジンＳＰＩ−１０６Ｎ、固形分６０％）１．６７部を加えた以外は参考例１と同様に感熱記録体を作製した。
[Example 2 ]
Reference Example 1 except that 2.22 parts of a modified polyamine resin (trade name: Sumirez Resin SPI-102A, solid content 45%) manufactured by Sumitomo Chemical Co., Ltd. was added to the U liquid (undercoat layer coating liquid) of Reference Example 1. A thermosensitive recording material was produced in the same manner as described above.
[Example 3 ]
Reference Example 1 except that 1.67 parts of a modified polyamide resin (trade name: Sumire Resin SPI-106N, solid content 60%) manufactured by Sumitomo Chemical Co., Ltd. was added to the U liquid (undercoat layer coating liquid) of Reference Example 1. A thermosensitive recording material was produced in the same manner as described above.
［実施例４］
参考例６のＵ液（下塗層塗液）に変性ポリアミン系樹脂（住友化学社製商品名：スミレーズレジンＳＰＩ−１０２Ａ、固形分４５％）２．２２部を加えた以外は参考例６と同様に感熱記録体を作製した。
［参考例７］
参考例１のＵ液（下塗層塗液）に配合した焼成カオリン１００部を焼成カオリン９５部と炭酸カルシウム（白石工業社製商品名：ブリリアント１５＜吸油量：４４ｃｃ／１００ｇ＞）５部に変えた以外は参考例１と同様に感熱記録体を作製した。
[Example 4 ]
Reference Example 6 except that 2.22 parts of a modified polyamine-based resin (trade name: Sumirez Resin SPI-102A, solid content 45%) manufactured by Sumitomo Chemical Co., Ltd. was added to the U liquid (undercoat layer coating liquid) of Reference Example 6. A thermosensitive recording material was produced in the same manner as described above.
[ Reference Example 7 ]
100 parts of calcined kaolin blended in the U solution (undercoat layer coating liquid) of Reference Example 1 into 95 parts of calcined kaolin and 5 parts of calcium carbonate (trade name: Brilliant 15 <oil absorption: 44 cc / 100 g> manufactured by Shiroishi Kogyo Co., Ltd.) A heat-sensitive recording material was produced in the same manner as in Reference Example 1 except that it was changed.
［参考例８］
参考例１のＵ液（下塗層塗液）に配合した焼成カオリン１００部を焼成カオリン８０部と炭酸カルシウム（白石工業社製商品名：ブリリアント１５＜吸油量：４４ｃｃ／１００ｇ＞）２０部に変えた以外は参考例１と同様に感熱記録体を作製した。
［参考例９］
参考例１のＵ液（下塗層塗液）に配合した焼成カオリン１００部を焼成カオリン６０部と炭酸カルシウム（白石工業社製商品名：ブリリアント１５＜吸油量：４４ｃｃ／１００ｇ＞）４０部に変えた以外は参考例１と同様に感熱記録体を作製した。
[ Reference Example 8 ]
100 parts of calcined kaolin blended in the U liquid (undercoat layer coating liquid) of Reference Example 1 into 80 parts of calcined kaolin and 20 parts of calcium carbonate (trade name: Brilliant 15 <oil absorption: 44 cc / 100 g> manufactured by Shiroishi Kogyo Co., Ltd.) A heat-sensitive recording material was produced in the same manner as in Reference Example 1 except that it was changed.
[ Reference Example 9 ]
100 parts of calcined kaolin blended with the U liquid (undercoat layer coating liquid) of Reference Example 1 into 60 parts of calcined kaolin and 40 parts of calcium carbonate (trade name: Brilliant 15 <oil absorption: 44 cc / 100 g> manufactured by Shiroishi Kogyo Co., Ltd.) A heat-sensitive recording material was produced in the same manner as in Reference Example 1 except that it was changed.
［比較例１］
実施例１のＵ液（下塗層塗液）に配合したカルボキシ変性ポリビニルアルコールを完全鹸化ポリビニルアルコール（クラレ社製商品名：ＰＶＡ１１７＜重合度：約１７００、鹸化度：９８〜９９モル％、酢酸ナトリウム：１％以下＞）に変えた以外は実施例１と同様に感熱記録体を作製した。
［比較例２］
実施例１のＵ液（下塗層塗液）に配合したカルボキシ変性ポリビニルアルコールを部分鹸化ポリビニルアルコール（クラレ社製商品名：ＰＶＡ２１７＜重合度：約１７００、鹸化度：８７〜８９モル％、酢酸ナトリウム：１％以下＞）に変えた以外は実施例１と同様に感熱記録体を作製した。
[Comparative Example 1]
The carboxy-modified polyvinyl alcohol blended in the U solution (undercoat layer coating solution) of Example 1 was completely saponified polyvinyl alcohol (trade name: PVA117 manufactured by Kuraray Co., Ltd .: polymerization degree: about 1700, saponification degree: 98 to 99 mol%, acetic acid A heat-sensitive recording material was produced in the same manner as in Example 1 except that sodium was changed to 1% or less>).
