JP2017177346A - Thermosensitive recording linerless label and method for manufacturing the same - Google Patents
Thermosensitive recording linerless label and method for manufacturing the same Download PDFInfo
- Publication number
- JP2017177346A JP2017177346A JP2016063496A JP2016063496A JP2017177346A JP 2017177346 A JP2017177346 A JP 2017177346A JP 2016063496 A JP2016063496 A JP 2016063496A JP 2016063496 A JP2016063496 A JP 2016063496A JP 2017177346 A JP2017177346 A JP 2017177346A
- Authority
- JP
- Japan
- Prior art keywords
- support
- linerless label
- layer
- developer
- sensitizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000010410 layer Substances 0.000 claims abstract description 89
- 239000000853 adhesive Substances 0.000 claims abstract description 30
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 29
- 230000001070 adhesive effect Effects 0.000 claims abstract description 28
- 239000011241 protective layer Substances 0.000 claims abstract description 25
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 15
- 239000000194 fatty acid Substances 0.000 claims abstract description 15
- 229930195729 fatty acid Natural products 0.000 claims abstract description 15
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 15
- BGLZECVIKIGPIF-UHFFFAOYSA-N 1-[2-(benzenesulfonamido)phenyl]-3-phenylurea Chemical compound C=1C=CC=C(NS(=O)(=O)C=2C=CC=CC=2)C=1NC(=O)NC1=CC=CC=C1 BGLZECVIKIGPIF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 37
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 37
- 238000000576 coating method Methods 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 239000012790 adhesive layer Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003860 storage Methods 0.000 abstract description 8
- 238000000586 desensitisation Methods 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 4
- 229920002472 Starch Polymers 0.000 abstract description 3
- 239000008107 starch Substances 0.000 abstract description 3
- 235000019698 starch Nutrition 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000006185 dispersion Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 16
- -1 3-phenylureido Chemical group 0.000 description 15
- 239000000975 dye Substances 0.000 description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 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 8
- 239000002245 particle Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- 238000007127 saponification reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000011161 development Methods 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
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 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
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- SLZWSYPJQQIDJB-UHFFFAOYSA-N n-[6-(octadecanoylamino)hexyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCCCNC(=O)CCCCCCCCCCCCCCCCC SLZWSYPJQQIDJB-UHFFFAOYSA-N 0.000 description 3
- OSJJOWRIYDWQPO-UHFFFAOYSA-N n-[[2-[(octadecanoylamino)methyl]phenyl]methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCC1=CC=CC=C1CNC(=O)CCCCCCCCCCCCCCCCC OSJJOWRIYDWQPO-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000001993 wax Substances 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
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- 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 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000001454 recorded image Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000013053 water resistant agent 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
- QRIKMBDKRJXWBV-CLFAGFIQSA-N (z)-n-[6-[[(z)-octadec-9-enoyl]amino]hexyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC QRIKMBDKRJXWBV-CLFAGFIQSA-N 0.000 description 1
- 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
- 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
- AJXHXSKQHBJNPB-UHFFFAOYSA-N 1-methoxy-4-[2-[2-(4-methoxyphenoxy)ethoxy]ethoxy]benzene Chemical compound C1=CC(OC)=CC=C1OCCOCCOC1=CC=C(OC)C=C1 AJXHXSKQHBJNPB-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
- FYGFTTWEWBXNMP-UHFFFAOYSA-N 10-amino-10-oxodecanoic acid Chemical compound NC(=O)CCCCCCCCC(O)=O FYGFTTWEWBXNMP-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 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
- UEJVSOJRGUIWCY-UHFFFAOYSA-N 2-hydroxybenzoic acid;zinc Chemical compound [Zn].OC(=O)C1=CC=CC=C1O UEJVSOJRGUIWCY-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
- 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 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
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- JMHSCWJIDIKGNZ-UHFFFAOYSA-N 4-carbamoylbenzoic acid Chemical compound NC(=O)C1=CC=C(C(O)=O)C=C1 JMHSCWJIDIKGNZ-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
- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 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
- 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
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Chemical class 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 241000047703 Nonion Species 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
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 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
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000008901 benefit Effects 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
- 239000011230 binding agent Substances 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical group NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical group CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 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
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 238000007598 dipping method Methods 0.000 description 1
- OJLOUXPPKZRTHK-UHFFFAOYSA-N dodecan-1-ol;sodium Chemical compound [Na].CCCCCCCCCCCCO OJLOUXPPKZRTHK-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000009499 grossing 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
- 239000000314 lubricant Substances 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
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 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
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- HETBCUMLBCUVKC-UHFFFAOYSA-N n-[2-(dodecanoylamino)ethyl]dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC HETBCUMLBCUVKC-UHFFFAOYSA-N 0.000 description 1
- LCZJLVYYBRTSAQ-UHFFFAOYSA-N n-[4-(octadecanoylamino)butyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCNC(=O)CCCCCCCCCCCCCCCCC LCZJLVYYBRTSAQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000005375 organosiloxane 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
- 239000003973 paint Substances 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
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000019271 petrolatum Nutrition 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
- FMIORWSKZKIJQZ-UHFFFAOYSA-N phenol;pyrrole-2,5-dione Chemical group OC1=CC=CC=C1.O=C1NC(=O)C=C1 FMIORWSKZKIJQZ-UHFFFAOYSA-N 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 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)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、電子供与性化合物と電子受容性化合物との発色反応を利用し、特に熱エネルギーによる発色反応により記録像が得られる感熱記録体に関するものである。 The present invention relates to a heat-sensitive recording material that utilizes a color-forming reaction between an electron-donating compound and an electron-accepting compound and that can obtain a recorded image by a color-forming reaction by thermal energy.
熱エネルギーにより電子供与性化合物と電子受容性化合物を接触させて記録像を得るようにした感熱記録体はよく知られている。このような感熱記録体は比較的安価であり、記録機器がコンパクトで、その保守も容易なため、ファクシミリや各種計算機等の記録媒体に使用されている。 A heat-sensitive recording material in which a recorded image is obtained by bringing an electron-donating compound and an electron-accepting compound into contact with each other by thermal energy is well known. Such a heat-sensitive recording material is relatively inexpensive, has a compact recording device, and is easy to maintain. Therefore, it is used for recording media such as facsimiles and various computers.
特に近年は、ガス、水道、電気料金等の領収書、金融機関のATMの利用明細書、各種レシート等、財務関係の記録用紙(所謂、ハンディターミナル用)やPOSシステム用の感熱記録ラベル或いは感熱記録タグ等に、種々のバーコードを感熱記録印字して用いられる機会が増加しており、バーコード印字適性を有する感熱記録体が求められている。 In recent years, in particular, receipts for gas, water, electricity bills, ATM usage statements for financial institutions, various receipts, etc., financial record sheets (for so-called handy terminals), thermal recording labels for POS systems, and thermal recording labels. Opportunities to use various bar codes by thermal recording and printing on recording tags and the like are increasing, and there is a need for a thermal recording body having barcode printing suitability.
かかる用途の感熱記録体は、感熱記録層の裏面に粘着剤層を設けた上に剥離紙が貼り合わされ、巻取りの状態で記録機器に装填されている。このような感熱記録用粘着シートの紙厚は粘着層、剥離紙の講成により厚くなるため、記録機器に装填できる感熱記録用粘着シートの長さも制限され、記録後貼り合せ時に発生する剥離紙の処理も省資源の観点から問題である。 In such a heat-sensitive recording material, a pressure-sensitive adhesive layer is provided on the back surface of the heat-sensitive recording layer, and a release paper is bonded to the recording device in a wound state. Since the thickness of such a heat-sensitive recording adhesive sheet is increased by the preparation of the adhesive layer and release paper, the length of the heat-sensitive recording adhesive sheet that can be loaded into the recording device is also limited, and the release paper that is generated during pasting after recording This processing is also a problem from the viewpoint of resource saving.
剥離紙を用いない感熱記録用粘着シートは、種々提案されており、感熱記録体上にシリコーン樹脂等を含む剥離層、裏面に粘着剤層を設けた巻取りの状態で使用されている(特許文献1〜4参照)。しかしながら、剥離層と粘着剤層が感熱記録層と重ね合わされることによって問題が種々発生する。 Various pressure-sensitive adhesive sheets for thermal recording that do not use release paper have been proposed, and are used in a wound state in which a release layer containing a silicone resin or the like is provided on a thermal recording material and an adhesive layer is provided on the back surface (patent) References 1-4). However, various problems occur when the release layer and the pressure-sensitive adhesive layer are overlapped with the heat-sensitive recording layer.
一般に粘着剤は、溶剤系、エマルジョン系、ホットメルト系等があるが、環境面、製造設備面からエマルジョン系が使用されることが多い。エマルジョン系粘着剤は、主にアクリル酸エステルモノマーの乳化重合で得られるが、乳化剤、安定剤、分散剤等の添加剤が必要であり、粘着剤層にはこれらの添加物が含まれる。これらの添加剤が感熱記録層の発色成分に悪影響を与えることがあり、長期保管後、特に高温高湿環境下で保管されると感熱記録層の顕色剤や増感剤が粘着剤層に移動し、発色能力が著しく劣化する欠点、いわゆる糊減感の問題がある。 In general, the adhesive includes a solvent system, an emulsion system, a hot melt system, and the like, but an emulsion system is often used from the viewpoint of environment and manufacturing equipment. The emulsion-based pressure-sensitive adhesive is mainly obtained by emulsion polymerization of an acrylate monomer, but requires additives such as an emulsifier, a stabilizer, a dispersant, and the pressure-sensitive adhesive layer contains these additives. These additives may adversely affect the coloring components of the heat-sensitive recording layer, and when stored for a long time, especially in a high-temperature and high-humidity environment, the developer and sensitizer of the heat-sensitive recording layer are added to the pressure-sensitive adhesive layer. There is a defect that the color development ability is remarkably deteriorated, that is, the so-called glue desensitization.
即ち、剥離紙を用いない感熱記録ライナーレスラベルでは、粘着剤や剥離剤に由来する印字障害について十分に解決されておらず、剥離紙を用いた従来のラベルに比べて遥かに厳しい品質が要求されている。流通管理用途のような過酷な条件下で使用しても問題の起こらない、また高速発行にも対応でき、記録適性に優れ、且つ長期記録しても印字障害が起こらないメンテナンスの不要な感熱記録ライナーレスラベルが強く求められている。 In other words, thermal recording linerless labels that do not use release paper have not fully solved the printing obstacles caused by adhesives and release agents, and require far stricter quality than conventional labels that use release paper. Has been. Thermal recording that does not cause problems even when used under severe conditions such as distribution management applications, is compatible with high-speed issuance, has excellent recording suitability, and does not cause printing problems even if recorded for a long time. There is a strong demand for linerless labels.
本発明の課題は、長期保管後、特に高温高湿環境下で長期間保管されても発色能力が低下することのない、すなわち糊減感のない、白紙部の耐熱性に優れた感熱記録ライナーレスラベルを提供することを主な目的とする。 An object of the present invention is to provide a thermal recording liner that does not deteriorate in color development ability even after being stored for a long time in a high-temperature and high-humidity environment after long-term storage. The main purpose is to provide a less label.
