JP2006150594A - Thermal recording material - Google Patents
Thermal recording material Download PDFInfo
- Publication number
- JP2006150594A JP2006150594A JP2004339923A JP2004339923A JP2006150594A JP 2006150594 A JP2006150594 A JP 2006150594A JP 2004339923 A JP2004339923 A JP 2004339923A JP 2004339923 A JP2004339923 A JP 2004339923A JP 2006150594 A JP2006150594 A JP 2006150594A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- protective layer
- sensitive recording
- water
- polyvinyl alcohol
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011241 protective layer Substances 0.000 claims abstract description 40
- 239000010410 layer Substances 0.000 claims abstract description 35
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 34
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000000853 adhesive Substances 0.000 claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 claims abstract description 27
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 19
- 239000003086 colorant Substances 0.000 claims abstract description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004952 Polyamide Substances 0.000 claims abstract description 8
- 229920002647 polyamide Polymers 0.000 claims abstract description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 32
- -1 carbodiimide compound Chemical class 0.000 description 20
- 239000000975 dye Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- UEJVSOJRGUIWCY-UHFFFAOYSA-N 2-hydroxybenzoic acid;zinc Chemical compound [Zn].OC(=O)C1=CC=CC=C1O UEJVSOJRGUIWCY-UHFFFAOYSA-N 0.000 description 2
- ZTILAOCGFRDHBH-UHFFFAOYSA-N 4-(4-propan-2-yloxyphenyl)sulfonylphenol Chemical compound C1=CC(OC(C)C)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 ZTILAOCGFRDHBH-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 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
- 239000003054 catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 1
- KXCSYFARFKNDBV-UHFFFAOYSA-N 1-chloro-4-[2-(4-chlorophenoxy)ethoxy]benzene Chemical compound C1=CC(Cl)=CC=C1OCCOC1=CC=C(Cl)C=C1 KXCSYFARFKNDBV-UHFFFAOYSA-N 0.000 description 1
- WWHWOXMOOULLJQ-UHFFFAOYSA-N 1-methoxy-4-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound C1=CC(OC)=CC=C1OCCOC1=CC=CC(C)=C1 WWHWOXMOOULLJQ-UHFFFAOYSA-N 0.000 description 1
- VGMACPCJKUXETI-UHFFFAOYSA-N 1-methoxy-4-[2-(4-methoxyphenoxy)ethoxy]benzene Chemical compound C1=CC(OC)=CC=C1OCCOC1=CC=C(OC)C=C1 VGMACPCJKUXETI-UHFFFAOYSA-N 0.000 description 1
- KSCKDOYDPGLDKS-UHFFFAOYSA-N 1-methyl-2-(4-phenylphenyl)benzene Chemical group CC1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 KSCKDOYDPGLDKS-UHFFFAOYSA-N 0.000 description 1
- OAGNKYSIOSDNIG-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound CC1=CC=CC(OCCOC=2C=C(C)C=CC=2)=C1 OAGNKYSIOSDNIG-UHFFFAOYSA-N 0.000 description 1
- UIFAEJQCFLEWCF-UHFFFAOYSA-N 1-methyl-4-[2-(4-methylphenoxy)ethoxy]benzene Chemical compound C1=CC(C)=CC=C1OCCOC1=CC=C(C)C=C1 UIFAEJQCFLEWCF-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 description 1
- ZTIKWKHRZKWSSP-UHFFFAOYSA-N 2-[(4-methylphenyl)-[(4-methylphenyl)-thiophen-2-ylmethoxy]methyl]thiophene Chemical compound C1=CC(C)=CC=C1C(C=1SC=CC=1)OC(C=1C=CC(C)=CC=1)C1=CC=CS1 ZTIKWKHRZKWSSP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 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
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- PRMDDINQJXOMDC-UHFFFAOYSA-N 4-[4,4-bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-cyclohexyl-5-methylphenol Chemical compound C=1C(C2CCCCC2)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C2CCCCC2)C=1)C)C(C(=CC=1O)C)=CC=1C1CCCCC1 PRMDDINQJXOMDC-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- YMKWWHFRGALXLE-UHFFFAOYSA-N 4-methyl-1-phenyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C1CC(C)=CP1(=O)C1=CC=CC=C1 YMKWWHFRGALXLE-UHFFFAOYSA-N 0.000 description 1
- PRYWJRJCDPRFBO-UHFFFAOYSA-N 4-phenylsulfanylbutylsulfanylbenzene Chemical compound C=1C=CC=CC=1SCCCCSC1=CC=CC=C1 PRYWJRJCDPRFBO-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- BPLKDVGMXNZCQO-UHFFFAOYSA-N benzyl 4-phenylmethoxybenzoate Chemical compound C=1C=C(OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 BPLKDVGMXNZCQO-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- PHFOBODRSJGSMD-UHFFFAOYSA-N bis(2,3-dihydroxypropyl) benzene-1,4-dicarboxylate Chemical compound OCC(O)COC(=O)C1=CC=C(C(=O)OCC(O)CO)C=C1 PHFOBODRSJGSMD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 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
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZYZXGWGQYNTGAU-UHFFFAOYSA-N dibenzyl oxalate Chemical compound C=1C=CC=CC=1COC(=O)C(=O)OCC1=CC=CC=C1 ZYZXGWGQYNTGAU-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 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
- BWIIMRFKCNBWEH-UHFFFAOYSA-L dipotassium;octadecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCCCCCCCOP([O-])([O-])=O BWIIMRFKCNBWEH-UHFFFAOYSA-L 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
- 239000002612 dispersion medium Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- LZXGBBYVBJFKEL-UHFFFAOYSA-N heptatriacontanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O LZXGBBYVBJFKEL-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- MJGLMEMIYDUEHA-UHFFFAOYSA-N n-(4-methylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=C(C)C=C1 MJGLMEMIYDUEHA-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- RGQCAJMEHUBUKW-UHFFFAOYSA-N n-fluoro-n-methylaniline Chemical compound CN(F)C1=CC=CC=C1 RGQCAJMEHUBUKW-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 239000010893 paper waste Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- CPJSUEIXXCENMM-UHFFFAOYSA-N phenacetin Chemical compound CCOC1=CC=C(NC(C)=O)C=C1 CPJSUEIXXCENMM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 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
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
【課題】 特に耐水性に優れた効果を有する感熱記録体に関するものである。
【解決手段】 支持体上に、ロイコ染料、呈色剤および水性接着剤を含有する感熱記録層、並びに水性接着剤を含有する保護層を順次有する感熱記録体において、保護層の水性接着剤が変性ポリビニルアルコールであり、保護層中に分子量が２０００〜３０００であるカルボジイミド樹脂を含有することを特徴とする。保護層中にさらにポリアミドエピクロルヒドリン樹脂を含有することが好ましい。
【選択図】なしPROBLEM TO BE SOLVED: To relate to a heat-sensitive recording material having an effect particularly excellent in water resistance.
SOLUTION: In a heat-sensitive recording body having a heat-sensitive recording layer containing a leuco dye, a colorant and a water-based adhesive on a support, and a protective layer containing a water-based adhesive in order, the water-based adhesive of the protective layer is provided. It is modified polyvinyl alcohol, and contains a carbodiimide resin having a molecular weight of 2000 to 3000 in the protective layer. It is preferable to further contain a polyamide epichlorohydrin resin in the protective layer.
