JP7373699B1 - Pressure-sensitive copying paper containing dextrin in the color developer layer - Google Patents
Pressure-sensitive copying paper containing dextrin in the color developer layer Download PDFInfo
- Publication number
- JP7373699B1 JP7373699B1 JP2023547239A JP2023547239A JP7373699B1 JP 7373699 B1 JP7373699 B1 JP 7373699B1 JP 2023547239 A JP2023547239 A JP 2023547239A JP 2023547239 A JP2023547239 A JP 2023547239A JP 7373699 B1 JP7373699 B1 JP 7373699B1
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- JP
- Japan
- Prior art keywords
- dextrin
- pressure
- developer layer
- weight
- sensitive copying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001353 Dextrin Polymers 0.000 title claims abstract description 88
- 239000004375 Dextrin Substances 0.000 title claims abstract description 88
- 235000019425 dextrin Nutrition 0.000 title claims abstract description 88
- 229920002245 Dextrose equivalent Polymers 0.000 claims abstract description 29
- 239000002002 slurry Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000010025 steaming Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 238000010411 cooking Methods 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 34
- 238000010586 diagram Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 65
- 239000003094 microcapsule Substances 0.000 description 29
- 229920002472 Starch Polymers 0.000 description 21
- 239000008107 starch Substances 0.000 description 21
- 235000019698 starch Nutrition 0.000 description 21
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 20
- 239000000975 dye Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- -1 bis(p-hydroxyphenyl) Methyl Chemical group 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 239000002245 particle Substances 0.000 description 6
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- 239000011347 resin Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 239000002775 capsule Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- 239000004368 Modified starch Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
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- 229940099112 cornstarch Drugs 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
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- 239000011247 coating layer Substances 0.000 description 3
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- 150000002148 esters Chemical class 0.000 description 3
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
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- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 239000000654 additive Substances 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- XDIYNQZUNSSENW-UUBOPVPUSA-N (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O XDIYNQZUNSSENW-UUBOPVPUSA-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
- QTKIQLNGOKOPOE-UHFFFAOYSA-N 1,1'-biphenyl;propane Chemical group CCC.C1=CC=CC=C1C1=CC=CC=C1 QTKIQLNGOKOPOE-UHFFFAOYSA-N 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- GNPWYHFXSMINJQ-UHFFFAOYSA-N 1,2-dimethyl-3-(1-phenylethyl)benzene Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CC=CC=C1 GNPWYHFXSMINJQ-UHFFFAOYSA-N 0.000 description 1
- 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 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
- XECKTNQAABHDFZ-UHFFFAOYSA-N 1-(2-methylpropyl)-2-phenylbenzene Chemical group CC(C)CC1=CC=CC=C1C1=CC=CC=C1 XECKTNQAABHDFZ-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- CEGHCPGGKKWOKF-UHFFFAOYSA-N 2'-anilino-6'-[cyclohexyl(methyl)amino]-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C=C(C2(C3=CC=CC=C3C(=O)O2)C2=CC(NC=3C=CC=CC=3)=C(C)C=C2O2)C2=CC=1N(C)C1CCCCC1 CEGHCPGGKKWOKF-UHFFFAOYSA-N 0.000 description 1
- HUSIBQLZEMMTCQ-UHFFFAOYSA-N 2'-anilino-6'-[ethyl(3-methylbutyl)amino]-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CCC(C)C)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 HUSIBQLZEMMTCQ-UHFFFAOYSA-N 0.000 description 1
- HFFXLYHRNRKAPM-UHFFFAOYSA-N 2,4,5-trichloro-n-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C(=CC(Cl)=C(Cl)C=2)Cl)=N1 HFFXLYHRNRKAPM-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
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 description 1
- 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
- BFVIXPJSXHGXJK-UHFFFAOYSA-N 2-hydroxy-4-[3-(4-methylphenyl)sulfonylpropoxy]benzoic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)CCCOC1=CC=C(C(O)=O)C(O)=C1 BFVIXPJSXHGXJK-UHFFFAOYSA-N 0.000 description 1
- SVEQDNXIMBZUMH-UHFFFAOYSA-N 2-hydroxy-5-[2-[4-[2-(4-methoxyphenoxy)ethoxy]phenyl]propan-2-yl]benzoic acid Chemical compound C1=CC(OC)=CC=C1OCCOC1=CC=C(C(C)(C)C=2C=C(C(O)=CC=2)C(O)=O)C=C1 SVEQDNXIMBZUMH-UHFFFAOYSA-N 0.000 description 1
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- AKRLRQSMONHOTE-UHFFFAOYSA-N 3-[4-(diethylamino)-2-ethoxyphenyl]-3-(1-ethyl-2-methylindol-3-yl)-2-benzofuran-1-one Chemical compound CCOC1=CC(N(CC)CC)=CC=C1C1(C=2C3=CC=CC=C3N(CC)C=2C)C2=CC=CC=C2C(=O)O1 AKRLRQSMONHOTE-UHFFFAOYSA-N 0.000 description 1
- HOUWRQXIBSGOHF-UHFFFAOYSA-N 3-[4-(diethylamino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C1(C=2C3=CC=CC=C3N(CC)C=2C)C2=CC=CC=C2C(=O)O1 HOUWRQXIBSGOHF-UHFFFAOYSA-N 0.000 description 1
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002774 Maltodextrin Polymers 0.000 description 1
- 239000005913 Maltodextrin Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
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- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- ABBBVRIKCGBEMS-UHFFFAOYSA-N [7-(dimethylamino)-10H-phenothiazin-1-yl]-[3-(dimethylamino)phenyl]methanone Chemical compound CN(C=1C=C(C(=O)C2=CC=CC=3SC4=CC(=CC=C4NC23)N(C)C)C=CC1)C ABBBVRIKCGBEMS-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 102000004139 alpha-Amylases Human genes 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 description 1
- 229940024171 alpha-amylase Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical class CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- BKRRPNHAJPONSH-UHFFFAOYSA-N carbazole Chemical compound C1=CC=C2[C]3C=CC=CC3=NC2=C1 BKRRPNHAJPONSH-UHFFFAOYSA-N 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical class NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- ULNRRNBMNIIOJK-UHFFFAOYSA-N isocyanatourea Chemical compound NC(=O)NN=C=O ULNRRNBMNIIOJK-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229940035034 maltodextrin Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 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
- 238000007645 offset printing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002223 polystyrene 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229920003179 starch-based polymer Polymers 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
Abstract
発色性に優れ、高速印刷時に印刷強度の強い感圧複写紙を提供する。支持体上に顕色剤層を設けた感圧複写紙であって、該顕色剤層がデキストリンを含有し、該デキストリンの分子量が１５０ｋ～２００ｋであり、デキストロース当量（ＤＥ）が４．０～１５．０である感圧複写紙である。また、このデキストリンのＲＶＡ粘度は８５０～１２００ｍＰａ・ｓであることが好ましい。【選択図】 なしTo provide pressure-sensitive copying paper with excellent color development and strong printing strength during high-speed printing. A pressure-sensitive copying paper having a color developer layer provided on a support, the developer layer containing dextrin, the dextrin having a molecular weight of 150k to 200k, and a dextrose equivalent (DE) of 4.0. ~15.0 pressure sensitive copying paper. Further, the RVA viscosity of this dextrin is preferably 850 to 1200 mPa·s. [Selection diagram] None
Description
この発明は、高速印刷時に印刷強度の強い感圧複写紙に関する。 The present invention relates to pressure-sensitive copying paper that has high printing strength during high-speed printing.