本発明者等は、鋭意検討を重ねた結果、感熱記録層に特定の顕色剤と増感剤を含有させることにより、前記問題点を解決するに至った。即ち、本発明は、下記の感熱記録ライナーレスラベルに係る。 As a result of intensive studies, the present inventors have solved the above-mentioned problems by incorporating a specific developer and a sensitizer into the heat-sensitive recording layer. That is, the present invention relates to the following thermal recording linerless label.
項1:支持体、前記支持体の一方の面に、前記支持体に近い側から染料前駆体と顕色剤と増感剤とを含有する感熱記録層、接着剤を含有する保護層、並びに剥離層を有し、前記支持体の他方の面に粘着剤層を有する感熱記録ライナーレスラベルであって、前記顕色剤としてN−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミド、4−ヒドロキシ−4’−n−プロポキシジフェニルスルホン、及び4−ヒドロキシ−4’−アリルオキシジフェニルスルホンからなる群から選ばれる少なくとも1種を含有し、前記増感剤としてN−置換脂肪酸アミドを含有することを特徴とする感熱記録ライナーレスラベル。 Item 1: A support, a heat-sensitive recording layer containing a dye precursor, a developer, and a sensitizer on one side of the support from the side close to the support, a protective layer containing an adhesive, and A thermal recording linerless label having a release layer and having an adhesive layer on the other surface of the support, wherein the developer is N- [2- (3-phenylureido) phenyl] benzenesulfonamide, Contains at least one selected from the group consisting of 4-hydroxy-4′-n-propoxydiphenylsulfone and 4-hydroxy-4′-allyloxydiphenylsulfone, and contains an N-substituted fatty acid amide as the sensitizer. A thermal recording linerless label.
項2:前記N−置換脂肪酸アミドの融点が110〜160℃の範囲である、項1に記載の感熱記録ライナーレスラベル。 Item 2: The thermal recording linerless label according to Item 1, wherein the N-substituted fatty acid amide has a melting point in the range of 110 to 160 ° C.
項3:前記保護層に含有される接着剤が、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、及び珪素変性ポリビニルアルコールからなる群から選ばれる少なくとも1種である、項1または2に記載の感熱記録ライナーレスラベル。 Item 3: The adhesive contained in the protective layer is at least one selected from the group consisting of acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and silicon-modified polyvinyl alcohol, 2. The thermal recording linerless label according to 2.
項4:前記粘着剤層が水系粘着剤からなる、項1〜3のいずれか1項に記載の感熱記録ライナーレスラベル。 Item 4: The heat-sensitive recording linerless label according to any one of Items 1 to 3, wherein the pressure-sensitive adhesive layer comprises a water-based pressure-sensitive adhesive.
項5:支持体、前記支持体の一方の面に、前記支持体に近い側から染料前駆体と顕色剤と増感剤とを含有する感熱記録層、接着剤を含有する保護層、並びに剥離層を有し、支持体の他方の面に粘着剤層を有する感熱記録ライナーレスラベルの製造方法であって、前記顕色剤としてN−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミド、4−ヒドロキシ−4’−n−プロポキシジフェニルスルホン、及び4−ヒドロキシ−4’−アリルオキシジフェニルスルホンからなる群から選ばれる少なくとも1種を含有し、前記増感剤としてN−置換脂肪酸アミドを含有する感熱記録層用塗液を用いて支持体の一方の面に感熱記録層を形成する工程、及び粘着剤を含む粘着剤層用塗液を用いて支持体の他方の面に粘着剤層を形成する工程を含むことを特徴とする感熱記録ライナーレスラベルの製造方法。 Item 5: A support, a heat-sensitive recording layer containing a dye precursor, a developer, and a sensitizer from the side close to the support on one side of the support, a protective layer containing an adhesive, and A method for producing a thermal recording linerless label having a release layer and having an adhesive layer on the other side of the support, wherein N- [2- (3-phenylureido) phenyl] benzenesulfone is used as the developer. N-substituted fatty acid amide containing at least one selected from the group consisting of amide, 4-hydroxy-4′-n-propoxydiphenyl sulfone, and 4-hydroxy-4′-allyloxydiphenyl sulfone A step of forming a heat-sensitive recording layer on one side of the support using a heat-sensitive recording layer-containing coating liquid, and a pressure-sensitive adhesive on the other side of the support using a pressure-sensitive adhesive layer-containing coating liquid containing an adhesive Step of forming a layer Method for producing a thermosensitive recording linerless label comprising.
本発明の感熱記録ライナーレスラベルは、長期保管後、特に高温高湿環境下で長期間保管されても発色能力が低下することがなく、すなわち糊減感がなく、白紙部の耐熱性に優れる。また、薬品に対する耐性がある。 The thermal recording linerless label of the present invention is not deteriorated in coloring ability even when stored for a long period of time in a high temperature and high humidity environment after long-term storage, that is, there is no desensitization and the heat resistance of the white paper portion is excellent. . It is also resistant to chemicals.
本発明における感熱記録ライナーレスラベルは、支持体、前記支持体の一方の面に支持体に近い側から染料前駆体と顕色剤と増感剤とを含有する感熱記録層、接着剤を含有する保護層、並びに剥離層を有し、他方の面に粘着剤層を有している。 The heat-sensitive recording linerless label in the present invention contains a support, a heat-sensitive recording layer containing a dye precursor, a developer and a sensitizer from one side of the support close to the support, and an adhesive. A protective layer and a release layer, and an adhesive layer on the other surface.
感熱記録ライナーレスラベルでは、粘着剤としてアクリル系エマルジョンを使用することにより、感熱記録層内に含まれる顕色剤や増感剤が、経時的に保護層、剥離層を通して粘着剤層に移動する傾向がある。水溶けし易い顕色剤、増感剤ではその傾向が強く、特に高温高湿時に移動し易く、感熱記録層内の顕色剤や増感剤の含有量が少なくなり、著しく感熱発色性能を損ねることがある。感熱記録層に使用される顕色剤は、主にフェノール系化合物が使用され、ヒドロキシル基による水との相性で感熱記録層から粘着剤層に移動し易くなると考えられる。増感剤として使用される化合物の多くは、分子量が低いため、水溶けの影響が考えられる。 In the thermal recording linerless label, by using an acrylic emulsion as an adhesive, the developer and sensitizer contained in the thermal recording layer move over time to the adhesive layer through the protective layer and the release layer. Tend. This tendency is strong with developers and sensitizers that are easily soluble in water, especially when moving at high temperatures and high humidity, and the content of developers and sensitizers in the heat-sensitive recording layer is reduced, resulting in significantly improved thermal coloring performance. It may be damaged. As the developer used for the heat-sensitive recording layer, a phenolic compound is mainly used, and it is considered that the developer easily moves from the heat-sensitive recording layer to the pressure-sensitive adhesive layer due to compatibility with water due to hydroxyl groups. Many of the compounds used as sensitizers have a low molecular weight, so the effect of water solubility is considered.
支持体として紙基材を用いるラベルに使用される粘着剤は、ほとんどが乳化重合で得られる水系粘着剤や、乳化剤をほとんど含まないホットメルトタイプである。ホットメルトタイプは、ベースポリマーを加熱、溶融した状態で基材に塗工する方式で、乾燥工程が不要で設備収容のスペースは縮小することができるが、原料が特殊ポリマーであるため粘着剤の価格が高くなること、溶融、塗工工程への窒素ガスの導入が必要であること、また架橋による変性が容易でない等の問題がある。乳化重合で得られる水系粘着剤は、乾燥工程が必要であるが当初から水系専用に設計される設備であれば、経済的有利さもあり国内での使用が増加している。しかし、本質的に粘着剤は、乳化重合で製造されるため、界面活性剤を含んでおり、例えば軟質ポリ塩化ビニル等のフィルムに接触するとフィルムに含まれる可塑剤が粘着剤に移行する問題があり、粘着性能に影響することがある。感熱記録ライナーレスラベルの場合、感熱記録層に含まれる一般的な顕色剤、増感剤等は軟質ポリ塩化ビニル等のフィルムの可塑剤に接触すると、粘着剤層に移行する問題があり、特に、高温高湿環境下では移行する傾向が強くなる。 The pressure-sensitive adhesive used for a label using a paper substrate as a support is a water-based pressure-sensitive adhesive obtained by emulsion polymerization or a hot-melt type that hardly contains an emulsifier. The hot melt type is a method in which the base polymer is heated and melted and applied to the base material. A drying process is not required and the space for accommodating equipment can be reduced. However, since the raw material is a special polymer, There are problems such as high price, melting, introduction of nitrogen gas into the coating process, and difficulty in modification by crosslinking. The water-based pressure-sensitive adhesive obtained by emulsion polymerization requires a drying process, but if it is a facility designed exclusively for water-based from the beginning, there is an economic advantage and its use in Japan is increasing. However, since an adhesive is essentially produced by emulsion polymerization, it contains a surfactant. For example, when it comes into contact with a film such as soft polyvinyl chloride, there is a problem that the plasticizer contained in the film shifts to the adhesive. Yes, it may affect the adhesive performance. In the case of a thermal recording linerless label, when a general developer, a sensitizer, etc. contained in the thermal recording layer come into contact with a plasticizer of a film such as soft polyvinyl chloride, there is a problem of shifting to an adhesive layer. In particular, the tendency to shift becomes strong in a high temperature and high humidity environment.
乳化重合で得られる水系粘着剤の具体例としては、アクリル系粘着剤が主に使用されており、アクリル酸ブチル、同2エチレンヘキシル両アクリルモノマーを中心に、他のビニルポリマー、官能基モノマーを組み合わせ、一般的にはガラス転移点が−30℃以下になるように設計し、共重合させている。一般に界面活性剤としてアルキルフェノール型ノニオンを主として用い、アニオン型を少量併用する場合が多い。また、重合開始剤としては、過硫酸アンモニウム等の水溶性過酸化物触媒を用いるが、重合中の乳化安定性を良くするため、比較的低温で重合することが好ましく、酸性亜硫酸ソーダのような還元剤を併用するレドックス重合法が多く用いられている。これらは、エマルジョンの形態で用いられる。本発明では、支持体として通常水分を保持する紙支持体を用いて、粘着剤として水系粘着剤を用いたときに、水溶けに対する効果を著しく発揮させることができ好ましい。 As a specific example of the water-based pressure-sensitive adhesive obtained by emulsion polymerization, an acrylic pressure-sensitive adhesive is mainly used, and other vinyl polymers and functional group monomers are mainly composed of butyl acrylate and 2-ethylene hexyl acrylic monomers. In general, the glass transition point is designed to be −30 ° C. or lower and copolymerized. In general, an alkylphenol type nonion is mainly used as a surfactant, and an anionic type is often used in a small amount. As the polymerization initiator, a water-soluble peroxide catalyst such as ammonium persulfate is used. However, in order to improve the emulsion stability during the polymerization, the polymerization is preferably carried out at a relatively low temperature, and a reduction such as acidic sodium sulfite. A redox polymerization method using an agent in combination is often used. These are used in the form of an emulsion. In the present invention, when a paper support that normally retains moisture is used as the support and a water-based adhesive is used as the adhesive, the effect on water solubility can be remarkably exhibited.