[Selection figure] None
Description
本発明は、ロイコ染料と呈色剤との発色反応を利用した感熱記録体に関し、特に耐水性に優れた感熱記録体に関するものである。 The present invention relates to a heat-sensitive recording material utilizing a color development reaction between a leuco dye and a color former, and particularly to a heat-sensitive recording material excellent in water resistance.
熱エネルギーによりロイコ染料と呈色剤との発色反応を利用した感熱記録体は、比較的安価であり、しかもその記録体に記録するための記録機器がコンパクトで、その保守も容易なため、ファクシミリやレジ用紙やハンディーターミナル用紙、ＣＤ・ＡＴＭ用紙、乗車券、ラベル用紙、チケット用紙および各種計算機などの記録媒体等に使用されている。 A thermal recording medium using a color reaction between a leuco dye and a colorant by heat energy is relatively inexpensive, and the recording equipment for recording on the recording medium is compact and easy to maintain. It is used for printing media such as cash register paper, handy terminal paper, CD / ATM paper, ticket, label paper, ticket paper and various computers.
感熱記録体は利便性のため、上記のように多くの用途分野で使用されているが、特定分野においては感熱記録体に強度の耐水性特性が求められる。例えば屋外出力用に使用されるハンディーターミナル用感熱紙、チケット用紙、乗車券用紙、冷凍食品に貼付される感熱ラベル用紙など、雨水や露結水など水の付着が予想される分野での用途では従来以上の耐水性が必要とされる。特に感熱記録体が雨水や露結水などの水に濡れても感熱記録面同士が接触しても貼り付かないことが求められている。 For convenience, the thermal recording material is used in many fields of use as described above. However, in a specific field, the thermal recording material is required to have strong water resistance. For applications such as thermal paper for handy terminals used for outdoor output, ticket paper, ticket paper, thermal label paper affixed to frozen foods, etc. More water resistance than before is required. In particular, it is required that the heat-sensitive recording material does not stick even if the heat-sensitive recording surfaces come into contact with each other even if the heat-sensitive recording material gets wet with water such as rain water or dew condensation water.
感熱記録体に対する耐水性付与のため、感熱記録層上の保護層に架橋剤を添加する方法とは多く提案されている。例えば、水性樹脂を含有する保護層中に架橋剤としてカルボジイミド化合物を含有させた感熱記録体が記載されている（特許文献１、２、３を参照）が、保護層の耐水性がまだ不充分である。 Many methods have been proposed for adding a crosslinking agent to the protective layer on the heat-sensitive recording layer in order to impart water resistance to the heat-sensitive recording material. For example, a thermal recording material is described in which a carbodiimide compound is contained as a crosslinking agent in a protective layer containing an aqueous resin (see Patent Documents 1, 2, and 3), but the water resistance of the protective layer is still insufficient. It is.
本発明の課題は、強度の耐水性を有した感熱記録体を提供することにある。 An object of the present invention is to provide a heat-sensitive recording material having high water resistance.
支持体上に、ロイコ染料、呈色剤および水性接着剤を含有する感熱記録層、並びに水性接着剤を含有する保護層を順次有する感熱記録体において、保護層の水性接着剤が変性ポリビニルアルコールであり、保護層中に分子量が２０００〜３０００であるカルボジイミド樹脂とを含有することを特徴とする。
保護層中にさらにポリアミドエピクロルヒドリン樹脂を含有することが好ましい。
前記変性ポリビニルアルコールが、カルボキシ変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコールおよびアセトアセチル変性ポリビニルアルコールから選ばれる少なくとも一種であることが好ましい。
さらに耐水性をより向上させるためには、感熱記録層にホウ酸もしくは硼砂を含有することがより好ましい。
In the heat-sensitive recording body having a heat-sensitive recording layer containing a leuco dye, a colorant and a water-based adhesive on the support, and a protective layer containing the water-based adhesive in sequence, the water-based adhesive of the protective layer is a modified polyvinyl alcohol. And the protective layer contains a carbodiimide resin having a molecular weight of 2000 to 3000.
It is preferable to further contain a polyamide epichlorohydrin resin in the protective layer.
The modified polyvinyl alcohol is preferably at least one selected from carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, and acetoacetyl-modified polyvinyl alcohol.
In order to further improve the water resistance, it is more preferable that the heat-sensitive recording layer contains boric acid or borax.
本発明の感熱記録体は、特に耐水性に優れた効果を有するものである。 The heat-sensitive recording material of the present invention has an effect particularly excellent in water resistance.
保護層に、カルボジイミド樹脂を含有させることにより、保護層中の水性接着剤と架橋反応させて、耐水性を向上させ、感熱記録層中の水性接着剤とも反応が起こり、感熱記録層と保護層との接着性が高められる効果が得られる。しかも、保護層用塗液は、室温ではゲル化しないために取り扱いが容易であり、保護層中のカルボジイミド樹脂は水性接着剤と５０〜９０℃程度で架橋反応するため、感熱記録体を生産する場合に地肌カブリが発生することなく耐水性を高めることが可能となった。 By containing a carbodiimide resin in the protective layer, the water-based adhesive in the protective layer is subjected to a cross-linking reaction to improve water resistance, and the reaction with the aqueous adhesive in the heat-sensitive recording layer also occurs. The effect that the adhesiveness is improved is obtained. In addition, the coating liquid for the protective layer is easy to handle because it does not gel at room temperature, and the carbodiimide resin in the protective layer undergoes a crosslinking reaction with the aqueous adhesive at about 50 to 90 ° C., thus producing a thermal recording material. In this case, the water resistance can be increased without generating background fog.
本発明で使用する多価カルボジイミド樹脂は、触媒下でのジイソシアネート化合物の脱炭酸縮合反応により得られる。また、感熱記録体の塗料は水系塗料が主体であるため、多価カルボジイミド樹脂も水溶性タイプが好ましい。
水溶性タイプにする方法としては、多価カルボジイミド樹脂は疎水性であるためイソシアネート両末端部に親水性基を付与させる必要となる。こうした各種の親水性ゼグメントを付与させる方法が記載されている（特許文献４、５、６を参照）。
The polyvalent carbodiimide resin used in the present invention is obtained by a decarboxylation condensation reaction of a diisocyanate compound under a catalyst. Further, since the paint for the heat-sensitive recording body is mainly a water-based paint, the polyvalent carbodiimide resin is also preferably a water-soluble type.
As a method for forming the water-soluble type, since the polyvalent carbodiimide resin is hydrophobic, it is necessary to impart hydrophilic groups to both ends of the isocyanate. Methods for imparting such various hydrophilic segments are described (see Patent Documents 4, 5, and 6).