[Comparative Example 2]
Carboxy-modified polyvinyl alcohol blended in the U liquid (undercoat layer coating liquid) of Example 1 was partially saponified polyvinyl alcohol (trade name: PVA217 manufactured by Kuraray Co., Ltd .: degree of polymerization: about 1700, degree of saponification: 87 to 89 mol%, acetic acid A heat-sensitive recording material was produced in the same manner as in Example 1 except that sodium was changed to 1% or less>).
［比較例３］
実施例１のＵ液（下塗層塗液）に配合したポリアミドエピクロロヒドリン樹脂を配合しなかった以外は、実施例１と同様に感熱記録体を作製した。
［比較例４］
実施例１のＵ液（下塗層塗液）に配合したポリアミドエピクロロヒドリン樹脂４．０部をグリオキザール４０％水溶液２．５部に変えた以外は実施例１と同様に感熱記録体を作製した。
[Comparative Example 3]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that the polyamide epichlorohydrin resin blended in the U solution (undercoat layer coating solution) of Example 1 was not blended.
[Comparative Example 4]
A thermal recording medium was prepared in the same manner as in Example 1 except that 4.0 parts of the polyamide epichlorohydrin resin blended in the U liquid (undercoat layer coating liquid) of Example 1 was changed to 2.5 parts of a 40% aqueous solution of glyoxal. Produced.
［比較例５］
実施例７のＵ液（下塗層塗液）に配合したポリアミドエピクロロヒドリン樹脂４．０部をグリオキザール４０％水溶液２．５部に変えた以外は実施例７と同様に感熱記録体を作製した。
［比較例６］
実施例８のＵ液（下塗層塗液）に配合したポリアミドエピクロロヒドリン樹脂４．０部をグリオキザール４０％水溶液２．５部に変えた以外は実施例８と同様に感熱記録体を作製した。
[Comparative Example 5]
A thermal recording medium was prepared in the same manner as in Example 7 except that 4.0 parts of the polyamide epichlorohydrin resin blended in the U liquid (undercoat layer coating liquid) of Example 7 was changed to 2.5 parts of a 40% aqueous solution of glyoxal. Produced.
[Comparative Example 6]
A thermosensitive recording medium was prepared in the same manner as in Example 8 except that 4.0 parts of the polyamide epichlorohydrin resin blended in the U liquid (undercoat layer coating liquid) of Example 8 was changed to 2.5 parts of a 40% aqueous solution of glyoxal. Produced.
＜下塗層表面性評価＞
ベック式平滑度計で測定し評価した。
＜記録感度評価＞
作製した感熱記録体について、ＭＡＲＫＰＯＩＮＴ社製感熱プリンター（ＲＯＨＭ社製サーマルヘッド、ＫＭ２００４‐Ａ３を装着）を用い印加エネルギー０．０９６ｍＪ／ｄｏｔで印字した。記録部の記録濃度は、マクベス濃度計（ＲＤ−９１４、アンバーフィルター使用）で測定し評価した。
<Evaluation of surface properties of undercoat layer>
It was measured and evaluated with a Beck type smoothness meter.
<Recording sensitivity evaluation>
The produced thermal recording material was printed at a applied energy of 0.096 mJ / dot using a thermal printer manufactured by MARKPOINT (thermal head manufactured by ROHM, equipped with KM2004-A3). The recording density of the recording part was measured and evaluated with a Macbeth densitometer (RD-914, using an amber filter).
＜画質評価＞
作製した感熱記録体について、ＭＡＲＫＰＯＩＮＴ社製感熱プリンター（ＲＯＨＭ社製サーマルヘッド、ＫＭ２００４‐Ａ３を装着）を用い印加エネルギー０．０９６ｍＪ／ｄｏｔで印字したベタ印字部を目視で評価した。
◎：白抜け部分が観察されない
○：白抜け部分が僅かに観察されるが実用上問題ない
△：白抜け部分がやや多く観察されるが、実用可能である
×：白抜け部分が非常に多く、実用不可である
＜耐水性評価＞
記録感度評価で得られた記録後の感熱記録体の記録面に水を５０μｌ垂らし、記録面を指で強くこすり耐水性の程度の評価を行なった。評価基準については下記に示す。
◎：ぬるぬる感が全くなく、塗工層の剥離もない
○：僅かなぬるぬる感はあるが、塗工層の剥離がない
△：ぬるぬる感があり、若干の塗工層剥離が見受けられた
×：塗工層が溶け出し、かつ塗工層が剥がれたため記録部の判定が困難
<Image quality evaluation>
About the produced thermal recording body, the solid printing part printed by applied energy 0.096mJ / dot was visually evaluated using the thermal printer made from a MARKPOINT company (The thermal head made from ROHM, equipped with KM2004-A3).