本発明における保護層は、接着剤を含有している。接着剤としては、特に限定されないが、バリア性を高める観点から水溶性または水分散性の水性接着剤が好ましい。特に、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、及び珪素変性ポリビニルアルコールから選ばれる少なくとも1種の水溶性接着剤が好ましく用いられる。 The protective layer in the present invention contains an adhesive. Although it does not specifically limit as an adhesive agent, From a viewpoint of improving barrier property, a water-soluble or water-dispersible water-based adhesive agent is preferable. In particular, at least one water-soluble adhesive selected from acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and silicon-modified polyvinyl alcohol is preferably used.
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、及び珪素変性ポリビニルアルコールは、それぞれアセトアセチル基、ジアセトン基、カルボキシル基、及びシリル基を持つ単量体とビニルエステルとを共重合して得た樹脂を鹸化することにより製造される。 Acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and silicon-modified polyvinyl alcohol are obtained by copolymerizing a monomer having an acetoacetyl group, a diacetone group, a carboxyl group, and a silyl group with a vinyl ester, respectively. It is produced by saponifying the resin obtained.
鹸化度については、85モル%から完全鹸化の100モル%程度が好ましく、90〜100モル%程度がより好ましい。平均重合度については、300〜3000程度が好ましく、400〜2000程度がより好ましい。変性度は、耐水性を高める観点から0.5〜10モル%程度が好ましく、1〜9モル%程度がより好ましい。重合度、鹸化度が高いほど耐水性が良好になるが、塗料濃度、粘度、塗工性または乾燥性から状況に応じて選択する必要がある。 The degree of saponification is preferably about 85 mol% to 100 mol% of complete saponification, more preferably about 90 to 100 mol%. About average polymerization degree, about 300-3000 are preferable and about 400-2000 are more preferable. The degree of modification is preferably about 0.5 to 10 mol%, more preferably about 1 to 9 mol% from the viewpoint of improving water resistance. The higher the degree of polymerization and the degree of saponification, the better the water resistance, but it is necessary to select from the paint concentration, viscosity, coating property or drying property according to the situation.
保護層中に使用される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、及び珪素変性ポリビニルアルコールからなる群から選ばれる少なくとも1種の使用量としては、保護層の全固形量中、好ましくは10〜90質量%、より好ましくは15〜50質量%程度である。 At least one amount selected from the group consisting of acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and silicon-modified polyvinyl alcohol used in the protective layer is the total solid amount of the protective layer. , Preferably it is 10-90 mass%, More preferably, it is about 15-50 mass%.
本発明の効果を損なわない範囲において、その他の接着剤を併用することもできる。かかる接着剤としては、例えば完全鹸化ポリビニルアルコール、部分鹸化ポリビニルアルコール、澱粉、酸化澱粉、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塩、スチレン・無水マレイン酸共重合体塩、エチレン・アクリル酸共重合体塩、スチレン・アクリル酸共重合体塩、尿素樹脂、メラミン樹脂、アミド樹脂、アクリル樹脂系ラテックス、ウレタン樹脂系ラテックス等が挙げられる。 Other adhesives can be used in combination as long as the effects of the present invention are not impaired. Examples of the adhesive include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, starch, oxidized starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, diisobutylene / maleic anhydride copolymer salt, styrene Maleic anhydride copolymer salt, ethylene / acrylic acid copolymer salt, styrene / acrylic acid copolymer salt, urea resin, melamine resin, amide resin, acrylic resin latex, urethane resin latex and the like.
本発明における保護層は、顔料を含有していてもよい。顔料としては、例えば炭酸カルシウム、酸化亜鉛、酸化アルミニウム、二酸化チタン、非晶質シリカ、水酸化アルミニウム、硫酸バリウム、タルク、カオリン、焼成カオリン等の無機顔料が挙げられる。なかでも、カオリン、水酸化アルミニウムは可塑剤、油等の薬品に対するバリア性の低下が少なく、しかも記録濃度の低下も小さいため、特に好ましく用いられる。 The protective layer in the present invention may contain a pigment. Examples of the pigment include inorganic pigments such as calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, amorphous silica, aluminum hydroxide, barium sulfate, talc, kaolin, and calcined kaolin. Of these, kaolin and aluminum hydroxide are particularly preferably used since they have a small decrease in barrier properties against chemicals such as plasticizers and oils and a small decrease in recording density.
保護層に含有させることができる助剤としては、例えばステアリン酸亜鉛、ステアリン酸カルシウム、カルナバロウ、パラフィンワックス、エステルワックス等の滑剤、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等の界面活性剤、ジアルデヒド澱粉、メチロール尿素、グリオキシル酸塩、エポキシ系化合物、ヒドラジン系化合物等の耐水化剤、及び紫外線吸収剤、蛍光染料、着色染料、離型剤、酸化防止剤等が挙げられる。 Examples of auxiliary agents that can be contained in the protective layer include lubricants such as zinc stearate, calcium stearate, carnauba wax, paraffin wax, and ester wax, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sulfone-modified polyvinyl alcohol, and polyacrylic acid. Surfactants such as sodium, water resistant agents such as dialdehyde starch, methylol urea, glyoxylate, epoxy compounds, hydrazine compounds, and UV absorbers, fluorescent dyes, coloring dyes, mold release agents, antioxidants, etc. Is mentioned.
保護層は、例えば水を分散媒体として、好ましくは特定の接着剤、必要により顔料、助剤等を混合撹拌することにより調製された保護層用塗液を、塗布量が乾燥重量で好ましくは0.1〜8g/m2程度、より好ましくは0.5〜5g/m2程度、更に好ましくは1〜4g/m2程度となるように、感熱記録層上に塗布及び乾燥して形成される。 The protective layer is, for example, a coating solution for the protective layer prepared by mixing and stirring a specific adhesive, if necessary, a pigment, an auxiliary agent, etc., using water as a dispersion medium, and the coating amount is preferably 0 by dry weight. .1~8g / m 2 approximately, is formed and more preferably 0.5 to 5 g / m 2 approximately, more preferably such that 1 to 4 g / m 2 approximately, by coating and drying the heat-sensitive recording layer .
感熱記録ライナーレスラベルは、上記保護層上に剥離層を形成するが、剥離用シリコーンとしては、形態別では溶剤系、無溶剤系、エマルジョン系に、また硬化様式の違いからは熱硬化型、紫外線または電子線硬化型に大別される。環境問題や感熱記録層が発色しないことが求められる点から、紫外線または電子線硬化性シリコーン化合物を主成分とする剥離層用塗液の使用が好ましい。これらのシリコーン化合物の具体例としては、メルカプト基含有オルガノシロキサンとビニル基含有オルガノポリシロキサンとの混合組成物、アクリル基、メタクリル基またはシンナモイル基含有オルガノポリシロキサン組成物、マレイミド基またはフェノルマレイミド基含有アルガノポリシロキサン組成物、アジド基含有オルガノポリシロキサンとビニル基含有オルガノポリシロキサンとの混合組成物、チオアクリル基、チオメタクリル基またはチオシンナモイル基含有オルガノポリシロキサン組成物、アクリルアミド基、メタクリルアミド基またはシンナモイルアミド基含有オルガノポリシロキサン組成物等が挙げられ、また紫外線開始型カチオン重合を利用したエポキシ基含有オルガノポリシロキサンと光分解型開始剤のジアゾニウムルイス酸塩との混合組成物も利用することができる。紫外線硬化の場合は、光重合開始剤が必要であるが、具体例としては、ベンゾイルアルキルエーテル及びその誘導体、アセトフェノン及びその誘導体、チオキサントン及びその誘導体、硼素系カチオン誘導体等が挙げられる。 The thermal recording linerless label forms a release layer on the protective layer, but as the release silicone, solvent-based, solvent-free, emulsion-based depending on the form, and thermosetting type from the difference in curing mode, Broadly divided into ultraviolet and electron beam curable types. From the viewpoint of environmental problems and that the heat-sensitive recording layer is required not to develop color, it is preferable to use a coating solution for a release layer mainly composed of ultraviolet rays or an electron beam curable silicone compound. Specific examples of these silicone compounds include a mixture composition of a mercapto group-containing organosiloxane and a vinyl group-containing organopolysiloxane, an acrylic group, a methacryl group or a cinnamoyl group-containing organopolysiloxane composition, a maleimide group or a phenol maleimide group. Containing arganopolysiloxane composition, mixed composition of azido group-containing organopolysiloxane and vinyl group-containing organopolysiloxane, thioacryl group, thiomethacryl group or thiocinnamoyl group-containing organopolysiloxane composition, acrylamide group, methacrylamide group Or an organopolysiloxane composition containing a cinnamoylamide group, and an epoxy group-containing organopolysiloxane utilizing ultraviolet-initiated cationic polymerization and a photolytic initiator diazonium. Mixed composition of chair salts can also be utilized. In the case of UV curing, a photopolymerization initiator is required, and specific examples include benzoyl alkyl ether and derivatives thereof, acetophenone and derivatives thereof, thioxanthone and derivatives thereof, and boron-based cation derivatives.
本発明における感熱記録層は、染料前駆体と顕色剤と増感剤とを含有している。染料前駆体としてロイコ染料と顕色剤との組合せが発色濃度に優れるため、好ましく用いられる。 The heat-sensitive recording layer in the present invention contains a dye precursor, a developer, and a sensitizer. Since a combination of a leuco dye and a developer as a dye precursor is excellent in color density, it is preferably used.
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−(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−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、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−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−(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−ジ(n−ブチル)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、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’−ジメチルアミノ)フタリド等が挙げられる。 Specific examples of the leuco dye include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide and 3- (4-diethylamino-2-methylphenyl) -3- (4-dimethylaminophenyl). ) -6-dimethylaminophthalide, 3- (N-ethyl-Np-tolyl) amino-7-N-methylanilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6 -Methyl-7-chlorofluorane, 3-diethylamino-7-chlorofluorane, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane, 3-di (n-butyl) ) Amino-6-methyl-7-anilinofluorane, 3-di (n-pentyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-p) Toluidino) -6-methyl-7-anilinofluorane, 3-di (n-butyl) amino-6-chloro-7-anilinofluorane, 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- Examples include chlorofluorane, 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′-(6′-dimethylamino) phthalide, and the like.
勿論、これらに限定されるものではなく、また2種以上を併用することもできる。また、ロイコ染料の含有割合は、使用する顕色剤により異なるため限定できないが、感熱記録層の全固形量中、3〜50質量%程度が好ましく、5〜40質量%程度がより好ましい。 Of course, it is not limited to these, Moreover, 2 or more types can also be used together. The content of the leuco dye is not limited because it varies depending on the developer used, but is preferably about 3 to 50% by mass and more preferably about 5 to 40% by mass in the total solid content of the heat-sensitive recording layer.