例えば、親水性セグメントとしては（Ｒ１）２−Ｎ−Ｒ２−ＯＨ（式中、Ｒ１は炭素数1乃至４の低級アルキル基を、Ｒ２は炭素数1及乃至１０のアルキレンまたはオキシアルキレンを表す）で表されるジアルキルアミノアルコールの四級アンモニウム塩残基でありカチオン性を有する親水性セグメント、Ｒ３−ＳＯ３−Ｒ４−ＯＨ（式中、Ｒ４は炭素数1乃至１０のアルキレンを、Ｒ３はアルカリ金属を表す）で表される、反応性ヒドロキシル基を少なくとも１つ有するアルキルスルホン酸残基でありアニオン性を有する親水性セグメント、Ｒ５−（Ｏ−ＣＨＲ６−ＣＨ２）ｍ−ＯＨ（式中、ｍは４及乃至３０の整数、Ｒ５は炭素数１乃至４の低級アルキル基を、Ｒ６は水素元素またはメチル基をそれぞれ示す）で表される、反応性ヒドロシル基を少なくとも１つ有する、アルコキシ基で末端封鎖されたポリ（アルキレンオキサド）の残基でありノニオン性を有する親水性セグメント等が例示される。 For example, (R 1 ) 2 —N—R 2 —OH (wherein R 1 is a lower alkyl group having 1 to 4 carbon atoms, R 2 is alkylene or oxy having 1 to 10 carbon atoms) R 3 —SO 3 —R 4 —OH (in the formula, R 4 represents a carbon number of 1 to 10), which is a quaternary ammonium salt residue of a dialkylaminoalcohol represented by the following formula: the alkylene, R 3 is represented by an alkali metal), a hydrophilic segment having and anionic alkyl sulfonic acid residue having at least one reactive hydroxyl group, R 5 - (O-CHR 6 - CH 2) m -OH (wherein, m is represented by an integer 4及乃Itaru 30, R 5 is a lower alkyl group having 1 to 4 carbon atoms, R 6 is a hydrogen element or a methyl group respectively) Having at least one reactive hydrosilation group, the hydrophilic segment or the like having a residue and is nonionic poly end-capped with an alkoxy group (alkylene oxide De) is exemplified.
このように、使用される親水性セグメントによってカルボジイミド樹脂のイオン性が異なるが、感熱記録体に使用される場合は塗料凝集の観点からノニオン性のカルボジイミド樹脂を使用することが好ましい。 Thus, although the ionicity of the carbodiimide resin varies depending on the hydrophilic segment to be used, it is preferable to use a nonionic carbodiimide resin from the viewpoint of coating aggregation when used in a heat-sensitive recording material.
また、カルボジイミド樹脂の骨格を有するジイソシアネートは、例えばｍ−テトラメチルキシリレンジイソシアネート、ｐ−トラメチルキシリレンジイソシアネート、４，４’―ジシクロヘキシルメタンジイソシアナート、イシホロンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、２，４−トリレンジイソシアナートおよび２，６−トリレンジイソシアナート等から選ばれるが、特に品質面から４，４’―ジシクロヘキシルメタンジイソシアナートが好ましい。 Examples of the diisocyanate having a carbodiimide resin skeleton include m-tetramethylxylylene diisocyanate, p-tramethylxylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isifolone diisocyanate, 4,4-diphenylmethane diisocyanate, Although selected from 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate is particularly preferable in terms of quality.
本発明においては、保護層の水性接着剤として変性ポリビニルアルコールを使用し、かつ架橋剤として分子量が２０００〜３０００であるカルボジイミド樹脂を使用することにより、目的とする感熱記録体を得るが可能となった。 In the present invention, the use of modified polyvinyl alcohol as the aqueous adhesive for the protective layer and the use of a carbodiimide resin having a molecular weight of 2000 to 3000 as the cross-linking agent makes it possible to obtain the desired thermal recording material. It was.
本発明で使用する分子量が２０００〜３０００であるカルボジイミド樹脂は、例えばジイソシアネートとカルボジイミド化触媒例えば、３−メチル−１−フェニル−２−ホスホレン−１−オキシドを添加し１５０℃〜２００℃の高温で反応させ、反応時間を調整することで得ることができる。 The carbodiimide resin having a molecular weight of 2000 to 3000 used in the present invention includes, for example, a diisocyanate and a carbodiimidization catalyst such as 3-methyl-1-phenyl-2-phospholene-1-oxide and a high temperature of 150 ° C. to 200 ° C. It can be obtained by reacting and adjusting the reaction time.
分子量が２０００未満のカルボジイミド樹脂では高耐水性が得られなく、一方、分子量が３０００を超えると疎水性成分の増大に伴い、水への溶解性が低下するため良好な水溶液が得られにくく、水性接着剤と架橋する反応時間が長時間になり好ましくない。 A carbodiimide resin having a molecular weight of less than 2000 does not provide high water resistance. On the other hand, if the molecular weight exceeds 3000, the solubility in water decreases with the increase of the hydrophobic component, making it difficult to obtain a good aqueous solution. The reaction time for crosslinking with the adhesive is undesirably long.
分子量が２０００〜３０００のカルボジイミド樹脂の使用量としては特に限定されないが、保護層において保護層の全固形分に対して０．５〜２０質量％程度が好ましく、より好ましくは１〜１０質量％程度である。０．５質量％未満では目的とする耐水性は得られにくく、２０質量％を超えると逆に耐水性が悪化する恐れがあり好ましくない。 Although it does not specifically limit as usage-amount of the carbodiimide resin whose molecular weight is 2000-3000, About 0.5-20 mass% is preferable with respect to the total solid of a protective layer in a protective layer, More preferably, about 1-10 mass% It is. If it is less than 0.5% by mass, it is difficult to obtain the desired water resistance, and if it exceeds 20% by mass, the water resistance may be deteriorated.
保護層の架橋剤として分子量が２０００〜３０００のカルボジイミド樹脂が含有されるが、オキサゾリル基を有する化合物、グリオキサール、ホウ酸、ジアルデヒドデンプン、メチロール尿素、ポリアミドエピクロルヒドリン樹脂などの架橋剤を併用することもできる。なかでも、ポリアミドエピクロルヒドリン樹脂と併用することにより、耐水性の高い感熱記録体か得られる。 Although a carbodiimide resin having a molecular weight of 2000 to 3000 is contained as a crosslinking agent for the protective layer, a crosslinking agent such as a compound having an oxazolyl group, glyoxal, boric acid, dialdehyde starch, methylolurea, polyamide epichlorohydrin resin may be used in combination. it can. In particular, a thermosensitive recording material having high water resistance can be obtained by using it together with a polyamide epichlorohydrin resin.
