JPH02139277A - Thermal recording paper - Google Patents
Thermal recording paperInfo
- Publication number
- JPH02139277A JPH02139277A JP1203622A JP20362289A JPH02139277A JP H02139277 A JPH02139277 A JP H02139277A JP 1203622 A JP1203622 A JP 1203622A JP 20362289 A JP20362289 A JP 20362289A JP H02139277 A JPH02139277 A JP H02139277A
- Authority
- JP
- Japan
- Prior art keywords
- silicic acid
- base paper
- paper
- colloidal silicic
- recording paper
- 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.)
- Granted
Links
- 125000002091 cationic group Chemical group 0.000 claims abstract description 58
- 229920002472 Starch Polymers 0.000 claims abstract description 54
- 239000008107 starch Substances 0.000 claims abstract description 51
- 235000019698 starch Nutrition 0.000 claims abstract description 51
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 41
- -1 aluminum compound Chemical class 0.000 claims abstract description 25
- 239000013055 pulp slurry Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 238000006467 substitution reaction Methods 0.000 claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 230000000694 effects Effects 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000123 paper Substances 0.000 description 164
- 239000002585 base Substances 0.000 description 67
- 239000010410 layer Substances 0.000 description 62
- 238000000034 method Methods 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000000975 dye Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000003086 colorant Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000981 basic dye Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229920001592 potato starch Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 240000003183 Manihot esculenta Species 0.000 description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229930182830 galactose Natural products 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
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- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910052784 alkaline earth metal 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 1
- 229940116224 behenate Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
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- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- OJLOUXPPKZRTHK-UHFFFAOYSA-N dodecan-1-ol;sodium Chemical compound [Na].CCCCCCCCCCCCO OJLOUXPPKZRTHK-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- PSYDSRLQABJJAD-UHFFFAOYSA-N dodecylthiourea Chemical compound CCCCCCCCCCCCNC(N)=S PSYDSRLQABJJAD-UHFFFAOYSA-N 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000004088 foaming agent Substances 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
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IMRZFEJNJIFRDU-UHFFFAOYSA-K iron(3+);tetradecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O IMRZFEJNJIFRDU-UHFFFAOYSA-K 0.000 description 1
- 239000002655 kraft paper Substances 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- BXDUJMLIUYJHNH-UHFFFAOYSA-L mercury(2+);oxalate Chemical compound [Hg+2].[O-]C(=O)C([O-])=O BXDUJMLIUYJHNH-UHFFFAOYSA-L 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-M nonanoate Chemical compound CCCCCCCCC([O-])=O FBUKVWPVBMHYJY-UHFFFAOYSA-M 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WVJVHUWVQNLPCR-UHFFFAOYSA-N octadecanoyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCC WVJVHUWVQNLPCR-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- VCXNHCBXRKRKSO-UHFFFAOYSA-J oxalate;thorium(4+) Chemical class [Th+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VCXNHCBXRKRKSO-UHFFFAOYSA-J 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
- ZNSSPLQZSUWFJT-UHFFFAOYSA-N pentyl 4-hydroxybenzoate Chemical compound CCCCCOC(=O)C1=CC=C(O)C=C1 ZNSSPLQZSUWFJT-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/41—Base layers supports or substrates
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は感熱記録紙に関し、特に記録怒度及び画質に優
れた感熱記録紙に関する。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to thermal recording paper, and particularly to thermal recording paper that has excellent recording intensity and image quality.
「従来の技術」
従来、発色剤と該発色剤と接触して呈色する呈色剤との
呈色反応を利用し、熱により両光色物質を接触せしめて
発色像を得るようにした感熱記録紙は良く知られている
。かかる感熱記録紙は比較的安価であり、また記録方式
がノンインパクト方式で静粛であり、しかも記録速度が
速いため、ファクシミリ、サーマルプリンターバーコー
ド・ラベルプリンター等に幅広く利用されている。``Prior art'' Conventionally, thermosensitive technology utilizes a color reaction between a color former and a color former that develops color when it comes into contact with the color former, and brings both photochromic substances into contact with each other using heat to obtain a colored image. Recording paper is well known. Such thermal recording paper is relatively inexpensive, uses a non-impact recording method, is quiet, and has a fast recording speed, so it is widely used in facsimile machines, thermal printers, bar code printers, label printers, and the like.
また、近年の著しい情報量の増加に伴い、例えばファク
シミリでは、高速機（Ｃ，ＩＩＩ機）さらにはそれ以上
の超高速機（ＧｒＶ機）の開発が進められており、この
ような記録機器の高速化に伴い、これらに用いられる感
熱記録紙も記録ヘッドからの微少な熱エネルギーをより
有効に利用して高い印字濃度を得るべく、種々の提案が
なされている。Furthermore, with the remarkable increase in the amount of information in recent years, the development of high-speed machines (C, III machines) and even higher speed machines (GrV machines) in the field of facsimile, for example, is progressing. With the increase in speed, various proposals have been made for the thermal recording paper used in these applications in order to more effectively utilize the small amount of thermal energy from the recording head to obtain high print density.
しかし、従来から提案されているのは、主に発色剤、呈
色剤、熱可融性物質（増感剤）等の感熱記録層を構成す
る材料の改良に重点が置かれており、支持体の面からの
検討は殆どなされていないのが実情である２゜
通常、原紙はパルプ繊維を主成分とするパルプスラリー
を抄紙機によって抄紙、乾燥して得られるものであるが
、さらに紙の原価を下げたり、品質向上、例えば不透明
度、白色度、平滑性の改善又は手触り感触の改善等の目
的でパルプスラリー中に炭酸カルシウム、タルク或いは
二酸化チタン等の填料を添加することが一最に行われて
いる。However, conventional proposals have mainly focused on improving the materials constituting the heat-sensitive recording layer, such as coloring agents, color formers, and thermofusible substances (sensitizers). The reality is that very little research has been done from the physical point of view.2゜Usually, base paper is obtained by making pulp slurry, whose main component is pulp fiber, using a paper machine and drying it. It is best to add fillers such as calcium carbonate, talc, or titanium dioxide to pulp slurry for the purpose of reducing cost or improving quality, such as improving opacity, whiteness, smoothness, or improving hand feel. It is being done.
勿論、必要に応じて各種の内添用助剤を添加することも
できる。一方、感熱記録紙用原紙についても基本的には
前述の如き方法で製造されており、何ら異なるものでは
ない。Of course, various internal additives can be added as necessary. On the other hand, base paper for thermosensitive recording paper is also basically manufactured by the method described above, and is not different from the method described above.
近年、カチオン性の内添剤とアニオン性の無機物をパル
プスラリーに添加して両者の結合に基づく特性を利用し
て原紙の改善を図ろうとする新しい抄紙システム、例え
ば特開昭５７−５１９００号や６２１９１５９８等の提
案がなされている。In recent years, new papermaking systems have been developed that attempt to improve base paper by adding cationic internal additives and anionic inorganic substances to pulp slurry and utilizing the properties based on the combination of the two, such as JP-A No. 57-51900 and Proposals such as 62191598 have been made.
本発明者等は上記提案に基づき感熱記録紙の支持体用原
紙として、これらの提案について種々検討を加えた結果
、全ての点で満足するものではないことが判った。Based on the above-mentioned proposals, the present inventors conducted various studies on these proposals as a base paper for a support for thermosensitive recording paper, and as a result, it was found that they were not satisfactory in all respects.
「発明が解決しようとする課題」
上記の如き実情から、本発明者等は記録感度及び画質に
優れた感熱記録紙用原紙の有り方について鋭意研究を重
ねた結果、特定のコロイド状ケイ酸とカチオン性澱粉又
は更に水溶性アルミニウム化合物をパルプスラリーに添
加して抄紙した原紙を感熱記録紙用支持体として用いる
と、特に記録感度及び画質の点で極めて優れた感熱記録
紙が得られることを見出し、本発明を完成するに至った
。``Problems to be Solved by the Invention'' In light of the above-mentioned circumstances, the inventors of the present invention have conducted intensive research into the ideal base paper for thermal recording paper with excellent recording sensitivity and image quality. It has been discovered that when a base paper made by adding cationic starch or a water-soluble aluminum compound to a pulp slurry is used as a support for thermal recording paper, it is possible to obtain thermal recording paper that is extremely excellent in terms of recording sensitivity and image quality. , we have completed the present invention.