本発明では、顕色剤としてN−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミド、4−ヒドロキシ−4’−n−プロポキシジフェニルスルホン、及び4−ヒドロキシ−4’−アリルオキシジフェニルスルホンからなる群から選ばれる少なくとも1種を含有し、更に増感剤としてN−置換脂肪酸アミドを含有している。これらの顕色剤及び増感剤を含有させることにより、水溶けを抑えて、高温高湿環境下の長期保管にも発色性能を下げず、糊減感を抑えることができる。また、発色感度、耐熱性を高めて、薬品に対する耐性を向上できる。 In the present invention, N- [2- (3-phenylureido) phenyl] benzenesulfonamide, 4-hydroxy-4′-n-propoxydiphenylsulfone, and 4-hydroxy-4′-allyloxydiphenylsulfone are used as developers. And at least one selected from the group consisting of N-substituted fatty acid amides as sensitizers. By containing these color developers and sensitizers, it is possible to suppress glue desensitization without suppressing water solubility and without lowering the color development performance even during long-term storage in a high-temperature and high-humidity environment. In addition, the coloring sensitivity and heat resistance can be improved, and the resistance to chemicals can be improved.
顕色剤の含有割合は、使用するロイコ染料により異なるため限定できないが、感熱記録層の全固形量中10〜70質量%程度が好ましく、12〜50質量%程度がより好ましい。 The content of the developer is not limited because it varies depending on the leuco dye used, but is preferably about 10 to 70% by mass and more preferably about 12 to 50% by mass in the total solid content of the heat-sensitive recording layer.
他の顕色剤としては、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、4,4’−ビス[(4−メチル−3−フェノキシカルボニルアミノフェニル)ウレイド]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、下記一般式(1)で表されるジフェニルスルホン架橋型化合物等が挙げられる。これらの材料は、本発明の品質を阻害しない程度の量を添加してもよい。その含有量は特に限定されないが、通常、本発明における特定の顕色剤の合計量に対して50質量%未満であることが好ましい。 Examples of other developers include 4,4′-isopropylidene diphenol, 4,4′-cyclohexylidene diphenol, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4- Hydroxyphenyl) -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, 4,4 '-Bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] dipheni Sulfone, 4-hydroxybenzoic 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] zinc salicylate, diphenylsulfone cross-linked compound represented by the following general formula (1), and the like. These materials may be added in an amount that does not impair the quality of the present invention. The content is not particularly limited, but usually it is preferably less than 50% by mass with respect to the total amount of the specific developer in the present invention.
感熱記録層には保存性改良剤を含有させてもよい。これにより、記録部の保存安定性を高めることができる。かかる保存性改良剤の具体例としては、例えば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)プロパン等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型エポキシ樹脂等のエポキシ化合物、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)メタン等が挙げられる。 The heat-sensitive recording layer may contain a storability improving agent. Thereby, the storage stability of a recording part can be improved. Specific examples of such preservability improvers include, for example, 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 1 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 2,2 Hindered phenol compounds such as bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-diglycidyloxydiphenylsulfone, 4-benzyloxy-4 ′-(2-methylglycidyloxy) diphenylsulfone , Diglycidyl terephthalate, cresol novolac epoxy resin, phenol novolac epoxy resin, vinyl Epoxy compounds such as bisphenol A type epoxy resin, N, N'-di-2-naphthyl -p- phenylenediamine, bis (4-ethylene iminocarbonyl aminophenyl) include methane and the like.
保存性改良剤の含有割合は、特に限定されないが、感熱記録層の全固形量中1〜30質量%程度が好ましく、5〜20質量%程度がより好ましい。 Although the content rate of a preservability improving agent is not specifically limited, About 1-30 mass% is preferable in the total solid of a thermosensitive recording layer, and about 5-20 mass% is more preferable.
本発明では、増感剤として脂肪酸アミドのなかでも、窒素原子上に置換基を有するアミドであるN−置換脂肪酸アミドを含有させる。N−置換脂肪酸アミドは、本発明で使用する顕色剤であるN−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミド、4−ヒドロキシ−4’−n−プロポキシジフェニルスルホン、及び4−ヒドロキシ−4’−アリルオキシジフェニルスルホンからなる群から選ばれる少なくとも1種との発色性が良好で糊減感を抑える効果に優れる。しかも耐熱地肌カブリ性に優れた品質を得ることができる。これにより、感熱記録ライナーレスラベルに仕上げた後の、高温高湿環境下で長期間置かれても良好な発色性能を維持して、また、ラベル用途として80℃耐熱よりも厳しい条件である90℃耐熱を付与して地肌カブリを抑えることができる。N−置換脂肪酸アミドの融点は、特に限定されないが、110〜160℃の範囲のものが好ましく、125〜160℃の範囲のものがより好ましく使用される。その含有割合は特に限定されないが、感熱記録層の全固形量中1〜40質量%程度が好ましく、2〜30質量%程度がより好ましく、3〜25質量%程度が更に好ましい。 In the present invention, an N-substituted fatty acid amide, which is an amide having a substituent on a nitrogen atom, is contained as a sensitizer among fatty acid amides. N-substituted fatty acid amides include N- [2- (3-phenylureido) phenyl] benzenesulfonamide, 4-hydroxy-4′-n-propoxydiphenylsulfone, and 4-color developer used in the present invention. The color developability with at least one selected from the group consisting of hydroxy-4′-allyloxydiphenylsulfone is good, and the effect of suppressing desensitization is excellent. Moreover, it is possible to obtain a quality excellent in heat-resistant texture fogging. As a result, after the heat-sensitive recording linerless label is finished, good color development performance is maintained even if it is placed in a high temperature and high humidity environment for a long period of time. Heat resistance at ℃ can be applied to suppress background fogging. The melting point of the N-substituted fatty acid amide is not particularly limited, but is preferably in the range of 110 to 160 ° C, more preferably in the range of 125 to 160 ° C. The content is not particularly limited, but is preferably about 1 to 40% by mass, more preferably about 2 to 30% by mass, and still more preferably about 3 to 25% by mass in the total solid content of the thermosensitive recording layer.
N−置換脂肪酸アミドの具体例としては、N,N’−エチレンビスラウリン酸アミド、N,N’−メチレビスステアリン酸アミド、N,N’−エチレンビスステアリン酸アミド、N,N’−エチレンビスオレイン酸アミド、N,N’−エチレンベヘン酸アミド、N,N’−エチレンビス-12ヒドロキシステアリン酸アミド、N,N’−ブチレンビスステアリン酸アミド、N,N’−ヘキサメチレンビスステアリン酸アミド、N,N’−ヘキサメチレンビスオレイン酸アミド、N,N’−キシリレンビスステアリン酸アミド、ステアリン酸モノメチロールアミド、N,N’−ジオレイルアジピン酸アミド、N,N’−ジステアリルアジピン酸アミド、N,N’−ジステアリルセバシン酸アミド、N,N’−ジステアリルテレフタル酸アミド、N,N’−ジステアリルイソタル酸アミド等が挙げられる。 Specific examples of N-substituted fatty acid amides include N, N'-ethylenebislauric acid amide, N, N'-methylbisstearic acid amide, N, N'-ethylenebisstearic acid amide, N, N'-ethylene. Bisoleic acid amide, N, N′-ethylenebehenic acid amide, N, N′-ethylenebis-12 hydroxystearic acid amide, N, N′-butylene bisstearic acid amide, N, N′-hexamethylenebisstearic acid Amide, N, N'-hexamethylenebisoleic acid amide, N, N'-xylylenebisstearic acid amide, stearic acid monomethylol amide, N, N'-dioleyl adipic acid amide, N, N'-distearyl Adipic acid amide, N, N′-distearyl sebacic acid amide, N, N′-distearyl terephthalic acid amide, N , N'-distearylisotalic acid amide and the like.
他の増感剤として、例えば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、ジ(p−メトキシフェノキシエチル)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等が例示されるが、これらの材料は、本発明の品質を阻害しない程度の量を添加してもよい。その含有量は、特に限定されないが、通常、本発明における特定の増感剤の合計量に対して50質量%未満であることが好ましい。 Examples of other sensitizers include stearamide, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, 2-naphthylbenzyl ether, m-terphenyl, p-benzylbiphenyl, p-tolylbiphenyl ether, di (p- Methoxyphenoxyethyl) 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-acetoluidide, p-acetophenetide, N-acetoacetyl-p-tolui , Di (β-biphenylethoxy) benzene, oxalic acid di-p-chlorobenzyl ester, oxalic acid di-p-methylbenzyl ester, oxalic acid dibenzyl ester, and the like. You may add the quantity of the grade which does not inhibit the quality of. The content is not particularly limited, but it is usually preferably less than 50% by mass with respect to the total amount of the specific sensitizer in the present invention.
感熱記録層は、水を分散媒体とし、染料前駆体、顕色剤及び増感剤、必要により保存性改良剤等を共に、或いは別々にボールミル、アトライター、サンドミル等の撹拌・粉砕機により平均粒子径が2μm以下となるように微分散した後、水性接着剤等を添加して調製された感熱記録層用塗液を支持体の一方の面に塗布及び乾燥して形成される。なお、感熱記録層中の水性接着剤としても、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、及び珪素変性ポリビニルアルコールからなる群から選ばれる少なくとも1種を含有させることが好ましい。感熱記録層の塗布量は、乾燥重量で好ましくは2〜12g/m2程度、より好ましくは2〜6g/m2程度となるように、支持体上に塗布及び乾燥して形成される。 The heat-sensitive recording layer uses water as a dispersion medium, and is mixed with a dye precursor, a developer and a sensitizer, if necessary together with a preservability improver, or separately by a stirrer / pulverizer such as a ball mill, an attritor or a sand mill. After finely dispersing so that the particle diameter is 2 μm or less, a heat-sensitive recording layer coating solution prepared by adding an aqueous adhesive or the like is applied to one side of the support and dried. The aqueous adhesive in the heat-sensitive recording layer preferably contains at least one selected from the group consisting of acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and silicon-modified polyvinyl alcohol. The heat-sensitive recording layer is formed by coating and drying on the support so that the dry weight is preferably about 2 to 12 g / m 2 , more preferably about 2 to 6 g / m 2 .
更に、感熱記録層中には必要に応じて各種の助剤を含有させることもできる。助剤としては、例えばカオリン、軽質炭酸カルシウム、重質炭酸カルシウム、焼成カオリン、酸化チタン、炭酸マグネシウム、水酸化アルミニウム、無定形シリカ、尿素・ホルマリン樹脂フィラー等の顔料、ジオクチルスルホコハク酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ラウリルアルコール硫酸エステルナトリウム、脂肪酸金属塩等の分散剤、ステアリン酸亜鉛、ステアリン酸カルシウム、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、エステルワックス等のワックス類、ヒドラジン系化合物、グリオキザール、硼酸、ジアルデヒドデンプン、メチロール尿素、グリオキシル酸塩、エポキシ系化合物等の耐水化剤、消泡剤、着色染料及び蛍光染料等が挙げられる。 Furthermore, various auxiliary agents can be contained in the heat-sensitive recording layer as necessary. Examples of auxiliary agents include kaolin, light calcium carbonate, heavy calcium carbonate, calcined kaolin, titanium oxide, magnesium carbonate, aluminum hydroxide, amorphous silica, urea / formalin resin filler and other pigments, sodium dioctylsulfosuccinate, dodecylbenzene. Dispersants such as sodium sulfonate, sodium lauryl alcohol sulfate, fatty acid metal salts, zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, ester wax, hydrazine compounds, glyoxal, boric acid, dialdehyde Water resistant agents such as starch, methylol urea, glyoxylate, and epoxy compounds, antifoaming agents, colored dyes, fluorescent dyes and the like can be mentioned.