感圧複写紙は、支持体上の片面に、無色または淡色の電子供与性ロイコ染料（以下、「ロイコ染料」ともいう。）を溶解または分散状態で含有する疎水性液体（以下、「カプセルオイル」ともいう。）を内包したマイクロカプセルを含む層を設けた「上用紙」、ロイコ染料と接触して発色するフェノール性化合物等の電子受容性顕色剤（以下、「顕色剤」ともいう。）を含む層を設けた「下用紙」、支持体の片面に前記マイクロカプセルを含む層、他方の面に前記顕色剤を含む層を設けた「中用紙」を適宜組み合わせたものや、支持体の片面に前記マイクロカプセルを含む層、他方の面に前記顕色剤を含む層を設けた「中用紙」を適宜組み合わせたものがある。
これらの感圧複写紙は、上用紙もしくは中用紙の前記マイクロカプセルを含む層（以下、「マイクロカプセル層」ということがある。）と、下用紙もしくは中用紙の前記顕色剤を含む層（以下、「顕色剤層」ということがある。）とが接するように組合わされて、上用紙の非塗工面（マイクロカプセル層を設けていない面）もしくは中用紙の顕色剤層面から筆圧、プリンターなどで加圧されると、マイクロカプセル層中のマイクロカプセルが破壊され、ロイコ染料を含有するカプセルオイルが下用紙もしくは中用紙の顕色剤層面に移行する。その結果、ロイコ染料と顕色剤が反応して、発色する。
また、支持体の同一面にマイクロカプセル層と顕色剤層を積層、又は同一層に前記マイクロカプセルと前記顕色剤を混在させた「セルフコンティンド紙」などがある。セルフコンティンド紙においては、前記マイクロカプセルが破壊されると、支持体の同一面に前記マイクロカプセル層と前記顕色剤層を積層した場合は前記顕色剤層で、同一層に前記マイクロカプセルと前記顕色剤を混在させた場合は同一層で、それぞれロイコ染料と顕色剤が反応して、発色する。
そのため、発色能力、耐湿性、印刷強度のバランスなどを改善するために、顕色剤層にバインダー（または接着剤）としてデキストリンを含有する感圧複写紙が開示されている（特許文献１～３等）。Pressure-sensitive copying paper uses a hydrophobic liquid (hereinafter referred to as ``capsule oil'') containing a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as ``leuco dye'') in a dissolved or dispersed state on one side of the support. ``upper paper'' with a layer containing microcapsules encapsulating leuco dyes, electron-accepting color developers such as phenolic compounds that develop color upon contact with leuco dyes (hereinafter also referred to as ``color developers''). ), and an "inner paper" having a layer containing the microcapsules on one side of the support and a layer containing the color developer on the other side, as appropriate. There are suitable combinations of "inside paper" in which a layer containing the microcapsules is provided on one side of a support, and a layer containing the color developer is provided on the other side.
These pressure-sensitive copying papers consist of a layer containing the above-mentioned microcapsules (hereinafter sometimes referred to as "microcapsule layer") on the top paper or the middle paper, and a layer containing the color developer on the bottom paper or the middle paper (hereinafter sometimes referred to as the "microcapsule layer"). (Hereinafter, it may be referred to as the "color developer layer." When pressurized by a printer or the like, the microcapsules in the microcapsule layer are destroyed, and the capsule oil containing the leuco dye is transferred to the developer layer surface of the lower paper or inner paper. As a result, the leuco dye and the color developer react to develop color.
Further, there is a "self-contained paper" in which a microcapsule layer and a color developer layer are laminated on the same side of a support, or in which the microcapsules and the color developer are mixed on the same layer. In self-containing paper, when the microcapsules are destroyed, when the microcapsule layer and the color developer layer are laminated on the same side of the support, the color developer layer is the same layer as the microcapsules. When the color developer and the color developer are mixed, the leuco dye and the color developer react with each other in the same layer to develop color.
Therefore, pressure-sensitive copying papers containing dextrin as a binder (or adhesive) in the color developer layer have been disclosed in order to improve the balance of color development ability, moisture resistance, printing strength, etc. (Patent Documents 1 to 3) etc).
また、感圧複写紙は、多数枚複写が可能であるという機能を有することから各種帳票に適用され、通常オフセット印刷、インクジェット記録による印刷方式等によってフォーム印刷し用いられているが、下用紙あるいは中用紙の顕色剤層を設けた面に印刷が行われる場合、インキロール、ブランケット、あるいは印刷版に顕色剤層の一部が欠落、堆積し、色抜けや印刷汚れなどの問題が発生することがある。 In addition, pressure-sensitive copy paper has the ability to make multiple copies, so it is applied to various forms, and is usually used to print forms using offset printing, inkjet recording, etc. When printing is performed on the side of the inner paper that has a developer layer, part of the developer layer may be missing or deposited on the ink roll, blanket, or printing plate, causing problems such as color loss and printing stains. There are things to do.
従来の技術の感圧複写紙は、発色能力等が良好ではあっても、高速印刷時の印刷強度が充分ではなかった（例えば、後述の比較例１～４を参照されたい。）。従って、本願発明は、発色性に優れ、高速印刷時に印刷強度の強い感圧複写紙を提供することを目的とする。
ここで、高速印字とは、感圧紙の印刷機の印刷速度が３００ｍ／分以上であることをいう。また、印刷強度とは、ベタ印刷部の剥け（インキのタック（粘着性）により顕色剤層が引き剥がされること）に対する耐性をいう。Although the pressure-sensitive copying paper of the prior art has good color development ability, the printing strength during high-speed printing is not sufficient (for example, see Comparative Examples 1 to 4 described below). Therefore, an object of the present invention is to provide a pressure-sensitive copying paper that has excellent color development and strong printing strength during high-speed printing.
Here, high-speed printing means that the printing speed of a pressure-sensitive paper printing machine is 300 m/min or more. In addition, printing strength refers to the resistance to peeling of the solid printed area (the developer layer is peeled off due to the tack (adhesiveness) of the ink).
本発明者らは鋭意検討の結果、支持体上に顕色剤層を設けた感圧複写紙において、この顕色剤層に特定の分子量と特定のデキストロース当量（ＤＥ）を有するデキストリンを用いることにより、発色性に優れ、高速印刷時に印刷強度の強い感圧複写紙が得られることを見出し、本願発明を完成させるに至った。
即ち、本願発明は、支持体上に顕色剤層を設けた感圧複写紙であって、該顕色剤層がデキストリンを含有し、該デキストリンの分子量が１５０ｋ～２００ｋであり、デキストロース当量（ＤＥ）が４．０～１０．０である、感圧複写紙である。
As a result of extensive studies, the present inventors have found that in pressure-sensitive copying paper in which a color developer layer is provided on a support, a dextrin having a specific molecular weight and a specific dextrose equivalent (DE) is used in this developer layer. It was discovered that pressure-sensitive copying paper with excellent color development and strong printing strength during high-speed printing can be obtained by this method, and the present invention was completed.
That is, the present invention provides a pressure-sensitive copying paper in which a color developer layer is provided on a support, and the color developer layer contains dextrin, the molecular weight of the dextrin is 150k to 200k, and the dextrose equivalent ( It is a pressure-sensitive copying paper with a DE) of 4.0 to 10.0 .
本発明によれば、発色性に優れ、高速印刷時に印刷強度の強い感圧複写紙を得ることができる。 According to the present invention, it is possible to obtain pressure-sensitive copying paper that has excellent color development and strong printing strength during high-speed printing.
一般に、印刷時における顕色剤層の欠落の発生は、顕色剤層の強度が弱いことが大きな原因であると考えられるが、顕色剤層の強度が強すぎると、ロイコ染料及びカプセルオイルの顕色剤層への浸透が阻害され、発色能力が低下する。
これに対し、本願発明は、顕色剤層に特定の分子量と特定のデキストロース当量（ＤＥ）を有するデキストリンを含有させることにより、発色能力と印刷強度とのバランスが良好となることを見出しなされたものである。
本発明において顕色剤層とは、顕色剤を含有する層であり、マイクロカプセル層とはマイクロカプセルを含有する層をいう。例えば、本発明に係る感圧複写紙がセルフコンティンド紙であって、マイクロカプセルと顕色剤を同一層に混在させている場合、マイクロカプセルと顕色剤の両方が含まれる層は、顕色剤層でありマイクロカプセル層ということになる。In general, the main cause of the occurrence of missing color developer layers during printing is thought to be that the strength of the color developer layer is weak, but if the strength of the color developer layer is too strong, leuco dyes and capsule oil Penetration of the color developer into the color developer layer is inhibited, resulting in a decrease in color development ability.