感熱記録層中に含有されるロイコ染料および呈色剤としては、例えば各種公知のものが使用できる。かかるロイコ染料の具体例としては、例えば３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジメチルアミノフタリド、３−（４−ジエチルアミノ−２−メチルフェニル）−３−（４−ジメチルアミノフェニル）−６−ジメチルアミノフタリド、３−ジエチルアミノ−７−ジベンジルアミノ−ベンゾ〔ａ〕フルオラン等の青色発色性染料、３−（Ｎ−エチル−Ｎ−ｐ−トリル）アミノ−７−Ｎ−メチルアニリノフルオラン、３−ジエチルアミノ−７−アニリノフルオラン、３−ジエチルアミノ−７−ジベンジルアミノフルオラン等の緑色発色性染料、３−（Ｎ−エチル−Ｎ−イソアミルアミノ）−７−フェノキシフルオラン、３−シクロヘキシルアミノ−６−クロロフルオラン、３−ジエチルアミノ−６−メチル−７−クロロフルオラン、３−ジエチルアミノ−７−クロロフルオラン、ローダミン（ｏ−クロロアニリノ）ラクタム、３−ジエチルアミノ−６，８−ジメチルフルオラン等の赤色発色性染料、３−（Ｎ−エチル−Ｎ−イソアミル）アミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−メチル−Ｎ−シクロヘキシル）アミノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−メチル−７−アニリノフルオラン、３−ジ（ｎ−ブチル）アミノ−６−メチル−７−アニリノフルオラン、３−ジ（ｎ−ペンチル）アミノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−７−（ｏ−クロロアニリノ）フルオラン、３−ジ（ｎ−ブチル）アミノ−７−（ｏ−フルオロアニリノ）フルオラン、３−（Ｎ−エチル−ｐ−トルイジノ）−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−テトラヒドロフルフリルアミノ）−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−クロロ−７−アニリノフルオラン、３−ピロリジノ−６−メチル−７−アニリノフルオラン、３−ピペリジノ−６−メチル−７−アニリノフルオラン等の黒色発色性染料、３，３−ビス〔１−（４−メトキシフェニル）−１−（４−ジメチルアミノフェニル）エチレン−２−イル〕−４，５，６，７−テトラクロロフタリド、３−ｐ−（ｐ−ジメチルアミノアニリノ）アニリノ−６−メチル−７−クロロフルオラン、３−ｐ−（ｐ−クロロアニリノ）アニリノ−６−メチル−７−クロロフルオラン、３，６−ビス（ジメチルアミノ）フルオレン−９−スピロ−３’−（６’−ジュメチルアミノ）フタリド等の近赤外領域に吸収波長を有する染料等が挙げられる。 As the leuco dye and the colorant contained in the heat-sensitive recording layer, for example, various known ones can be used. Specific examples of such leuco dyes include, for example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-methylphenyl) -3- (4-dimethylamino) Blue color-forming dyes such as phenyl) -6-dimethylaminophthalide, 3-diethylamino-7-dibenzylamino-benzo [a] fluorane, 3- (N-ethyl-Np-tolyl) amino-7-N Green coloring dyes such as methylanilinofluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3- (N-ethyl-N-isoamylamino) -7 -Phenoxyfluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane Red coloring dyes such as 3-diethylamino-7-chlorofluorane, rhodamine (o-chloroanilino) lactam, 3-diethylamino-6,8-dimethylfluorane, 3- (N-ethyl-N-isoamyl) amino-6 -Methyl-7-anilinofluorane, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3 -Di (n-butyl) amino-6-methyl-7-anilinofluorane, 3-di (n-pentyl) amino-6-methyl-7-anilinofluorane, 3-diethylamino-7- (o- Chloroanilino) fluorane, 3-di (n-butyl) amino-7- (o-fluoroanilino) fluorane, 3- (N-ethyl-p-toluidino) -6-me Ru-7-anilinofluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, Black chromogenic dyes such as 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3,3-bis [1- (4-methoxyphenyl) -1- (4-Dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, 3-p- (p-dimethylaminoanilino) anilino-6-methyl-7- Chlorofluorane, 3-p- (p-chloroanilino) anilino-6-methyl-7-chlorofluorane, 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6'-jumeti And dyes having an absorption wavelength in the near-infrared region, such as (ruamino) phthalide.
勿論、これらに限定されるものではなく、また二種以上を併用することも可能である。また、ロイコ染料の使用量は、使用する呈色剤により異なるため限定できないが、感熱記録層全固形量に対して５〜３５質量％程度が好ましい。 Of course, it is not limited to these, It is also possible to use 2 or more types together. Further, the amount of the leuco dye used is not limited because it varies depending on the colorant used, but is preferably about 5 to 35% by mass with respect to the total solid content of the heat-sensitive recording layer.
呈色剤としては、例えば４，４’−イソプロピリデンジフェノール、４，４’−シクロヘキシリデンジフェノール、１，１−ビス（４−ヒドロキシフェニル）−エタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、４，４’−ジヒドロキシジフェニルスルホン、２，４’−ジヒドロキシジフェニルスルホン、４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン、３，３’−ジアリル−４，４’−ジヒドロキシジフェニルスルホン、２，２’−ビス〔４−（４−ヒドロキシフェニル）フェノキシ〕ジエチルエーテル、Ｎ−ｐ−トルエンスルホニル−Ｎ’−３−（ｐ−トルエンスルホニルオキシ）フェニルウレア、３，３’−ビス（ｐ−トルエンスルホニルアミノカルボニルアミノ）ジフェニルスルホン、４−ヒドロキシ安息香酸ベンジルエステル、Ｎ，Ｎ’−ジ−ｍ−クロロフェニルチオ尿素、Ｎ−ｐ−トリルスルホニル−Ｎ’−フェニルウレア、４，４’−ビス（ｐ−トリルスルホニルアミノカルボニルアミノ）ジフェニルメタン、４−〔２−（ｐ−メトキシフェノキシ）エチルオキシ〕サリチル酸亜鉛、４−｛３−（ｐ−トリルスルホニル）プロピルオキシ〕サリチル酸亜鉛、５−〔ｐ−（２−ｐ−メトキシフェノキシエトキシ）クミル〕サリチル酸亜鉛などが挙げられる。 Examples of the colorant include 4,4′-isopropylidenediphenol, 4,4′-cyclohexylidenediphenol, 1,1-bis (4-hydroxyphenyl) -ethane, 1,1-bis (4-hydroxy). Phenyl) -1-phenylethane, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 3,3′-diallyl-4,4′- Dihydroxydiphenylsulfone, 2,2′-bis [4- (4-hydroxyphenyl) phenoxy] diethyl ether, Np-toluenesulfonyl-N′-3- (p-toluenesulfonyloxy) phenylurea, 3,3 ′ -Bis (p-toluenesulfonylaminocarbonylamino) diphenylsulfone, 4-hydride Xybenzoic acid benzyl ester, N, N′-di-m-chlorophenylthiourea, Np-tolylsulfonyl-N′-phenylurea, 4,4′-bis (p-tolylsulfonylaminocarbonylamino) diphenylmethane, 4 -[2- (p-methoxyphenoxy) ethyloxy] salicylic acid zinc, 4- {3- (p-tolylsulfonyl) propyloxy] salicylic acid zinc, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid zinc Etc.
ロイコ染料に対する呈色剤の使用比率は、用いるロイコ染料や呈色剤の種類に応じて適宜選択されるものであり、特に限定するものではないが、一般にロイコ染料１質量部に対して１〜１０質量部、好ましくは１〜５質量部程度の呈色剤が使用される。勿論、これらに限定されるものではなく、また二種以上を併用することも可能である。 The use ratio of the colorant to the leuco dye is appropriately selected according to the type of the leuco dye and the colorant to be used, and is not particularly limited, but is generally 1 to 1 part by mass of the leuco dye. 10 parts by weight, preferably about 1 to 5 parts by weight of a colorant is used. Of course, it is not limited to these, It is also possible to use 2 or more types together.