本発明の感熱記録体に用いられる支持体としては、特に限定しないが、例えば、上質紙等の中性紙または酸性紙等の紙支持体、合成紙、透明または半透明のプラスチックフィルム、白色のプラスチックフィルム等が挙げられる。なお、支持体の厚みは特に限定しないが、通常、20〜200μm程度である。 The support used in the heat-sensitive recording material of the present invention is not particularly limited. For example, paper support such as neutral paper such as high-quality paper or acid paper, synthetic paper, transparent or translucent plastic film, white paper A plastic film etc. are mentioned. In addition, although the thickness of a support body is not specifically limited, Usually, it is about 20-200 micrometers.
本発明では、必要により、支持体と感熱記録層との間に下塗り層を設けることもできる。これにより、記録感度及び記録走行性をより高めることができる。下塗り層は、吸油量が70ml/100g以上、特に80〜150ml/100g程度の吸油性顔料及び/または有機中空粒子及び/または熱膨張性粒子、並びに接着剤を主成分とする下塗り層用塗液を支持体上に塗布及び乾燥して形成される。ここで、上記吸油量はJIS K 5101の方法に従い、求められる値である。 In the present invention, an undercoat layer can be provided between the support and the thermosensitive recording layer, if necessary. Thereby, the recording sensitivity and the recording running property can be further improved. The undercoat layer has an oil absorption amount of 70 ml / 100 g or more, in particular, about 80 to 150 ml / 100 g of an oil-absorbing pigment and / or organic hollow particles and / or thermally expandable particles, and an undercoat layer coating solution containing an adhesive as a main component. Is coated on a support and dried. Here, the oil absorption is a value determined according to the method of JIS K 5101.
上記吸油性顔料としては、各種のものが使用できるが、具体例としては、焼成カオリン、無定形シリカ、軽質炭酸カルシウム、タルク等の無機顔料が挙げられる。これら吸油性顔料の一次粒子の平均粒子径は0.01〜5μm程度が好ましく、0.02〜3μm程度がより好ましい。吸油性顔料の使用量は、広い範囲から選択できるが、一般に下塗り層の全固形量中2〜95質量%程度が好ましく、5〜90質量%程度がより好ましい。 Various types of oil-absorbing pigments can be used. Specific examples include inorganic pigments such as calcined kaolin, amorphous silica, light calcium carbonate, and talc. The average particle diameter of the primary particles of these oil-absorbing pigments is preferably about 0.01 to 5 μm, more preferably about 0.02 to 3 μm. The amount of the oil-absorbing pigment used can be selected from a wide range, but is generally preferably about 2 to 95% by mass and more preferably about 5 to 90% by mass in the total solid content of the undercoat layer.
本発明では、必要に応じて支持体の感熱記録層とは反対側の面に顔料とバインダーを主成分とする裏面層を設けることができる。これにより、保存性を一層高めたり、カール適性やプリンター走行性を高めたりすることができる。 In the present invention, a back layer comprising a pigment and a binder as main components can be provided on the surface of the support opposite to the thermosensitive recording layer, if necessary. As a result, the storage stability can be further improved, and the curl aptitude and the printer runnability can be improved.
支持体上に各層を形成する方法としては、例えばエアナイフ法、ブレード法、グラビア法、ロールコーター法、スプレー法、ディップ法、バー法、カーテン法、スロットダイ法、スライドダイ法及びエクストルージョン法等の既知の塗布方法、または印刷機による方法のいずれを利用してもよい。 Examples of methods for forming each layer on the support include air knife method, blade method, gravure method, roll coater method, spray method, dipping method, bar method, curtain method, slot die method, slide die method, and extrusion method. Either a known coating method or a printing press method may be used.
各層を形成し終えた後、また全ての層を形成し終えた後の任意の過程でスーパーカレンダー等による平滑化処理を施すこともできる。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。 It is possible to perform a smoothing process using a super calender or the like in an arbitrary process after the formation of each layer or after the formation of all the layers. Various known techniques in the heat-sensitive recording material production field can be added as necessary.
本発明は、支持体、支持体の一方の面に、支持体に近い側から染料前駆体と顕色剤と増感剤とを含有する感熱記録層、接着剤を含有する保護層、並びに剥離層を有し、支持体の他方の面に粘着剤層を有する感熱記録ライナーレスラベルの製造方法であって、顕色剤としてN−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミド、4−ヒドロキシ−4’−n−プロポキシジフェニルスルホン、及び4−ヒドロキシ−4’−アリルオキシジフェニルスルホンからなる群から選ばれる少なくとも1種を含有し、増感剤としてN−置換脂肪酸アミドを含有する感熱記録層用塗液を用いて支持体の一方の面に感熱記録層を形成する工程、及び粘着剤を含む粘着剤層用塗液を用いて支持体の他方の面に粘着剤層を形成する工程を含むことを特徴とする感熱記録ライナーレスラベルの製造方法である。これにより、塗液が支持体中に浸透しても、あるいはまた、巻取状態で支持体の表裏が重ね合わされても、層中の成分が拡散して糊減感を生じる恐れがない。 The present invention relates to a support, a heat-sensitive recording layer containing a dye precursor, a developer and a sensitizer from one side close to the support, a protective layer containing an adhesive, and a release on one side of the support. A thermosensitive recording linerless label having a layer and an adhesive layer on the other side of the support, wherein N- [2- (3-phenylureido) phenyl] benzenesulfonamide as a developer, Contains at least one selected from the group consisting of 4-hydroxy-4′-n-propoxydiphenylsulfone and 4-hydroxy-4′-allyloxydiphenylsulfone, and contains an N-substituted fatty acid amide as a sensitizer. The step of forming a heat-sensitive recording layer on one side of the support using the coating liquid for the heat-sensitive recording layer, and the formation of the pressure-sensitive adhesive layer on the other side of the support using the coating liquid for the pressure-sensitive adhesive layer containing the pressure-sensitive adhesive Including the process of A method for producing a thermosensitive recording linerless labels to symptoms. Thereby, even if the coating liquid penetrates into the support, or even when the front and back of the support are overlapped in the wound state, there is no fear that the components in the layer will diffuse and cause glue desensitization.
本発明を実施例により更に詳しく説明するが、本発明はこれらにより限定されるものではない。なお、特に断わらない限り、「部」及び「%」は、それぞれ「質量部」及び「質量%」を示す。 The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” indicate “part by mass” and “% by mass”, respectively.
実施例1
・下塗り層用塗液の調製
焼成カオリン(商品名:アンシレックス93、BASF社製)60部を水80部に分散して得られた分散物に、微小中空粒子(商品名:ローペイクSN−1055、ダウ ケミカル社製、固形分濃度26.5%)75部、スチレン・ブタジエン系ラテックス(商品名:L−1571、旭化成ケミカルズ社製、固形分濃度48%)31部と、カルボキシメチルセルロース(商品名:セロゲン7A、第一工業製薬社製)2.5部、同じくカルボキシメチルセルロース(商品名:セロゲンAGガム、第一工業製薬社製)1部、及び水95.5部を混合攪拌して、下塗り層用塗液を得た。
Example 1
-Preparation of undercoat layer coating solution Fine hollow particles (trade name: Ropaque SN-1055) were dispersed in a dispersion obtained by dispersing 60 parts of calcined kaolin (trade name: Ansilex 93, manufactured by BASF) in 80 parts of water. , 75 parts by Dow Chemical Co., Ltd., solid content concentration 26.5%), 31 parts styrene / butadiene latex (trade name: L-1571, solid content concentration 48% by Asahi Kasei Chemicals), and carboxymethyl cellulose (trade name) : Serogen 7A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts, similarly carboxymethylcellulose (trade name: Serogen AG gum, Daiichi Kogyo Seiyaku Co., Ltd.) 1 part, and 95.5 parts of water are mixed and stirred to undercoat. A layer coating solution was obtained.
・ロイコ染料分散液の調製
3−ジ−(n−ブチル)アミノ−6−メチル−7−アニリノフルオラン10部、メチルセルロースの5%水溶液5部及び水15部からなる組成物を、サンドミルでレーザー回折式粒度分布測定装置SALD−2200((株)島津製作所製)によるメジアン径が0.5μmになるまで粉砕してロイコ染料分散液(以下、A液ともいう)を得た。
-Preparation of leuco dye dispersion liquid A composition comprising 10 parts of 3-di- (n-butyl) amino-6-methyl-7-anilinofluorane, 5 parts of a 5% aqueous solution of methylcellulose and 15 parts of water was obtained with a sand mill. A leuco dye dispersion (hereinafter also referred to as A liquid) was obtained by pulverizing until a median diameter of 0.5 μm by a laser diffraction particle size distribution analyzer SALD-2200 (manufactured by Shimadzu Corporation).
・顕色剤分散液の調製
N−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミド(商品名:NKK−1304、日本曹達社製)10部、メチルセルロースの5%水溶液5部及び水15部からなる組成物を、サンドミルでレーザー回折式粒度分布測定装置SALD−2200((株)島津製作所製)によるメジアン径が1.5μmになるまで粉砕して顕色剤分散液(以下、B液ともいう)を得た。
-Preparation of developer dispersion 10 parts of N- [2- (3-phenylureido) phenyl] benzenesulfonamide (trade name: NKK-1304, manufactured by Nippon Soda Co., Ltd.), 5 parts of a 5% aqueous solution of methylcellulose, and water 15 The composition consisting of parts is pulverized with a sand mill using a laser diffraction particle size distribution analyzer SALD-2200 (manufactured by Shimadzu Corporation) until the median diameter becomes 1.5 μm, and a developer dispersion (hereinafter referred to as B solution) Also called).
・増感剤分散液の調製
N,N’−エチレンビスステアリン酸アミド(商品名:スリパックスE、日本化成社製、融点145℃)10部、メチルセルロースの5%水溶液5部及び水15部からなる組成物を、サンドミルでレーザー回折式粒度分布測定装置SALD−2200((株)島津製作所製)によるメジアン径が1.0μmになるまで粉砕して増感剤分散液(以下、C液ともいう)を得た。
-Preparation of sensitizer dispersion liquid: 10 parts of N, N'-ethylenebisstearic acid amide (trade name: SLIPAX E, Nippon Kasei Co., Ltd., melting point 145 ° C), 5 parts of 5% aqueous solution of methylcellulose and 15 parts of water. The composition is pulverized by a sand mill with a laser diffraction particle size distribution analyzer SALD-2200 (manufactured by Shimadzu Corporation) until the median diameter becomes 1.0 μm, and a sensitizer dispersion (hereinafter also referred to as “C solution”). Got.