「課題を解決する為の手段」
本発明は、パルプスラリーにコロイド状ケイ酸とカチオ
ン性澱粉を添加するか、或いはパルプスラリーにコロイ
ド状ケイ酸、カチオン性澱粉、更に水溶性アルミニウム
化合物を添加して得た原紙上に感熱記録層を設けたこと
を特徴とする感熱記録紙である。"Means for Solving the Problems" The present invention involves adding colloidal silicic acid and cationic starch to pulp slurry, or adding colloidal silicic acid, cationic starch, and a water-soluble aluminum compound to pulp slurry. This heat-sensitive recording paper is characterized in that a heat-sensitive recording layer is provided on a base paper obtained by the process.
「作用」
本発明で用いられるコロイド状ケイ酸は、−ｉに市場で
人手できるコロイド状ケイ酸であるが、活性表面を有す
るものであればよい。通常は、その平均粒子径が１〜２
０ｎｍのものが好ましく使用でき、より好ましくは１〜
１０ｎｍ程度のものである。"Function" The colloidal silicic acid used in the present invention is a commercially available colloidal silicic acid, but any colloidal silicic acid that has an active surface may be used. Usually, the average particle size is 1 to 2
0 nm can be preferably used, more preferably 1 to 0 nm.
The thickness is about 10 nm.
具体的な例としては商品名ＢＭ［ｌ （口座エカノーベ
ル社製）やスノーテックス（口座化学工業社製）、アプ
ライド（旭電化工業社製）等からなる市販品が好適に使
用し得るものである。As specific examples, commercially available products such as BM[l (manufactured by Kakan Eka Nobel Co., Ltd.), Snowtex (manufactured by Kakan Kagaku Kogyo Co., Ltd.), and Applied (manufactured by Asahi Denka Kogyo Co., Ltd.) can be suitably used. .
なお、コロイド状ケイ酸の製造方法については各種の方
法があり特に限定するものではないが、イオン交換樹脂
を用いる方法で行われているものが一般的である。例え
ば、ケイ酸ナトリウム水溶液を陽イオン交換樹脂に通し
て、５ｉＯｚ ： ＭＺＯのモル比が１０＝１〜３００
： １ 、好ましくは１５ ： １〜１００：１（Ｍ
はＮａ 、 ＫＸＬｉ、Ｎ１）４からなる群より選ばれ
たイオンである）となるようにアルカリを用いて安定化
させ、更に濃縮して得られるもの等がある。また、本発
明で使用するコロイド状ケイ酸には、少なくとも１種類
のケイ酸アルミニウム或いはアルミニウム改質ケイ酸の
表面層を有するコロイド粒子からなり、粒子の表面基が
ケイ素原子及びアルミニウム原子を９．５ ： ０．５
〜？、５ ： ２．５の比率で存するコロイド状ケイ酸
をも含むものである。There are various methods for producing colloidal silicic acid, and there are no particular limitations, but a method using an ion exchange resin is generally used. For example, by passing an aqueous sodium silicate solution through a cation exchange resin, the molar ratio of 5iOz:MZO is 10 = 1 to 300.
: 1, preferably 15:1 to 100:1 (M
is an ion selected from the group consisting of Na, KXLi, and N1)4. Further, the colloidal silicic acid used in the present invention consists of colloidal particles having a surface layer of at least one type of aluminum silicate or aluminum-modified silicic acid, and the surface groups of the particles include silicon atoms and aluminum atoms. 5: 0.5
~? , 5:2.5.
本発明で使用するカチオン性澱粉は通常の澱粉製造原料
から得られる澱粉、例えば玉蜀黍澱粉、小麦澱粉、馬鈴
薯澱粉、タピオカ澱粉、サツマイモ澱粉、モチトウモロ
コシ澱粉、サゴ澱粉、高アミロース含有澱粉や米澱粉等
の澱粉及びこれらの混合物を公知の技術でカチオン変性
して得ることができ、特に限定するものではない。なお
、本発明で使用されるカチオン性澱粉としてはカチオン
性澱粉は勿論、カチオン性とアニオン性の両イオす両性
澱粉も含まれる。The cationic starch used in the present invention is starch obtained from common starch manufacturing raw materials, such as onion starch, wheat starch, potato starch, tapioca starch, sweet potato starch, waxy corn starch, sago starch, high amylose-containing starch, and rice starch. It can be obtained by cationically modifying starch and mixtures thereof using known techniques, and is not particularly limited. The cationic starch used in the present invention includes not only cationic starch but also amphoteric starch that is both cationic and anionic.
カチオン性澱粉を得る方法としては、各種の方法があり
、３級アミノ又は４級アンモニウム化合物で処理する方
法等がよく行われているが、好ましくは４級アンモニウ
ム化合物、例えば、３−クロロ−２−ヒドロキシプロピ
ル−トリメチルアンモニウムクロライド又は２．３−エ
ポキシプロピルトリメチルアンモニウムクロライド等で
処理して得られるものでカチオン性基の置換度（Ｄ、Ｓ
）が０．０２〜０．０５となるように反応させたものが
特に好ましい。There are various methods for obtaining cationic starch, and methods such as treatment with tertiary amino or quaternary ammonium compounds are often used, but preferably quaternary ammonium compounds, such as 3-chloro-2 The degree of substitution of cationic groups (D, S
) is particularly preferably 0.02 to 0.05.
上述の如く、本発明の所望の効果を最大限発揮するのは
カチオン性基のり、Ｓが０．０２〜０．０５の場合であ
る。因みに、Ｄ、Ｓが０．０２未満の場合は効果が小さ
く、０．０５を越えると凝集力が強過ぎて原紙の地合が
崩れ、結果として記録画像が低下するので好ましくない
。As mentioned above, the desired effect of the present invention is maximized when the cationic group S is 0.02 to 0.05. Incidentally, if D and S are less than 0.02, the effect will be small, and if they exceed 0.05, the cohesive force will be too strong and the texture of the base paper will collapse, resulting in a deteriorated recorded image, which is not preferable.
而して、本発明の感熱記録紙はパルプ繊維を主成分とす
る原紙を基材に使用するものであるが、必須要件として
パルプスラリーに上記のコロイド状ケイ酸とカチオン性
澱粉の両者又はその上に水溶性アルミニウム化合物を添
加して紙料を調製し、抄紙、乾燥して得られた原紙上に
感熱記録層を形成して得られるものである。The heat-sensitive recording paper of the present invention uses a base paper containing pulp fiber as a main component, but as an essential requirement, the pulp slurry contains both or both of the above-mentioned colloidal silicic acid and cationic starch. A water-soluble aluminum compound is added thereto to prepare a paper stock, and a heat-sensitive recording layer is formed on the resulting base paper by papermaking and drying.
コロイド状ケイ酸とカチオン性澱粉をパルプスラリーへ
添加する方法としては、両者を水に混合し、水性スラリ
ーとして用いる方法、或いは水性ゾル形のコロイド状ケ
イ酸成分と、カチオン性澱粉水溶液とを別々に添加する
方法等がある。また、添加場所、添加順序等特に限定す
るものではないが、より好ましい結果を得る為には、例
えばカチオン性澱粉をマシンチエストやマシンスクリー
ンの入口等に、コロイド状ケイ酸を出来るだけ抄紙機の
ヘッドボックス（ストックインレット）に近いファンポ
ンプ或いはマシンスクリーンの入口又は出口等に、別々
に添加する方法が望ましい。Colloidal silicic acid and cationic starch can be added to the pulp slurry by mixing them with water and using them as an aqueous slurry, or by separately adding the colloidal silicic acid component in the form of an aqueous sol and the cationic starch aqueous solution. There are ways to add it to. In addition, although there are no particular limitations on the place or order of addition, in order to obtain more preferable results, for example, cationic starch should be added to the entrance of the machine chest or machine screen, and colloidal silicic acid should be added to the head of the paper machine as much as possible. It is preferable to add it separately to the inlet or outlet of a fan pump or machine screen near the box (stock inlet).
なお、コロイド状ケイ酸とカチオン性澱粉の添加量は両
成分の合計量でパルプ繊維分に対し０゜１〜１０重量％
、より好ましくは０．３〜５重量％である。因みに、０
．１重量％未満の場合は本発明の所望の効果が期待でき
ず、ｌＯ重贋％を越えると画質が低下するので好ましく
ない。また、コロイド状ケイ酸とカチオン性澱粉との添
加比率は重量比で１：１〜１：２５、好ましくば１ ：
１．５〜１：１０であるが、コロイド状ケイ酸の量が
少ないと記録濃度に顕著な効果が発現されないので、少
なくともパルプ繊維分に対し０．０５重量％以上のコロ
イド状ケイ酸を添加しなければならない。The amount of colloidal silicic acid and cationic starch added is 0.1 to 10% by weight based on the pulp fiber content, based on the total amount of both components.