感熱記録層には、記録部の保存安定性を高めるために保存性改良剤、および記録感度を高めるために増感剤を含有させることもできる。かかる保存性改良剤の具体例としては、例えば１，３，５−トリス（４−tert−ブチル−３−ヒドロキシ−２，６−ジメチルベンジル）イソシアヌル酸、２，２’−エチリデンビス（４，６−ジ−tert−ブチルフェノール）、４，４’−チオビス（２−メチル−６−tert−ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−tert−ブチルフェニル）ブタン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−シクロヘキシルフェニル）ブタン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパンなどのヒンダードフェノール化合物、４，４’−ジグリシジルオキシジフェニルスルホン、４−ベンジルオキシ−４’−（２−メチルグリシジルオキシ）ジフェニルスルホン、テレフタル酸ジグリシジル、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂などのエポキシ化合物、Ｎ，Ｎ’−ジ−２−ナフチル−ｐ−フェニレンジアミン、ビス（４−エチレンイミノカルボニルアミノフェニル）メタンなどが挙げられる。 The heat-sensitive recording layer may contain a storability improving agent for increasing the storage stability of the recording portion and a sensitizer for increasing the recording sensitivity. Specific examples of such preservability improvers include, for example, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 2,2′-ethylidenebis (4, 6-di-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Hindered phenol compounds such as butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-diglycidyloxydiphenylsulfone, 4-benzyloxy-4 ′-(2-methylglycidyloxy) diphenylsulfone, diglyceryl terephthalate Zir, cresol novolac type epoxy resin, phenol novolac type epoxy resin, epoxy compound such as bisphenol A type epoxy resin, N, N′-di-2-naphthyl-p-phenylenediamine, bis (4-ethyleneiminocarbonylaminophenyl) Examples include methane.
増感剤の具体例としては、例えばステアリン酸アミド、メチレンビスステアリン酸アミド、テレフタル酸ジベンジル、ｐ−ベンジルオキシ安息香酸ベンジル、２−ナフチルベンジルエーテル、ｍ−ターフェニル、ｐ−ベンジルビフェニル、ｐ−トリルビフェニルエーテル１，２−ジ（３−メチルフェノキシ）エタン、１，２−ジ（４−メチルフェノキシ）エタン、１，２−ジ（４−メトキシフェノキシ）エタン、１，２−ジ（４−クロロフェノキシ）エタン、１，２−ジフェノキシエタン、１−（４−メトキシフェノキシ）−２−（３−メチルフェノキシ）エタン、ｐ−メチルチオフェニルベンジルエーテル、１，４−ジ（フェニルチオ）ブタン、ｐ−アセトトルイジド、ｐ−アセトフェネチジド、Ｎ−アセトアセチル−ｐ−トルイジン、ジ（β−ビフェニルエトキシ）ベンゼン、シュウ酸ジ−ｐ−クロロベンジルエステル、シュウ酸ジ−ｐ−メチルベンジルエステル、シュウ酸ジベンジルエステルなどが挙げられる。 Specific examples of the sensitizer include, for example, stearamide, methylenebisstearate, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, 2-naphthylbenzyl ether, m-terphenyl, p-benzylbiphenyl, p- Tolylbiphenyl ether 1,2-di (3-methylphenoxy) ethane, 1,2-di (4-methylphenoxy) ethane, 1,2-di (4-methoxyphenoxy) ethane, 1,2-di (4- Chlorophenoxy) ethane, 1,2-diphenoxyethane, 1- (4-methoxyphenoxy) -2- (3-methylphenoxy) ethane, p-methylthiophenylbenzyl ether, 1,4-di (phenylthio) butane, p -Acetotoluizide, p-acetophenetide, N-acetoacetyl-p-toluidine, di β- biphenyl ethoxy) benzene, oxalic acid di -p- chlorobenzyl ester, oxalic acid di -p- methylbenzyl ester, oxalic acid dibenzyl ester.
これらの保存性改良剤および増感剤の使用量は特に限定されないが、一般にロイコ染料１質量部に対して０．２〜４質量部程度ある。勿論、これらに限定されるものではなく、また二種以上を併用することも可能である。 Although the usage-amount of these preservatives and a sensitizer is not specifically limited, Generally it is about 0.2-4 mass parts with respect to 1 mass part of leuco dyes. Of course, it is not limited to these, It is also possible to use 2 or more types together.
感熱記録層は、水を分散媒体とし、ロイコ染料、呈色剤、必要により増感剤、保存性改良剤などを共に、或いは別々にボールミル、アトライター、サンドミルなどの撹拌・粉砕機により平均粒子径が２μｍ以下となるように微粉砕した後、接着剤、顔料等を添加して調製された感熱記録層用塗液を支持体の少なくとも一方の面に塗布乾燥して形成される。 The heat-sensitive recording layer uses water as a dispersion medium, leuco dye, colorant, if necessary, sensitizer, preservability improver, etc., or separately with an agitator / pulverizer such as a ball mill, attritor, sand mill, etc. After finely pulverizing to have a diameter of 2 μm or less, a heat-sensitive recording layer coating solution prepared by adding an adhesive, a pigment, and the like is applied to and dried on at least one surface of the support.
かかる接着剤としては、例えば完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、アセトアセチル変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、ケイ素変性ポリビニルアルコール等の変性ポリビニルアルコール、デンプン、酸化デンプン、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、ジイソブチレン・無水マレイン酸共重合体、スチレン−無水マレイン酸共重合体、エチレン−アクリル酸共重合体などの水溶性接着剤並びにアクリル樹脂系ラテックス、ウレタン樹脂系ラテックス、スチレン−ブタジエン系ラテックス、スチレン−アクリル系ラテックスなどの水分散性接着剤が挙げられる。 Examples of such an adhesive include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, modified polyvinyl alcohol such as silicon-modified polyvinyl alcohol, starch, oxidized starch, Water-soluble adhesives such as hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, gum arabic, diisobutylene / maleic anhydride copolymer, styrene-maleic anhydride copolymer, ethylene-acrylic acid copolymer, and acrylic resin Water-dispersible adhesives such as latex, urethane resin latex, styrene-butadiene latex, and styrene-acrylic latex That.
感熱記録層中の接着剤の使用量としては、感熱記録層の全固形分に対して５〜３５質量％程度が好ましい。勿論、上記の水性接着剤に限定されるものではなく、また二種以上の併用も可能である。 The amount of the adhesive used in the heat-sensitive recording layer is preferably about 5 to 35% by mass with respect to the total solid content of the heat-sensitive recording layer. Of course, the water-based adhesive is not limited to the above, and two or more types can be used in combination.