・感熱記録層用塗液の調製
A液33.5部、B液68部、C液10.5部、完全鹸化ポリビニルアルコール(商品名:PVA110、鹸化度:99モル%、平均重合度:1000、クラレ社製)の10%水溶液30部、部分鹸化ポリビニルアルコール(商品名:PVA205、鹸化度:88モル%、平均重合度:500、クラレ社製)の20%水溶液5部、ブタジエン系共重合体ラテックス(商品名:P−OY72、日本A&L社製、固形分濃度48%)16.5部、軽質炭酸カルシウム(商品名:Brilliant−15、白石工業社製)46.8部、パラフィンワックスエマルジョン(商品名:ハイドリンL−700、中京油脂社製、固形分濃度30%)10部、及び水90.5部を混合撹拌して感熱記録層用塗液を得た。
-Preparation of coating solution for heat-sensitive recording layer A solution 33.5 parts, solution B 68 parts, solution C 10.5 parts, fully saponified polyvinyl alcohol (trade name: PVA110, saponification degree: 99 mol%, average polymerization degree: 1000) 30 parts of a 10% aqueous solution of Kuraray Co., Ltd., 5 parts of a 20% aqueous solution of partially saponified polyvinyl alcohol (trade name: PVA205, degree of saponification: 88 mol%, average degree of polymerization: 500, made by Kuraray Co., Ltd.), butadiene copolymer Combined latex (trade name: P-OY72, manufactured by Japan A & L, solid concentration 48%) 16.5 parts, light calcium carbonate (trade name: Brilliant-15, manufactured by Shiroishi Kogyo Co., Ltd.) 46.8 parts, paraffin wax emulsion (Product name: Hydrin L-700, manufactured by Chukyo Yushi Co., Ltd., solid content concentration 30%) 10 parts and 90.5 parts of water were mixed and stirred to obtain a thermal recording layer coating solution.
・保護層用塗液の調製
アセトアセチル変性ポリビニルアルコールA(商品名:ゴーセネックスZ−200、鹸化度:99.4モル%、平均重合度:1000、変性度:5モル%、日本合成化学工業社製)の10%水溶液210部、アセトアセチル変性ポリビニルアルコールB(商品名:ゴーセネックスZ−100、鹸化度:99.4モル%、平均重合度:500、変性度:5モル%、日本合成化学工業社製)の20%水溶液80部、カオリン(商品名:HYDRAGLOSS90、KaMin LLC社製)58.5部、水酸化アルミニウム(商品名:ハイジライトH−42M、昭和電工社製)4部、グルオキシル酸ナトリウム(商品名:SPM−01、日本合成化学工業社製)の10%水溶液5部、及び水53部からなる組成物を混合撹拌し、10%酢酸水溶液でpH5となるように調整して保護層用塗液を得た。
Preparation of coating solution for protective layer Acetoacetyl-modified polyvinyl alcohol A (trade name: Gohsenx Z-200, degree of saponification: 99.4 mol%, average degree of polymerization: 1000, degree of modification: 5 mol%, Nippon Synthetic Chemical Industry Co., Ltd. 210 parts of an aqueous solution of 10% aqueous solution of acetoacetyl-modified polyvinyl alcohol B (trade name: Gohsenx Z-100, degree of saponification: 99.4 mol%, average degree of polymerization: 500, degree of modification: 5 mol%, Nippon Synthetic Chemical Industry) 80 parts of 20% aqueous solution, 58.5 parts of kaolin (trade name: HYDRAGLOSS 90, manufactured by KaMin LLC), 4 parts of aluminum hydroxide (trade name: Heidilite H-42M, manufactured by Showa Denko KK), glyoxylic acid A composition comprising 5 parts of a 10% aqueous solution of sodium (trade name: SPM-01, manufactured by Nippon Synthetic Chemical Industry) and 53 parts of water is mixed and stirred. To obtain a protective layer coating solution was adjusted to a pH5 with 10% aqueous acetic acid.
・感熱記録体の作製
支持体として坪量60g/m2の上質紙の一方の面に、下塗り層用塗液、感熱記録層用塗液、及び保護層用塗液を乾燥後の塗布量がそれぞれ6.0g/m2、3.5g/m2、及び2.0g/m2となるようにカーテン法によって塗布及び乾燥して、下塗り層、感熱記録層、及び保護層を順次形成した後、スーパーカレンダーで表面を平滑化して感熱記録体を得た。
-Preparation of thermal recording material The coating amount after drying the coating solution for the undercoat layer, the coating solution for the thermal recording layer, and the coating solution for the protective layer on one surface of a high-quality paper having a basis weight of 60 g / m 2 as a support. each 6.0 g / m 2, was coated and dried by a curtain method so that 3.5 g / m 2, and 2.0 g / m 2, the undercoating layer, thermosensitive recording layer, and after sequentially forming a protective layer The surface was smoothed with a super calendar to obtain a heat-sensitive recording material.
・剥離層の形成
無溶剤型紫外線硬化性シリコーン化合物(商品名:UV−271、荒川化学社製)100部、光重合開始剤(商品名:CATA211、硼素系カチオン硬化触媒、荒川化学社製)5部を混合撹拌した剥離層用塗液を印刷機で保護層上に、乾燥後の塗布量が0.35g/m2となるよう塗布した後、紫外線を照射して剥離層を形成した。
-Formation of release layer 100 parts of solvent-free ultraviolet curable silicone compound (trade name: UV-271, manufactured by Arakawa Chemical Co., Ltd.), photopolymerization initiator (trade name: CATA 211, boron-based cationic curing catalyst, manufactured by Arakawa Chemical Co., Ltd.) The release layer coating solution obtained by mixing and stirring 5 parts was applied on the protective layer with a printing machine so that the coating amount after drying was 0.35 g / m 2, and then irradiated with ultraviolet rays to form a release layer.
・粘着剤層の形成
支持体の他方の面に粘着剤層用塗液として水系粘着剤のアクリル系エマルジョン粘着剤(商品名:L−145、日本カーバイト工業社製)を乾燥後の塗布量が25g/m2となるようにロールコーター法で塗布及び乾燥して粘着剤層を形成した後、巻取り状の感熱記録ライナーレスラベルを得た。
-Formation of pressure-sensitive adhesive layer Amount of coating after drying an aqueous emulsion acrylic emulsion pressure-sensitive adhesive (trade name: L-145, manufactured by Nippon Carbide Industries Co., Ltd.) as a coating liquid for the pressure-sensitive adhesive layer on the other surface of the support Was applied and dried by a roll coater method so as to be 25 g / m 2 to form a pressure-sensitive adhesive layer, and then a wound thermal recording linerless label was obtained.
実施例2
実施例1の顕色剤分散液の調製において、N−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミドに代えて、4−ヒドロキシ−4’−n−プロポキシジフェニルスルホン(商品名:トミラックKN、APIコーポレーション社製)を用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Example 2
Instead of N- [2- (3-phenylureido) phenyl] benzenesulfonamide in the preparation of the developer dispersion of Example 1, 4-hydroxy-4′-n-propoxydiphenylsulfone (trade name: Tomirac) A heat-sensitive recording linerless label was obtained in the same manner as in Example 1 except that KN (manufactured by API Corporation) was used.
実施例3
実施例1の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、N,N’−エチレンビスオレイン酸アミド(商品名:スリパックスO、日本化成社製、融点119℃)を用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Example 3
In the preparation of the sensitizer dispersion of Example 1, N, N′-ethylenebisstearic acid amide instead of N, N′-ethylenebisstearic acid amide (trade name: SLIPAX O, Nippon Kasei Co., Ltd., melting point) A thermal recording linerless label was obtained in the same manner as in Example 1 except that 119 ° C. was used.
実施例4
実施例2の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、N,N’−エチレンビスオレイン酸アミド(商品名:スリパックスO、日本化成社製、融点119℃)を用いた以外は、実施例2と同様にして感熱記録ライナーレスラベルを得た。
Example 4
In the preparation of the sensitizer dispersion of Example 2, N, N′-ethylenebisstearic acid amide (trade name: SLIPAX O, manufactured by Nippon Kasei Co., Ltd., melting point) was used instead of N, N′-ethylenebisstearic acid amide. A heat-sensitive recording linerless label was obtained in the same manner as in Example 2 except that 119 ° C. was used.
実施例5
実施例1の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、N,N’−キシリレンビスステアリン酸アミド(商品名:スリパックスPXS、日本化成社製、融点123℃)を用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Example 5
In the preparation of the sensitizer dispersion of Example 1, instead of N, N′-ethylenebisstearic acid amide, N, N′-xylylene bisstearic acid amide (trade name: SLIPAX PXS, manufactured by Nippon Kasei Co., Ltd., A thermal recording linerless label was obtained in the same manner as in Example 1 except that the melting point was 123 ° C.
実施例6
実施例2の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、N,N’−キシリレンビスステアリン酸アミド(商品名:スリパックスPXS、日本化成社製、融点123℃)を用いた以外は、実施例2と同様にして感熱記録ライナーレスラベルを得た。
Example 6
In the preparation of the sensitizer dispersion of Example 2, instead of N, N′-ethylenebisstearic acid amide, N, N′-xylylene bisstearic acid amide (trade name: SLIPAX PXS, manufactured by Nippon Kasei Co., Ltd., A thermal recording linerless label was obtained in the same manner as in Example 2 except that the melting point was 123 ° C.
実施例7
実施例1の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、N,N’−ヘキサメチレンビスステアリン酸アミド(商品名:スリパックスZHS、日本化成社製、融点140℃)を用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Example 7
In the preparation of the sensitizer dispersion liquid of Example 1, instead of N, N′-ethylenebisstearic acid amide, N, N′-hexamethylenebisstearic acid amide (trade name: SLIPAX ZHS, manufactured by Nippon Kasei Co., Ltd., A thermal recording linerless label was obtained in the same manner as in Example 1 except that the melting point was 140 ° C.
実施例8
実施例2の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、N,N’−ヘキサメチレンビスステアリン酸アミド(商品名:スリパックスZHS、日本化成社製、融点140℃)を用いた以外は、実施例2と同様にして感熱記録ライナーレスラベルを得た。
Example 8
In the preparation of the sensitizer dispersion liquid of Example 2, instead of N, N′-ethylenebisstearic acid amide, N, N′-hexamethylenebisstearic acid amide (trade name: SLIPAX ZHS, manufactured by Nippon Kasei Co., Ltd., A heat-sensitive recording linerless label was obtained in the same manner as in Example 2 except that the melting point was 140 ° C.
実施例9
実施例1の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、N,N’−ジステアリルアジピン酸酸アミド(商品名:スリパックスZSS、日本化成社製、融点141℃)を用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Example 9
In the preparation of the sensitizer dispersion liquid of Example 1, instead of N, N′-ethylenebisstearic acid amide, N, N′-distearyl adipic acid amide (trade name: SLIPAX ZSS, manufactured by Nippon Kasei Co., Ltd., A heat-sensitive recording linerless label was obtained in the same manner as in Example 1 except that the melting point was 141 ° C.
実施例10
実施例2の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、N,N’−ジステアリルアジピン酸酸アミド(商品名:スリパックスZSS、日本化成社製、融点141℃)を用いた以外は、実施例2と同様にして感熱記録ライナーレスラベルを得た。
Example 10
In the preparation of the sensitizer dispersion liquid of Example 2, instead of N, N′-ethylenebisstearic acid amide, N, N′-distearyl adipic acid amide (trade name: SLIPAX ZSS, manufactured by Nippon Kasei Co., Ltd., A thermal recording linerless label was obtained in the same manner as in Example 2 except that the melting point was 141 ° C.