On the other hand, the present invention has discovered that by containing a dextrin having a specific molecular weight and a specific dextrose equivalent (DE) in the color developer layer, a good balance between coloring ability and printing strength can be achieved. It is something.
In the present invention, the color developer layer is a layer containing a color developer, and the microcapsule layer is a layer containing microcapsules. For example, when the pressure-sensitive copying paper according to the present invention is a self-containing paper and microcapsules and a color developer are mixed in the same layer, the layer containing both the microcapsules and the color developer is This is a colorant layer and a microcapsule layer.
デキストリンは、澱粉を加水分解して得られる澱粉系高分子であり、α-グルコースがグリコシド結合によって重合しており、糊精（こせい）とも呼ばれる。デキストリンは、低分子化の度合いによってグレード分けされており、その指標にデキストロース当量（ＤＥ）が用いられる。ＤＥはデキストロース（ブドウ糖）の還元力を１００とした場合の相対的な尺度である。ＤＥが０に近いほど澱粉に近い特性であり、１００に近いほど澱粉の加水分解が進み、平均分子量が小さくなり、ブドウ糖に似た特性となる。一般的にデキストリンまたはマルトデキストリンと呼ばれる範囲はＤＥが２０以下であり、２０以上を粉あめと呼ぶ。ＤＥが大きいと、水への分散時に蒸煮が必要無く、容易に水に分散する冷水可溶性のデキストリンとなる。本発明で用いるデキストリンのＤＥは４．０～１５．０であり、好ましくは１０以下であり、また、好ましくは５．０以上、より好ましくは６．０以上である。ＤＥ値がこの範囲であることで、高速印刷時に印刷強度の強い感圧複写紙を得ることができる。本発明において、デキストリンのＤＥは、フェーリング・レーマン・ショール法（例えば、澱粉糖関連工業分析法（食品化学新聞社）を参照されたい。）によって算出することができる。 Dextrin is a starch-based polymer obtained by hydrolyzing starch, in which α-glucose is polymerized through glycosidic bonds, and is also called starch. Dextrins are graded according to the degree of molecular weight reduction, and dextrose equivalent (DE) is used as an indicator. DE is a relative measure when the reducing power of dextrose (glucose) is set as 100. The closer the DE is to 0, the closer the properties are to starch, and the closer the DE is to 100, the more the starch is hydrolyzed, the lower the average molecular weight, and the properties are similar to glucose. The DE range generally referred to as dextrin or maltodextrin is 20 or less, and the DE of 20 or more is called powdered candy. When the DE is high, no boiling is required during dispersion in water, resulting in a cold water soluble dextrin that is easily dispersed in water. The DE of the dextrin used in the present invention is 4.0 to 15.0, preferably 10 or less, and preferably 5.0 or more, more preferably 6.0 or more. When the DE value is within this range, it is possible to obtain pressure-sensitive copying paper with strong printing strength during high-speed printing. In the present invention, the DE of dextrin can be calculated by the Fehling-Lehmann-Shaul method (see, for example, Starch Sugar Related Industrial Analysis Method (Food Chemical Newspaper)).
デキストリンは澱粉を酸の存在下又は非存在下で加熱処理を行い、加水分解と再結合により得られる。酸触媒の非存在下は加水分解が起こり難く、焙焼デキストリンを得るのは難しいので、本発明で用いる焙焼デキストリンを得るためには、酸触媒を用いたほうが好ましい。酸触媒を使用する際は鉱酸であれば何でもよく制限されない。酸触媒の添加量が少なすぎるとデキストリン化反応が進み難いので、塩酸であれば、澱粉絶乾重量１ｋｇに対して０．００８ｍｏｌ以上添加するのが望ましい。また、加熱温度は低すぎるとデキストリン化反応が進み難いので１１０℃以上で加熱するのが望ましいが、温度が高すぎると褐色に着色してしまうので着色しない温度、特に１５０℃以下で加熱するのが好ましい。加熱時間は酸触媒量と加熱温度に左右されるが、塩酸の添加量が澱粉絶乾重量１ｋｇに対して０．００５ｍｏｌ以上、１１０℃以上であれば９０分以内に加熱を停止するのが好ましい。 Dextrin is obtained by heating starch in the presence or absence of an acid, hydrolyzing it, and recombining it. Since hydrolysis is difficult to occur in the absence of an acid catalyst and it is difficult to obtain a torrefied dextrin, it is preferable to use an acid catalyst to obtain the torrefied dextrin used in the present invention. When using an acid catalyst, there are no restrictions as long as it is a mineral acid. If the amount of acid catalyst added is too small, the dextrinization reaction will be difficult to proceed, so if it is hydrochloric acid, it is desirable to add 0.008 mol or more per 1 kg of starch bone dry weight. Also, if the heating temperature is too low, the dextrinization reaction will not proceed easily, so it is desirable to heat at 110°C or higher, but if the temperature is too high, the color will turn brown, so it is best to heat at a temperature that does not cause coloring, especially 150°C or lower. is preferred. Heating time depends on the amount of acid catalyst and heating temperature, but if the amount of hydrochloric acid added is 0.005 mol or more per 1 kg of starch bone-dry weight and 110°C or higher, it is preferable to stop heating within 90 minutes. .
通常の澱粉は分子量が大きいが、デキストリンは澱粉の加水分解の工程で生ずる中間生成物であり、澱粉と比較して分子量が小さく、従来はオリゴマー（グルコースが数個～数十個程度が結合したもの）程度の分子量が一般的であった。本発明に用いるデキストリンの分子量は、１５０ｋ～２００ｋであることが好ましい。分子量が数千になると、蒸煮処理の必要がない冷水可溶性のデキストリンとなる。分子量が低く１０ｋ以下のデキストリンが多く存在していると、塗工層は密になるが、強度への寄与が低く、印刷時のパイリング等の問題が生じやすい。一方で、分子量が２５０ｋより高くなると、デキストリンを水に分散した際の粘度が上がり、塗料のハンドリングが困難となる。 Ordinary starch has a large molecular weight, but dextrin is an intermediate product produced in the process of starch hydrolysis, and has a smaller molecular weight than starch. Molecular weights of about 100% were common. The molecular weight of the dextrin used in the present invention is preferably 150k to 200k. When the molecular weight reaches several thousand, the dextrin becomes cold water soluble and does not require steaming. If a large amount of dextrin with a low molecular weight of 10k or less is present, the coating layer will be dense, but its contribution to strength will be low and problems such as piling will easily occur during printing. On the other hand, when the molecular weight is higher than 250k, the viscosity when dextrin is dispersed in water increases, making it difficult to handle the paint.
本発明に用いるデキストリンの冷水可溶量は１２％以下であることが好ましく、９．５％以下であることがより好ましい。この冷水可溶量は、以下のように測定する。デキストリンを有姿で１０ｇ採取し、蒸留水で１００ｇとする。このスラリーを１０分間攪拌し、その後１０分間整置する。この上澄みをＢｒｉｘ計で測定し、固形分換算を行い算出する。分子量が非常に低いと、冷水可溶量が１２％より大きくなる。冷水可溶性のデキストリンは、蒸煮が不要であるが、塗工層の強度が不足することから、本発明には好ましくない。 The cold water soluble amount of the dextrin used in the present invention is preferably 12% or less, more preferably 9.5% or less. This cold water soluble amount is measured as follows. Collect 10g of dextrin and add distilled water to make 100g. The slurry is stirred for 10 minutes and then allowed to sit for 10 minutes. This supernatant is measured with a Brix meter, and the solid content is calculated. Very low molecular weights result in cold water solubility greater than 12%. Dextrins that are soluble in cold water do not require steaming, but are not preferred for the present invention because the strength of the coating layer is insufficient.
本発明のデキストリンとしては、焙焼デキストリンを好適に用いることができる。焙焼デキストリンは酸を加えて乾熱で焼いて生成したデキストリンであり、白色デキストリン、黄色デキストリン、ブリティッシュガムなどの種類がある。焙焼デキストリンは、水中で加熱・酸処理したデキストリンより網目構造が多いため、印刷強度に優れる。また、本発明では、紙の白色度の観点から白色デキストリンの使用が特に好ましい。 As the dextrin of the present invention, roasted dextrin can be suitably used. Roasted dextrin is a dextrin produced by adding acid and baking with dry heat, and there are various types such as white dextrin, yellow dextrin, and British gum. Roasted dextrin has a larger network structure than dextrin heated and acid-treated in water, so it has superior printing strength. Further, in the present invention, it is particularly preferable to use white dextrin from the viewpoint of paper whiteness.
本発明において、ＲＶＡ粘度が特定の範囲のデキストリンを用いることが好ましい。このＲＶＡ粘度とは、固形分濃度３５重量％の水性スラリーを、ラピッドビスコアナライザーを用いて、０～５分の５分間で９８℃まで昇温、５～９分の４分間は９８℃に保持、９～１２分の３分間で５０℃まで冷却、１２～１６分の４分間は５０℃に保持という蒸煮条件で蒸煮したときの、蒸煮１６分後における蒸煮液の粘度のことをいう。
具体的には、本発明においては、ＲＶＡ粘度が８５０～１２００ｍＰａ・ｓであるデキストリンを使用することが好ましい。ＲＶＡ粘度が８５０ｍＰａ・ｓより低いと塗工層の表面強度が不足し、印刷時のパイリング等の問題が生じやすい。ＲＶＡ粘度が１２００Ｐａ・ｓより高いと、デキストリンを水に分散した際の粘度が上がり、ハンドリングが困難となる。In the present invention, it is preferable to use a dextrin having an RVA viscosity within a specific range. This RVA viscosity means that an aqueous slurry with a solid content concentration of 35% by weight is heated to 98°C for 5 minutes from 0 to 5 minutes using a rapid viscoanalyzer, and maintained at 98°C for 4 minutes from 5 to 9 minutes. , refers to the viscosity of the steamed liquid after 16 minutes of steaming when steaming is performed under the steaming conditions of cooling to 50°C for 3 minutes from 9 to 12 minutes and maintaining the temperature at 50°C for 4 minutes from 12 to 16 minutes.
Specifically, in the present invention, it is preferable to use a dextrin having an RVA viscosity of 850 to 1200 mPa·s. If the RVA viscosity is lower than 850 mPa·s, the surface strength of the coating layer will be insufficient and problems such as piling will easily occur during printing. If the RVA viscosity is higher than 1200 Pa·s, the viscosity when dextrin is dispersed in water increases, making handling difficult.
また、本発明において、デキストリンのｐＨは、４．０～６．０であることが好ましく、４．５～５．５であることがより好ましい。ｐＨがこの範囲であるデキストリンを感圧記録紙に用いると、良好な発色性と保存性を持つ感圧記録体が得られる。 Further, in the present invention, the pH of the dextrin is preferably 4.0 to 6.0, more preferably 4.5 to 5.5. When a dextrin having a pH within this range is used in a pressure-sensitive recording paper, a pressure-sensitive recording material having good color development and storage stability can be obtained.
次に、本発明の顕色剤層で使用される各種材料を例示する。
本発明の顕色剤層に含まれる顕色剤としては、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、単一種類の顕色剤を用いることもできるし、２種以上の顕色剤を混合して使用することもできる。これに制限されるものではないが、顕色剤としては、例えば、活性白土、アタパルジャイト、コロイダルシリカ、珪酸アルミニウム等の無機酸性物質、４，４'－イソプロピリデンジフェノール、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、４，４'－ジヒドロキシジフェニルスルフィド、ヒドロキノンモノベンジルエーテル、４－ヒドロキシ安息香酸ベンジル、４，４'－ジヒドロキシジフェニルスルホン、２，４'－ジヒドロキシジフェニルスルホン、４－ヒドロキシ－４'－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４'－ｎ－プロポキシジフェニルスルホン、ビス（３－アリル－４－ヒドロキシフェニル）スルホン、４－ヒドロキシ－４'－メチルジフェニルスルホン、４－ヒドロキシフェニル－４'－ベンジルオキシフェニルスルホン、３，４－ジヒドロキシフェニル－４'－メチルフェニルスルホン、特開平８－５９６０３号公報記載のアミノベンゼンスルホンアミド誘導体、ビス（４－ヒドロキシフェニルチオエトキシ）メタン、１，５－ジ（４－ヒドロキシフェニルチオ）－３－オキサペンタン、ビス（ｐ－ヒドロキシフェニル）酢酸ブチル、ビス（ｐ－ヒドロキシフェニル）酢酸メチル、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、１，４－ビス［α－メチル－α－（４'－ヒドロキシフェニル）エチル］ベンゼン、１，３－ビス［α－メチル－α－（４'－ヒドロキシフェニル）エチル］ベンゼン、ジ（４－ヒドロキシ－３－メチルフェニル）スルフィド、２，２'－チオビス（３－tert－オクチルフェノール）、２，２'－チオビス（４－tert－オクチルフェノール）、国際公開ＷＯ９７／１６４２０号に記載のジフェニルスルホン架橋型化合物等のフェノール性化合物、国際公開ＷＯ０２／０８１２２９号あるいは特開２００２－３０１８７３号記載のフェノール性化合物、国際公開ＷＯ０２／０９８６７４号あるいはＷＯ０３／０２９０１７号に記載のフェノールノボラック型縮合組成物、国際公開ＷＯ００／１４０５８号あるいは特開２０００－１４３６１１号に記載のウレアウレタン化合物、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、３、５－ジ(α－メチルベンジル)サリチル酸、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。このほか、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。Next, various materials used in the color developer layer of the present invention will be illustrated.
As the color developer contained in the color developer layer of the present invention, all those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and a single type of color developer can also be used. , it is also possible to use a mixture of two or more types of color developers. Examples of color developers include, but are not limited to, activated clay, attapulgite, colloidal silica, inorganic acidic substances such as aluminum silicate, 4,4'-isopropylidenediphenol, 1,1-bis( 4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4'- Dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, bis(3-allyl-4-hydroxyphenyl)sulfone , 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, aminobenzene described in JP-A-8-59603 Sulfonamide derivative, bis(4-hydroxyphenylthioethoxy)methane, 1,5-di(4-hydroxyphenylthio)-3-oxapentane, bis(p-hydroxyphenyl)butyl acetate, bis(p-hydroxyphenyl) Methyl acetate, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,4-bis[α-methyl-α-(4'-hydroxyphenyl)ethyl]benzene, 1,3-bis[α -Methyl-α-(4'-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 crosslinked compounds described in International Publication WO 97/16420, phenolic compounds described in International Publication WO 02/081229 or JP 2002-301873, International Publication WO 02/ Phenol novolac type condensation compositions described in No. 098674 or WO03/029017, urea urethane compounds described in International Publication No. WO00/14058 or JP2000-143611, N,N'-di-m-chlorophenylthiourea, etc. Thiourea compound, p-chlorobenzoic acid, stearyl gallate, bis[4-(n-octyloxycarbonylamino)zinc salicylate] dihydrate, 3,5-di(α-methylbenzyl)salicylic acid, 4-[ Aromatic carboxylic acids such as 2-(p-methoxyphenoxy)ethyloxy]salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid , and salts of these aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, etc., as well as antipyrine complexes of zinc thiocyanate, terephthalaldehydic acid and other aromatics. Examples include complex zinc salts with group carboxylic acids. In addition, metal chelate type coloring components such as higher fatty acid metal double salts and polyvalent hydroxy aromatic compounds described in JP-A-10-258577 can also be contained.
本発明において、デキストリンと各種バインダーとを併用してもよい。併用できるバインダーとしては、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、アセトアセチル化ポリビニルアルコール、カルボキシル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などの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、クマロン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できる。本発明においてデキストリンと併用するバインダーとして、ポリビニルアルコールが好ましく、完全ケン化ポリビニルアルコールがより好ましい。 In the present invention, dextrin and various binders may be used in combination. Binders that can be used in combination include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, Polyvinyl alcohols such as nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, and other modified polyvinyl alcohols, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer and cellulose derivatives such as ethylcellulose, acetylcellulose, casein, gum arabic, oxidized starch, etherified starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrene. Examples include loin and copolymers thereof, polyamide resins, silicone resins, petroleum resins, terpene resins, ketone resins, coumaron resins, and the like. These polymeric substances are used by dissolving them in solvents such as water, alcohol, ketones, esters, and hydrocarbons, or by emulsifying them or dispersing them in paste form in water or other media to meet the required quality. They can also be used together depending on the situation. As the binder used in combination with dextrin in the present invention, polyvinyl alcohol is preferred, and fully saponified polyvinyl alcohol is more preferred.
顕色剤層中のバインダー（デキストリンを含む）の含有量（固形分重量）は、通常８～２５重量％、好ましくは１０～２０重量％である。
本発明において、顕色剤層中のデキストリンの含有量（固形分重量）は、顕色剤層の全固形分１００重量部に対して３～３０重量部であることが好ましく、５～２５重量部であることがより好ましく、１０～２０重量部であることがさらに好ましく、９～２０重量部であることが最も好ましい。デキストリンの配合量が３０重量部以上の場合、発色性が不足し、３部以下の場合、十分な表面強度が得られない。
顕色剤層中に、デキストリンと他のバインダーを併用してもよい。顕色剤層中のデキストリンの含有量（固形分重量）は、顕色剤層中の全バインダー（デキストリンと他の各種バインダーの合計）１００重量部に対して、５～１００重量部が好ましく、２０～９５重量部がより好ましく、２０～９０重量部がさらに好ましく、２５～９０重量部がよりさらに好ましく、３０～９０重量部が最も好ましく、４０～７５重量部としてもよい。
またデキストリンとポリビニルアルコールを併用する場合、本発明中のポリビニルアルコールの含有量（固形分重量）は、顕色剤層中の全バインダー１００重量部に対して、５～２５重量部が好ましく、１０～２０重量部がより好ましい。The content (solid weight) of the binder (including dextrin) in the color developer layer is usually 8 to 25% by weight, preferably 10 to 20% by weight.
In the present invention, the content (solid weight) of dextrin in the color developer layer is preferably 3 to 30 parts by weight, and 5 to 25 parts by weight based on 100 parts by weight of the total solid content of the color developer layer. parts by weight, more preferably from 10 to 20 parts by weight, and most preferably from 9 to 20 parts by weight. When the amount of dextrin added is 30 parts by weight or more, color development is insufficient, and when it is less than 3 parts, sufficient surface strength cannot be obtained.
Dextrin and other binders may be used together in the developer layer. The content (solid weight) of dextrin in the color developer layer is preferably 5 to 100 parts by weight based on 100 parts by weight of all binders (total of dextrin and other various binders) in the color developer layer. It is more preferably 20 to 95 parts by weight, even more preferably 20 to 90 parts by weight, even more preferably 25 to 90 parts by weight, most preferably 30 to 90 parts by weight, and may be 40 to 75 parts by weight.
Further, when dextrin and polyvinyl alcohol are used together, the content (solid weight) of polyvinyl alcohol in the present invention is preferably 5 to 25 parts by weight, and 10 to 25 parts by weight, based on 100 parts by weight of the total binder in the color developer layer. ~20 parts by weight is more preferred.
本発明の感圧複写紙が、支持体の同一面に前記マイクロカプセル層と前記顕色剤層を積層、又は同一層に前記マイクロカプセルと前記顕色剤を混在させたセルフコンティンド紙の場合、本発明のマイクロカプセルで使用される各種材料として、マイクロカプセルの壁膜材料、ロイコ染料、カプセルオイルなどを例示することができる。 When the pressure-sensitive copying paper of the present invention is a self-contained paper in which the microcapsule layer and the color developer layer are laminated on the same side of a support, or the microcapsules and the color developer are mixed on the same layer. Examples of various materials used in the microcapsules of the present invention include microcapsule wall materials, leuco dyes, and capsule oils.
本発明においては、マイクロカプセルの壁膜材料として、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、メラミン－ホルムアルデヒド縮重合物、またはウレタン・ウレア－イソシアネート縮重合物を壁膜材料とすることが好ましい。 In the present invention, as the wall material of the microcapsules, any material known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, including but not limited to melamine-formaldehyde condensation products, Alternatively, it is preferable to use a urethane/urea-isocyanate condensation product as the wall film material.
また、ロイコ染料は、従来の感圧あるいは感熱記録紙の分野で公知のものを使用可能であり、特に制限されるものではない。
青染料として使用できるものとして、例えば、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、３-(４－ジエチルアミノフェニル)－３－（１－エチル－２－メチル－３－インドリル）フタリド、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－３－インドリル）フタリド、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－３－インドリル）－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－ｎ－オクチル－２－メチル－３－インドリル）－４－アザフタリド、Ｎ－ｎ－ブチル－３－[４,４'－ビス(Ｎ－メチルアニリノ)ベンズヒドリル]カルバゾール等が挙げられる。
黒染料として使用できるものとして、例えば、２－アニリノ－３－メチル－６－ジエチルアミノフルオラン、２－アニリノ－３－メチル－６－ジ－ｎ－ブチルアミノフルオラン、２－アニリノ－３－メチル－６－ジ－ｎ－アミルアミノフルオラン、２－アニリノ－３－メチル－６－(Ｎ－メチル－Ｎ－ｎ－プロピルアミノ)フルオラン、２－アニリノ－３－メチル－６－(Ｎ－エチル－Ｎ－イソブチルアミノ)フルオラン、２－アニリノ－３－メチル－６－(Ｎ－エチル－Ｎ－イソアミルアミノ)フルオラン、２－アニリノ－３－メチル－６－(Ｎ－シクロヘキシル－Ｎ－メチルアミノ)フルオラン、２－アニリノ－３－メチル－６－[Ｎ－エチル－Ｎ－(３－エトキシプロピル)アミノ]フルオラン、２－アニリノ－３－メチル－６－(Ｎ－エチル－４－メチルアニリノ)フルオラン、２－(３－トリフルオロメチルアニリノ)－６－ジエチルアミノフルオラン、３，７－ビスジメチルアミノベンゾイルフェノチアジン、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等が挙げられる。Further, the leuco dye is not particularly limited, and any one known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used.
Examples of blue dyes that can be used include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methyl- 3-Indolyl) phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methyl-3-indolyl) phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3 -(1-ethyl-2-methyl-3-indolyl)-4-azaphthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-n-octyl-2-methyl-3-indolyl)- Examples include 4-azaphthalide, Nn-butyl-3-[4,4'-bis(N-methylanilino)benzhydryl]carbazole, and the like.
Examples of black dyes that can be used include 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, and 2-anilino-3-methyl. -6-di-n-amylaminofluorane, 2-anilino-3-methyl-6-(N-methyl-N-n-propylamino)fluorane, 2-anilino-3-methyl-6-(N-ethyl -N-isobutylamino)fluoran, 2-anilino-3-methyl-6-(N-ethyl-N-isoamylamino)fluoran, 2-anilino-3-methyl-6-(N-cyclohexyl-N-methylamino) Fluoran, 2-anilino-3-methyl-6-[N-ethyl-N-(3-ethoxypropyl)amino]fluoran, 2-anilino-3-methyl-6-(N-ethyl-4-methylanilino)fluoran, 2-(3-trifluoromethylanilino)-6-diethylaminofluorane, 3,7-bisdimethylaminobenzoylphenothiazine, 3-N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane etc.
ロイコ染料を溶解または分散状態で含有するカプセルオイルとしては、例えば、フェニルキシリルエタン、ジアリールエタン、ジイソプロピルナフタレン、モノイソプロピルビフェニル、イソブチルビフェニル、部分水素添加ターフェニル、塩素化パラフィン、飽和炭化水素、フタル酸エステルなどが使用できる。 Examples of capsule oils containing leuco dyes in a dissolved or dispersed state include phenylxylylethane, diarylethane, diisopropylnaphthalene, monoisopropylbiphenyl, isobutylbiphenyl, partially hydrogenated terphenyl, chlorinated paraffin, saturated hydrocarbon, and phthalate. Acid esters etc. can be used.
さらに、マイクロカプセルが破壊されないように保護するために、ステー剤をマイクロカプセル層に含有させることが好ましい。本発明に使用されるステー剤としては、例えば、澱粉粒、セルロース繊維、天然高分子の微粒子などが挙げられる。ステー剤の粒子径はマイクロカプセルの粒子径の１．５～４倍のものが好ましい。１．５倍より小さいとステー剤による保護が十分でないことがある。また、４倍より大きいと、ステー剤による保護が過剰となり、発色能力が低下することがある。 Furthermore, in order to protect the microcapsules from being destroyed, it is preferable to include a stay agent in the microcapsule layer. Examples of the stay agent used in the present invention include starch granules, cellulose fibers, and fine particles of natural polymers. The particle size of the stay agent is preferably 1.5 to 4 times the particle size of the microcapsule. If it is smaller than 1.5 times, protection by the stay agent may not be sufficient. Moreover, when it is larger than 4 times, the protection by the stay agent becomes excessive, and the coloring ability may decrease.
本発明のマイクロカプセルは、例えば、コアセルベーション法、界面重合法、in-situ法など、公知の方法で作製することができる。本発明で用いられるロイコ染料は、カプセルオイルに溶解または分散した状態で芯物質としてマイクロカプセルに内包される。 The microcapsules of the present invention can be produced by known methods such as coacervation, interfacial polymerization, and in-situ methods. The leuco dye used in the present invention is encapsulated in microcapsules as a core substance while being dissolved or dispersed in capsule oil.
本発明において、必要に応じて、顕色剤層に顔料を含有させることができる。顔料としてはカオリン、（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、珪酸アルミニウム、珪酸マグネシウム、珪酸カルシウム、水酸化アルミニウム、シリカ等を例示することができるが、これらに限定されるものではない。 In the present invention, the color developer layer may contain a pigment if necessary. Examples of pigments include, but are not limited to, kaolin, (calcined) kaolin, calcium carbonate, aluminum oxide, titanium oxide, magnesium carbonate, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, and silica. It's not a thing.
本発明において、必要に応じて顕色剤層に架橋剤を添加することが可能である。架橋剤としては、グリオキザール、メチロールメラミン、メラミンホルムアルデヒド樹脂、メラミン尿素樹脂、ポリアミンエピクロロヒドリン樹脂、ポリアミドエピクロロヒドリン樹脂、過硫酸カリウム、過硫酸アンモニウム、過硫酸ソーダ、塩化第二鉄、塩化マグネシウム、ホウ砂、ホウ酸、ミョウバン、塩化アンモニウムなどを例示することができる。 In the present invention, it is possible to add a crosslinking agent to the color developer layer if necessary. Crosslinking agents include glyoxal, methylolmelamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, magnesium chloride. , borax, boric acid, alum, ammonium chloride and the like.
本発明において、必要に応じて顕色剤層に滑材を添加することが可能である。滑剤としては、ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸金属塩、ワックス類、シリコーン樹脂類などが挙げられる。 In the present invention, it is possible to add a lubricant to the color developer layer if necessary. Examples of the lubricant include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, and silicone resins.
また、本発明においては、上記課題に対する所望の効果を阻害しない範囲で、記録画像の耐油性効果などを示す画像安定剤として、４，４'－ブチリデン（６－ｔ－ブチル－３－メチルフェノール）、２，２'－ジ－ｔ－ブチル－５，５'－ジメチル－４，４'－スルホニルジフェノール、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－シクロヘキシルフェニル）ブタン、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、４－ベンジルオキシ－４'－（２，３－エポキシ－２－メチルプロポキシ）ジフェニルスルホン等を添加することもできる。 In the present invention, 4,4'-butylidene (6-t-butyl-3-methylphenol ), 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)diphenylsulfone, etc. can also be added.
このほかにも、ベンゾフェノン系やトリアゾール系の紫外線吸収剤、分散剤、消泡剤、酸化防止剤、蛍光染料等、感圧複写紙に添加することが知られている各種添加剤を本発明において使用することができる。 In addition, various additives known to be added to pressure-sensitive copying paper, such as benzophenone-based and triazole-based ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, and fluorescent dyes, are also used in the present invention. can be used.
本発明において、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ことができる。粒径（平均粒子径）は、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下がさらに好ましい。この塗液に用いる溶媒としては、水あるいはアルコール、それらの混合溶媒等を用いることができる。 In the present invention, the color developer and materials to be added as necessary are pulverized to a particle size of several microns or less using a pulverizer such as a ball mill, attritor, or sand glider, or an appropriate emulsifying device, and then used as a binder and for the purpose. Depending on the application, various additive materials can be added to form a coating liquid. The particle size (average particle size) is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. As the solvent used in this coating liquid, water, alcohol, a mixed solvent thereof, etc. can be used.
本発明の感圧複写紙は、常法に従って製造することができる。例えば、顕色剤を顔料とともにバインダー中に分散するなどの方法で調製された塗液を、上質紙、再生紙、合成紙などからなる支持体上に塗工・乾燥することによって、支持体上に顕色剤層を有する感圧複写紙が得られる。支持体上に顕色剤層を設ける方法は特に限定されるものではなく、例えば、エアナイフコーター、ロールコーター、ブレードコーター、ロッドコーター、カーテンコーターなど適当な塗工装置を用いることができる。また、顕色剤層の塗工量（固形分）は２ｇ／ｍ２～７ｇ／ｍ２程度が一般的である。
The pressure-sensitive copying paper of the present invention can be manufactured according to conventional methods. For example, a coating solution prepared by dispersing a color developer together with a pigment in a binder is coated on a support made of high-quality paper, recycled paper, synthetic paper, etc. and dried. A pressure-sensitive copying paper having a color developer layer is obtained. The method of providing the color developer layer on the support is not particularly limited, and for example, an appropriate coating device such as an air knife coater, roll coater, blade coater, rod coater, curtain coater, etc. can be used. Further, the coating amount (solid content) of the color developer layer is generally about 2 g/m 2 to 7 g/m 2 .
以下、実施例にて本発明を例証するが本発明を限定することを意図するものではない。なお、デキストリンのＤＥはフェーリング・レーマン・ショール法によって算出した。また、特にことわらない限り、部および％は重量部および重量％を示す。 Hereinafter, the present invention will be illustrated by Examples, but they are not intended to limit the present invention. Note that the DE of dextrin was calculated by the Fehring-Lehmann-Schor method. Moreover, unless otherwise specified, parts and % indicate parts by weight and % by weight.
［製造例１］
白色焙焼デキストリンスラリーＡ～Ｆを、次に示す方法で作製した。
とうもろこし澱粉に、硝酸を０．５％の割合で添加混合した。得られた水分２２％の澱粉を、５０℃で予備乾燥し、水分５％とした。次にこの澱粉を１３０℃で９０分間加熱し、デキストリンスラリーＡを得た。
同様の作業工程で、澱粉の加熱を、それぞれ（Ｂ）１３０℃で８５分間、（Ｃ）１３０℃で８０分間、（Ｄ）１３０℃で９５分間、（Ｅ）１３０℃で１００分間、（Ｆ）１３０℃で５０分間、として、デキストリンスラリーＢ～Ｆを得た。[Manufacture example 1]
White roasted dextrin slurries A to F were prepared by the following method.
Nitric acid was added to corn starch at a ratio of 0.5% and mixed. The obtained starch with a water content of 22% was pre-dried at 50°C to have a water content of 5%. Next, this starch was heated at 130° C. for 90 minutes to obtain dextrin slurry A.
In similar working steps, starch was heated (B) at 130°C for 85 minutes, (C) at 130°C for 80 minutes, (D) at 130°C for 95 minutes, (E) at 130°C for 100 minutes, and (F) at 130°C for 100 minutes. ) at 130° C. for 50 minutes to obtain dextrin slurries B to F.
［実施例１］
サンドグラインダーにより、平均粒径２μｍにした３、５－ジ(α－メチルベンジル)サリチル酸亜鉛塩の水分散液（固形分４５％）２２部、炭酸カルシウム９０部、カオリン１０部、白色焙焼デキストリンスラリーＡ（ＲＶＡ粘度（固形分３５％：蒸煮１６分後の１６０ｒ．ｐ．ｍ）９１０ｍＰａ・ｓ、冷水可溶量１２％、分子量１８２ｋ、ｐＨ５．１、ＤＥ：８．９）５７部を混合し、水で濃度調整を行い固形分２５％の顕色剤層用塗工液を得た。
この塗工液を坪量４０ｇ／ｍ２の上質紙上に固形塗工量で５ｇ／ｍ２となるようにブレードコーターで塗工、乾燥し、感圧複写紙を得た。
［実施例２］
白色焙焼デキストリンスラリーＡの代わりに、白色焙焼デキストリンスラリーＢ（ＲＶＡ粘度９３０ｍＰａ・ｓ、冷水可溶量１２％、分子量１８５ｋ、ｐＨ５．０、ＤＥ：８．８）を配合した以外は実施例１と同様にして感圧複写紙を得た。[Example 1]
22 parts of an aqueous dispersion of zinc salt of 3,5-di(α-methylbenzyl)salicylate (solid content 45%), which had an average particle size of 2 μm using a sand grinder, 90 parts of calcium carbonate, 10 parts of kaolin, and white roasted dextrin. Mix 57 parts of slurry A (RVA viscosity (solid content 35%: 160 rpm after 16 minutes of steaming) 910 mPa・s, cold water soluble amount 12%, molecular weight 182k, pH 5.1, DE: 8.9) Then, the concentration was adjusted with water to obtain a developer layer coating solution with a solid content of 25%.
This coating solution was applied to a high-quality paper having a basis weight of 40 g/m 2 to a solid coating weight of 5 g/m 2 using a blade coater and dried to obtain pressure-sensitive copying paper.
[Example 2]
Example except that white roasted dextrin slurry B (RVA viscosity 930 mPa・s, cold water soluble amount 12%, molecular weight 185k, pH 5.0, DE: 8.8) was blended instead of white roasted dextrin slurry A. Pressure-sensitive copying paper was obtained in the same manner as in Example 1.
［実施例３］
白色焙焼デキストリンスラリーＡの代わりに、白色焙焼デキストリンスラリーＣ（ＲＶＡ粘度９６５ｍＰａ・ｓ、冷水可溶量１２％、分子量１８８ｋ、ｐＨ６．０、ＤＥ：８．２）を配合した以外は実施例１と同様にして感圧複写紙を得た。
［実施例４］
白色焙焼デキストリンスラリーＡ５７部の代わりに、白色焙焼デキストリンスラリーＢ４３部および完全ケン化ポリビニルアルコール（クラレ社製、商品名：ＰＶＡ１１７）水溶液（固形分１０％）５０部を配合した以外は実施例２と同様にして感圧複写紙を得た。
［実施例５］
白色焙焼デキストリンスラリーＢ５７部の代わりに、白色焙焼デキストリンスラリーＢ２８部および酸化澱粉（王子コーンスターチ社製、商品名：王子エースＢ)水溶液（固形分２０％）５０部を配合した以外は実施例２と同様にして感圧複写紙を得た。
［実施例６］
白色焙焼デキストリンスラリーＢ５７部の代わりに、白色焙焼デキストリンスラリーＢ２８部およびスチレン－ブタジエン共重合体エマルジョン（旭化成ケミカルズ社製、商品名：Ｆ－１７６６Ｆ、固形分５０％）５０部を配合した以外は実施例２と同様にして感圧複写紙を得た。[Example 3]
Example except that white roasted dextrin slurry C (RVA viscosity 965 mPa・s, cold water soluble amount 12%, molecular weight 188k, pH 6.0, DE: 8.2) was blended instead of white roasted dextrin slurry A. Pressure-sensitive copying paper was obtained in the same manner as in Example 1.
[Example 4]
Example except that instead of 57 parts of white roasted dextrin slurry A, 43 parts of white roasted dextrin slurry B and 50 parts of a completely saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA117) aqueous solution (solid content 10%) were blended. Pressure-sensitive copying paper was obtained in the same manner as in Example 2.
[Example 5]
Example except that 28 parts of white roasted dextrin slurry B and 50 parts of oxidized starch (manufactured by Oji Cornstarch Co., Ltd., trade name: Oji Ace B) aqueous solution (solid content 20%) were blended instead of 57 parts of white roasted dextrin slurry B. Pressure-sensitive copying paper was obtained in the same manner as in Example 2.
[Example 6]
Instead of 57 parts of white roasted dextrin slurry B, 28 parts of white roasted dextrin slurry B and 50 parts of styrene-butadiene copolymer emulsion (manufactured by Asahi Kasei Chemicals, trade name: F-1766F, solid content 50%) were blended. A pressure-sensitive copying paper was obtained in the same manner as in Example 2.
［実施例７］
白色焙焼デキストリンスラリーＡの代わりに、白色焙焼デキストリンスラリーＤ（ＲＶＡ粘度８８０ｍＰａ・ｓ、冷水可溶量１１．５％、分子量１６８ｋ、ｐＨ５．０、ＤＥ：６．０）を配合した以外は実施例１と同様にして感圧複写紙を得た。
［実施例８］
白色焙焼デキストリンスラリーＡの代わりに、白色焙焼デキストリンスラリーＥ（ＲＶＡ粘度８５４ｍＰａ・ｓ、冷水可溶量１１．６％、分子量１５５ｋ、ｐＨ５．０、ＤＥ：９．３）を配合した以外は実施例１と同様にして感圧複写紙を得た。[Example 7]
Except that instead of white roasted dextrin slurry A, white roasted dextrin slurry D (RVA viscosity 880 mPa s, cold water soluble amount 11.5%, molecular weight 168 k, pH 5.0, DE: 6.0) was blended. Pressure-sensitive copying paper was obtained in the same manner as in Example 1.
[Example 8]
Except that instead of white roasted dextrin slurry A, white roasted dextrin slurry E (RVA viscosity 854 mPa s, cold water soluble amount 11.6%, molecular weight 155k, pH 5.0, DE: 9.3) was blended. Pressure-sensitive copying paper was obtained in the same manner as in Example 1.
［比較例１］
白色焙焼デキストリンスラリーＡの代わりに、白色焙焼デキストリンスラリーＦ（ＲＶＡ粘度２３７０ｍＰａ・ｓ、冷水可溶量１２％、分子量２６４ｋ、ｐＨ５．０、ＤＥ：０．６）を配合した以外は実施例１と同様にして感圧複写紙を得た。
このデキストリンスラリーは、粘度が高すぎる為、ポンプで送液できず、サンプル作製が困難であった。
［比較例２］
白色焙焼デキストリンスラリーＡ５７部の代わりに、冷水可溶性デキストリン５７部を配合した以外は、実施例１と同様にして感圧複写紙を得た。
この冷水可溶性デキストリンは、次に示す方法で作製した：とうもろこし澱粉に、硝酸を０．５％の割合で添加混合した。得られた水分２２％の澱粉を、５０℃で予備乾燥し、水分５％とした。次にこの澱粉を１８０℃で８時間加熱し、冷水可溶性デキストリン（分子量８千）を得た。
［比較例３］
白色焙焼デキストリンスラリーＡ５７部の代わりに、完全ケン化ポリビニルアルコール（クラレ社製、商品名：ＰＶＡ１０５）水溶液（固形分１０％）１７５部および完全ケン化ポリビニルアルコール（クラレ社製、商品名：ＰＶＡ１１７）水溶液（固形分１０％）２５部を配合した以外は実施例１と同様にして感圧複写紙を得た。[Comparative example 1]
Example except that white roasted dextrin slurry F (RVA viscosity 2370 mPa・s, cold water soluble amount 12%, molecular weight 264k, pH 5.0, DE: 0.6) was blended instead of white roasted dextrin slurry A. Pressure-sensitive copying paper was obtained in the same manner as in Example 1.
This dextrin slurry had too high a viscosity and could not be pumped, making sample preparation difficult.
[Comparative example 2]
A pressure-sensitive copying paper was obtained in the same manner as in Example 1, except that 57 parts of cold water-soluble dextrin was added instead of 57 parts of white roasted dextrin slurry A.
This cold water soluble dextrin was produced by the following method: nitric acid was added to corn starch at a ratio of 0.5% and mixed. The obtained starch with a water content of 22% was pre-dried at 50°C to have a water content of 5%. Next, this starch was heated at 180° C. for 8 hours to obtain cold water-soluble dextrin (molecular weight: 8,000).
[Comparative example 3]
Instead of 57 parts of white roasted dextrin slurry A, 175 parts of fully saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA105) aqueous solution (solid content 10%) and completely saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA117) ) A pressure-sensitive copying paper was obtained in the same manner as in Example 1, except that 25 parts of an aqueous solution (solid content: 10%) was blended.
［比較例４］
白色焙焼デキストリンスラリーＡ５７部の代わりに、酵素変性澱粉５７部を配合した以外は、実施例１と同様にして感圧複写紙を得た。
この酵素変性澱粉は、次に示す方法で作製した：とうもろこし澱粉製造工程における澱粉乳液をボーメ２０度の濃度に調整した。次いで、消石灰を加えてｐＨを６～７に調整した。これにα―アミラーゼを対澱粉に約０．３重量％添加し、約９０℃で３０分間加熱糊化し、酵素液化反応を行った。反応の終了後、１２５℃まで加圧・加熱し酵素を不活性化した。得られた酵素変性澱粉含有の駅を噴霧乾燥し、２０メッシュの篩で凝塊物を除去して、ＤＥが５の酵素変性澱粉を得た。
［比較例５］
白色焙焼デキストリンスラリーＡの代わりに、白色焙焼デキストリンスラリーＧ（ＲＶＡ粘度２２０ｍＰａ・ｓ、冷水可溶量１４％、分子量９０ｋ、ｐＨ５．０）を配合した以外は実施例１と同様にして感圧複写紙を得た。[Comparative example 4]
Pressure-sensitive copying paper was obtained in the same manner as in Example 1, except that 57 parts of enzyme-modified starch was added instead of 57 parts of white roasted dextrin slurry A.
This enzyme-modified starch was produced by the following method: A starch emulsion in the corn starch manufacturing process was adjusted to a concentration of 20 degrees Baumé. Then, slaked lime was added to adjust the pH to 6-7. Approximately 0.3% by weight of α-amylase was added to the starch, and gelatinization was performed by heating at approximately 90° C. for 30 minutes to perform an enzyme liquefaction reaction. After the reaction was completed, the enzyme was inactivated by applying pressure and heating to 125°C. The resulting enzyme-modified starch-containing station was spray-dried, and the coagulum was removed using a 20-mesh sieve to obtain an enzyme-modified starch with a DE of 5.
[Comparative example 5]
Sensitivity was carried out in the same manner as in Example 1, except that instead of white roasted dextrin slurry A, white roasted dextrin slurry G (RVA viscosity 220 mPa·s, cold water soluble amount 14%, molecular weight 90 k, pH 5.0) was blended. Pressure copy paper was obtained.
作成した感圧複写紙を以下のように評価した。
（１）発色能力
作製した感圧複写紙の顕色剤層面の上に市販の上用紙ＮＷ４０Ｔ（日本製紙製）のマイクロカプセル層面を重ね合わせ、ドットインパクトプリンター（エプソン社製）で全面に印字して、１時間後の発色濃度をハンター白色度計（アンバーフィルター使用）で測定した。値が小さい程発色能力が高く、一般に数値が２０以下であれば実用上大きな問題は無い。The prepared pressure-sensitive copy paper was evaluated as follows.
(1) Color development ability The microcapsule layer surface of commercially available top paper NW40T (manufactured by Nippon Paper Industries) was superimposed on the developer layer surface of the prepared pressure-sensitive copying paper, and printing was performed on the entire surface using a dot impact printer (manufactured by Epson Corporation). After 1 hour, the color density was measured using a Hunter whiteness meter (using an amber filter). The smaller the value, the higher the coloring ability, and generally, if the value is 20 or less, there are no major problems in practice.
（２）印刷強度
作製した感圧複写紙について、プリューフバウ印刷機を用いて顕色剤層面上に下表の条件にてベタ印刷を行い、印刷強度を評価した。
印刷強度は、ベタ印刷部の剥け（インキのタック（粘着性）により顕色剤層が引き剥がされること）を目視で観察し、下記の基準により４段階で評価した。
良 ：剥けが見られない。
可 ：剥けが僅かに見られる。
不可 ：剥けが見られる。
評価不能：ベタ印刷部の全面が剥ける。The printing strength was evaluated by visually observing the peeling of the solid printed area (the developer layer is peeled off due to the tackiness of the ink), and was evaluated on a four-grade scale based on the following criteria.
Good: No peeling observed.
Fair: Slight peeling is seen.
Not acceptable: Peeling is visible.
Unevaluable: The entire surface of the solid printed area peels off.
評価結果を表２に示す。
Claims (10)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022058950 | 2022-03-31 | ||
| JP2022058950 | 2022-03-31 | ||
| PCT/JP2023/012158 WO2023190313A1 (en) | 2022-03-31 | 2023-03-27 | Pressure-sensitive copying paper including color developer layer containing dextrin |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPWO2023190313A1 JPWO2023190313A1 (en) | 2023-10-05 |
| JP7373699B1 true JP7373699B1 (en) | 2023-11-02 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58175691A (en) * | 1982-04-08 | 1983-10-14 | Shizuokaken | Preparation of coating liquid of developable sheet for pressure sensitive copying paper |
| JP2013176983A (en) * | 2012-02-06 | 2013-09-09 | Nippon Paper Industries Co Ltd | Pressure-sensitive copying paper containing dextrin in color developer layer, and method for manufacturing the same |
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- 2023-03-27 WO PCT/JP2023/012158 patent/WO2023190313A1/en active Application Filing
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58175691A (en) * | 1982-04-08 | 1983-10-14 | Shizuokaken | Preparation of coating liquid of developable sheet for pressure sensitive copying paper |
| JP2013176983A (en) * | 2012-02-06 | 2013-09-09 | Nippon Paper Industries Co Ltd | Pressure-sensitive copying paper containing dextrin in color developer layer, and method for manufacturing the same |
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| WO2023190313A1 (en) | 2023-10-05 |
| JPWO2023190313A1 (en) | 2023-10-05 |
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