更に、感熱記録層用塗液中には、炭酸カルシウム、酸化亜鉛、酸化アルミニウム、二酸化チタン、無定形シリカ、水酸化アルミニウム、硫酸バリウム、タルク、カオリン、クレー、焼成カオリン、ナイロン樹脂フィラー、尿素・ホルマリン樹脂フィラーなどの顔料類、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリルリン酸エステルカリウム塩、ポリエチレンワックス、カルナバロウ、パラフィンワックス、エステルワックスなどの滑剤類、アルキルベンゼンスルホン酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、スルホン変性ポリビニルアルコール、ポリアクリル酸ナトリウムなどの界面活性剤類、および消泡剤、紫外線吸収剤、蛍光染料、着色染料、離型剤、酸化防止剤などの助剤を添加することもできる。 Furthermore, in the coating solution for the thermal recording layer, calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, amorphous silica, aluminum hydroxide, barium sulfate, talc, kaolin, clay, calcined kaolin, nylon resin filler, urea Pigments such as formalin resin filler, lubricants such as zinc stearate, calcium stearate, potassium stearyl phosphate, polyethylene wax, carnauba wax, paraffin wax, ester wax, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sulfone-modified polyvinyl Surfactants such as alcohol and sodium polyacrylate, and auxiliary agents such as antifoaming agents, ultraviolet absorbers, fluorescent dyes, colored dyes, mold release agents, and antioxidants can also be added.
保護層は、例えば水を媒体とし、接着剤として変性ポリビニルアルコールや所望の効果を阻害しない程度に上記の感熱記録層用塗液中の接着剤として例示された接着剤が使用され、カルボジイミド樹脂、さらに好ましくはポリアミドエピクロルヒドリン樹脂や上記の各種助剤とを混合撹拌して調製された保護層用塗液を感熱記録層上に塗布乾燥して形成される。 As the protective layer, for example, water is used as a medium, and an adhesive exemplified as an adhesive in the above-described thermal recording layer coating liquid is used to such an extent that the polyvinyl alcohol or the desired effect is not impaired as an adhesive. More preferably, the protective layer coating liquid prepared by mixing and stirring the polyamide epichlorohydrin resin and the above-mentioned various auxiliary agents is applied to the heat-sensitive recording layer and dried.
保護層中の水性接着剤の使用量としては保護層の全固形分に対して２０〜９５質量％程度が好ましい。勿論、上記の水性接着剤に限定されるものではなく、また二種以上の併用も可能である。 As the usage-amount of the water-based adhesive in a protective layer, about 20-95 mass% is preferable with respect to the total solid of a protective layer. Of course, the water-based adhesive is not limited to the above, and two or more types can be used in combination.
保護層に含有される上記の水性接着剤のなかでも、カルボキシ変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコールおよびアセトアセチル変性ポリビニルアルコールから選ればれる変性ポリビルアルコールが好ましい。 Among the aqueous adhesives contained in the protective layer, a modified polyvinyl alcohol selected from carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, and acetoacetyl-modified polyvinyl alcohol is preferable.
保護層、感熱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、例えばエアーナイフコーティング、バリバーブレードコーティング、ピュアーブレードコーティング、ロッドブレードコーティング、カーテンコーティング、ダイコーティング、グラビアコーティング、スライドビードコーティング、オフセットグラビアコーティング、５本ロールコーティングなどの適当な塗布方法により形成される。 The method for forming the protective layer and the thermosensitive recording layer is not particularly limited. For example, air knife coating, varibar blade coating, pure blade coating, rod blade coating, curtain coating, die coating, gravure coating, slide bead coating, It is formed by an appropriate application method such as offset gravure coating or five-roll coating.
支持体としては、２０〜２００μｍのプラスチックフィルム、合成紙あるいは紙（中性紙、酸性紙、脱墨古紙パルプが含有された紙）、コート紙などを適宜選択して使用される。 As the support, a plastic film of 20 to 200 μm, synthetic paper or paper (neutral paper, acid paper, paper containing deinked waste paper pulp), coated paper, and the like are appropriately selected and used.
感熱記録層用塗液の塗布量は乾燥重量で２〜１０ｇ／ｍ２、好ましくは３〜８ｇ／ｍ２程度、保護層用塗液の塗布量は乾燥重量で０．５〜５ｇ／ｍ２程度である。 The coating amount of the heat-sensitive recording layer coating composition is 2 to 10 g / m 2 by dry weight, preferably 3 to 8 g / m 2 approximately, the coating amount of the protective layer coating liquid for a dry weight 0.5 to 5 g / m 2 Degree.
支持体と感熱記録層の間に、接着剤と有機中空粒子または吸油性顔料とを主成分とした下塗り層中に含有させることにより、記録感度と記録画質が高められる。 Inclusion of an adhesive and organic hollow particles or an oil-absorbing pigment between the support and the heat-sensitive recording layer in an undercoat layer improves recording sensitivity and recording image quality.
なお、必要に応じて感熱記録体の支持体の裏面側にも保護層、印刷層、磁気記録層、帯電防止層、粘着剤層、或いはインクジェット記録層を設けたり、各層塗抹後にスーパーカレンダー掛けなどの平滑化処理を施すことなどの感熱記録体製造分野における各種の公知技術が必要に応じて付加し得るものである。更に、感熱記録層を多色記録が可能な構成にすることもできる。 If necessary, a protective layer, a printing layer, a magnetic recording layer, an antistatic layer, an adhesive layer, or an ink jet recording layer may be provided on the back side of the support of the heat-sensitive recording medium, or a super calendering may be applied after coating each layer. Various known techniques in the heat-sensitive recording material manufacturing field, such as the above-mentioned smoothing treatment, can be added as necessary. Furthermore, the thermosensitive recording layer can be configured to be capable of multicolor recording.
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。なお、例中の「部」及び「％」は、特に断らない限りそれぞれ「質量部」、「質量％」を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the examples, “parts” and “%” respectively represent “parts by mass” and “% by mass” unless otherwise specified.
実施例１
（下塗り層用塗液の調製）
焼成カオリン（ＪＩＳ Ｋ ５１０１に基づく吸油量が９０ｍｌ／１００ｇ）９０部、軽質炭酸カルシウム１０部、ポリアクリル酸ソーダの４０％水溶液１部、固形分濃度４８％のスチレンアクリル共重合エマルジョン（商品名：Ｌ−１５７１、旭化成社製）１０部、および水５０部からなる組成物を混合撹拌して下塗り層用塗液を調製した。
Example 1
(Preparation of coating solution for undercoat layer)
90 parts of calcined kaolin (90 ml / 100 g oil absorption based on JIS K 5101), 10 parts of light calcium carbonate, 1 part of 40% aqueous solution of sodium polyacrylate, 48% solid content styrene acrylic copolymer emulsion (trade name: A composition comprising 10 parts of L-1571 (manufactured by Asahi Kasei Co., Ltd.) and 50 parts of water was mixed and stirred to prepare an undercoat layer coating solution.
（ロイコ染料分散液の調製・Ａ液調製）
３−ジ（ｎ−ペンチル）アミノ−６−メチル−７−アニリノフルオラン１５部、ハリコートＢＩ６８０（成分：ポリビニールーアルコール、アクリルアミド、アクリルニトリル共重合物、ハリマ化成社製）の３０％水溶液２０部および水２５部からなる組成物を縦型サンドミル（アイメックス（株）製、サンドグラインダー）を用いて、平均粒子径が０．８μｍとなるように微粉砕してロイコ染料分散液・Ａ液を調製した。
(Preparation of leuco dye dispersion and preparation of solution A)
15% aqueous solution of 3-di (n-pentyl) amino-6-methyl-7-anilinofluorane, Haricoat BI680 (component: polyvinyl alcohol, acrylamide, acrylonitrile copolymer, Harima Chemicals) A composition consisting of 20 parts and 25 parts of water is pulverized to a mean particle size of 0.8 μm using a vertical sand mill (manufactured by Imex Co., Ltd., sand grinder), and a leuco dye dispersion liquid / liquid A Was prepared.
（呈色剤分散液の調製・Ｂ液調製）
４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン３０部、ハリコートＢＩ６８０（成分：ポリビニールアルコール、アクリルアミド、アクリルニトリル共重合物、ハリマ化成社製）の３０％水溶液１０部および、水７０部からなる組成物を縦型サンドミル（アイメックス（株）製、サンドグラインダー）を用いて、平均粒子径が１．０μｍとなるように微粉砕して呈色剤分散液・Ｂ液を調製した。
(Preparation of colorant dispersion and preparation of solution B)
A composition comprising 30 parts of 4-hydroxy-4'-isopropoxydiphenylsulfone, 10 parts of 30% aqueous solution of Haricoat BI680 (components: polyvinyl alcohol, acrylamide, acrylonitrile copolymer, manufactured by Harima Chemicals) and 70 parts of water. The product was finely pulverized using a vertical sand mill (Sand Grinder, manufactured by IMEX Co., Ltd.) so as to have an average particle diameter of 1.0 μm to prepare a colorant dispersion liquid B.
（増感剤分散液の調製・Ｃ液調製）
シュウ酸ジ−ｐ−メチルベンジル３０部、ハリコートＢＩ６８０（成分：ポリビニールーアルコール、アクリルアミド、アクリルニトリル共重合物、ハリマ化成社製）の３０％水溶液１０部および水７０部からなる組成物を縦型サンドミル（アイメックス（株）製、サンドグラインダー）を用いて、平均粒子径が１．０μｍとなるように微粉砕して増感剤分散液・Ｃ液を調製した。
(Preparation of sensitizer dispersion / C liquid preparation)
A composition comprising 30 parts of di-p-methylbenzyl oxalate, 10 parts of 30% aqueous solution of Haricoat BI680 (components: polyvinyl alcohol, acrylamide, acrylonitrile copolymer, manufactured by Harima Kasei Co., Ltd.) and 70 parts of water is vertically A sensitizer dispersion / liquid C was prepared by pulverizing using a mold sand mill (sand grinder, manufactured by Imex Co., Ltd.) so that the average particle diameter was 1.0 μm.
（感熱記録層用塗液の調製）
Ａ液６０部、Ｂ液１１０部、Ｃ液１１０部、軽質炭酸カルシウム１０部、変性スチレンブタジエン共重合エマルジョン(商品名：Ｎｉｐｏｌ ＰＴ−１０５１：日本ゼオン社製)４８％を２０．８部、ホウ酸５％水溶液６０部からなる組成物を混合撹拌して感熱記録層用塗液を調製した。
(Preparation of thermal recording layer coating solution)
60 parts of A liquid, 110 parts of B liquid, 110 parts of C liquid, 10 parts of light calcium carbonate, modified styrene butadiene copolymer emulsion (trade name: Nipol PT-1051: manufactured by Nippon Zeon Co., Ltd.) 48%, 20.8 parts A composition comprising 60 parts of an acid 5% aqueous solution was mixed and stirred to prepare a thermal recording layer coating solution.
（保護層用塗液の調製）
カルボキシ変性ポリビニルアルコール（商品名：ゴーセーナールＴ−２１５、日本合成化学社製）の１０％水溶液４００部、カオリンの７０％分散液８５部、ポリアミドエピクロルヒドリン樹脂（商品名：ＷＳ４０２４、星光ＰＭＣ社製）２５％水溶液２４部、カルボジイミド樹脂（商品名：カルボジライトＶ−０２−Ｌ２、日清紡績社製、分子量２４００）の４０％水溶液１２．５部、ステアリン酸亜鉛分散体の３６％水分散液４．５部、および水１００部からなる組成物を混合撹拌して保護層用塗液を調製した。
(Preparation of coating solution for protective layer)
400 parts of a 10% aqueous solution of carboxy-modified polyvinyl alcohol (trade name: Goseinal T-215, manufactured by Nippon Synthetic Chemical Co., Ltd.), 85 parts of a 70% dispersion of kaolin, polyamide epichlorohydrin resin (trade name: WS4024, manufactured by Seiko PMC) 25 24 parts of aqueous solution, 12.5 parts of 40% aqueous solution of carbodiimide resin (trade name: Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., molecular weight 2400), 4.5 parts of 36% aqueous dispersion of zinc stearate dispersion And a composition comprising 100 parts of water were mixed and stirred to prepare a protective layer coating solution.
（感熱記録体の作成）
坪量６０ｇ／ｍ２の上質紙（中性紙）の一方の面に、下塗り層用塗液、感熱記録層用塗液および保護層用塗液を乾燥後の塗布量がそれぞれ８ｇ／ｍ２、５ｇ／ｍ２および３ｇ／ｍ２となるように順次塗布乾燥した後、スーパーカレンダーにて保護層面側のベック平滑度（ＪＩＳ Ｐ ８１１９に基づく）が１２００秒となるように処理して感熱記録体を得た。
得られた感熱記録体を４０℃５５％ＲＨの環境下で９６時間キュアーリングを施した。
(Creation of thermal recording material)
On one side of a high-quality paper (neutral paper) having a basis weight of 60 g / m 2 , the coating amount after drying the undercoat layer coating solution, the thermal recording layer coating solution and the protective layer coating solution is 8 g / m 2, respectively. After sequentially coating and drying so as to be 5 g / m 2 and 3 g / m 2 , it was processed with a super calender so that the Beck smoothness (based on JIS P 8119) on the surface of the protective layer was 1200 seconds. Got the body.
The obtained thermal recording material was cured for 96 hours in an environment of 40 ° C. and 55% RH.
実施例２
実施例１の保護層用塗液の調製において、カルボキシ変性ポリビニルアルコールの代わりにジアセトン変性ポリビニルアルコール（商品名：Ｄ−６１０、ユニチカ社製）の１０％水溶液４００部を用いた以外は、実施例１と同様にして感熱記録体を得た。
Example 2
In the preparation of the coating solution for the protective layer of Example 1, Example was used except that 400 parts of a 10% aqueous solution of diacetone-modified polyvinyl alcohol (trade name: D-610, manufactured by Unitika) was used instead of carboxy-modified polyvinyl alcohol. In the same manner as in No. 1, a heat-sensitive recording material was obtained.
実施例３
実施例１の保護層用塗液の調製において、カルボキシ変性ポリビニルアルコールの代わりにアセトアセチル変性ポリビニルアルコール（商品名：ゴーセファイマーＺ−１００、日本合成化学社製）の１０％水溶液４００部を用いた以外は、実施例１と同様にして感熱記録体を得た。
Example 3
In the preparation of the coating solution for the protective layer of Example 1, 400 parts of a 10% aqueous solution of acetoacetyl-modified polyvinyl alcohol (trade name: Goosefimmer Z-100, manufactured by Nippon Synthetic Chemical Co., Ltd.) was used instead of carboxy-modified polyvinyl alcohol. A heat-sensitive recording material was obtained in the same manner as in Example 1 except that.