, more preferably 0.3 to 5% by weight. By the way, 0
．． If it is less than 1% by weight, the desired effect of the present invention cannot be expected, and if it exceeds 10% by weight, the image quality will deteriorate, which is not preferable. Further, the addition ratio of colloidal silicic acid and cationic starch is 1:1 to 1:25 by weight, preferably 1:
1.5 to 1:10, but if the amount of colloidal silicic acid is small, no noticeable effect on recording density will be expressed, so at least 0.05% by weight or more of colloidal silicic acid is added to the pulp fiber content. Must.
また、本発明で使用される水溶性アルミニウム化合物と
しては、例えば硫酸バンド、塩化アルミニウム、アルミ
ン酸ソーダや塩基性塩化アルミニウム、塩基性硫酸アル
ミニウム、ポリ水酸化アルミニウム等の塩基性アルミニ
ウム化合物及び水に易分散性のアルミナヅル等が挙げら
れる。水溶性アルミニウム化合物はカチオン性澱粉の作
用効果を補う目的のために併用されるものであるが、そ
の添加量はパルプ繊維分に対し０．０１〜５重量％、よ
り好ましくは０．０５〜３重世％である。因みに、０．
０１重量％未満の場合は水溶性アルミニウム化合物の添
加効果が期待できず、一方、５重■％を越えると、水溶
性アルミニウム化合物がコロイド状ケイ酸とカチオン性
澱粉との凝集体の形成を妨害するので好ましくない。な
お、より好ましい効果を得るためには、水溶性アルミニ
ウム化合物の添加方法も重要である。例えば、水溶性ア
ルミニウム化合物とコロイド状ケイ酸とが直接接触しな
いように、少なくとも２分間以上の添加間隔をもたせて
添加すること、また、カチオン性澱粉と水溶性アルミニ
ウム化合物との添加間隔を１分間以内とし、殆ど同時、
或いは連続して添加する方法等が好ましい実施態様であ
る。特に、炭酸カルシウム等のアルカリ性填料を含むパ
ルプスラリーにおいては、上記の如き添加方法が有効で
ある。The water-soluble aluminum compounds used in the present invention include basic aluminum compounds such as aluminum sulfate, aluminum chloride, sodium aluminate, basic aluminum chloride, basic aluminum sulfate, polyaluminum hydroxide, and water-soluble aluminum compounds. Examples include dispersible alumina crane. A water-soluble aluminum compound is used in combination for the purpose of supplementing the effects of cationic starch, and the amount added is 0.01 to 5% by weight, more preferably 0.05 to 3% by weight based on the pulp fiber content. It is a heavy percentage. By the way, 0.
If the amount is less than 1% by weight, no effect can be expected from the addition of the water-soluble aluminum compound, while if it exceeds 5% by weight, the water-soluble aluminum compound will interfere with the formation of aggregates between colloidal silicic acid and cationic starch. Therefore, it is not desirable. In addition, in order to obtain more preferable effects, the method of adding the water-soluble aluminum compound is also important. For example, to prevent direct contact between the water-soluble aluminum compound and colloidal silicic acid, the addition interval should be at least 2 minutes, and the addition interval between the cationic starch and the water-soluble aluminum compound should be 1 minute. Within, almost simultaneously,
Alternatively, a method of adding continuously is a preferred embodiment. Particularly in pulp slurries containing alkaline fillers such as calcium carbonate, the above-mentioned addition method is effective.
さらに、内添用填料としては当業界で一般に公知公用の
、例えばタルク、カオリン、クレー、焼成カオリン、炭
酸カルシウム、水酸化アルミニウム、二酸化チタン、珪
酸マグネシウム、硫酸マグネシウム、アルミノ珪酸塩、
シリカ、ベントナイト等の鉱物質填料やポリスチレン樹
脂微粒子、尿素ホルマリン樹脂微粒子、及び熱膨張性微
小中空粒子或いは非熱膨張性微小中空粒子やその他の有
機系填料が適宜使用される。Further, fillers for internal addition include those commonly known and used in the art, such as talc, kaolin, clay, calcined kaolin, calcium carbonate, aluminum hydroxide, titanium dioxide, magnesium silicate, magnesium sulfate, aluminosilicate,
Mineral fillers such as silica and bentonite, fine polystyrene resin particles, fine urea-formalin resin particles, thermally expandable or non-thermally expandable fine hollow particles, and other organic fillers are used as appropriate.
勿論、パルプスラリー中にはこれらの他にロジン系サイ
ズ、石油樹脂系サイズ、アルキルケテンダイマー系サイ
ズ、アルケニル無水コハク酸系サイズ及び無水ステアリ
ン酸系サイズ等のサイズ剤、アニオン性、カチオン性、
ノニオン性又は両性のポリアクリルアミド系重合体、ポ
リエチレンイミン及びその誘導体、ポリアミン、ポリア
ミド・ポリアミン及びその誘導体、ポリエチレンオキサ
イド、植物ガム、ポリビニルアルコール、カチオン性う
テンクス、カチオン性尿素ホルマリン樹脂、メラミンホ
ルマリン樹脂、ポリアミド樹脂等の有機系化合物、さら
に染料、ｐ ｌ ｇ整剤、ピッチコントロール剤、スラ
イムコントロール剤、消ｍ剤等を必要に応じて適宜添加
することができる。Of course, in addition to these, the pulp slurry contains sizing agents such as rosin size, petroleum resin size, alkyl ketene dimer size, alkenyl succinic anhydride size and stearic anhydride size, anionic, cationic,
Nonionic or amphoteric polyacrylamide polymer, polyethyleneimine and its derivatives, polyamine, polyamide/polyamine and its derivatives, polyethylene oxide, vegetable gum, polyvinyl alcohol, cationic wax, cationic urea-formalin resin, melamine-formalin resin, An organic compound such as a polyamide resin, a dye, a PlG control agent, a pitch control agent, a slime control agent, a demulcent agent, etc. can be added as appropriate.
また、サイズプレス等の方法で成紙の表面に澱粉、ポリ
ビニルアルコール、各種表面サイズ剤、顔料等を塗布す
ることも可能である。It is also possible to apply starch, polyvinyl alcohol, various surface sizing agents, pigments, etc. to the surface of the paper by a method such as a size press.
一方パルプ繊維としては、クラフト法等によって得られ
る針葉樹パルプや広葉樹パルプ等の化学パルプの他ＢＣ
ＴＭＰ、 ＣＴＭＰ、、ＳＧＰ 、 ＲＧＰ等の各種機
械パルプやＤＩＰ等が適宜組合わされて使用される。On the other hand, pulp fibers include chemical pulp such as softwood pulp and hardwood pulp obtained by the kraft method, as well as BC.
Various mechanical pulps such as TMP, CTMP, SGP, RGP, DIP, etc. are used in appropriate combinations.
本発明における感熱記録紙用原紙の抄紙方法としては、
所謂酸性抄紙或いは中性抄紙と限定するものではなく、
全ての抄紙方法が対象となる。The method for making base paper for thermal recording paper in the present invention is as follows:
It is not limited to so-called acid paper making or neutral paper making,
This applies to all papermaking methods.
しかしながら、本発明の場合は特に炭酸カルシウムを主
成分とする填料を含んだ抄紙ｐＨが約６の弱酸性から約
９の弱アルカリ性で行う中性抄紙方法で得られる原紙を
用いたときに、より顕著な効果が得られるものである。However, in the case of the present invention, especially when using a base paper obtained by a neutral papermaking method in which the papermaking pH is from weakly acidic (about 6) to weakly alkaline (about 9), which contains a filler mainly composed of calcium carbonate, It is possible to obtain a remarkable effect.
前述した如く、本発明の感熱記録紙は填料を含むパルプ
スラリー中に、特定のコロイド状ケイ酸とカチオン性澱
粉を、又はその上に水溶性アルミニウム化合物を添加し
て抄紙、乾燥して得られる原紙を用いるところに重大な
特徴を有するものである。即ち、このようにして得られ
た原紙を感熱記録紙用支持体に用いると、感熱記録紙と
しての記録濃度、平滑度及び画質が極めて効果的に向上
することがわかった。As mentioned above, the heat-sensitive recording paper of the present invention is obtained by adding specific colloidal silicic acid and cationic starch to a pulp slurry containing filler, or adding a water-soluble aluminum compound thereon, followed by paper-making and drying. It has an important feature in that it uses base paper. That is, it has been found that when the base paper thus obtained is used as a support for thermal recording paper, the recording density, smoothness, and image quality of the thermal recording paper are extremely effectively improved.