◎: No white portion is observed ○: White portion is slightly observed but there is no problem in practical use △: Some white portions are observed, but practical use ×: There are many white portions <Practice of water resistance>
50 μl of water was dropped on the recording surface of the heat-sensitive recording material after recording obtained by the recording sensitivity evaluation, and the recording surface was strongly rubbed with a finger to evaluate the degree of water resistance. The evaluation criteria are shown below.
◎: No slimy feeling, no peeling of coating layer ○: There is a slight slimy feeling, but there is no peeling of coating layer △: There is a slimy feeling and some peeling of coating layer was observed × : It is difficult to judge the recording part because the coating layer has melted and the coating layer has been peeled off.
＜印字走行性評価＞
（１）ヘッドカス試験
大倉電機社製のＴＨ−ＰＭＤ（感熱記録紙印字試験機、京セラ社製サーマルヘッドを装着）を使用し、作製した感熱記録体に印加エネルギー０．４１ｍＪ／ｄｏｔで印字を行なった際の、ヘッドカス付着の有無について次の基準で評価した。
◎：ヘッドカスの付着が全く見られない
○：ヘッドカスの付着が僅かに見られるが、印字障害は発生しない
△：ヘッドカスの付着が多く見られるが、印字障害は発生しない
×：ヘッドカスの付着が顕著に見られ、印字障害が発生した
（２）スティック試験
大倉電機社製のＴＨ−ＰＭＤ（感熱記録紙印字試験機、京セラ社製サーマルヘッドを装着）を使用し、作製した感熱記録体に印加エネルギー０．４１ｍＪ／ｄｏｔ、−１０℃の環境下で印字を行なった際の、スティックの具合および記録時の騒音について次の基準で評価した。
◎：白飛びの発生がなく、騒音もほとんどない
○：白飛びの発生はないが、僅かに騒音がある
△：若干の白飛びが発生し、騒音も大きい
×：白飛びが頻発し、騒音も大きい
<Print running evaluation>
(1) Head-cass test Using TH-PMD (equipped with thermal recording paper printing tester, Kyocera thermal head) manufactured by Okura Electric Co., Ltd., printing was performed on the produced thermal recording medium with an applied energy of 0.41 mJ / dot. In this case, the presence or absence of head residue was evaluated according to the following criteria.
◎: No adhesion of head residue is observed. ○: Adhesion of head residue is slightly observed, but printing failure does not occur. Δ: Adhesion of head residue is observed frequently, but printing failure does not occur. (2) Stick test Energy applied to the thermal recording medium produced using TH-PMD (equipped with thermal recording paper printing tester, Kyocera thermal head) manufactured by Okura Electric Co., Ltd. The condition of stick and noise during recording were evaluated according to the following criteria when printing was performed in an environment of 0.41 mJ / dot and −10 ° C.
◎: No whiteout occurs and almost no noise ○: No whiteout occurs but slightly noise △: Some whiteout occurs and noise is high ×: Whiteout occurs frequently and noise Is also big
Claims (3)
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| JP2005021172A JP4459074B2 (en) | 2005-01-28 | 2005-01-28 | Thermal recording material |
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| JP2005021172A JP4459074B2 (en) | 2005-01-28 | 2005-01-28 | Thermal recording material |
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| JP4459074B2 true JP4459074B2 (en) | 2010-04-28 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20090128551A (en) | 2007-05-10 | 2009-12-15 | 닛폰세이시가부시키가이샤 | Heat-sensitive recording body |
| EP2181853B1 (en) | 2007-08-21 | 2015-09-23 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
| KR101128212B1 (en) | 2007-08-29 | 2012-03-22 | 닛폰세이시가부시키가이샤 | Thermosensitive recording medium |
| KR101239106B1 (en) | 2009-03-24 | 2013-03-06 | 닛폰세이시가부시키가이샤 | Heat-sensitive recording material |
| KR101367871B1 (en) | 2009-06-05 | 2014-02-27 | 닛폰세이시가부시키가이샤 | Heat-sensitive recording body |
| US8871678B2 (en) | 2010-03-15 | 2014-10-28 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
| JP2017056726A (en) * | 2015-09-16 | 2017-03-23 | 日本製紙株式会社 | Thermosensitive recording medium |
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