実施例４
実施例１の感熱記録層用塗液の調製においてホウ酸を使用しなかった以外は、実施例１と同様にして感熱記録体を得た。
Example 4
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that boric acid was not used in the preparation of the heat-sensitive recording layer coating liquid of Example 1.
実施例５
実施例１の保護層層用塗液の調製において、ポリアミドエピクロルヒドリン樹脂（前出）を使用しなかった以外は、実施例４と同様にして感熱記録体を得た。
Example 5
A thermosensitive recording material was obtained in the same manner as in Example 4 except that the polyamide epichlorohydrin resin (described above) was not used in the preparation of the protective layer coating solution of Example 1.
比較例１
実施例１の保護層用塗液の調製において、カルボジイミド樹脂（商品名：カルボジライトＶ−０２−Ｌ２、日清紡績社製）の４０％水溶液１２．５部の代わりにカルボジイミド樹脂（商品名：カルボジライトＶ−０２、日清紡績社製、分子量１６００）の４０％水溶液１２．５部を用いた以外は、実施例１と同様にして感熱記録体を得た。
Comparative Example 1
In the preparation of the coating liquid for protective layer of Example 1, carbodiimide resin (trade name: Carbodilite V) was used instead of 12.5 parts of 40% aqueous solution of carbodiimide resin (trade name: Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd.). A heat-sensitive recording material was obtained in the same manner as in Example 1 except that 12.5 parts of a 40% aqueous solution having a molecular weight of 1600), manufactured by Nisshinbo Industries Inc.
比較例２
実施例１の保護層用塗液の調製において、カルボキシ変性ポリビニルアルコールの代わりに完全ケン化ポリビニルアルコール（商品名：ＰＶＡ１０５、クラレ社製）の１０％水溶液４００部を用いた以外は、実施例１と同様にして感熱記録体を得た。
Comparative Example 2
In the preparation of the protective layer coating solution of Example 1, Example 1 was used except that 400 parts of a 10% aqueous solution of completely saponified polyvinyl alcohol (trade name: PVA105, manufactured by Kuraray Co., Ltd.) was used instead of carboxy-modified polyvinyl alcohol. In the same manner, a heat-sensitive recording material was obtained.
かくして得られた感熱記録体について、下記の評価試験をおこない、その結果を表１に示す。 The thermal recording material thus obtained was subjected to the following evaluation test, and the results are shown in Table 1.
（記録方法）
感熱記録評価試験機（商品名：ＴＨ−ＰＭＤ、大倉電気社製）を用いて、０．２４ｍＪ／ｄｏｔの条件にて文字情報を記録した。
(Recording method)
Character information was recorded under the condition of 0.24 mJ / dot using a thermal recording evaluation tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.).
（耐水性）
文字情報を記録した感熱記録体において、記録面の一方に水滴を垂らした後、記録面が内側になるように２つ折り、水滴を垂らした部分に単一電池を載せ、室温で２４時間放置後２つ折り部分を剥がして目視観察し、以下のように評価した。
◎：剥離時に抵抗無く容易に剥離する。
○：剥離時にやや抵抗があるが、記録部は鮮明で判読は可能である。
△：記録面に剥がれが少しあるが、記録部は判読は可能である。
×：記録層面が剥がれ、記録部は判読できない。
(water resistant)
In a heat-sensitive recording medium on which character information is recorded, after dripping a water drop on one side of the recording surface, fold it in half so that the recording surface is inside, place a single battery on the dripped part, and leave it at room temperature for 24 hours The half-folded part was peeled off and visually observed, and evaluated as follows.
(Double-circle): It peels easily without resistance at the time of peeling.
○: There is a slight resistance when peeling, but the recorded part is clear and legible.
Δ: There is a little peeling on the recording surface, but the recording part can be read.
X: The recording layer surface peels off, and the recording part cannot be read.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004339923A JP2006150594A (en) | 2004-11-25 | 2004-11-25 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004339923A JP2006150594A (en) | 2004-11-25 | 2004-11-25 | Thermal recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006150594A true JP2006150594A (en) | 2006-06-15 |
Family
ID=36629465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004339923A Pending JP2006150594A (en) | 2004-11-25 | 2004-11-25 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006150594A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009066852A (en) * | 2007-09-12 | 2009-04-02 | Ricoh Co Ltd | Thermosensitive recording material |
| JP2011062874A (en) * | 2009-09-16 | 2011-03-31 | Oji Paper Co Ltd | Thermal recording material |
| JP2015083391A (en) * | 2015-01-22 | 2015-04-30 | 三菱製紙株式会社 | Method of producing heat-sensitive recording material |
| JP2017215587A (en) * | 2016-05-31 | 2017-12-07 | 三洋化成工業株式会社 | Toner binder and toner |
| CN110552241A (en) * | 2019-07-12 | 2019-12-10 | 华南理工大学 | Method for deacidifying and enhancing acidified and aged paper documents by using sodium silicate or borax and polyamide epichlorohydrin compound |
-
2004
- 2004-11-25 JP JP2004339923A patent/JP2006150594A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009066852A (en) * | 2007-09-12 | 2009-04-02 | Ricoh Co Ltd | Thermosensitive recording material |
| JP2011062874A (en) * | 2009-09-16 | 2011-03-31 | Oji Paper Co Ltd | Thermal recording material |
| JP2015083391A (en) * | 2015-01-22 | 2015-04-30 | 三菱製紙株式会社 | Method of producing heat-sensitive recording material |
| JP2017215587A (en) * | 2016-05-31 | 2017-12-07 | 三洋化成工業株式会社 | Toner binder and toner |
| CN110552241A (en) * | 2019-07-12 | 2019-12-10 | 华南理工大学 | Method for deacidifying and enhancing acidified and aged paper documents by using sodium silicate or borax and polyamide epichlorohydrin compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5025029B2 (en) | Thermal recording material | |
| JP5878271B1 (en) | Thermal recording material | |
| JP2014226848A (en) | Heat-sensitive recording body | |
| JP7127684B2 (en) | Thermal recording medium | |
| JP2008012879A (en) | Heat-sensitive recording medium | |
| JP4457814B2 (en) | Thermal recording material | |
| JP4182625B2 (en) | Thermal recording material | |
| JP2006150594A (en) | Thermal recording material | |
| JP6773544B2 (en) | Thermal recording body | |
| JP7413098B2 (en) | heat sensitive recording material | |
| JP2002316482A (en) | Thermal recording medium | |
| CN115515796A (en) | thermal recorder | |
| JP2007203580A (en) | Thermal recording medium | |
| JP7494713B2 (en) | Thermal recording medium | |
| JP7354483B1 (en) | heat sensitive recording material | |
| JP7146148B1 (en) | Thermal recording medium | |
| JP2004106435A (en) | Thermal recording medium | |
| JP2013086402A (en) | Heat-sensitive recording body | |
| JP4999358B2 (en) | Thermal recording material | |
| JP2009083181A (en) | Thermosensitive recording body | |
| JP2024162422A (en) | Thermal recording medium | |
| JP6070477B2 (en) | Thermal recording material | |
| JP5741133B2 (en) | Thermal recording material | |
| WO2023190314A1 (en) | Heat-sensitive recording body | |
| JP4508106B2 (en) | Thermal recording material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070405 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090604 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090609 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20091020 |