実施例11
実施例1の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコールA及びアセトアセチル変性ポリビニルアルコールBに代えて、ジアセトン変性ポリビニルアルコール(商品名:DF−10、日本合成化学社製)の17.6%水溶液290部を用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Example 11
In preparation of the coating liquid for protective layer of Example 1, instead of acetoacetyl-modified polyvinyl alcohol A and acetoacetyl-modified polyvinyl alcohol B, 17 of diacetone-modified polyvinyl alcohol (trade name: DF-10, manufactured by Nippon Synthetic Chemical Co., Ltd.) A heat-sensitive recording linerless label was obtained in the same manner as in Example 1 except that 290 parts of a 6% aqueous solution was used.
実施例12
実施例1の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコールA及びアセトアセチル変性ポリビニルアルコールBに代えて、珪素変性ポリビニルアルコール(商品名:R−1130、クラレ社製)の12%水溶液308部用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Example 12
In the preparation of the protective layer coating solution of Example 1, instead of acetoacetyl-modified polyvinyl alcohol A and acetoacetyl-modified polyvinyl alcohol B, a 12% aqueous solution of silicon-modified polyvinyl alcohol (trade name: R-1130, manufactured by Kuraray Co., Ltd.) A thermal recording linerless label was obtained in the same manner as in Example 1 except that 308 parts were used.
実施例13
実施例1の顕色剤分散液の調製において、N−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミドに代えて、4−ヒドロキシ−4’−アリルオシジフェニルスルホン(商品名:BPS−MAE、日華化学社製)を用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Example 13
Instead of N- [2- (3-phenylureido) phenyl] benzenesulfonamide in the preparation of the developer dispersion of Example 1, 4-hydroxy-4′-allylacidiphenylsulfone (trade name: BPS- A thermal recording linerless label was obtained in the same manner as in Example 1 except that MAE (manufactured by Nikka Chemical Co., Ltd.) was used.
比較例1
実施例1の顕色剤分散液の調製において、N−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミドに代えて、4−ヒドロキシ−4’−イソプロキシジフェニルスルホンを使用し、増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、シュウ酸ジ−p−メチルベンジルエステル(商品名:HS3520、DIC社製)を使用した以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Comparative Example 1
In the preparation of the developer dispersion of Example 1, 4-hydroxy-4′-isoproxydiphenylsulfone was used in place of N- [2- (3-phenylureido) phenyl] benzenesulfonamide, and sensitization was performed. Example 1 except that di-p-methylbenzyl oxalate (trade name: HS3520, manufactured by DIC) was used in place of N, N′-ethylenebisstearic acid amide in the preparation of the agent dispersion. Similarly, a thermal recording linerless label was obtained.
比較例2
実施例1の顕色剤分散液の調製において、N−[2−(3−フェニルウレイド)フェニル]ベンゼンスルホンアミドに代えて、4−ヒドロキシ−4’−イソプロキシジフェニルスルホンを用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Comparative Example 2
In the preparation of the developer dispersion of Example 1, except that 4-hydroxy-4′-isoproxydiphenylsulfone was used instead of N- [2- (3-phenylureido) phenyl] benzenesulfonamide, A thermal recording linerless label was obtained in the same manner as in Example 1.
比較例3
実施例1の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、シュウ酸ジ−p−メチルベンジルエステル(商品名:HS3520、DIC社製)を用いた以外は、実施例1と同様にして感熱記録ライナーレスラベルを得た。
Comparative Example 3
In the preparation of the sensitizer dispersion of Example 1, oxalic acid di-p-methylbenzyl ester (trade name: HS3520, manufactured by DIC) was used instead of N, N′-ethylenebisstearic acid amide. Obtained a thermal recording linerless label in the same manner as in Example 1.
比較例4
実施例2の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、シュウ酸ジ−p−メチルベンジルエステル(商品名:HS3520、DIC社製)を用いた以外は、実施例2と同様にして感熱記録ライナーレスラベルを得た。
Comparative Example 4
In the preparation of the sensitizer dispersion of Example 2, oxalic acid di-p-methylbenzyl ester (trade name: HS3520, manufactured by DIC) was used in place of N, N′-ethylenebisstearic acid amide. Obtained a thermal recording linerless label in the same manner as in Example 2.
比較例5
実施例2の増感剤分散液の調製において、N,N’−エチレンビスステアリン酸アミドに代えて、ステアリン酸アミド(商品名:アマイドAP−1、日本化成社製、融点101℃)を用いた以外は、実施例2と同様にして感熱記録ライナーレスラベルを得た。
Comparative Example 5
In the preparation of the sensitizer dispersion of Example 2, stearamide (trade name: Amide AP-1, Nippon Kasei Co., Ltd., melting point: 101 ° C.) was used instead of N, N′-ethylenebisstearic acid amide. A heat-sensitive recording linerless label was obtained in the same manner as in Example 2 except that.
かくして得られた感熱記録ライナーレスラベルを40℃、50%RHの環境下で24時間放置後、以下の評価を行った。その結果は、表1に示す通りであった。 The thermal recording linerless label thus obtained was allowed to stand for 24 hours in an environment of 40 ° C. and 50% RH, and then evaluated as follows. The results were as shown in Table 1.
・記録濃度
感熱記録評価機(商品名:TH−PMD、大倉電機社製)を用い、印加エネルギー:0.24mJ/dotによって記録した。得られた印字部の反射濃度をマクベス濃度計(RD−914、マクベス社製)のビジュアルモードで測定した。記録濃度については、実用上1.30以上が好ましい。
Recording density Using a thermal recording evaluation machine (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.), recording was performed at an applied energy of 0.24 mJ / dot. The reflection density of the obtained printed part was measured in a visual mode of a Macbeth densitometer (RD-914, manufactured by Macbeth). The recording density is preferably 1.30 or more for practical use.
・白紙保存性
各感熱記録ライナーレスラベルを、40℃、90%RHの環境下で7日間保管後、上記の記録濃度の評価と同様に記録して、反射濃度を測定した。記録濃度については、保管前に記録して測定された上記の記録濃度に近いほど好ましい。
-White paper storage stability Each thermal recording linerless label was stored in an environment of 40 ° C. and 90% RH for 7 days, and then recorded in the same manner as in the evaluation of the recording density, and the reflection density was measured. The recording density is preferably as close as possible to the above-mentioned recording density recorded and measured before storage.
・耐熱性
記録前の感熱記録ライナーレスラベルを、90℃で1時間放置した後、白紙部の反射濃度をマクベス濃度計(前述)で同様にして測定した。反射濃度については、0.20以下であることが好ましい。
-Heat resistance The thermal recording linerless label before recording was allowed to stand at 90 ° C for 1 hour, and then the reflection density of the blank paper portion was measured in the same manner with a Macbeth densitometer (described above). The reflection density is preferably 0.20 or less.
・耐可塑剤性
ポリカーボネイトパイプ(40mm径)の上にラップフィルム(商品名:ハイラップKMA−W、三井化学社製)を3重に巻きつけ、その上に記録濃度の評価における記録後の感熱記録ライナーレスラベルを置き、更にその上にラップフィルムを3重に巻きつけ、40℃で24時間放置した後、ラップフィルムを剥がして、印字部の反射濃度をマクベス濃度計(前述)のビジュアルモードで測定した。処理後の記録濃度については、実用上1.00以上が好ましい。
・ Plasticizer resistance A wrap film (trade name: High Wrap KMA-W, manufactured by Mitsui Chemicals) is wrapped around a polycarbonate pipe (40 mm diameter) in a triple layer, and thermal recording after recording in recording density evaluation is performed on the film. Place the linerless label, wrap the wrap film in three layers on it, leave it at 40 ° C for 24 hours, peel off the wrap film, and check the reflection density of the printed part in the Macbeth densitometer (described above) visual mode. It was measured. The recording density after the treatment is preferably 1.00 or more for practical use.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016063496A JP6649618B2 (en) | 2016-03-28 | 2016-03-28 | Thermal recording linerless label and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016063496A JP6649618B2 (en) | 2016-03-28 | 2016-03-28 | Thermal recording linerless label and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2017177346A true JP2017177346A (en) | 2017-10-05 |
JP6649618B2 JP6649618B2 (en) | 2020-02-19 |
Family
ID=60003201
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016063496A Active JP6649618B2 (en) | 2016-03-28 | 2016-03-28 | Thermal recording linerless label and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6649618B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021066015A (en) * | 2019-10-17 | 2021-04-30 | 王子ホールディングス株式会社 | Thermosensitive recording medium and method for manufacturing the same |
JP2021511982A (en) * | 2018-01-31 | 2021-05-13 | ミツビシ ハイテック ペーパー ヨーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Thermal recording material |
WO2021123490A1 (en) * | 2019-12-20 | 2021-06-24 | Upm Raflatac Oy | A double-side printable psa thermal label |
JP2021146642A (en) * | 2020-03-19 | 2021-09-27 | 株式会社リコー | Thermosensitive recording medium, method for producing thermosensitive recording medium, and article |
EP3746308B1 (en) | 2018-01-31 | 2022-02-23 | Mitsubishi HiTec Paper Europe GmbH | Coating composition, heat-sensitive recording layer, heat-sensitive recording material, and corresponding uses and methods |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20230286243A1 (en) * | 2020-09-29 | 2023-09-14 | Upm Raflatac Oy | Linerless label |
Citations (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5662188A (en) * | 1979-10-29 | 1981-05-27 | Mitsubishi Paper Mills Ltd | Heat-sensitive recording material having improved image stability |
JPS5672994A (en) * | 1979-11-19 | 1981-06-17 | Ricoh Co Ltd | Thermal recording material |
JPS57181890A (en) * | 1981-05-06 | 1982-11-09 | Kohjin Co Ltd | Improved heat sensitive recording paper |
JPS6054842A (en) * | 1983-09-06 | 1985-03-29 | 日本製紙株式会社 | Thermal-sensing color-developing tacky label and manufacturethereof |
JPH02165989A (en) * | 1988-12-20 | 1990-06-26 | Ricoh Co Ltd | Label for thermal recording |
JPH0446986A (en) * | 1990-06-14 | 1992-02-17 | Toppan Printing Co Ltd | Reversible heat-sensitive color developing and extinguishing composition |
JPH058541A (en) * | 1991-07-05 | 1993-01-19 | Mitsubishi Paper Mills Ltd | Release type thermal recording material and preparation thereof |
JPH0664320A (en) * | 1992-08-13 | 1994-03-08 | Mitsubishi Paper Mills Ltd | Thermal recording material |
JPH06222717A (en) * | 1992-11-30 | 1994-08-12 | Moore Business Forms Inc | Label sheet and its manufacture |
JPH07108765A (en) * | 1993-10-08 | 1995-04-25 | Mitsubishi Paper Mills Ltd | Thermal recording material |
JPH0986052A (en) * | 1995-09-27 | 1997-03-31 | Mitsubishi Paper Mills Ltd | Thermal recording material |
JPH09127871A (en) * | 1995-10-31 | 1997-05-16 | Oji Paper Co Ltd | Thermosensitive recording label |
JP2000351275A (en) * | 1999-06-11 | 2000-12-19 | Mitsubishi Paper Mills Ltd | Heat-sensitive recording medium |
JP2001328352A (en) * | 2000-05-19 | 2001-11-27 | Saito Kaseihin Kenkyusho:Kk | Thermal recording material |
JP2002059655A (en) * | 2000-08-23 | 2002-02-26 | Saito Kaseihin Kenkyusho:Kk | Thermal recording material |
JP2002283735A (en) * | 2001-03-26 | 2002-10-03 | Mitsubishi Paper Mills Ltd | Thermal recording material |
JP2003285557A (en) * | 2002-03-28 | 2003-10-07 | Nippon Paper Industries Co Ltd | Thermal recording material |
JP2009067045A (en) * | 2007-08-23 | 2009-04-02 | Nicca Chemical Co Ltd | Thermosensitive recording material |
JP2013086402A (en) * | 2011-10-20 | 2013-05-13 | Oji Holdings Corp | Heat-sensitive recording body |
JP2013121718A (en) * | 2011-11-07 | 2013-06-20 | Ricoh Co Ltd | Thermosensitive recording label |
JP2013195889A (en) * | 2012-03-22 | 2013-09-30 | Ricoh Co Ltd | Thermal recording linerless label |
US20140057783A1 (en) * | 2011-02-11 | 2014-02-27 | Gerhard Stork | Method for producing a heat-sensitive recording material |
JP2014218062A (en) * | 2013-05-10 | 2014-11-20 | 王子ホールディングス株式会社 | Thermosensitive recording material |
WO2014189044A1 (en) * | 2013-05-22 | 2014-11-27 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP2014226848A (en) * | 2013-05-22 | 2014-12-08 | 王子ホールディングス株式会社 | Heat-sensitive recording body |
JP2015003403A (en) * | 2013-06-19 | 2015-01-08 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP2015013422A (en) * | 2013-07-05 | 2015-01-22 | 王子ホールディングス株式会社 | Thermosensitive recording body |
JP2015013470A (en) * | 2013-06-05 | 2015-01-22 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP2015150764A (en) * | 2014-02-13 | 2015-08-24 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP2015157478A (en) * | 2014-01-27 | 2015-09-03 | 三菱製紙株式会社 | heat-sensitive recording material |
JP5794021B2 (en) * | 2011-07-27 | 2015-10-14 | 王子ホールディングス株式会社 | Linerless thermal recording label |
JP2016028847A (en) * | 2012-12-18 | 2016-03-03 | 日本製紙株式会社 | Thermosensitive recording medium |
JP2016030441A (en) * | 2014-07-25 | 2016-03-07 | 三菱製紙株式会社 | Heat-sensitive recording material |
JP2016165835A (en) * | 2015-03-10 | 2016-09-15 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP6011471B2 (en) * | 2013-06-13 | 2016-10-19 | 王子ホールディングス株式会社 | Thermal recording material |
JP2017177627A (en) * | 2016-03-31 | 2017-10-05 | 王子ホールディングス株式会社 | Thermosensitive recording linerless label and method for manufacturing the same |
-
2016
- 2016-03-28 JP JP2016063496A patent/JP6649618B2/en active Active
Patent Citations (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5662188A (en) * | 1979-10-29 | 1981-05-27 | Mitsubishi Paper Mills Ltd | Heat-sensitive recording material having improved image stability |
JPS5672994A (en) * | 1979-11-19 | 1981-06-17 | Ricoh Co Ltd | Thermal recording material |
JPS57181890A (en) * | 1981-05-06 | 1982-11-09 | Kohjin Co Ltd | Improved heat sensitive recording paper |
JPS6054842A (en) * | 1983-09-06 | 1985-03-29 | 日本製紙株式会社 | Thermal-sensing color-developing tacky label and manufacturethereof |
JPH02165989A (en) * | 1988-12-20 | 1990-06-26 | Ricoh Co Ltd | Label for thermal recording |
JPH0446986A (en) * | 1990-06-14 | 1992-02-17 | Toppan Printing Co Ltd | Reversible heat-sensitive color developing and extinguishing composition |
JPH058541A (en) * | 1991-07-05 | 1993-01-19 | Mitsubishi Paper Mills Ltd | Release type thermal recording material and preparation thereof |
JPH0664320A (en) * | 1992-08-13 | 1994-03-08 | Mitsubishi Paper Mills Ltd | Thermal recording material |
JPH06222717A (en) * | 1992-11-30 | 1994-08-12 | Moore Business Forms Inc | Label sheet and its manufacture |
JPH07108765A (en) * | 1993-10-08 | 1995-04-25 | Mitsubishi Paper Mills Ltd | Thermal recording material |
JPH0986052A (en) * | 1995-09-27 | 1997-03-31 | Mitsubishi Paper Mills Ltd | Thermal recording material |
JPH09127871A (en) * | 1995-10-31 | 1997-05-16 | Oji Paper Co Ltd | Thermosensitive recording label |
JP2000351275A (en) * | 1999-06-11 | 2000-12-19 | Mitsubishi Paper Mills Ltd | Heat-sensitive recording medium |
JP2001328352A (en) * | 2000-05-19 | 2001-11-27 | Saito Kaseihin Kenkyusho:Kk | Thermal recording material |
JP2002059655A (en) * | 2000-08-23 | 2002-02-26 | Saito Kaseihin Kenkyusho:Kk | Thermal recording material |
JP2002283735A (en) * | 2001-03-26 | 2002-10-03 | Mitsubishi Paper Mills Ltd | Thermal recording material |
JP2003285557A (en) * | 2002-03-28 | 2003-10-07 | Nippon Paper Industries Co Ltd | Thermal recording material |
JP2009067045A (en) * | 2007-08-23 | 2009-04-02 | Nicca Chemical Co Ltd | Thermosensitive recording material |
US20140057783A1 (en) * | 2011-02-11 | 2014-02-27 | Gerhard Stork | Method for producing a heat-sensitive recording material |
JP5794021B2 (en) * | 2011-07-27 | 2015-10-14 | 王子ホールディングス株式会社 | Linerless thermal recording label |
JP2013086402A (en) * | 2011-10-20 | 2013-05-13 | Oji Holdings Corp | Heat-sensitive recording body |
JP2013121718A (en) * | 2011-11-07 | 2013-06-20 | Ricoh Co Ltd | Thermosensitive recording label |
JP2013195889A (en) * | 2012-03-22 | 2013-09-30 | Ricoh Co Ltd | Thermal recording linerless label |
JP2016028847A (en) * | 2012-12-18 | 2016-03-03 | 日本製紙株式会社 | Thermosensitive recording medium |
JP2014218062A (en) * | 2013-05-10 | 2014-11-20 | 王子ホールディングス株式会社 | Thermosensitive recording material |
JP2014226848A (en) * | 2013-05-22 | 2014-12-08 | 王子ホールディングス株式会社 | Heat-sensitive recording body |
WO2014189044A1 (en) * | 2013-05-22 | 2014-11-27 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP2015013470A (en) * | 2013-06-05 | 2015-01-22 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP6011471B2 (en) * | 2013-06-13 | 2016-10-19 | 王子ホールディングス株式会社 | Thermal recording material |
JP2015003403A (en) * | 2013-06-19 | 2015-01-08 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP2015013422A (en) * | 2013-07-05 | 2015-01-22 | 王子ホールディングス株式会社 | Thermosensitive recording body |
JP2015157478A (en) * | 2014-01-27 | 2015-09-03 | 三菱製紙株式会社 | heat-sensitive recording material |
JP2015150764A (en) * | 2014-02-13 | 2015-08-24 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP2016030441A (en) * | 2014-07-25 | 2016-03-07 | 三菱製紙株式会社 | Heat-sensitive recording material |
JP2016165835A (en) * | 2015-03-10 | 2016-09-15 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
JP2017177627A (en) * | 2016-03-31 | 2017-10-05 | 王子ホールディングス株式会社 | Thermosensitive recording linerless label and method for manufacturing the same |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021511982A (en) * | 2018-01-31 | 2021-05-13 | ミツビシ ハイテック ペーパー ヨーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Thermal recording material |
EP3746308B1 (en) | 2018-01-31 | 2022-02-23 | Mitsubishi HiTec Paper Europe GmbH | Coating composition, heat-sensitive recording layer, heat-sensitive recording material, and corresponding uses and methods |
JP7307735B2 (en) | 2018-01-31 | 2023-07-12 | ミツビシ ハイテック ペーパー ヨーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツング | thermal recording material |
US11752793B2 (en) | 2018-01-31 | 2023-09-12 | Mitsubishi Hitec Paper Europe Gmbh | Heat-sensitive recording material |
JP2021066015A (en) * | 2019-10-17 | 2021-04-30 | 王子ホールディングス株式会社 | Thermosensitive recording medium and method for manufacturing the same |
JP7302427B2 (en) | 2019-10-17 | 2023-07-04 | 王子ホールディングス株式会社 | Thermal recording material and its manufacturing method |
WO2021123490A1 (en) * | 2019-12-20 | 2021-06-24 | Upm Raflatac Oy | A double-side printable psa thermal label |
EP4062393A4 (en) * | 2019-12-20 | 2023-08-16 | UPM Raflatac Oy | A double-side printable psa thermal label |
JP2021146642A (en) * | 2020-03-19 | 2021-09-27 | 株式会社リコー | Thermosensitive recording medium, method for producing thermosensitive recording medium, and article |
Also Published As
Publication number | Publication date |
---|---|
JP6649618B2 (en) | 2020-02-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6586915B2 (en) | Thermal recording linerless label and method for producing the same | |
JP6649618B2 (en) | Thermal recording linerless label and method for producing the same | |
JP4636017B2 (en) | Thermal recording material | |
US11912052B2 (en) | Thermosensitive recording medium | |
WO2014126018A1 (en) | Heat-sensitive recording body | |
JP2015150764A (en) | Thermosensitive recording medium | |
JP7363886B2 (en) | Thermal recording linerless label | |
JP2013188955A (en) | Thermal recording body | |
JP2013107294A (en) | Heat-sensitive recording medium | |
JP5569030B2 (en) | Thermal recording material | |
JP2017177351A (en) | Thermosensitive recording linerless label and method for manufacturing the same | |
JP2002240430A (en) | Thermal recording body | |
WO2011049159A1 (en) | Heat-sensitive recording medium | |
JP2017030301A (en) | Thermosensitive recording medium | |
JP6079555B2 (en) | Thermal recording material | |
JP7392638B2 (en) | Thermal recording linerless label | |
JP6716947B2 (en) | Thermal recording linerless label | |
JP2010058467A (en) | Thermosensitive recording body | |
JP7367659B2 (en) | Thermal recording linerless label | |
JPH10193791A (en) | Adhesive label for heat-sensitive recording | |
JP5025017B2 (en) | Thermal recording material | |
JP2014091290A (en) | Thermosensitive recording body | |
JP2010076185A (en) | Thermosensitive recording body | |
JP5453988B2 (en) | Thermal recording material | |
JP6070472B2 (en) | Method for producing thermal recording material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180510 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190411 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190423 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20190521 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190621 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191008 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191205 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20191218 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20191231 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6649618 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |