JPH01306281A - Heat-sensitive recording material - Google Patents
Heat-sensitive recording materialInfo
- Publication number
- JPH01306281A JPH01306281A JP63137868A JP13786888A JPH01306281A JP H01306281 A JPH01306281 A JP H01306281A JP 63137868 A JP63137868 A JP 63137868A JP 13786888 A JP13786888 A JP 13786888A JP H01306281 A JPH01306281 A JP H01306281A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- binder
- recording material
- dispersant
- thermal deformation
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 36
- 239000002270 dispersing agent Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229920002907 Guar gum Polymers 0.000 claims description 22
- 239000000665 guar gum Substances 0.000 claims description 22
- 235000010417 guar gum Nutrition 0.000 claims description 22
- 229960002154 guar gum Drugs 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 21
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 4
- 239000010419 fine particle Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 24
- 238000004040 coloring Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 17
- 239000000049 pigment Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- -1 waxite Chemical compound 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
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- 239000002245 particle Substances 0.000 description 5
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 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 4
- 239000000243 solution Substances 0.000 description 4
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- 235000014113 dietary fatty acids Nutrition 0.000 description 3
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- 239000000194 fatty acid Substances 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- CMHMMKSPYOOVGI-UHFFFAOYSA-N Isopropylparaben Chemical compound CC(C)OC(=O)C1=CC=C(O)C=C1 CMHMMKSPYOOVGI-UHFFFAOYSA-N 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
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- 150000003457 sulfones Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Chemical class C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-UHFFFAOYSA-N 0.000 description 1
- ZDRSNHRWLQQICP-UHFFFAOYSA-N 2-tert-butyl-4-[2-(3-tert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 ZDRSNHRWLQQICP-UHFFFAOYSA-N 0.000 description 1
- ZKUWHPNJONEJEE-UHFFFAOYSA-N 3-[4-(dimethylamino)phenyl]-3-(2-methyl-1h-indol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C3=CC=CC=C3NC=2C)C2=CC=CC=C2C(=O)O1 ZKUWHPNJONEJEE-UHFFFAOYSA-N 0.000 description 1
- WKMGGJIKSXAHAM-UHFFFAOYSA-N 3-[4-(dimethylamino)phenyl]-3-(2-phenyl-1h-indol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C3=CC=CC=C3NC=2C=2C=CC=CC=2)C2=CC=CC=C2C(=O)O1 WKMGGJIKSXAHAM-UHFFFAOYSA-N 0.000 description 1
- MTMKZABGIQJAEX-UHFFFAOYSA-N 4,4'-sulfonylbis[2-(prop-2-en-1-yl)phenol] Chemical compound C1=C(CC=C)C(O)=CC=C1S(=O)(=O)C1=CC=C(O)C(CC=C)=C1 MTMKZABGIQJAEX-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- ZQTPHEAGPRFALE-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)hexan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCC)C1=CC=C(O)C=C1 ZQTPHEAGPRFALE-UHFFFAOYSA-N 0.000 description 1
- WCUDAIJOADOKAW-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)pentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCC)C1=CC=C(O)C=C1 WCUDAIJOADOKAW-UHFFFAOYSA-N 0.000 description 1
- KFMASHHCLJTUDI-UHFFFAOYSA-N 4-[2-[2,2-bis[4-(dimethylamino)phenyl]-1-phenylethoxy]-1-[4-(dimethylamino)phenyl]-2-phenylethyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C(C=1C=CC=CC=1)OC(C=1C=CC=CC=1)C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 KFMASHHCLJTUDI-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RNRINRUTVAFUCG-UHFFFAOYSA-N 5-(dimethylamino)-3,3-bis(1,2-dimethylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC=C2C(C3(C=4C5=CC=CC=C5N(C)C=4C)OC(=O)C4=CC=C(C=C43)N(C)C)=C(C)N(C)C2=C1 RNRINRUTVAFUCG-UHFFFAOYSA-N 0.000 description 1
- KGYNGVVNFRUOOZ-UHFFFAOYSA-N 5-chloro-2-hydroxy-n-phenylbenzamide Chemical class OC1=CC=C(Cl)C=C1C(=O)NC1=CC=CC=C1 KGYNGVVNFRUOOZ-UHFFFAOYSA-N 0.000 description 1
- XAICWTLLSRXZPB-UHFFFAOYSA-N 5-tert-butyl-2-hydroxybenzoic acid Chemical class CC(C)(C)C1=CC=C(O)C(C(O)=O)=C1 XAICWTLLSRXZPB-UHFFFAOYSA-N 0.000 description 1
- AMIKAFQVXXDUHJ-UHFFFAOYSA-N 6-n,6-n-diethyl-2-n-fluorooctane-2,6-diamine Chemical compound CCN(CC)C(CC)CCCC(C)NF AMIKAFQVXXDUHJ-UHFFFAOYSA-N 0.000 description 1
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical class CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 1
- 206010016807 Fluid retention Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 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
- 229910052791 calcium 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
- 238000003490 calendering Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960002216 methylparaben Drugs 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- BRNPAEUKZMBRLQ-UHFFFAOYSA-N octadecyl 3,4,5-trihydroxybenzoate Chemical class CCCCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 BRNPAEUKZMBRLQ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- WKEDVNSFRWHDNR-UHFFFAOYSA-N salicylanilide Chemical class OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 WKEDVNSFRWHDNR-UHFFFAOYSA-N 0.000 description 1
- 229950000975 salicylanilide Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
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- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
(A)産業上の利用分野
本発明は感熱記録材料に係わる物で、更に詳細には通常
無色乃至淡色の染料前駆体と、加熱時反応して該染料前
駆体を発色させる顕色剤及び増感剤を分散剤と共に水中
に微細粒子状に分散し、夫々の分散液をバインダー、と
共に混合して支持体に塗布して屹燥する事により製造さ
れる感熱記録材料に係わる物である。DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Field of Application The present invention relates to a heat-sensitive recording material, and more specifically, the present invention relates to a heat-sensitive recording material. A heat-sensitive recording material manufactured by dispersing a color developer and a sensitizer for color development into fine particles in water together with a dispersant, mixing each dispersion liquid with a binder, applying the mixture to a support, and drying it. It is related to.
(B)従来技術及び問題点 感熱記録材料は基本的に下記手順で製造される。(B) Prior art and problems A thermosensitive recording material is basically manufactured by the following procedure.
即ち、先ず染料前駆体、顕色剤及び増感剤を単独あるい
は混合して分散剤を含む水中に分散し、サンドミル、又
はボールミル等で処理して微細化し、微細粒子よりなる
分散液とする。That is, first, a dye precursor, a color developer, and a sensitizer are dispersed alone or in combination in water containing a dispersant, and the mixture is milled using a sand mill or a ball mill to form a dispersion of fine particles.
次に染料前駆体微細分散液、顕色剤微細分散液及び増感
剤微細分散液ならびにバインダー等をよく攪拌、混合し
て得た感熱塗液を紙等の基材上に均一に塗布、乾燥し感
熱発色層を形成する。しかる後、スーパーカレンダーで
表面を平滑にして感熱記録材料が得られる。Next, the dye precursor fine dispersion, color developer fine dispersion, sensitizer fine dispersion, binder, etc. are thoroughly stirred and mixed to obtain a heat-sensitive coating liquid, which is then uniformly applied onto a substrate such as paper and dried. to form a thermosensitive coloring layer. Thereafter, the surface is smoothed using a supercalender to obtain a heat-sensitive recording material.
上記の感熱塗液に用いられる分散剤及びバインダーには
次の性質が要求される。The following properties are required of the dispersant and binder used in the above heat-sensitive coating liquid.
(1)分散剤とバインダーは相溶性が良好で、染料前駆
体、顕色剤及び増感剤の分散液とバインダーを混合する
際に均一に混合すること。(1) The dispersant and the binder should have good compatibility and be uniformly mixed when the dispersion of the dye precursor, developer, and sensitizer is mixed with the binder.
(2)分散剤の粘度が過度に高く、その結果としてサン
ドミル等の破砕効率を低下させる事が無いこと。又、発
泡性が低く、且つ消泡が早いこと。(2) The viscosity of the dispersant is not excessively high, which will not reduce the crushing efficiency of a sand mill or the like. Also, the foaming property is low and defoaming is quick.
(3)染料前駆体、顕色剤又は増感剤と反応を生じたり
する好ましくない相互作用が無いこと。(3) There is no unfavorable interaction with the dye precursor, color developer, or sensitizer that would cause a reaction.
(4)バインダーは膠着力が高く、感熱記録材料とした
際に充分なピッキング強度を示すこと。(4) The binder must have high adhesion and exhibit sufficient picking strength when used as a heat-sensitive recording material.
このような分散剤及びバインダーは非常に限られており
、主たる分散剤、兼バインダーとしてポリビニルアルコ
ールが用いられる例が多い(例えば特開昭59−227
92号公報)が、更に破砕効率を上げる目的でスチレン
−無水マイレン酸コポリマーの如き水溶性高分子である
分散剤を用いて染料前駆体微細分散液、顕色剤微細分散
液及び増感剤微細分散液を得た後、ポリビニルアルコー
ルを混合し使用される。Such dispersants and binders are very limited, and polyvinyl alcohol is often used as the main dispersant and binder (for example, JP-A-59-227
92), in order to further increase the crushing efficiency, a fine dispersion of a dye precursor, a fine color developer, and a fine sensitizer was prepared using a dispersant which is a water-soluble polymer such as a styrene-maleic anhydride copolymer. After obtaining the dispersion, polyvinyl alcohol is mixed and used.
しかし、上記の構成では、プリンター等に装着されてい
る加熱によって感熱発色層を発色させるサーマルヘッド
の発熱部の付近に熱可融性物質か付着してサーマルヘッ
ドを損傷したり印字品質の低下をきたす所謂カスが発生
する為、多くの場合カスの発生量を抑える目的で高い吸
油量を示すケイ酸、尿素樹脂顔料、又は軽質炭酸カルシ
ウム等の顔料が単独、又は混合使用される。しかし顔料
の添加量が多くなると同じ温度迄昇温させるに要する熱
母が増加し、同一印加エネルギーでの発色濃度が低下す
る所謂感度低下を起す等悪影響を生ずる。又、カス抑制
効果も不満足なレベルであった。However, with the above configuration, a thermofusible substance may adhere to the vicinity of the heat generating part of the thermal head installed in the printer, which generates color in the heat-sensitive coloring layer by heating, damaging the thermal head or degrading print quality. In many cases, pigments such as silicic acid, urea resin pigments, or light calcium carbonate, which exhibit high oil absorption, are used alone or in combination in order to suppress the amount of dregs generated. However, when the amount of pigment added increases, the heat source required to raise the temperature to the same temperature increases, causing adverse effects such as a so-called decrease in sensitivity, in which the color density decreases with the same applied energy. Moreover, the scum suppression effect was also at an unsatisfactory level.
(C)発明の目的
本発明の目的は感熱記録材料に於てカスの発生量が少な
い感熱記録材料を得る事である。(C) Purpose of the Invention The purpose of the present invention is to obtain a heat-sensitive recording material in which the amount of residue generated is small.
(D>問題点を解決するための手段
本発明者等は、主として微粒子化した通常無色乃至淡色
の染料前駆体と、加熱時反応して該染料前駆体を発色さ
せる顕色剤及び増感剤、並びにバインダーを含有する感
熱発色層を支持体に設けた感熱記録材料に於いて、分散
剤及びバインダーの混合物の、デュポン製熱分析システ
ム990型のTMAモジューノい0943を用いて熱機
械分析を行なって得られた熱変形率Cは、室温での試料
の厚みをaとし、70℃での試料の厚みをbとした場合
、c= (a−b)x100/a (%)で求められ、
この熱変形率の値が4%以下である組合わせを用いるこ
とにより感度を低下させることなくカスの付着量を低減
させ得る事を見出した。(D> Means for Solving the Problems The present inventors mainly used a normally colorless to light-colored dye precursor that has been made into fine particles, and a color developer and a sensitizer that react with the dye precursor when heated to develop a color. , and a heat-sensitive recording material in which a heat-sensitive coloring layer containing a binder is provided on a support, a thermomechanical analysis of a mixture of a dispersant and a binder is performed using a DuPont thermal analysis system 990 model TMA module 0943. The thermal deformation coefficient C obtained is calculated as c = (a-b) x 100/a (%), where a is the thickness of the sample at room temperature and b is the thickness of the sample at 70 ° C.
It has been found that by using a combination with a thermal deformation rate of 4% or less, the amount of deposits can be reduced without reducing sensitivity.
分散剤とバインダーは従来技術の項で記した特性を有し
、且つ直上の条件を満たす組合わせであれば如何なる組
合わせでもよいが、その選択は簡単ではない。唯、単に
ぞの一方、又は双方に70°Cに於ける熱変形率が少な
い組合わせを選択しても混合物の70°Cに於ける熱変
形率はかえって増加する場合が多い。例えば分散剤とし
てメチルセルロースと、バインダーとしてポリビニルア
ルコールの70’Cに於ける上記熱変形率は夫々3.2
%、4.0%であるが、重量比1:3の混合物の熱変形
率は18%であった。Any combination of dispersant and binder may be used as long as it has the characteristics described in the prior art section and satisfies the above conditions, but the selection is not easy. However, even if a combination is selected in which one or both of them has a small thermal deformation rate at 70°C, the thermal deformation rate of the mixture at 70°C will often increase on the contrary. For example, the above heat distortion rate at 70'C of methylcellulose as a dispersant and polyvinyl alcohol as a binder is 3.2, respectively.
%, 4.0%, but the heat distortion rate of the mixture with a weight ratio of 1:3 was 18%.
又、ヒドロキシエチルセルロースの70°Ck:於ける
変形量は4%であるが、ヒドロキシエチルセルロースと
ポリビニルアルコールの重量比1:3の混合物の変形量
は5.3%であった。Further, the amount of deformation of hydroxyethyl cellulose at 70°Ck was 4%, but the amount of deformation of the mixture of hydroxyethyl cellulose and polyvinyl alcohol at a weight ratio of 1:3 was 5.3%.
これらの中で分散剤がスルホンMl含有ポリビニルアル
コールであり、バインダーがグアーガム又はグアーガム
誘導体である組合わせ、夫々がメチルセルロースとグア
ーガム又はグアーガム誘導体である組合わせ、夫々がヒ
ドロキシエチルセルロースとグアーガム又はグアーガム
誘導体である組合わせ、及び夫々がヒドロキシエチルセ
ルロースとポリアクリルアミドである組合わせが諸条件
を満たす。Among these, a combination in which the dispersant is polyvinyl alcohol containing sulfone Ml and a binder is guar gum or a guar gum derivative, a combination in which each is methyl cellulose and guar gum or a guar gum derivative, and a combination in which each is hydroxyethyl cellulose and guar gum or a guar gum derivative. The combination, and the combination of hydroxyethyl cellulose and polyacrylamide, respectively, satisfy the conditions.
染料前駆体、顕色剤及び増感剤に対する分散剤の添加率
は1〜7%か適当である。1%未満であるとホールミル
或いはサンドミル等での破砕効率が低下し、又7%以上
であると感度が低下する。The addition ratio of the dispersant to the dye precursor, color developer and sensitizer is 1 to 7%, which is appropriate. If it is less than 1%, the crushing efficiency in a whole mill or sand mill will be reduced, and if it is 7% or more, the sensitivity will be reduced.
更に好ましい添加率は1〜3%である。A more preferable addition rate is 1 to 3%.
バインダーの添加率は7〜20%が適当である。The appropriate binder addition rate is 7 to 20%.
7%より少なくなるに従って感熱発色層のピッキング強
度か低下し、遂にはカレンダー処理工程で塗層の一部が
ロールを汚すトラブルを起す。As it becomes less than 7%, the picking strength of the heat-sensitive coloring layer decreases, and eventually a part of the coating layer stains the roll during the calendering process.
又、多くなるに従って感度の低下が認められるが、20
%を超えるとこれが著しくなる。Also, as the number increases, the sensitivity decreases, but 20
%, this becomes noticeable.
更に好ましい添加率は7〜10%である。A more preferable addition rate is 7 to 10%.
又、本発明による分散剤とバインダーの組合わぜの他に
感熱塗液の保水性向上、或いはカブリ防止の目的でその
他の水溶性高分子が添加される場合がある。In addition to the combination of dispersant and binder according to the present invention, other water-soluble polymers may be added for the purpose of improving the water retention of the heat-sensitive coating liquid or preventing fogging.
上記の場合、これ等すべての混合物の70℃に於ける熱
変形率が4%以下であれば同等の効果が得られる。In the above case, the same effect can be obtained if the thermal deformation rate of all these mixtures at 70° C. is 4% or less.
本発明の感熱記録材料は通常支持体として紙、合成紙、
或いはフィルムが用いられ、エアーナイフ、ブレード、
ロール等のコーターヘッドを有するit工装置を用いて
該支持体上に感熱発色層を塗布する事によって1qられ
る。The heat-sensitive recording material of the present invention usually uses paper, synthetic paper,
Alternatively, a film is used, and an air knife, blade,
1q is obtained by coating the heat-sensitive coloring layer on the support using IT equipment having a coater head such as a roll.
又、カス、感度、及び印字品質の改良のため、支持体と
感熱発色層の間に1乃至2層の、主として白色乃至淡色
の顔料及びバインダーよりなる中間層が設けられる場合
が多い。Furthermore, in order to improve scum, sensitivity, and print quality, one or two intermediate layers consisting mainly of a white or light-colored pigment and a binder are often provided between the support and the thermosensitive coloring layer.
中間層に用いられる吸油性顔料としては、吸油度JIS
K−5101に定める測定法において60d/100g
以上が望ましいが60m1/1003以下の顔料を併用
しても良い。顔料の粒径は、その平滑性の点から体積平
均粒径で5.0ミクロン以下、好ましくは1μ以下が望
ましい。具体的には、ケイ酸、炭酸カルシウム被覆ケイ
酸、カオリン、焼成カオリン、タルク、ろう石、ケイソ
ウ土、炭酸カルシ「クム、水酸化アルミニウム、水酸化
マグネシウム、炭酸マグネシウム、酸化チタン、炭酸バ
リウム、尿素−ホルマリンピグメント、バルーン状プラ
スチックピグメント等から選ばれる。The oil-absorbing pigment used in the intermediate layer has an oil absorption JIS
60d/100g according to the measurement method specified in K-5101
Although the above is desirable, a pigment of 60 m1/1003 or less may be used in combination. The particle size of the pigment is preferably 5.0 microns or less, preferably 1 μm or less in terms of volume average particle size, from the viewpoint of smoothness. Specifically, silicic acid, calcium carbonate-coated silicic acid, kaolin, calcined kaolin, talc, waxite, diatomaceous earth, calcicarbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, titanium oxide, barium carbonate, urea. - Selected from formalin pigments, balloon-shaped plastic pigments, etc.
支持体に塗布する際は、これらの顔料を分散剤と共に分
散し、でんぷん誘導体、ポリビニルアルコール、スチレ
ン−無水マイレン酸等の水溶性高分子接着剤、スチレン
−ブタジェンラテックス、アクリル樹脂エマルシコン等
の疎水性ポリマーのエマルシヨンを加えることが一般的
である。When coating on a support, these pigments are dispersed together with a dispersant, and a hydrophobic adhesive such as starch derivatives, polyvinyl alcohol, water-soluble polymer adhesives such as styrene-maleic anhydride, styrene-butadiene latex, or acrylic resin emulsicone is used. It is common to add emulsions of polymers.
中間図1は染料前駆体、顕色剤、増感剤のうち1種、又
は2種以上を同時に添加する事も可能である。In FIG. 1, one or more of a dye precursor, a color developer, and a sensitizer can be added at the same time.
中間層上に設けられる感熱発色層としては、染料前駆体
、顕色剤、増感剤、バインダー及び前記成分の微細化の
際に加えられる分散剤を主成分とするが、必要に応じヘ
ッド摩耗防止、スティッキング防止等の目的でワックス
類、金属石ケンなどが添加され、さらに前記の吸油性顔
料か混入されても良い。The heat-sensitive color forming layer provided on the intermediate layer mainly contains a dye precursor, a color developer, a sensitizer, a binder, and a dispersant added when the above components are made fine. Waxes, metal soaps, etc. may be added for the purpose of preventing sticking, and the above-mentioned oil-absorbing pigments may also be mixed.
本発明に用いられる染料前駆体としては、一般の感圧記
録紙、感熱記録紙等に用いられるものであれば特に制限
されない、具体的な例をあげれば(1)トリアリールメ
タン系化合物として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(クリスタル
・バイオレット・ラクトン)1.3.3−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、3−(p−ジメチルアミノフェニル) −3
−(2−フェニルインドール−3−イル)フタリド、3
,3−ビス−(1,2−ジメチルインドール−3−イル
)−5−ジメチルアミノフタリド、3.3−ビス−(1
,2−ジメチルインドール−3−イル)−6−ジメチル
アミノフタリド、3,3−ビスー(9−エチルカルバゾ
ール−
−ジメチルアミノフタリド、3,3−ビス−(2−フェ
ニルインドール−3−イル)−5−ジメチルアミノフタ
リド、3−p−ジメチルアミノフェニル−3−(1−メ
チルピロール−2−イル)−6−ジメチルアミノフタリ
ド等:(2)ジフェニルメタン系化合物として、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−トリクロロフェニルロイコオーラミン等:(3)
キサンチン系化合物として、ローダミンB−アニリノラ
クタム、ローダミンB−p−クロロアニリノラクタム、
3−ジエチルアミノ−7−ジベンジルアミノフルオラン
、3−ジエヂルアミノ−7−オクチルアミノフルオラン
、3−ジエチルアミン−7−フェニルフルオラン、3−
ジエチルアミノ−7−(3,4−ジクロルアニリノ)フ
ルオラン、3−ジエチルアミノ−7−(2−クロロアニ
リノ〉フルオラン、3−ジエチルアミノ−6−メチル−
7−アニリノフルオラン、3−ピペリジノ−6−メチル
−7−アニリノフルオラン、3−エチル−トリルアミノ
−6−メチル−7−アニリノフルオラン、3−エチル−
トリルアミノ−6−メチル−7−7エニチルフルオラン
、3−ジエチルアミノ−7−(4−ニトロアニリノ)フ
ルオラン、3−ジブチルアミノ−6−メチル−7−アニ
リノフルオラン、3−(N−メチル−N−プロピル)ア
ミノ−6−メチル−7−7ニリノフルオラン、3− (
N−エチル−N−イソプロピル)アミノ−6−メヂルー
7ーアニリノフルオラン、3−(N−エチル−N−テト
ラヒドロフルフリル)アミノ−6−メチル−7−アニリ
ノフルオラン等:(4)デアジン系化合物として、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:(5)スピロ系化合物として、
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、3,3′−シクロロースピロー
ジナフトピラン、3−ベンジル−スピロ−ジナフトピラ
ン、3−メチルナフト−(3−メトキシ−ベンゾ)スピ
ロピラン、3−プロピル−スピロ−ジベンゾピラン等、
或いはこれらの混合物を挙げることができる。The dye precursor used in the present invention is not particularly limited as long as it is used in general pressure-sensitive recording paper, heat-sensitive recording paper, etc. Specific examples include (1) 3 as a triarylmethane compound; , 3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (crystal violet lactone) 1.3.3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl) -3-(1,2-dimethylindol-3-yl>phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)
Phthalide, 3-(p-dimethylaminophenyl)-3
-(2-phenylindol-3-yl)phthalide, 3
, 3-bis-(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3.3-bis-(1
, 2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis-(9-ethylcarbazole- -dimethylaminophthalide, 3,3-bis-(2-phenylindol-3-yl) )-5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylpyrrol-2-yl)-6-dimethylaminophthalide, etc.: (2) As a diphenylmethane compound, 4,4
'-Bis-dimethylaminobenzhydrylbenzyl ether, N-halophenylleucoolamine, N-2.4
.. 5-Trichlorophenylleucoauramine etc.: (3)
As xanthine compounds, rhodamine B-anilinolactam, rhodamine B-p-chloroanilinolactam,
3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamine-7-phenylfluorane, 3-
Diethylamino-7-(3,4-dichloroanilino)fluoran, 3-diethylamino-7-(2-chloroanilino)fluoran, 3-diethylamino-6-methyl-
7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-ethyl-tolylamino-6-methyl-7-anilinofluorane, 3-ethyl-
Tolylamino-6-methyl-7-7enylfluorane, 3-diethylamino-7-(4-nitroanilino)fluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-(N-methyl- N-propyl)amino-6-methyl-7-7nilinofluorane, 3-(
N-ethyl-N-isopropyl)amino-6-medy-7-anilinofluorane, 3-(N-ethyl-N-tetrahydrofurfuryl)amino-6-methyl-7-anilinofluorane, etc.: (4) As a deazine compound, benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc.: (5) As a spiro compound,
3-Methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-cyclospirodinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methylnaphtho-(3-methoxy-benzo)spiropyran, 3 -propyl-spiro-dibenzopyran, etc.
Alternatively, a mixture thereof can be mentioned.
これらは用途及び希望する特性により決定される。These are determined by the application and desired properties.
顕色剤としては、一般に感熱記録紙に使用される酸性物
質、すなわち電子受容性の化合物が用いられ、特にフェ
ノール誘導体、芳香族カルボン酸誘導体が用いられる。As the color developer, acidic substances generally used in thermosensitive recording paper, ie, electron-accepting compounds, are used, and in particular, phenol derivatives and aromatic carboxylic acid derivatives are used.
例えば、フェノール、p−t−ブチルフェノール、p−
フェニルフェノール、1−ナフトール、2−ナフトール
、p−ヒドロキシアセトフェノン、2、2′−ジビドロ
キシビフェニル、4.4′−イソプロピリデンジフェノ
ール、4,4′−イソプロピリデンビス(2−t−ブチ
ルフェノール)、4.4’−イソプロピリデンビス(2
−クロロフェノール)、4。For example, phenol, p-t-butylphenol, p-
Phenylphenol, 1-naphthol, 2-naphthol, p-hydroxyacetophenone, 2,2'-dividroxybiphenyl, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene bis(2-t-butylphenol) ), 4,4'-isopropylidene bis(2
-chlorophenol), 4.
4′−シクロへキシリデンジフェノール、2,2−ビス
(4−ヒドロキシフェニル)ブタン、2,2−ビス(4
−ヒドロキシフェニル)ペンタン、2.2−ビス(4−
ヒドロキシフェニル)ヘキサン、ジフェノール酢酸メチ
ルエステル、ビス(4−ヒドロキシフェニル)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−4′−イソプロピルオキシジフェニ
ルスルホン、ビス(4−ヒドロキシフェニル)スルフィ
ド、4、4′−チオビス(2−t−ブチル−5〜メチル
)フェノール、7ービス(4−ヒドロキシフェニルヂオ
)−3.5−ジオキシへブタン、ノボラック型フェノー
ル樹脂等があり、芳香族カルボン酸誘導体としては、例
えば、安息香酸、p−t−ブチル安息香酸、p−ヒドロ
キシ安息香酸メチルエステル、p−ヒドロキシ安息香酸
イソプロピルエステル、p−ヒドロキシ安息@酸ベンジ
ルエステル、没食子酸ラウリルエステル、没食子酸ステ
アリルエステル、サリチルアニリド、5−クロロサリチ
ルアニリド、5−t−ブチルサリチル酸の亜鉛等の金属
塩、ヒドロキシナフトエ酸の亜鉛等の金属塩等が挙げら
れる。4'-cyclohexylidene diphenol, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4
-hydroxyphenyl)pentane, 2,2-bis(4-
hydroxyphenyl)hexane, diphenol acetic acid methyl ester, bis(4-hydroxyphenyl)sulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4' -isopropyloxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-thiobis(2-t-butyl-5-methyl)phenol, 7-bis(4-hydroxyphenyldio)-3,5-dioxy Examples of aromatic carboxylic acid derivatives include benzoic acid, p-t-butylbenzoic acid, p-hydroxybenzoic acid methyl ester, p-hydroxybenzoic acid isopropyl ester, and p-hydroxybenzoic acid isopropyl ester. Hydroxybenzoic acid benzyl ester, gallic acid lauryl ester, gallic acid stearyl ester, salicylanilide, 5-chlorosalicylanilide, metal salts such as zinc of 5-t-butylsalicylic acid, metal salts such as zinc of hydroxynaphthoic acid, etc. Can be mentioned.
ワックス類としては、パラフィンワックス、カルナバロ
ウワックス、マイクロクリスタリンワツクス、ポリエチ
レンワックスの他、高級脂肪酸アミド、例えばステアリ
ン酸アミド、エチレンビスステアロアミド、高級脂肪酸
エステル等があげられる。Examples of waxes include paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax, and higher fatty acid amides such as stearic acid amide, ethylene bisstearamide, and higher fatty acid esters.
金属石鹸としては、高級脂肪酸多価金属塩即ち、ステア
リン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸
カルシウム、オレイン酸亜鉛等があげられる。Examples of metal soaps include polyvalent metal salts of higher fatty acids, such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate.
増感剤としては、融点が80〜140℃のシャープな融
点をもつもので、熱応答性の良好なもので具体的には、
安息香酸やテレフタル酸のエステル類、ナフタレンスル
ホン酸エステル類、ナフチルエーテル誘導体、アントリ
ルエーテル誘導体、脂肪族エーテル系その他フェナント
レン、フルオレン等の増感剤が使用できる。又、前記の
ワックス類も増感剤として使用できる。The sensitizer has a sharp melting point of 80 to 140°C and has good thermal responsiveness. Specifically,
Sensitizers such as benzoic acid and terephthalic acid esters, naphthalene sulfonic acid esters, naphthyl ether derivatives, anthryl ether derivatives, aliphatic ethers, phenanthrene, fluorene, etc. can be used. The waxes mentioned above can also be used as sensitizers.
(E)作用
感熱記録材料はサーマルプリンター等に装着されている
サーマルヘッドを押圧し、発熱部に通電、加熱して発色
させる。この際、発熱部の付近に染料前駆体等の熱可融
性化合物が付着して所謂カスを生ずる。ところが、分散
剤とバインダーの混合物の70’Cに於ける熱変形率を
特定する事によりカスは箸しく低減される。(E) Function The heat-sensitive recording material is pressed against a thermal head installed in a thermal printer or the like, and the heat-generating portion is energized and heated to develop color. At this time, a thermofusible compound such as a dye precursor adheres to the vicinity of the heat generating part, producing so-called scum. However, by specifying the thermal deformation rate at 70'C of the mixture of dispersant and binder, the amount of debris can be significantly reduced.
この差は、通常カス低減の目的で感熱発色層に添加され
る顔料の添加♀が低い場合に顕著になり、70’Cに於
ける熱変形率が4%以下である場合は顔わ1を加えない
場合でもカスはほとんど発生しないか、熱変形率が多く
なるに従って増加し、6%以上では著しく多くなる。This difference becomes noticeable when the amount of pigment added to the heat-sensitive coloring layer is low, and when the thermal deformation rate at 70'C is 4% or less, Even if it is not added, hardly any scum is generated, or it increases as the thermal deformation rate increases, and when it is 6% or more, it increases significantly.
上記のカス吊の差が生ずる機構の全ては明らかではない
が、主な機構はバインダーと分散剤の混合物がサーマル
ヘッドと溶融した熱可融性化合物との接触を妨げる支柱
として機能する事に起因すると考えられる。第1図、第
2図は中間層を有し、感熱発色層は顔料を含まず、分散
剤として70’Cに於ける熱変形率が8.5%のスルホ
ン酸基含有ポリビニルアルコールを染料前駆体、顕色剤
、増感剤の夫々に対して5%、バインダーとして70’
Cに於ける熱変形率が4%のポリビニルアルコールを同
10%用いた(垂辺比1:2の混合物の70°Cに於け
、る熱変形率は7.1%であった。、)感熱記録材料に
印字した際の発色部の走査型電子顕微鏡写真である。(
印字は株式会社大倉電気(大阪)製、印字装置TH−P
MD、サーマルヘッドの抵抗は185Ω、ドツト密度8
ドツト/m、印加電圧1’lv、通電時間1.3 m
sで行なった。)第3図、第4図はバインダーをポリビ
ニルアルコールより70’Cに於ける熱変形率が0.4
%であるグアーガムAにかえ、(重量化1:2の混合物
の70’Cに於ける熱変形率は0.5%であった。)他
は同様にして得た感熱記録材料に印字した際の発色部の
走査型電子顕微鏡写真である。Although the mechanism behind the above difference in scum suspension is not entirely clear, the main mechanism is that the binder and dispersant mixture acts as a support that prevents the thermal head from coming into contact with the molten thermofusible compound. It is thought that then. Figures 1 and 2 have an intermediate layer, and the heat-sensitive coloring layer does not contain any pigment, and uses sulfonic acid group-containing polyvinyl alcohol with a heat deformation rate of 8.5% at 70'C as a dye precursor as a dispersant. 5% each for body, developer, and sensitizer, and 70' as binder.
10% polyvinyl alcohol with a thermal deformation rate of 4% in C was used (the thermal deformation rate at 70°C of a mixture with a vertical side ratio of 1:2 was 7.1%. ) This is a scanning electron micrograph of a colored area when printed on a heat-sensitive recording material. (
Printing is made by Okura Electric Co., Ltd. (Osaka), printing device TH-P
MD, thermal head resistance 185Ω, dot density 8
Dots/m, applied voltage 1'lv, energizing time 1.3 m
I did it with s. ) Figures 3 and 4 show that the binder has a thermal deformation rate of 0.4 at 70'C compared to polyvinyl alcohol.
% (the thermal deformation rate at 70'C of the mixture with a weight ratio of 1:2 was 0.5%). This is a scanning electron micrograph of the color-developing area.
第3図、第4図の方が、バインダーが形成していると考
えられる頂部が平らに見える台、又は支柱の如き構造か
目立ち、その間は空間になっているように見える。即ち
、その間に存在した染料前駆体等の有機可融物は中間層
に吸収されているように児える。In FIGS. 3 and 4, the structure, which is thought to be formed by the binder and looks like a platform with a flat top, or supports is more noticeable, and there appears to be a space between them. In other words, the organic fusible materials such as dye precursors that existed between the layers are absorbed into the intermediate layer.
このような支柱の如き構造は溶融した染料前駆体、顕色
剤及び増感剤とサーマルヘッドとの接触を妨げる機能を
有し、且つ溶融した染料前駆体等の中間層への移行、な
らびに混合を容易にしていると考えられる。This pillar-like structure has the function of preventing the molten dye precursor, developer, and sensitizer from coming into contact with the thermal head, and also prevents the molten dye precursor from migrating to the intermediate layer and from mixing. It is thought that this makes it easier.
一方、第1図、第2図では溶融乃至軟化したバインダー
を含む有機可融物が中間層の表面を覆っている。このよ
うな構造は溶融した染料前駆体等と【ナーマルヘッドと
の接触を容易にし、且つ中間層への移行を妨げていると
考えられ、カスには不利であろう。On the other hand, in FIGS. 1 and 2, an organic fusible material containing a melted or softened binder covers the surface of the intermediate layer. It is thought that such a structure facilitates contact between the molten dye precursor and the like and prevents it from transferring to the intermediate layer, which is disadvantageous for dregs.
(「)実施例 次に本発明を実施例により更に詳細に説明する。(")Example Next, the present invention will be explained in more detail with reference to Examples.
部及び%はいずれも重量基準である。All parts and percentages are by weight.
実施例1 中間層塗イ11紙の調製。Example 1 Preparation of intermediate layer coating A11 paper.
焼成カオリン(エングルハード製
アンシレックス) 100部へキサメタ
リン酸ソーダ 0.8部48%スチレン−ブ
タジェンラテックス(日本合成’!!JSRO692)
130部水
130部以上をホモジナイザーで分散液とし、これ
に20%リン酸エステル化澱粉(日本食品製、MS−4
600)水溶液を25部加え、よく混合した後、40g
/rdの上質紙に固形分6g/m塗布乾燥した。Calcined kaolin (Ansilex manufactured by Englehard) 100 parts Sodium hexametaphosphate 0.8 parts 48% styrene-butadiene latex (Nippon Gosei'!! JSRO692)
130 parts water
130 parts or more were made into a dispersion liquid using a homogenizer, and 20% phosphoric acid ester starch (Nihon Shokuhin Co., Ltd., MS-4) was added to this.
600) After adding 25 parts of the aqueous solution and mixing well, 40 g
/rd high quality paper with a solid content of 6 g/m and dried.
■染料前駆体分散液の調製・・・・・・A液3−ジエチ
ルアミノ−6−メチル
−7−アニリノフルオラン 1部10%スルホ
ンM基含有ポリビニル
アルコール水溶液 0.5部水
3.5部この混合
物をビーズミルで平均粒径2μになる迄粉砕した。■Preparation of dye precursor dispersion...Liquid A 3-diethylamino-6-methyl-7-anilinofluorane 1 part 10% sulfone M group-containing polyvinyl alcohol aqueous solution 0.5 part water
3.5 parts of this mixture was ground in a bead mill until the average particle size was 2 μm.
■顕色剤分散液の調製・・・・・・B液2.2−ビス(
4−ヒドロキシフェニル)プロパン
1部10%スルホン酸基含有ポリビニル
アルコール水溶液 0.5部水
3.5部この混
合物をビーズミルで平均粒径2μになる迄粉砕した。■Preparation of developer dispersion liquid...B liquid 2.2-bis(
4-hydroxyphenyl)propane
1 part 10% polyvinyl alcohol aqueous solution containing sulfonic acid groups 0.5 part water
3.5 parts of this mixture was ground in a bead mill until the average particle size was 2 μm.
■増感剤分散液の調製・・・・・・C液2−ベンジルオ
キシナフタレン 1部10%スルホン酸基含有ポ
リじ゛ニルアルコール水溶液
0.5部水
3.5部この混合物をビーズミルで平均粒径2μ
になる迄粉砕した。■Preparation of sensitizer dispersion...Liquid C 2-benzyloxynaphthalene 1 part 10% aqueous polyvinyl alcohol solution containing sulfonic acid groups
0.5 part water
3.5 parts This mixture was milled with a bead mill to an average particle size of 2μ.
It was crushed until it became
■感熱発色層め形成
A液 15部B液
20部C液
25部10%ポリビニルアルコール水溶液 12
部水
8部を混合、撹拌して塗液とした。これを中間層を設
けた紙に染料前駆体の量で0.5g/mになる様に塗布
、乾燥し、次に感熱発色層の表面のBEKK平滑度が4
00〜500 secになるようにスーパーカレンダー
処理し感熱記録材料を得た。■Thermosensitive coloring layer forming liquid A 15 parts liquid B
20 parts C liquid
25 parts 10% polyvinyl alcohol aqueous solution 12
Department water
8 parts were mixed and stirred to prepare a coating liquid. This was applied to paper with an intermediate layer in an amount of dye precursor of 0.5 g/m, dried, and then the BEKK smoothness of the surface of the thermosensitive coloring layer was 4.
A heat-sensitive recording material was obtained by supercalendering to obtain a heat-sensitive recording material of 0.00 to 500 sec.
これを試料Nα1(比較例)とする。This is designated as sample Nα1 (comparative example).
(試料Nα2(実施例)、N(13(実施例)、Nα4
(実施例)の調製〕
試料Nα1(比較例)に於いて、■感熱発色層の形成に
於けるバインダー水溶液である10%ポリビニルアルコ
ール水溶液にかえて2%グアーガムA水溶液60部を用
い、且つ追加水8部をゼロとした他は、試料Nα1(比
較例)と全く同様にして試料Nα2(実施例)を得た。(Sample Nα2 (Example), N(13 (Example), Nα4
(Preparation of Example)] In sample Nα1 (comparative example), 60 parts of a 2% guar gum A aqueous solution was used instead of the 10% polyvinyl alcohol aqueous solution that was the binder aqueous solution in the formation of the thermosensitive coloring layer, and additionally. Sample Nα2 (Example) was obtained in exactly the same manner as Sample Nα1 (Comparative Example) except that 8 parts of water was changed to zero.
更に試料Nα2(実施例)に於いて、■感熱発色層の形
成に於ける2%グアーガムA水溶液60部にかえて2%
グアーガムC水溶液60部を用いた他は全く同様にして
試料Nα3(実施例)を、1.5%グアーガムC水溶液
80部を用いた他は全く同様にして試料N04(実施例
)を得た。Furthermore, in sample Nα2 (Example), 2% guar gum A aqueous solution was added in place of 60 parts of the 2% guar gum A aqueous solution in forming the heat-sensitive coloring layer.
Sample Nα3 (Example) was obtained in exactly the same manner except that 60 parts of guar gum C aqueous solution was used, and sample N04 (Example) was obtained in exactly the same manner except that 80 parts of 1.5% guar gum C aqueous solution was used.
〔試料Nα5(比較例)、Nα6(実施例)Nα(実施
例)の調成〕
試料Nα1(比較例)に於いて、■染料前駆体、■顕色
剤、■増感剤の各分散液の調製に於ける分散剤水溶液で
ある10%スルホン酸基含有ポリビニルアルコール水溶
液にかえて10%メチルセルロース水溶液を用いた伯は
全く同様にしてNα5(比較例)を得た。[Preparation of samples Nα5 (comparative example), Nα6 (example) and Nα (example)] In sample Nα1 (comparative example), each dispersion of ■dye precursor, ■color developer, and ■sensitizer was prepared. Nα5 (comparative example) was obtained in exactly the same manner as in the preparation except that a 10% aqueous methyl cellulose solution was used in place of the aqueous 10% sulfonic acid group-containing polyvinyl alcohol solution as the dispersant aqueous solution.
更に試料Nα5(比較例)に於いて、■感熱発色層の形
成に於ける10%ポリビニルアルコール水溶液12部に
かえて2%グアーガムA水溶液60部を用い、且つ追加
水8部をゼロとした他は全く同様にして試料N06(実
施例)を更に試料Nα6(実施例)に於いて、■感熱発
色層の形成に於ける2%グアーガムA水溶液60部にか
えて2%グアーガムC水溶液60部を用いた他は全く同
様にして試料Nα7(実施例)を(qた。Furthermore, in sample Nα5 (comparative example), 60 parts of a 2% guar gum A aqueous solution was used instead of 12 parts of a 10% polyvinyl alcohol aqueous solution in the formation of the heat-sensitive coloring layer, and 8 parts of additional water was set to zero. Sample N06 (Example) and Sample Nα6 (Example) were prepared in exactly the same manner, except that (1) 60 parts of a 2% guar gum C aqueous solution was added in place of 60 parts of a 2% guar gum A aqueous solution in forming the heat-sensitive coloring layer. Sample Nα7 (Example) was prepared in exactly the same manner except that it was used.
〔試料N08(比較例)、Nα9(実施例)の調製〕試
料Nα1(比較例)に於いて、■染料前駆体、■顕色剤
、■増感剤の各分散液の調製に於ける10%スルホン酸
基含有ポリビニルアルコール水溶液にかえて10%とド
ロキシエチルセルロース水溶液を用いた他は全く同様に
してNo、8(比較例)を得た。[Preparation of sample N08 (comparative example), Nα9 (example)] In sample Nα1 (comparative example), 10 in the preparation of each dispersion of ■dye precursor, ■color developer, and ■sensitizer. Sample No. 8 (comparative example) was obtained in exactly the same manner except that a 10% and droxyethyl cellulose aqueous solution was used instead of the sulfonic acid group-containing polyvinyl alcohol aqueous solution.
更に、試料Nα8(比較例)に於いて■感熱発色層の形
成に於ける10%ポリビニルアルコール水溶液12部に
かえて2%グアーガムA水溶液60部を用い、且つ追加
水8部をゼロとした他は全く同様にして試料Nα9(実
施例)を得た。Furthermore, in sample Nα8 (comparative example), 60 parts of a 2% guar gum A aqueous solution was used instead of 12 parts of a 10% polyvinyl alcohol aqueous solution in the formation of the heat-sensitive coloring layer, and 8 parts of additional water was set to zero. Sample Nα9 (Example) was obtained in exactly the same manner.
又、試料Nα8(比較例)に於いて、■感熱発色層の形
成に於ける10%ポリビニルアルコール水溶液にかえて
10%ポリアクリルアミド水溶液12部を用いた他は全
く同様にして試料N(110(実施例)を得た。In addition, in sample Nα8 (comparative example), sample N (110( Example) was obtained.
以上の全試料の一覧を表1に示す。A list of all the above samples is shown in Table 1.
以上の試料を印字装置TH−PMDで印字し、マクベス
濃度計で印字部の反射濃度を測定し、又、1ナーマルヘ
ツドに付着したカスの屯を顕微鏡WA察により評価した
。結果を表1に示す。The above sample was printed using a printing device TH-PMD, the reflection density of the printed portion was measured using a Macbeth densitometer, and the amount of debris adhering to the normal head was evaluated using a WA microscope. The results are shown in Table 1.
又、分散剤とバインダーを実添加量のff1ffl比で
混合し、0.0247 ’j/ctri、 (風乾)相
当のフィルムを用いて70’Cに於ける熱変形率を測定
した。Further, the dispersant and the binder were mixed at the actual addition amount of ff1ffl ratio, and the thermal deformation rate at 70'C was measured using a film equivalent to 0.0247'j/ctri (air-dried).
試験法は後にまとめて示す。本結果も表1に示す。The test methods will be summarized later. The results are also shown in Table 1.
試験方法
〔熱変形率の測定〕 −
分散剤及びバインダーの水溶液の所定量を採取、よく混
合し、風乾で0.0247 ’j/ciになる量をシャ
ーレにとり、40’Cの恒温乾燥機中で8時間以上乾燥
して測定用試料を得る。Test method [Measurement of thermal deformation rate] - Take a predetermined amount of an aqueous solution of a dispersant and a binder, mix well, take an amount that will become 0.0247'j/ci when air-dried, and place it in a constant temperature dryer at 40'C. Dry for 8 hours or more to obtain a sample for measurement.
軟化点は25℃の室内でデュポン製熱分析システム99
0型のTMAモジュールN(1943を用いて熱機械分
析を行なって測定した。The softening point was measured using a DuPont thermal analysis system 99 in a room at 25°C.
The measurements were carried out by thermomechanical analysis using a Model 0 TMA module N (1943).
熱機械分析は、昇温速度10℃/分、で室温から昇温し
、荷110gをかけた直径2.5Mの針で加圧して行っ
た。熱変形率Cは、室温での試料の厚みをaとし、70
℃での試料の厚みをbとした場合、c= (a−b)x
100/a (%)で求めた。The thermomechanical analysis was performed by raising the temperature from room temperature at a heating rate of 10° C./min and applying pressure with a 2.5 M diameter needle carrying a load of 110 g. The thermal deformation rate C is 70, where the thickness of the sample at room temperature is a.
If the thickness of the sample at °C is b, then c= (a-b)x
It was calculated as 100/a (%).
[印字]
株式会社人愈電気(大阪)製印字装置TH−PMD、サ
ーマルヘッドの抵抗185Ω、ドツト密度8ドツト/M
、印加電圧11V、通電時間1.3msで行なった。[Printing] Printing device TH-PMD manufactured by Jinyu Denki Co., Ltd. (Osaka), thermal head resistance 185Ω, dot density 8 dots/M
, the applied voltage was 11 V, and the current application time was 1.3 ms.
マクベス濃度計で反射濃度を測定した。 Reflection density was measured with a Macbeth densitometer.
印字を終えたサーマルヘッドの発熱部分近傍を肉眼、な
らびに顕微鏡で観察し、5段階評価した。After printing, the vicinity of the heat generating part of the thermal head was observed with the naked eye and with a microscope, and evaluated on a five-point scale.
評価基準は下記の通り。The evaluation criteria are as follows.
1・・・・・・顕微鏡観察でもカスの付着がほとんど認
められない物。実用的に可。1: Items with almost no residue observed even when observed under a microscope. Practically possible.
2・・・・・・カスの付着量が極めてわずかである物。2: Items with extremely small amount of residue attached.
実用的に許容出来る限度。Practically acceptable limit.
3・・・・・・カスの付着量が評価1と同5の中間であ
る物。実用的に不可。3: The amount of deposits is between the evaluations of 1 and 5. Practically impossible.
4・・・・・・カスの付着量が評価5に次いで多く、肉
眼でも明らかに認められる物。実用的に不可。4: The amount of deposits is the second highest after evaluation 5, and it can be clearly seen with the naked eye. Practically impossible.
5・・・・・・カスの付着量が最も多いグループ。5...Group with the largest amount of deposits.
実施例2
実施例1の■感熱発色層の形成に於いてA液
15部B液
20部C液 25部焼
成カオリン(エンゲルハード製
7ンシレツクス) 2部軽質炭酸カル
シウム(白石カルシウム
株式会社製ユニバフ0) 3部10%ポリビ
ニルアルコール水溶液 17部水
50.3部を混合、攪拌して塗
液とした。本塗液を、中間層を設けた紙にかえて40g
/mの上質紙に染料前駆体の量で055g/mになる様
に塗布、乾燥し、次に感熱発色層の表面のBEKK平滑
度が400〜500 secになるようにスーパーカレ
ンダー処理し、感熱記録材料を得た。Example 2 Liquid A in the formation of the heat-sensitive coloring layer in Example 1
15 parts B liquid
20 parts Solution C 25 parts Calcined kaolin (Engelhard 7Ncilex) 2 parts Light calcium carbonate (Shiraishi Calcium Co., Ltd. Unibuff 0) 3 parts 10% polyvinyl alcohol aqueous solution 17 parts Water
50.3 parts were mixed and stirred to prepare a coating liquid. 40g of this coating liquid was changed to paper with an intermediate layer.
The dye precursor was coated on high-quality paper in an amount of 0.55 g/m, dried, and then supercalendered so that the BEKK smoothness of the surface of the heat-sensitive coloring layer was 400 to 500 sec. Obtained recording materials.
これを試料Nα11(比較例)とする。This is designated as sample Nα11 (comparative example).
次に上記実施例試料No、11(比較例)に於いて、1
0%ポリビニルアルコール水溶液17部にかえて2%グ
アーガムA水溶液85部を用いた他は全く同様にして試
料Nα12(実施例)を1qだ。Next, in the above example sample No. 11 (comparative example), 1
1 q of sample Nα12 (Example) was prepared in exactly the same manner except that 85 parts of a 2% guar gum A aqueous solution was used instead of 17 parts of a 0% polyvinyl alcohol aqueous solution.
試料は印字後発色濃度を測定し、カスを評価した。結果
を表2に示す。After printing, the color density of the sample was measured and residue was evaluated. The results are shown in Table 2.
表2
(以下余白)
(G)発明の効宋
表1に明らかな如く、分散剤とバインダーの混合物の7
0’Cに於(プる熱変形率が4%以下である組合わせで
あると、通常カス発生量低減の目的で感熱発色層に添加
される顔料を省いても実用的なレベル迄カス発生串が減
少する。Table 2 (Left below)
If the combination has a thermal deformation rate of 4% or less at 0'C, scum will not be generated to a practical level even if the pigment that is normally added to the heat-sensitive coloring layer for the purpose of reducing the amount of scum is omitted. Skewers decrease.
又、表2に見る如く、顔料を添加した場合にも、やtま
り本発明の方が有効であることが判る。Further, as shown in Table 2, it can be seen that the present invention is more effective even when a pigment is added.
第1図及び第2図は、本発明外の印字発色後の感熱記録
材料の表面電子顕微鏡写真を示し、第3図及び第4図は
本発明の印字発色後の感熱記録材料の表面電子顕微鏡写
真を示す。1 and 2 show electron micrographs of the surface of a heat-sensitive recording material after coloring prints other than the present invention, and FIGS. 3 and 4 show electron micrographs of the surface of a heat-sensitive recording material after coloring prints according to the present invention. Show photos.
Claims (1)
体、加熱時反応して該染料前駆体を発色させる顕色剤及
び増感剤、並びにバインダーよりなる感熱発色層を支持
体上に設けた感熱記録材料に於て、分散剤及びバインダ
ーの混合物の70℃、160g/cm^3荷重加圧時の
熱変形率(熱変形率=熱変形前の厚み−熱変形後の厚み
×100/熱変形前の厚み)が4%以下であることを特
徴とする感熱記録材料。 2)染料前駆体、顕色剤及び増感剤に対する分散剤の添
加率が1〜7%であり、且つバインダーの添加率が7〜
20%である請求項1の感熱記録材料。 3)分散剤がスルホン酸基含有ポリビニルアルコールで
あり、バインダーがグアーガム又はグアーガム誘導体で
ある請求項2の感熱記録材料。 4)分散剤がメチルセルロールであり、バインダーがグ
アーガム又はグアーガム誘導体である請求項2の感熱記
録材料。 5)分散剤がヒドロキシエチルセルロースであり、バイ
ンダーがグアーガム又はグアーガム誘導体である請求項
2の感熱記録材料。 6)分散剤がヒドロキシエチルセルロースであり、バイ
ンダーがポリアクリルアミドである請求項2の感熱記録
材料。[Scope of Claims] 1) Supports a heat-sensitive color forming layer mainly consisting of a finely divided dye precursor that is usually colorless to light-colored, a color developer and a sensitizer that react with the dye precursor to develop color when heated, and a binder. In a heat-sensitive recording material provided on a body, the thermal deformation rate of a mixture of a dispersant and a binder at 70°C and a load of 160 g/cm^3 (thermal deformation rate = thickness before thermal deformation - after thermal deformation) 1. A heat-sensitive recording material having a thickness x 100/thickness before thermal deformation) of 4% or less. 2) The addition rate of the dispersant to the dye precursor, developer, and sensitizer is 1 to 7%, and the addition rate of the binder is 7 to 7%.
20%. The heat-sensitive recording material according to claim 1. 3) The heat-sensitive recording material according to claim 2, wherein the dispersant is a sulfonic acid group-containing polyvinyl alcohol, and the binder is guar gum or a guar gum derivative. 4) The heat-sensitive recording material according to claim 2, wherein the dispersant is methylcellulose and the binder is guar gum or a guar gum derivative. 5) The heat-sensitive recording material according to claim 2, wherein the dispersant is hydroxyethylcellulose and the binder is guar gum or a guar gum derivative. 6) The heat-sensitive recording material according to claim 2, wherein the dispersant is hydroxyethylcellulose and the binder is polyacrylamide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63137868A JPH01306281A (en) | 1988-06-03 | 1988-06-03 | Heat-sensitive recording material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63137868A JPH01306281A (en) | 1988-06-03 | 1988-06-03 | Heat-sensitive recording material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01306281A true JPH01306281A (en) | 1989-12-11 |
Family
ID=15208602
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63137868A Pending JPH01306281A (en) | 1988-06-03 | 1988-06-03 | Heat-sensitive recording material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01306281A (en) |
-
1988
- 1988-06-03 JP JP63137868A patent/JPH01306281A/en active Pending
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