本発明者等は、この理由について鋭意考察を行った結果
、必ずしも明らかではないが次のような結論を得ている
。即ち、カチオン性基の置換度が０．０２〜０．０５の
範囲にある特定のカチオン性澱粉と粒子径が１〜２０ｎ
ｍであるコロイド状ケイ酸のミクロ粒子との相互作用に
よって、パルプ中の填料や微細繊維等が吸着されミクロ
なフロックを形成し、これらがパルプ繊維上に均一に分
布することによって、従来の原紙に比較し平滑性が改善
され然も地合の優れた原紙が得られること、更には、サ
イズ剤の歩留が良好でサイズ効果の優れた原紙が得られ
るために、原紙上に塗被する感熱記録用塗液に対する原
紙のバリヤー性が高められること等に起因して、極めて
平滑な感熱記録層が形成されるためと思われる。The inventors of the present invention have conducted extensive studies on the reason for this, and have come to the following conclusion, although it is not necessarily clear. That is, a specific cationic starch having a degree of substitution of cationic groups in the range of 0.02 to 0.05 and a particle size of 1 to 20 nm.
Fillers and fine fibers in the pulp are adsorbed by interaction with microparticles of colloidal silicic acid, which is m, to form microflocs, which are uniformly distributed on the pulp fibers, making it possible to It is possible to obtain a base paper with improved smoothness and excellent texture compared to the sizing agent, and also to obtain a base paper with good sizing agent retention and excellent sizing effect. This is thought to be because an extremely smooth heat-sensitive recording layer is formed due to the improved barrier properties of the base paper against the heat-sensitive recording coating liquid.
かくして得られた原紙は、地合や平滑性が極めて良好で
あるために、あらゆる等級及び種類の紙製品、例えば、
書籍用紙、新聞用紙、グラビア用紙、アート紙、コート
紙、キャストコート紙、徽塗工紙等の印刷紙等や感熱記
録紙、感圧記録紙、静電記録紙、インクジェット用紙等
の情報用紙やタック紙等の特殊紙等にも適用可能である
が、特に感熱記録紙において、極めて顕著に所望の効果
が得られるものである。なお、本発明の方法で得られた
原紙は常法に従って、感熱記録層が形成されるが、感熱
記録層を構成する発色物質としては各種の組合わせを適
用することができ、具体的には、例えば下記が例示され
る。The base paper thus obtained has very good texture and smoothness and can be used for all grades and types of paper products, such as
Printing paper such as book paper, newsprint, gravure paper, art paper, coated paper, cast coated paper, and coated paper; information paper such as heat-sensitive recording paper, pressure-sensitive recording paper, electrostatic recording paper, and inkjet paper; Although it can be applied to special papers such as tack paper, the desired effect can be obtained particularly with heat-sensitive recording paper. Note that a heat-sensitive recording layer is formed on the base paper obtained by the method of the present invention according to a conventional method, but various combinations can be applied as the color-forming substances constituting the heat-sensitive recording layer. For example, the following are exemplified.
（ａ）特公昭４１−１４５１０号公報に記載されている
第二級アルコール性水酸基を有する融点１００〜１８０
℃の化合物、硫黄及び金属無機塩類又は金属の酢酸塩類
よりなる組合わせ。(a) Melting point 100-180 having a secondary alcoholic hydroxyl group as described in Japanese Patent Publication No. 41-14510
℃ compound, sulfur and metal inorganic salts or metal acetates.
此処で、第二級アルコール性水酸基を有する化合物とし
てはベンゾイン、２−メトキシベンゾイン、４−クロル
ベンゾイン、４−ジメチルアミノヘンジインの如きベン
ゾイン化合物、ジフェニルカルビノールの如きカルビノ
ール類、レゾルシン、ピロガロール、３−ヒドロキシト
ルエン−４−スルフォン酸の如きフェノール性化合物、
エリトリット、ソルビット、ガラクトーゼ、マルトーゼ
、マンニット、サッカローズの如き脂肪酸多価アルコー
ル類等が挙げられる。また、金属無機塩類及び金属の酢
酸塩類としては、硫化水素と反応して着色硫化物を生成
する金属の多数のものが挙げられ、例えば銅、鉛、錫、
モリブデン、ニッケル、マンガン、チタン、アンチモン
、ロジウム、オスミウム、マグネシウム、インジウム、
イリジウム等がある−
（ｂ）特公昭４１−１４５１）号公報に記載されている
、前記（ａ）の組成物中の各種無機金属塩をヘキサメチ
レンテトラミン・金属塩付加物に置き換えた組合せ。Here, the compounds having a secondary alcoholic hydroxyl group include benzoin compounds such as benzoin, 2-methoxybenzoin, 4-chlorobenzoin, and 4-dimethylaminohendiin, carbinols such as diphenylcarbinol, resorcinol, pyrogallol, phenolic compounds such as 3-hydroxytoluene-4-sulfonic acid,
Examples include fatty acid polyhydric alcohols such as erythritol, sorbitol, galactose, maltose, mannitol, and sucrose. Metal inorganic salts and metal acetates include many metals that react with hydrogen sulfide to produce colored sulfides, such as copper, lead, tin,
Molybdenum, nickel, manganese, titanium, antimony, rhodium, osmium, magnesium, indium,
(b) A combination described in Japanese Patent Publication No. 41-1451, in which various inorganic metal salts in the composition (a) are replaced with hexamethylenetetramine/metal salt adducts.
（ｃ）特公昭４２−１３２３７号公報に記載されている
炭水化物と脱水剤の組合せ。(c) A combination of a carbohydrate and a dehydrating agent as described in Japanese Patent Publication No. 13237/1983.
此処で、炭水化物とは、例えばサッカローズ、フルクト
ーゼ、ガラクトーゼ、澱粉等が挙げられ、脱水剤として
は硫酸、無水酢酸、無水塩化亜鉛、パラトルエンスルホ
ン酸等が挙げられる。Here, carbohydrates include, for example, saccharose, fructose, galactose, starch, etc., and dehydrating agents include sulfuric acid, acetic anhydride, anhydrous zinc chloride, para-toluenesulfonic acid, and the like.
（ｄ）ステアリン酸第２鉄、ミリスチン酸第２鉄の如き
長鎖脂肪酸鉄塩とタンニン酸、没食子酸、サリチル酸ア
ンモニウムの如きフェノール類との組合せ。(d) Combinations of long chain fatty acid iron salts such as ferric stearate and ferric myristate with phenols such as tannic acid, gallic acid and ammonium salicylate.
（ｅ）酢酸、ステアリン酸、パルミチン酸等のニッケル
、コバルト、鉛、銅、鉄、水銀、銀塩の如き有機酸重金
属塩と硫化カルシウム、硫化ストロンチウム、硫化バリ
ウムの如きアルカリ土類金属硫化物との組合せ、又は前
記有機酸重金属塩とＳジフェニルカルバジド、ジフェニ
ルカルバゾンの如き有機キレート剤との組合せ。(e) Organic acid heavy metal salts such as nickel, cobalt, lead, copper, iron, mercury, and silver salts such as acetic acid, stearic acid, and palmitic acid; and alkaline earth metal sulfides such as calcium sulfide, strontium sulfide, and barium sulfide. or a combination of the organic acid heavy metal salt and an organic chelating agent such as S diphenylcarbazide or diphenylcarbazone.
（ｆ）銀、鉛、水銀、トリウムの蓚酸塩の如き重金属蓚
酸塩とＮａ−テトラチオネート、チオ硫酸ソーダ、チオ
尿素の如き硫黄化合物との組合せ。(f) Combinations of heavy metal oxalates such as silver, lead, mercury, thorium oxalates and sulfur compounds such as Na-tetrathionate, sodium thiosulfate, thiourea.
（ｇ）ステアリン酸第２鉄の如き脂肪酸第２鉄塩と３．
４−ジヒドロキシテトラフェニルメタンの如き芳香族ポ
リヒドロキシ化合物との組合せ。(g) a ferric fatty acid salt such as ferric stearate; 3.
Combination with aromatic polyhydroxy compounds such as 4-dihydroxytetraphenylmethane.
（ｈ）蓚酸銀、蓚酸水銀の如き有機酸貴金属塩とポリヒ
ドロキシアルコール、グリセリン、グリコールの如き有
機ポリヒドロキシ化合物との組合せ。(h) A combination of a noble metal salt of an organic acid such as silver oxalate or mercury oxalate and an organic polyhydroxy compound such as polyhydroxy alcohol, glycerin, or glycol.
（ｉ）ベヘン酸銀、ステアリン酸銀の如き有機酸貴金属
塩とプロトカテキン酸、スピロインダン、ハイドロキノ
ンの如き芳香族有機還元剤との組合せ。(i) A combination of a noble metal salt of an organic acid such as silver behenate or silver stearate and an aromatic organic reducing agent such as protocatechuic acid, spiroindane or hydroquinone.
（ｊ）ペラルゴン酸第２鉄、ラウリル酸第２鉄の如き脂
肪酸第２鉄塩とチオセミカルバジド又はイソチオセミカ
ルバジド誘導体との組合せ。(j) A combination of a fatty acid ferric salt such as ferric pelargonic acid or ferric lauric acid with thiosemicarbazide or isothiosemicarbazide derivative.
（ｋ）カプロン酸鉛、ペラルゴン酸鉛、ベヘン酸鉛の如
き有機酸鉛塩とエチレンチオ尿素、Ｎ−ドデシルチオ尿
素の如きチオ尿素誘導体との組合せ。(k) Combinations of organic acid lead salts such as lead caproate, lead pelargonate, lead behenate and thiourea derivatives such as ethylenethiourea and N-dodecylthiourea.
（１）ステアリン酸第２鉄、ステアリン酸銅の如き高級
脂肪酸重金属塩とジアルキルジチオカルバミン酸亜鉛と
の組合せ。(1) A combination of a higher fatty acid heavy metal salt such as ferric stearate or copper stearate and zinc dialkyldithiocarbamate.
（ｍ） レゾルシンと二１−ロソ化合物との組合せの
如きオキサジン染料を形成するもの、或いはアゾ染料を
形成するもの。(m) Those that form oxazine dyes, such as the combination of resorcinol and 21-roso compounds, or those that form azo dyes.
（ｎ）ジアゾニウム塩とカプラー化合物との組合せの如
きアブ染料を形成するもの。(n) Those forming ab dyes, such as combinations of diazonium salts and coupler compounds.
（ｏ）クリスタルバイオレットラクトンの如き無色乃至
は淡色の塩基性染料とビスフェノールの如き呈色剤との
組合せ。(o) A combination of a colorless or light-colored basic dye such as crystal violet lactone and a coloring agent such as bisphenol.
上記の如き各種組合せのうちでも、塩基性染料と呈色剤
の組合せを用いた感熱記録紙が一般的であるため、この
組み合わせの場合について以下に具体的に説明する。Among the various combinations described above, heat-sensitive recording paper using a combination of a basic dye and a coloring agent is common, so this combination will be specifically explained below.
先ず、塩基性染料としては各種のものが公知であり、例
えば下記が例示される。First, various types of basic dyes are known, and the following are exemplified.
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、３．３−ビス（ｐ−ジメチルアミ
ノフェニル）フタリド、３−（ｐ−ジメチルアミノフェ
ニル）−３−（１，２−ジメチルインドール−３−イル
）フタリド、３− （ｐ−ジメチルアミノフェニル）−
３−（２−メチルインドール３−イル）フタリド等のト
リアリルメタン系染料、４．４”−ビス−ジメチルアミ
ノベンズヒドリルベンジルエーテル、Ｎ−ハロフェニル
−ロイコオーラミン、Ｎ−２，４，５−）リクロ口フェ
ニルロイコオ−ラミン等のジフェニルメタン系染料、ベ
ンゾイルロイコメチレンブルー、ｐ−ニトロベンゾイル
ロイコメチレンブルー等のチアジン系染料、３メチル−
スピロ−ジナフトピラン、３−エチルスピロ−ジナフト
ピラン、３−フェニル−スピロ−ジナフトピラン等のス
ピロ系染料、ローダミン−Ｂ−アニリノラクタム、ロー
ダミン（ｐ−ニトロアニリノ）ラクタム等のラクタム系
染料、３−ジメチルアミノ−７−メトキシフルオラン、
３−ジエチルアミノ−６−メトキシフルオラン、３−ジ
エチルアミンー７−メトキシフルオラン、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′
−６−メチル−７−クロロフルオラン等のフルオラン系
染料等。勿論、これらの染料に限定されるものではなく
、二種以上の染料の併用も可能である。3.3-bis(p-dimethylaminophenyl)-6dimethylaminophthalide, 3.3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2- dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-
Triallylmethane dyes such as 3-(2-methylindol-3-yl)phthalide, 4.4''-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leucoolamine, N-2,4,5 -) Diphenylmethane dyes such as cyclophenylleucoolamine, thiazine dyes such as benzoylleucomethylene blue, p-nitrobenzoylleucomethylene blue, 3-methyl-
Spiro dyes such as spiro-dinaphthopyran, 3-ethylspiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, lactam dyes such as rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, 3-dimethylamino-7 -methoxyfluorane,
3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino'
Fluoran dyes such as -6-methyl-7-chlorofluoran, etc. Of course, the dyes are not limited to these dyes, and two or more types of dyes can be used in combination.
また、上記塩基性染料と組合せて使用される呈色剤につ
いても各種の化合物が知られており、例えば下記が例示
される。Furthermore, various compounds are known as coloring agents to be used in combination with the above basic dyes, for example, the following are exemplified.
４−ｔｅｒｔ−ブチルフェノール、α−ナフトール、β
−ナフトール、４−アセチルフェノール、４ヒドロキシ
−４゛ −メトキシジフェニルスルホン、４−ヒドロキ
シ−３’、４’ −テトラメチレンジフェニルスルホン
、４−ヒドロキシ安息香酸ペンチル、４−ヒドロキシ安
息香酸ベンジル、サリチル酸、３−イソプロピルサリチ
ル酸等の芳香族カルボン酸、及びこれらフェノール性化
合物、芳香族カルボン酸と例えば亜鉛、マグネシウム、
アルミニウム等の多価金属との塩等の有機酸性物質等。4-tert-butylphenol, α-naphthol, β
-Naphthol, 4-acetylphenol, 4-hydroxy-4'-methoxydiphenylsulfone, 4-hydroxy-3',4'-tetramethylenediphenylsulfone, pentyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, salicylic acid, 3 - aromatic carboxylic acids such as isopropyl salicylic acid, and these phenolic compounds, aromatic carboxylic acids such as zinc, magnesium,
Organic acidic substances such as salts with polyvalent metals such as aluminum.
なお、これらの呈色剤も勿論必要に応じて２種以上を併
用することができる。Note that, of course, two or more of these coloring agents can be used in combination as necessary.
塩基性染料と呈色剤の使用比率は用いられる塩基性染料
や呈色剤の種類に応じて適宜選択されるもので、特に限
定されるものではないが、一般に塩基性染料１００重量
部に対して１００〜７００重量部、より好ましくは１５
０〜４００重量部程度の呈色剤が使用される。The ratio of the basic dye and coloring agent to be used is appropriately selected depending on the type of basic dye and coloring agent used, and is not particularly limited, but generally, the ratio is based on 100 parts by weight of the basic dye. 100 to 700 parts by weight, more preferably 15
About 0 to 400 parts by weight of coloring agent is used.
これらを含む塗液の調製は、一般に水を分散媒体とし、
ボールミル、アトライター、サンドミル等の攪拌、粉砕
機により、染料と呈色剤とを一緒に又は別々に分散する
などして調製される。Preparation of coating liquids containing these generally uses water as a dispersion medium,
It is prepared by dispersing the dye and coloring agent together or separately using a stirring or pulverizing machine such as a ball mill, attritor, or sand mill.
かかる塗）夜中には、通常接着剤として澱粉類、ヒドロ
キシエチルセルロース、メチルセルロース、カルボキシ
メチルセルロース、ゼラチン、カゼイン、アラビアガム
、ポリビニルアルコール、スチレン・無水マレイン酸共
重合体塩、スチレン・アクリル酸共重合体塩、スチレン
・ブタジェン共重合体エマルジョン等が全固形分の２〜
４０重量％、より好ましくは５〜２５重量％程度が配合
される。During the night, adhesives such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, gum arabic, polyvinyl alcohol, styrene/maleic anhydride copolymer salt, styrene/acrylic acid copolymer salt are used. , styrene-butadiene copolymer emulsion, etc. with a total solids content of 2~
It is blended in an amount of about 40% by weight, more preferably about 5 to 25% by weight.
さらに、塗液中には各種の助剤を添加することができ、
例えばジオクチルスルフォコハク酸ナトリウム、ドデシ
ルベンゼンスルフオン酸ナトリウム、ラウリルアルコー
ル硫酸エステル・ナトリウム塩、脂肪酸金属塩等の分散
剤、その他項泡剤、蛍光染料、着色染料等が挙げられる
。Furthermore, various auxiliary agents can be added to the coating liquid.
Examples include dispersants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, fatty acid metal salts, other foaming agents, fluorescent dyes, and coloring dyes.
また、ヘッドへのカス付着を改善するためにカオリン、
クレー、タルク、炭酸カルシウム等の無機顔料を添加す
ることもできる。その他必要に応じて紫外線吸収剤や増
感剤を本発明の所望の効果を損なわない範囲で適宜添加
することができる。In addition, kaolin is added to improve the adhesion of residue to the head.
Inorganic pigments such as clay, talc, calcium carbonate, etc. can also be added. In addition, ultraviolet absorbers and sensitizers may be added as appropriate within a range that does not impair the desired effects of the present invention.
本発明の感熱記録紙において、記録層の形成方法につい
ては特に限定されるものではなく、従来から周知慣用の
技術に従って形成することができる。例えば感熱記録層
用の塗液を、原紙上に塗布する方法ではエヤーナイフコ
ーター、ブレードコーター、バーコーター、グラビヤコ
ーター、カーテンコーター等の適当な塗布装置が用いら
れる。In the thermal recording paper of the present invention, the method of forming the recording layer is not particularly limited, and can be formed according to conventionally well-known and commonly used techniques. For example, in a method of applying a coating liquid for a heat-sensitive recording layer onto a base paper, an appropriate coating device such as an air knife coater, a blade coater, a bar coater, a gravure coater, a curtain coater, etc. is used.
又、塗液の塗布量についても特に限定されるものではな
く、一般に乾燥重量で２〜１２ ｇ ／ ｒｄ、好まし
くは３〜１０ ｇ ／ ｃｄの範囲で調節される。Further, the amount of the coating liquid to be applied is not particularly limited, and is generally adjusted in the range of 2 to 12 g/rd, preferably 3 to 10 g/cd in terms of dry weight.
なお、記録層上には記録層を保護する等の目的でオーバ
ーコート層を設けることも可能であり、原紙の裏面に保
護層を設けたり、原紙と感熱記録層との間に下塗り層を
設けることも勿論可能であり、さらには粘着加工を施す
など感熱記録紙製造分野における各種の公知技術が付加
し得るものである。Note that it is also possible to provide an overcoat layer on the recording layer for the purpose of protecting the recording layer, etc. A protective layer can be provided on the back side of the base paper, or an undercoat layer can be provided between the base paper and the heat-sensitive recording layer. Of course, this is also possible, and various known techniques in the field of heat-sensitive recording paper manufacturing, such as applying adhesive processing, can be added.
なお、コロイド状ケイ酸の粒子径は電子類ｗＬ鏡法によ
って測定した。また、カチオン性澱粉のカチオン性基の
置換度（Ｄ、Ｓ）は下記の式により算出して求めた。In addition, the particle diameter of colloidal silicic acid was measured by electronic wL mirror method. Further, the degree of substitution (D, S) of the cationic groups of the cationic starch was calculated and determined using the following formula.
Ｄ、Ｓ ；カチオン性基の置換度
Ｎ ：ケルプール法により測定した
チッ素含有量（％ａｓＮ）
「実施例」
以下に実施例を挙げて本発明をより具体的に説明するが
、勿論これらに限定されるものではない。D, S: Substitution degree of cationic group N: Nitrogen content (%asN) measured by Kelpool method "Example" The present invention will be explained in more detail by referring to Examples below, but of course there are It is not limited.
なお、例中の部及び％は、特に断らない限りそれぞれ重
量部及び重量％を示す。Note that parts and % in the examples indicate parts by weight and % by weight, respectively, unless otherwise specified.
実施例１
〔原紙の調製〕
ＬＢＫＰ （フリーネス／ＣＳＦ：４００ ｍｌ） ７
５部とＮＢＫＰ （フリーネス／Ｃ３Ｆ：４６０ ｍｌ
） ２５部の配合からなるノぐルプスラリーに重質炭酸
カルシウム（商品名；ラフトン１２００．備北粉化工業
社製）２０部を添加し、６部Ｍバンド０．５部、Ｄ、Ｓ
が０．０３５のカチオン＋１ 馬鈴薯澱粉（商品名；
ＢＭＢ、日量エカノーベル社製）０．５部及びアルキル
ケテンダイマー（商品名；サイズパインに−９０２，洗
用化学社製）１．０部を加えた。更に、白水で希釈した
後、平均粒子径が５部ｍのコロイド状ケイ酸（商品名；
ＢＭＡ、口座エカノーヘル社製）０．１部をよく撹拌
しながら添加してｐｉ８．０ 、濃度０．７％の紙料を
調製した。このようにして得た紙料を角型シートマシン
を用いて手抄きシートを作成し、乾燥シートを得た。Example 1 [Preparation of base paper] LBKP (Freeness/CSF: 400 ml) 7
Part 5 and NBKP (Freeness/C3F: 460 ml
) Added 20 parts of heavy calcium carbonate (trade name: Laughton 1200, manufactured by Bihoku Funka Kogyo Co., Ltd.) to Nogurupu slurry consisting of 25 parts, 6 parts M band 0.5 part, D, S
0.035 cation + 1 potato starch (product name;
0.5 part of BMB (manufactured by Eka Nobel Co., Ltd.) and 1.0 part of alkyl ketene dimer (trade name: Size Pine ni-902, manufactured by Senyou Kagaku Co., Ltd.) were added. Further, after diluting with white water, colloidal silicic acid (trade name;
0.1 part of BMA (manufactured by Ekanohel Co., Ltd.) was added with thorough stirring to prepare a paper stock having a pi of 8.0 and a concentration of 0.7%. A handsheet was prepared from the paper stock thus obtained using a square sheet machine, and a dry sheet was obtained.
次いで、予め濃度２８％、９５℃、３０分間蒸煮して得
た酸化澱粉（商品名；エースＡ、王子ナショナルスター
チ社製）を３．０％に希釈し、サイズプレス装置を用い
て、先に調製した手抄きシートに乾燥重量がＬｇ／ｒｄ
となるように塗布した。乾燥後、米坪が４０ｇ／ｒ＋（
の原紙を得た。Next, oxidized starch (trade name: Ace A, manufactured by Oji National Starch Co., Ltd.) obtained by steaming in advance at 28% concentration at 95°C for 30 minutes was diluted to 3.0%, and using a size press device, The prepared handmade sheet has a dry weight of Lg/rd.
It was applied so that After drying, the weight is 40g/r+(
The original paper was obtained.
焼成カオリン１００部、スチレン−ブタジェン共重合体
ラテンクス（固形分濃度：４８％）１２部、１０％ポリ
ビニルアルコール水溶液６０部、水２７５部を混合・分
散して下塗り履用の塗液を調製した。A coating liquid for undercoating was prepared by mixing and dispersing 100 parts of calcined kaolin, 12 parts of styrene-butadiene copolymer Latinx (solid content concentration: 48%), 60 parts of a 10% aqueous polyvinyl alcohol solution, and 275 parts of water.
この塗液を上記で得た原紙上に、乾燥後の塗布量が８．
５ｇ／ｍとなるように塗布・乾燥して下塗り層を形成し
た。This coating liquid was applied onto the base paper obtained above, and the coating amount after drying was 8.
An undercoat layer was formed by coating and drying to a concentration of 5 g/m.
３−（Ｎ−シクロへキシル−Ｎ−メチルアミノ−６メチ
ル一７−フエニルアミノフルオラン１０部
メチルセルロース ５％水溶液 ２０部水
ｉｏ部この
組成物をサンドミルで平均粒子径が３μｍとなるまで粉
砕した。3-(N-cyclohexyl-N-methylamino-6methyl-7-phenylaminofluorane 10 parts Methyl cellulose 5% aqueous solution 20 parts water
io part This composition was ground in a sand mill until the average particle size was 3 μm.
ビスフェノールＡ ３０部メチ
ルセルロース ５％水溶液 ７０部水
２０部この組成物
をサンドミルで平均粒子径が３μｍとなるまで粉砕した
。Bisphenol A 30 parts Methylcellulose 5% aqueous solution 70 parts Water
20 parts of this composition was ground in a sand mill until the average particle size was 3 μm.
Ａ液４０部、Ｂ液８０部、酸化珪素顔料（吸油Ｍ：１８
０ ｍｌ／１００ ｇ）３０部、２０％酸化澱粉水溶液
１００部、水７０部を混合、攪拌して感熱記録用塗液を
調製した。得られた塗液を、上記下塗り層を有する原紙
上に乾燥後の塗布量が１ｇ／ｎｒとなるように塗布、乾
燥して感熱記録紙を得た。40 parts of liquid A, 80 parts of liquid B, silicon oxide pigment (oil absorption M: 18
0 ml/100 g), 100 parts of a 20% oxidized starch aqueous solution, and 70 parts of water were mixed and stirred to prepare a coating liquid for thermal recording. The obtained coating liquid was applied onto the base paper having the undercoat layer so that the coating amount after drying was 1 g/nr, and dried to obtain a heat-sensitive recording paper.
実施例２
〔原紙の調製〕
実施例１において、カチオン性澱粉及びコロイド状ケイ
酸をそれぞれ１部及び０．５部添加に代えた以外は同様
にして米坪４０ｇ／ｍの原紙を得た。Example 2 [Preparation of base paper] A base paper with a basis weight of 40 g/m was obtained in the same manner as in Example 1, except that 1 part and 0.5 parts of cationic starch and colloidal silicic acid were added, respectively.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
実施例３
〔原紙の調製〕
実施例１と同じバルブスラリーに填料として軽質炭酸カ
ルシウム（商品名：タフパール１２１．奥多摩工業社製
）１０部とタルク１０部を添加し、硫酸バンド０゜５部
、実施例１で使用のカチオン性澱粉１．５部及び予めカ
チオン性澱粉（商品名、 ＣＡＴＯ１５，王子ナショナ
ルスターチ社製）で乳化しておいたアルケニル無水コハ
ク酸（商品名；ファイブラン６８゜玉子ナショナルスタ
ーチ社製）１部を添加した。Example 3 [Preparation of base paper] To the same valve slurry as in Example 1, 10 parts of light calcium carbonate (trade name: Tough Pearl 121, manufactured by Okutama Kogyo Co., Ltd.) and 10 parts of talc were added as fillers, and 0.5 parts of sulfate band, 1.5 parts of the cationic starch used in Example 1 and alkenyl succinic anhydride (trade name: Fiveran 68° Egg National) which had been emulsified in advance with cationic starch (trade name: CATO15, manufactured by Oji National Starch Co., Ltd.) 1 part (manufactured by Starch) was added.
次いで、これを白水で希釈し、実施例１で使用のコロイ
ド状ケイ酸を１部添加した。その他は実施例１と同様に
して米坪４０ｇ／ｒｙｒの原紙を得た。This was then diluted with white water and 1 part of the colloidal silicic acid used in Example 1 was added. Otherwise, a base paper having a basis weight of 40 g/ryr was obtained in the same manner as in Example 1.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
実施例４
〔原紙の調製〕
実施例１で使用したものと同一のカチオン性澱粉及びコ
ロイド状ケイ酸をそれぞれ３部及び２部とした以外は実
施例１と同様にして米坪４０ｇ／ｎ（の原紙を得た。Example 4 [Preparation of base paper] A paper was prepared in the same manner as in Example 1 except that the same cationic starch and colloidal silicic acid used in Example 1 were changed to 3 parts and 2 parts, respectively. The original paper was obtained.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
実施例５
〔原紙の調製〕
実施例２で使用のカチオン性澱粉をり、Ｓが０．０４の
カチオン性タピオカ澱粉（商品名；ネオポジバリン＃３
５．松谷化学社製）１部に置換えた以外は実施例２と同
様にして米坪４０ ｇ ／ ｒｒｒの原紙を得た。Example 5 [Preparation of base paper] The cationic starch used in Example 2 was filtered and the cationic tapioca starch with S of 0.04 (trade name: Neoposibalin #3
5. A base paper having a weight of 40 g/rrr was obtained in the same manner as in Example 2, except that 1 part (manufactured by Matsutani Chemical Co., Ltd.) was used.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
実施例６
〔原紙の調製〕
実施例２で使用のカチオン性澱粉をり、Ｓが０．０４５
のカチオン性馬鈴薯澱粉（商品名；アミロファックスＨ
３，アベベ社製）１部に置換えた以外は実施例２と同様
にして米坪４０ｇ／ｎ？の原紙を得た。Example 6 [Preparation of base paper] The cationic starch used in Example 2 was removed, and S was 0.045.
cationic potato starch (product name: Amylofax H)
3, manufactured by Abebe Co., Ltd.) in the same manner as in Example 2 except that the weight was 40 g/n? The original paper was obtained.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
実施例７
〔原紙の調製〕
硫酸バンドに代えて、塩基性ポリ水酸化アルミニウム（
商品名；Ｐａｈｏ＃２Ｓ、浅田化学工業社製）を０．２
部添加した以外は、実施例２と同様にして米坪４０ｇ／
ｒｄの原紙を得た。Example 7 [Preparation of base paper] Basic polyaluminum hydroxide (
Product name: Paho#2S, manufactured by Asada Chemical Industry Co., Ltd.) at 0.2
The same procedure as in Example 2 was carried out except that 40 g of
A rd base paper was obtained.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
実施例８
〔原紙の調製〕
実施例２で使用したコロイド状ケイ酸を粒子径が１０〜
２０ｎｍのコロイド状ケイ酸（商品名；スノーテックス
２０１日照化学社製）の０．５部添加に代えた以外は実
施例２と同様にして米坪４０ ｇ ／ ｒｄの原紙を得
た。Example 8 [Preparation of base paper] The colloidal silicic acid used in Example 2 was
A base paper weighing 40 g/rd was obtained in the same manner as in Example 2, except that 0.5 part of 20 nm colloidal silicic acid (trade name: Snowtex 201 manufactured by Nissho Kagaku Co., Ltd.) was added.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
実施例９
〔原紙の調製〕
実施例２で、硫酸バンドを添加しなかった以外は、実施
例２と同様にして米坪４０ ｇ ／ ｒｒｒの原紙を得
た。Example 9 [Preparation of base paper] A base paper having a basis weight of 40 g/rrr was obtained in the same manner as in Example 2, except that sulfate was not added.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
比較例１
〔原紙の調製〕
実施例２で使用したコロイド状ケイ酸に代えてアニオン
性ポリアクリルアミド（商品名：パーコール１５５．ア
ライド・コロイド社製）を０．０２部添加とした以外は
、同様にして米坪４０ｇ／ｎ（の原紙を得た。Comparative Example 1 [Preparation of base paper] Same procedure except that 0.02 part of anionic polyacrylamide (trade name: Percoll 155, manufactured by Allied Colloid) was added instead of the colloidal silicic acid used in Example 2. A base paper with a weight of 40 g/n was obtained.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
比較例２
〔原紙の調製〕
実施例２で使用したカチオン性Ｒ粉をカチオン性基の置
換度が０．０１８のカチオン性馬鈴薯澱粉（商品名；ア
ミロファックスＯＯ，アベヘ社製）１部に代えた以外は
実施例２と同様にして米坪４０ｇ／ｍ′の原紙を得た。Comparative Example 2 [Preparation of base paper] The cationic R powder used in Example 2 was replaced with 1 part of cationic potato starch (trade name: Amylofax OO, manufactured by Abehe Co., Ltd.) with a degree of substitution of cationic groups of 0.018. A base paper having a basis weight of 40 g/m' was obtained in the same manner as in Example 2 except for the above.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
比較例３
〔原紙の調製〕
実施例２で使用のカチオン性澱粉をカチオン性基の置換
度０．０７のカチオン性馬鈴薯澱粉（商品名；ボーザミ
ルＥ７．アベベ社製）１部に置換えた以外は実施例２と
同様にして米坪４０ｇ／ｒｄの原紙を得た。Comparative Example 3 [Preparation of base paper] Except that the cationic starch used in Example 2 was replaced with 1 part of cationic potato starch (trade name: Bozamil E7, manufactured by Abebe) with a degree of substitution of cationic groups of 0.07. A base paper having a weight of 40 g/rd was obtained in the same manner as in Example 2.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
比較例４
〔原紙の調製〕
実施例２で使用のコロイド状ケイ酸を粒子径が４０〜５
０ｎｍのコロイド状ケイ酸（商品名ニスノーテックス２
０Ｌ、口座化学社製）の０．５部添加に代えた以外は実
施例２と同様にして米坪４０ ｇ ／ ｒｄの原紙を得
た。Comparative Example 4 [Preparation of base paper] The colloidal silicic acid used in Example 2 was prepared with a particle size of 40 to 5.
0nm colloidal silicic acid (product name Nisnortex 2)
A base paper having a weight of 40 g/rd was obtained in the same manner as in Example 2, except that 0.5 part of 0L (manufactured by Kaguchi Kagaku Co., Ltd.) was added.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
以上で得られた１０種類の感熱記録紙はいずれも所謂中
性紙を支持体として調製されたものである。The ten types of thermal recording papers obtained above were all prepared using so-called neutral paper as a support.
次に、酸性紙を支持体とした感熱記録紙について実施例
を挙げて説明する。Next, a thermal recording paper using acidic paper as a support will be described with reference to examples.
実施例ＩＯ
〔原紙の調製〕
実施例１と同じパルプ配合スラリーにタルク２０部を添
加し、ロジン１．０部、硫酸バンド２．０部を添加し、
白水で希釈した。次いで、実施例１で使用したコロイド
状ケイ酸（商品名、 ＢＭＡ）０．５部及びカチオン性
澱粉（商品名ｉ ＢＭＢ） １部をよく攪拌しながら順
次添加し、ｐｌ＋ ４．６、濃度０．７％の紙料を調製
した。以後の工程は実施例１と同様にして米坪４０ ｇ
／ ｇの原紙を得た。Example IO [Preparation of base paper] To the same pulp blend slurry as in Example 1, 20 parts of talc was added, 1.0 parts of rosin, and 2.0 parts of aluminum sulfate were added,
Diluted with white water. Next, 0.5 part of colloidal silicic acid (trade name, BMA) used in Example 1 and 1 part of cationic starch (trade name i BMB) were added one after another with good stirring to give a pl+ of 4.6 and a concentration of 0. A .7% stock was prepared. The subsequent steps were carried out in the same manner as in Example 1.
/g of base paper was obtained.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
実施例１）
〔原紙の調製〕
実施例１０で使用したカチオン性澱粉を実施例５で使用
したカチオン性タピオカ澱粉１部と置換えた以外は実施
例１０と同様にして米坪４０ｇ／ｒｄの原紙を得た。Example 1) [Preparation of base paper] A base paper with a basis weight of 40 g/rd was prepared in the same manner as in Example 10, except that the cationic starch used in Example 10 was replaced with 1 part of the cationic tapioca starch used in Example 5. I got it.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして怒言外記録紙を得た。A recording paper for angry words was obtained in the same manner as in Example 1, except that the base paper having the above-mentioned undercoat layer was used.
比較例５
〔原紙の調製〕
実施例１０で、コロイド状ケイ酸を添加しなかった以外
は実施例ＩＯと同様にして米坪４０ ｇ ／ ｒｄの原
紙を得た。Comparative Example 5 [Preparation of Base Paper] A base paper having a basis weight of 40 g/rd was obtained in the same manner as in Example IO except that no colloidal silicic acid was added in Example 10.
実施例１と同様にして上記原紙上に下塗り層を形成した
。An undercoat layer was formed on the base paper in the same manner as in Example 1.
〔感熱記録紙の作成〕
実施例１において、上記下塗り層を有する原紙を使用し
た以外は同様にして感熱記録紙を得た。[Preparation of thermal recording paper] A thermal recording paper was obtained in the same manner as in Example 1 except that the base paper having the above-mentioned undercoat layer was used.
以上の１６種類の感熱記録紙をサーマルプリンター （
ＵＰ−１０３，ソニー社製）を用いて印字プリンター巾
５ｍＳで印字し、その画像濃度をマクベス濃度計（アン
バーフィルター使用）にて測定した。また、平滑度はＪ
ＩＳ Ｐ ８１）９ （ベック平滑度計を使用）に準じ
て測定し、得られた結果を表−１に示した。The above 16 types of thermal recording paper can be printed on a thermal printer (
UP-103, manufactured by Sony Corporation) to print with a printer width of 5 mS, and the image density was measured with a Macbeth densitometer (using an amber filter). Also, the smoothness is J
It was measured according to ISP 81) 9 (using a Beck smoothness meter), and the obtained results are shown in Table 1.
なお、記録層表面の画質を目視評価し、その結果を併せ
て表−１に示した。The image quality on the surface of the recording layer was visually evaluated, and the results are also shown in Table 1.
なお、評価基準は以下の通りである。The evaluation criteria are as follows.
画像濃度；値が大きい程、濃度が高い。Image density: The larger the value, the higher the density.
画質； ◎−画質が極めて優れている。image quality; ◎-The image quality is extremely excellent.
〇−画質が良好である。- Image quality is good.
△＝画質が微かに劣っている。△=Image quality is slightly inferior.
平滑度：値が大きい程、平滑度が良い。Smoothness: The larger the value, the better the smoothness.
表−１
「効果」
表−１の結果から明らかなように、本発明の感熱記録紙
はいずれも記録感度が優れ、且つ平滑度及び画質の優れ
たものであった。Table 1 "Effects" As is clear from the results in Table 1, all of the thermal recording papers of the present invention had excellent recording sensitivity, as well as excellent smoothness and image quality.
Claims (7)
澱粉を添加して得た原紙上に感熱記録層を設けたことを
特徴とする感熱記録紙。(1) A thermal recording paper characterized in that a thermal recording layer is provided on a base paper obtained by adding colloidal silicic acid and cationic starch to pulp slurry.
澱粉及び水溶性アルミニウム化合物を添加して得た原紙
上に感熱記録層を設けたことを特徴とする感熱記録紙。(2) A thermosensitive recording paper characterized in that a thermosensitive recording layer is provided on a base paper obtained by adding colloidal silicic acid, cationic starch, and a water-soluble aluminum compound to pulp slurry.
２〜０．０５である請求項（１）又は（２）記載の感熱
記録紙。(3) The degree of substitution of cationic groups in cationic starch is 0.0
2-0.05. The thermal recording paper according to claim 1 or 2, wherein
ｍである請求項（１）、（２）又は（３）記載の感熱記
録紙。(4) The average particle diameter of colloidal silicic acid is 1 nm to 20 nm.
The heat-sensitive recording paper according to claim (1), (2) or (3), which is m.
０．０５重量％以上且つコロイド状ケイ酸とカチオン性
澱粉の合計量が０．１〜１０重量％である請求項（１）
、（２）、（３）又は（４）記載の感熱記録紙。(5) Claim (1) wherein the amount of colloidal silicic acid added is 0.05% by weight or more based on the pulp fiber content, and the total amount of colloidal silicic acid and cationic starch is 0.1 to 10% by weight.
, (2), (3) or (4).
分に対し０．０１〜５重量％である請求項（１）、（２
）、（３）、（４）又は（５）記載の感熱記録紙。(6) Claims (1) and (2) wherein the amount of water-soluble aluminum compound added is 0.01 to 5% by weight based on the pulp fiber content.
), (3), (4) or (5).
料を含む請求項（１）、（２）、（３）、（４）、（５
）又は（６）記載の感熱記録紙。(7) Claims (1), (2), (3), (4), (5) in which the pulp slurry contains a filler mainly composed of calcium carbonate.
) or the thermal recording paper described in (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1203622A JPH0749232B2 (en) | 1988-08-15 | 1989-08-03 | Thermal recording paper |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20298088 | 1988-08-15 | ||
| JP63-202980 | 1988-08-15 | ||
| JP1203622A JPH0749232B2 (en) | 1988-08-15 | 1989-08-03 | Thermal recording paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02139277A true JPH02139277A (en) | 1990-05-29 |
| JPH0749232B2 JPH0749232B2 (en) | 1995-05-31 |
Family
ID=26513677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1203622A Expired - Fee Related JPH0749232B2 (en) | 1988-08-15 | 1989-08-03 | Thermal recording paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0749232B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62138286A (en) * | 1985-12-11 | 1987-06-22 | Honshu Paper Co Ltd | Thermal recording element |
-
1989
- 1989-08-03 JP JP1203622A patent/JPH0749232B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62138286A (en) * | 1985-12-11 | 1987-06-22 | Honshu Paper Co Ltd | Thermal recording element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0749232B2 (en) | 1995-05-31 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |