EP3274184A1 - Wärmeempfindliches aufzeichnungsmaterial - Google Patents
Wärmeempfindliches aufzeichnungsmaterialInfo
- Publication number
- EP3274184A1 EP3274184A1 EP16717087.7A EP16717087A EP3274184A1 EP 3274184 A1 EP3274184 A1 EP 3274184A1 EP 16717087 A EP16717087 A EP 16717087A EP 3274184 A1 EP3274184 A1 EP 3274184A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- radical
- recording material
- sensitive recording
- color
- 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
- 239000000463 material Substances 0.000 title claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- -1 heteroaryl radical Chemical class 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 11
- 150000005840 aryl radicals Chemical group 0.000 claims description 9
- 238000007766 curtain coating Methods 0.000 claims description 9
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 7
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000006730 (C2-C5) alkynyl group Chemical group 0.000 claims description 4
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 3
- HEVGMYPGMWZOBU-UHFFFAOYSA-N [3-[(4-methylphenyl)sulfonylcarbamoylamino]phenyl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(=O)NC1=CC=CC(OS(=O)(=O)C=2C=CC(C)=CC=2)=C1 HEVGMYPGMWZOBU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- MGXKBIYKSZJUEO-UHFFFAOYSA-N $l^{2}-azanylmethylbenzene Chemical compound [NH]CC1=CC=CC=C1 MGXKBIYKSZJUEO-UHFFFAOYSA-N 0.000 claims description 2
- OLJWHVOMCKSWOX-UHFFFAOYSA-N 1-(4-methylphenyl)-3-[(4-methylphenyl)sulfamoyl]urea Chemical compound CC1=CC=C(C=C1)NC(=O)NS(=O)(=O)NC1=CC=C(C=C1)C OLJWHVOMCKSWOX-UHFFFAOYSA-N 0.000 claims description 2
- VVJIPKRKCQXEKM-UHFFFAOYSA-N 1-naphthalen-1-yl-3-(naphthalen-1-ylsulfamoyl)urea Chemical compound C1(=CC=CC2=CC=CC=C12)NC(=O)NS(=O)(=O)NC1=CC=CC2=CC=CC=C12 VVJIPKRKCQXEKM-UHFFFAOYSA-N 0.000 claims description 2
- QWBOUWUYHMQMSW-UHFFFAOYSA-N 1-phenyl-3-(phenylsulfamoyl)urea Chemical group C=1C=CC=CC=1NS(=O)(=O)NC(=O)NC1=CC=CC=C1 QWBOUWUYHMQMSW-UHFFFAOYSA-N 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- LAEGMZAEBQCDNB-UHFFFAOYSA-N N-[(4-nitrophenyl)sulfamoyl]benzamide Chemical compound [N+](=O)([O-])C1=CC=C(C=C1)NS(=O)(=O)NC(C1=CC=CC=C1)=O LAEGMZAEBQCDNB-UHFFFAOYSA-N 0.000 claims description 2
- MJJHRZIMYSKPED-UHFFFAOYSA-N N-[[2-(phenylcarbamoylamino)phenyl]sulfamoyl]benzamide Chemical compound C1(=CC=CC=C1)NC(=O)NC1=C(C=CC=C1)NS(=O)(=O)NC(C1=CC=CC=C1)=O MJJHRZIMYSKPED-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- PKVPQUVCBXSQNS-UHFFFAOYSA-N ethyl 4-[(4-ethoxycarbonylphenyl)sulfamoylcarbamoylamino]benzoate Chemical compound C(C)OC(=O)C1=CC=C(C=C1)NC(=O)NS(=O)(=O)NC1=CC=C(C=C1)C(=O)OCC PKVPQUVCBXSQNS-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- CUTZDKNMCNWBLN-UHFFFAOYSA-N methyl 4-(benzoylsulfamoylamino)benzoate Chemical compound COC(=O)C1=CC=C(C=C1)NS(=O)(=O)NC(C1=CC=CC=C1)=O CUTZDKNMCNWBLN-UHFFFAOYSA-N 0.000 claims description 2
- BVFMYNNAEUPDCO-UHFFFAOYSA-N n-(phenylsulfamoyl)benzamide Chemical compound C=1C=CC=CC=1C(=O)NS(=O)(=O)NC1=CC=CC=C1 BVFMYNNAEUPDCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 abstract description 2
- 125000001072 heteroaryl group Chemical group 0.000 abstract 2
- 125000001769 aryl amino group Chemical group 0.000 abstract 1
- 125000004104 aryloxy group Chemical group 0.000 abstract 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 1
- 125000005241 heteroarylamino group Chemical group 0.000 abstract 1
- 125000005553 heteroaryloxy group Chemical group 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 35
- 239000010410 layer Substances 0.000 description 35
- 238000003860 storage Methods 0.000 description 13
- 238000003801 milling Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000011324 bead Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 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
- 238000001035 drying Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229940100389 Sulfonylurea Drugs 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical class NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007651 thermal printing Methods 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- HUSIBQLZEMMTCQ-UHFFFAOYSA-N 2'-anilino-6'-[ethyl(3-methylbutyl)amino]-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CCC(C)C)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 HUSIBQLZEMMTCQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000533901 Narcissus papyraceus Species 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000006101 laboratory sample Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012170 montan wax Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 230000008542 thermal sensitivity Effects 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- LJSLYKNKVQMIJY-UHFFFAOYSA-N 1,4-diethoxynaphthalene Chemical compound C1=CC=C2C(OCC)=CC=C(OCC)C2=C1 LJSLYKNKVQMIJY-UHFFFAOYSA-N 0.000 description 1
- XVSRGZPKJKLORS-UHFFFAOYSA-N 1-(4-methylphenyl)sulfonyl-3-[4-[[4-[(4-methylphenyl)sulfonylcarbamoylamino]phenyl]methyl]phenyl]urea Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(=O)NC(C=C1)=CC=C1CC(C=C1)=CC=C1NC(=O)NS(=O)(=O)C1=CC=C(C)C=C1 XVSRGZPKJKLORS-UHFFFAOYSA-N 0.000 description 1
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 1
- VITPICOSHHCBFU-UHFFFAOYSA-N 1-sulfonylguanidine Chemical class NC(=N)N=S(=O)=O VITPICOSHHCBFU-UHFFFAOYSA-N 0.000 description 1
- JFNWGAYGVJGNBG-UHFFFAOYSA-N 2'-anilino-3'-methyl-6'-pyrrolidin-1-ylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound CC1=CC=2OC3=CC(N4CCCC4)=CC=C3C3(C4=CC=CC=C4C(=O)O3)C=2C=C1NC1=CC=CC=C1 JFNWGAYGVJGNBG-UHFFFAOYSA-N 0.000 description 1
- FPIAKQHHSBQHDE-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enamide;prop-2-enoic acid Chemical compound NC(=O)C=C.OC(=O)C=C.CC(=C)C(O)=O FPIAKQHHSBQHDE-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
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-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
- NHCBGOLCVIYTMT-UHFFFAOYSA-N 3-ethoxy-n-ethylpropan-1-amine Chemical compound CCNCCCOCC NHCBGOLCVIYTMT-UHFFFAOYSA-N 0.000 description 1
- JKYWRCFCKIREMM-UHFFFAOYSA-N 4-butyl-2-cyclohexyl-5-methylphenol Chemical compound C1=C(C)C(CCCC)=CC(C2CCCCC2)=C1O JKYWRCFCKIREMM-UHFFFAOYSA-N 0.000 description 1
- WTHKAJZQYNKTCJ-UHFFFAOYSA-N 4-methyl-N-(phenylmethyl)benzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NCC1=CC=CC=C1 WTHKAJZQYNKTCJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical class CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 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
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- QWHCTYYBLDCYIT-UHFFFAOYSA-N bis[(4-chlorophenyl)methyl] oxalate Chemical compound C1=CC(Cl)=CC=C1COC(=O)C(=O)OCC1=CC=C(Cl)C=C1 QWHCTYYBLDCYIT-UHFFFAOYSA-N 0.000 description 1
- FPFZBTUMXCSRLU-UHFFFAOYSA-N bis[(4-methylphenyl)methyl] oxalate Chemical compound C1=CC(C)=CC=C1COC(=O)C(=O)OCC1=CC=C(C)C=C1 FPFZBTUMXCSRLU-UHFFFAOYSA-N 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019589 hardness Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 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 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229940102689 lustra Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000011160 magnesium carbonates Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 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
- HLSDMLXXPIEJFI-UHFFFAOYSA-N n-(oxolan-2-ylmethyl)ethanamine Chemical compound CCNCC1CCCO1 HLSDMLXXPIEJFI-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- FNLUJDLKYOWMMF-UHFFFAOYSA-N n-ethyl-2-methylpropan-1-amine Chemical compound CCNCC(C)C FNLUJDLKYOWMMF-UHFFFAOYSA-N 0.000 description 1
- XAUGWFWQVYXATQ-UHFFFAOYSA-N n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1 XAUGWFWQVYXATQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000721 toxic potential Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids
Definitions
- the present invention relates to a heat-sensitive recording material comprising a support substrate and a heat-sensitive color-forming layer containing at least a color former and at least one phenol-free color developer, a process for producing the same, and the use of the phenol-free color developer contained in the heat-sensitive recording material.
- Thermosensitive recording materials for the direct thermal printing application which have a heat-sensitive color-forming layer (thermal reaction layer) applied to a support substrate have been known for a long time.
- a color former and a color developer are usually present, which react with one another under the action of heat and thus lead to color development.
- heat-sensitive recording materials containing a non-phenolic color developer in the heat-sensitive color-forming layer have been developed to improve the durability of the typeface, especially when the printed thermosensitive recording material is stored for a long time or comes into contact with hydrophobic substances such as plasticized materials or oils.
- EP 0 620 122 Bl discloses non-phenolic color developers of the aromatic sulfonylurea class. With these, heat-sensitive recording materials excellent in image resistance can be obtained. Further, the heat-sensitive recording materials based on these color developers have a useful thermal sensitivity with good surface white, so that, with appropriate formulation of the heat-sensitive color-forming layer, it is comparatively easy to produce high print densities using commercial thermal printers.
- N, N '- [methylenebis (4, 1-phenyleneiminocarbonyl)] bis [4-methylbenzenesulfonamide] (B-TUM) has prevailed in particular.
- a common in practice non-phenolic developer from this class 4-methyl-N - [[[3 - [[(4-methylphenyl) sulfonyl] oxy] phenyl] amino] carbonyl] - benzenesulfonamide (trade name Pergafast 201 ®, BASF ) is characterized by the
- WO 2014/080615 A1 discloses developers with urea and sulfonamide substructures, which in addition to a good dynamic
- non-phenolic developers are a higher structural complexity of the molecules as compared to the (bis) phenolic developers. This usually requires a multi-step synthesis in the Production and the need to use a larger number of often expensive raw materials. All these factors adversely affect the manufacturing costs and the price of such materials and prevent the use of such materials on a broad basis.
- heat-sensitive recording materials are primarily concerned with the following aspects: a) the stability of the unprinted ("white”) heat-sensitive recording material in the case of long-term storage and / or severe climatic conditions, in particular with regard to the retention of the specified dynamic response values and White, and b) the resistance of the typeface generated by the thermal pressure, which should in particular withstand the (even longer-term) effect of temperature, atmospheric oxygen, light, moisture, hydrophobic agents, etc. (archiving capability).
- the requirements mentioned under a) relate to the constancy of the composition of the heat-sensitive color-forming layer, in particular the chemical resistance of the color-forming components, even during long-term storage and under severe climatic conditions
- the requirements mentioned under b) are aimed at the stability of the during the printing process in the heat-sensitive color-forming layer forming color complex.
- thermosensitive recording materials with color developers based on sulfonylureas meet the requirements mentioned under b), but show weaknesses in terms of the requirements listed under a).
- the sulphonylureas are chemically unstable, especially in the presence of water. This tendency to decompose the sulfonylureas over a wide pH range is known and well documented (AK Sarmah, J. Sabadie, J. Agric. Food Chem., 50, 6253 (2002)).
- Object of the present invention is therefore to overcome the above-described disadvantages of the prior art.
- the object of the present invention is to provide a heat-sensitive recording material, which uses inexpensive from readily available raw materials and partly produced by one-step syntheses, non-phenolic color developer.
- the heat-sensitive recording material is a balanced
- the object of the present invention is therefore a
- Color developers which can be easily synthesized to provide, while this a balanced performance ratio with respect to various
- the at least one color developer comprises a compound of the formula (I)
- Ar is an aryl radical, a heteroaryl radical or a benzyl radical and Y is an aryl radical, a heteroaryl radical, a benzyl radical, an aryloxy radical, a heteroaryloxy radical, a benzyloxy radical, is an arylamino radical, a heteroarylamino radical or a benzylamino radical.
- aryl radical is meant a monovalent atomic group derived from aromatic hydrocarbons by removal of one attached to the ring
- heteroaryl radical a monovalent atomic group derived from heteroaromatic hydrocarbons by removal of a hydrogen atom bound to the ring.
- benzyl radical is meant a -CH 2 -C 6 H 5 group.
- An aryloxy radical (Ar-O-) is understood as meaning a monovalent atomic group in which an aryl radical is bonded to a molecule via an oxygen atom.
- heteroaryloxy radical is meant a monovalent atomic group in which a heteroaryl radical is attached to a molecule via an oxygen atom.
- benzyloxy group is meant an -OCH 2 -C 6 H 5 group.
- An arylamino radical (Ar-NH-) is understood as meaning a monovalent atomic group in which an aryl radical is bonded to a molecule via an NH group via the nitrogen.
- a heteroarylamino radical is understood to mean a monovalent atomic group in which a heteroaryl radical is bonded to a molecule via an NH group via the nitrogen.
- a benzylamino group is meant a -NHCH 2 -C 6 H 5 group.
- Ar may be unsubstituted or substituted.
- the substitution can be single or multiple.
- the substituents may be the same or different.
- C 1 -C 5 -alkyl preferably methyl and ethyl radicals, C 2 -C 5 -alkenyl, C 2 -C 5 -alkynyl, alkoxy (RO), halide, carboxyl (ROCO -), cyanide, Ar 0 2 SO-, nitro and / or -NH-CO-NH-Ari radicals, wherein R is a Ci-C 5 alkyl, preferably a methyl and / or ethyl radical is a C 2 -C 5 alkenyl, a C 2 -C 5 alkynyl or a phenyl radical and wherein Ari is an aromatic radical, preferably a phenyl radical, which is optionally substituted by one or more Ci-C 5 Alkyl, preferably methyl and / or ethyl radicals, C 2 -C 5 alkenyl, and / or C 2 -C 5 alkynyl radicals is substituted.
- R
- Ar is an aryl radical, in particular a phenyl, a 1- or a 2-naphthyl radical.
- Y is an aryl radical, in particular a phenyl, a 1- or a 2-naphthyl radical, or an arylamino radical, in particular a phenylamino or a naphthylamino radical.
- Ar is a phenyl radical and Y is a phenyl or a phenylamino radical.
- Ar is a 4-methoxycarbonylphenyl radical and Y is a phenyl or a phenylamino radical.
- thermosensitive recording material selected from the group consisting of N-phenyl-N '[(phenylamino) sulfonyl] urea, N- (4-methylphenyl) -N' [(4-methylphenylamino) sulfonyl] urea, N- (4- ethoxycarbonylphenyl) -N '[(4-ethoxycarbonylphenylamino) sulfonyl] urea, N- (1-naphthyl) -N' [(1-naphthylamino) sulfonyl] urea, N - [(phenylamino) sulfonyl] benzamide, N- [(4-methoxycarbonylphenyl) aminosulfonyl] benzamide, N - ( ⁇ 2 - [(phenylcarbamoyl) amino] phenyl ⁇ sulfamoy
- the compounds of the formula I can be prepared by known processes.
- the compound of formula (I) is preferably present in an amount of from about 3 to about 35% by weight, more preferably in an amount of from about 10 to about 25% by weight, based on the total solids content of the heat-sensitive layer.
- the carrier substrate is not critical. However, it is preferred to use paper, synthetic paper and / or a plastic film as the carrier substrate.
- at least one further intermediate layer is present between the carrier substrate and the heat-sensitive layer.
- heat-sensitive recording material according to the invention, wherein these layers are applied to the front or back of the substrate.
- the present invention is also not subject to any significant restrictions.
- the color former is preferably one
- Triphenylmethane type, fluoran type, azaphthalide type and / or fluorene type dyes are particularly preferred.
- a particularly preferred color former is a fluoran-type dye because of its availability and balanced properties
- fluoran-type dyes are:
- color formers may be used individually as well as mixtures of two or more
- At least two compounds covered by formula I are present as color developers.
- one or more further (bis) phenolic or non-phenolic color developers may be present in the heat-sensitive color-forming layer in addition to the compound (s) of formula (I).
- the one or more other non-phenolic color developers are preferably 4-methyl-N - [[[3 - [[(4-methylphenyl) sulfonyl] oxy] phenyl] amino] carbonyl] benzenesulfonamide or N- [2 - [[(phenylamino) carbonyl] amino] phenyl] benzenesulfonamide.
- one or more sensitizers also called thermal solvents
- one or more sensitizers may be present in the heat-sensitive color-forming layer, which has the advantage that the control of the thermal pressure sensitivity is easier to implement.
- suitable sensitizing agents are substances whose melting point is between about 90 and about 150 ° C. and which in the molten state dissolve the color-forming components (color former and color developer) without disturbing the formation of the color complex.
- the sensitizer is a fatty acid amide, such as stearamide,
- Beheneamid or palmitamide an ethylene-bis-fatty acid amide, such as N, N'-ethylene-bis-stearic acid amide or ⁇ , ⁇ '-ethylene-bis-oleic acid amide, a wax, such as polyethylene wax or montan wax, a carboxylic acid ester, such as dimethyl terephthalate,
- at least one stabilizer is present in the heat-sensitive color-forming layer.
- the stabilizer is preferably sterically hindered phenols, more preferably l, l, 3-tris (2-methyl-4-hydroxy-5-cyclohexyl-phenyl) -butane, l, l, 3-tris ( 2-methyl-4-hydroxy-5-tert-butylphenyl) -butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butyl-phenyl) -butane.
- the stabilizer is preferably present in an amount of from 0.2 to 0.5 parts by weight, based on the at least one phenol-free color developer of the compound of the formula (I).
- at least one binder is present in the heat-sensitive color-forming layer.
- These are preferably water-soluble starches, starch derivatives, starch-based biomatices of the EcoSphere® type, methylcellulose, hydroxyethylcellulose, carboxymethylcelluloses, partially or completely saponified polyvinyl alcohols, chemically modified
- At least one release agent (anti-sticking agent) or lubricant is present in the heat-sensitive color-forming layer.
- These agents are preferably fatty acid metal salts, such as. As zinc stearate or calcium stearate, or else behenate salts, synthetic waxes, z. B. in the form of fatty acid amides, such as. Stearic acid amide and behenic acid amide,
- Fatty acid alkanolamides e.g. Stearic acid methylolamide, paraffin waxes of various melting points, ester waxes of different molecular weights, ethylene, waxes, propylene waxes of different hardnesses and / or natural waxes, such as. As carnauba wax or montan wax.
- the heat-sensitive color-forming layer contains pigments.
- pigments can fix the chemical melt produced in the thermal printing process on their surface.
- pigments can control the surface whiteness and opacity of the heat-sensitive color-forming layer and their printability with conventional inks.
- pigments have an "extender function", for example, for the relatively expensive coloring
- pigments are inorganic pigments of both synthetic and natural origin, preferably clays, precipitated or natural calcium carbonates, aluminum oxides, aluminum hydroxides, silicas, precipitated and pyrogenic silicic acids (eg Aerodisp® types), diatomaceous earths,
- optical brighteners may be incorporated in the heat-sensitive color-forming layer. These are preferably silene bene.
- the mandatory constituents of the heat-sensitive recording material according to the invention further constituents, in particular rheology aids such. As thickeners and / or surfactants to add.
- the surface application weight of the (dry) heat-sensitive layer is preferably about 1 to about 10 g / m 2 , preferably about 3 to about 6 g / m 2 .
- the heat-sensitive recording material is one according to claim 2, wherein a colorant of the flurane type is used and additionally a sensitizer selected from the group consisting of fatty acid amides, aromatic sulfones and / or aromatic ethers , is present.
- a sensitizer selected from the group consisting of fatty acid amides, aromatic sulfones and / or aromatic ethers .
- the heat-sensitive recording material according to the invention can be obtained by known production methods.
- the recording material of the present invention by a method of applying and drying, on a support substrate, an aqueous suspension containing the starting materials of the heat-sensitive color-forming layer, the aqueous application suspension comprising
- Solids content of about 20 to about 75 wt .-%, preferably from about 30 to about 50 wt.%, And applied by the curtain coating coating process at an operating speed of the coater of at least about 400 m / min and dried.
- This method is particularly advantageous from an economic point of view.
- curtain-coating method is known to the person skilled in the art and is characterized by the following criteria:
- DE 10196052 Tl discloses the use of the curtain-coating process in the production of information recording materials, among others. also of heat-sensitive recording materials, wherein multi-layered recording layers are formed by applying the curtain consisting of several coating dispersion films to substrates (Geschmax max 200 m / min).
- the setting of the operating speed of the coater to at least about 400 m / min has both economic and technical advantages.
- the operating speed is particularly preferably at least about 750 m / min, very particularly preferably at least about 1000 m / min and very particularly preferably at least about 1500 m / min. It was particularly surprising that even at the latter speed, the resulting heat-sensitive recording material is impaired in any way and that the operation is carried out optimally even at this high speed.
- the aqueous deaerated application suspension has a viscosity of about 150 to about 800 mPas (Brookfield, 100 rpm, 20 ° C). If the value falls below about 150 mPas or exceeds the value of about 800 mPas, then this leads to a poor runnability of the coating on the coating unit. More preferably, the viscosity of the aqueous deaerated application suspension is about 200 to about 500 mPas.
- the surface tension of the aqueous application suspension may be about 25 to about 60 mN / m, preferably about 35 to about 50 mN / m (measured according to the static ring method according to Du Noüy, DIN 53914).
- the formation of the heat-sensitive color-forming layer can be done on-line or in a separate coating process off-line. This also applies to any subsequently applied layers or intermediate layers.
- the dried heat-sensitive color-forming layer is subjected to a smoothing action.
- the smoothing of the surface of the recording material preferably takes place with a shoe calender according to DE 10 2004 029 261 B4. It is advantageous here to adjust the Bekk smoothness, measured in accordance with ISO 5627, to about 100 to about 1000 seconds, preferably to about 250 to about 600 seconds.
- the surface roughness (PPS) according to ISO 8791-4 is preferably in the range of about 0.50 to about 2.50 pm, particularly preferably between 1.00 and 2.00 pm.
- the present invention also relates to a heat-sensitive recording material obtainable by the above-described method.
- the process described above is advantageous from an economic point of view and allows a high process control of the coating system even at a speed of more than 1500 m / min, without causing any impairment of the process product, that is the heat-sensitive invention
- Recording material comes.
- the process can be done on-line and off-line, resulting in desirable flexibility.
- the heat-sensitive recording material according to the invention is phenol-free, and well suited for POS (point-of-sale) and / or label applications. It is also suitable for the production of parking tickets, tickets, tickets, lottery and betting tickets, etc., which can be printed in direct thermal processes and a high resistance of the images recorded thereon under long-term storage, even under severe climatic conditions in terms of temperature and ambient humidity, and the contacting the typeface with hydrophobic substances such as plasticizers, greasy or oily substances, etc., guaranteed.
- POS point-of-sale
- the heat-sensitive recording material according to the invention is phenol-free, and well suited for POS (point-of-sale) and / or label applications. It is also suitable for the production of parking tickets, tickets, tickets, lottery and betting tickets, etc., which can be printed in direct thermal processes and a high resistance of the images recorded thereon under long-term storage, even under severe climatic conditions in terms of temperature and ambient humidity, and the contacting the typeface
- Base paper (Yupo® FP680) of 63 g / m 2 (coating formulations Rl, R2) or of a primer-bearing paper of 45 g / m 2 (coating formulations R3 to RH), the precoat with organic hollow-sphere pigments (of the Ropaque TM type) was formulated. After drying, a thermal recording sheet was obtained. The application amount of the heat-sensitive color-forming layer was from 4.0 to 4.5 g / m 2 .
- the aqueous application suspension was applied to a paper web having a basis weight of 43 g / m 2 by means of the curtain-coating process.
- the viscosity of the aqueous coating suspension was 450 mPas (Brookfield, 100 rpm, 20 ° C.) (in the deaerated state).
- the drying process of the coated paper support was carried out in a customary manner.
- the basis weight of the dry heat-sensitive layer was 4.0 - 4.5 g / m 2 .
- aqueous dispersion AI color former dispersion
- ODB-2 3-Nn-dibutylamine-6-methyl-7-anilinofluoran
- Aqueous dispersion A2 (2-component color former dispersion) is a mixture of two color formers which is prepared by mixing a first dispersion which has been prepared by milling 12 parts by weight of 3-Nn-dibutylamine-6-methyl-7-anilinofluoran (ODB).
- ODB 3-Nn-dibutylamine-6-methyl-7-anilinofluoran
- the aqueous dispersion Bl (color developer dispersion) is prepared by milling 40 parts by weight of the color developer along with 66 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in the bead mill.
- the aqueous dispersion B2 (2-component color developer dispersion of FE I and FE II) was prepared by mixing a first dispersion prepared by milling 20 parts of FE I with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in one Bead mill and a second color developer dispersion prepared by milling 20 parts by weight of FE II with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a bead mill (in terms of
- the aqueous dispersion B3 (2-component color developer dispersion of FE I and FE II) was prepared by mixing a first dispersion obtained by milling 28 parts FE I with 46 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in one Bead mill and a second color developer dispersion prepared by milling 12 parts by weight FE II with 20 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a bead mill.
- aqueous dispersion C (sensitizer dispersion) was prepared by milling 40 parts by weight sensitizer with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a bead mill.
- the aqueous dispersion D antioxidant or stabilizer dispersion
- UU urea urethanes
- Ghosenex TM L-3266 urea urethanes
- All dispersions produced by milling have an average particle size D (4i3) of 0.80-1.20 pm.
- the dispersion E is a 20% zinc stearate dispersion consisting of 9 parts by weight of Zn stearate, 1 part by weight of Ghosenex TM L-3266 and 40 parts by weight of water.
- Pigment PI is a 72% coating kaolin suspension (Lustra ® S, BASF)
- Pigment P2 is a 56% PCC dispersion (precipitated calcium carbonate)
- Pigment P3 is a 56% aluminum hydroxide dispersion (Marti Gloss ®, Albemarle Corp.)
- P4 pigment is obtained by adding to 132 parts of a 56% dispersion Aluminiumhydroxyd- (Marti Gloss ®, Albemarle Corp.) 31.5 parts of a precipitated silica
- the binder consists of a 10% aqueous polyvinyl alcohol solution (Mowiol 28-99, Kuraray Europe)
- the application suspension is prepared by mixing while stirring the dispersions
- Table 2 summarizes the developers used in the example formulations.
- thermal recording materials shown in Tables 3, 4 and 5 were evaluated as follows.
- the paper white line on the strip side was determined according to DIN / ISO 2470 with an Elrepho 3000 spectrophotometer.
- the papers (6 cm wide strips) were thermally scanned using the Atlantek 200 test printer (Atlantek, USA) with a Kyocera print bar of 200 dpi and 560 ohms at an applied voltage of 20.6 V and a maximum pulse width of 0.8 ms printed with a chessboard pattern with 10 energy gradations.
- the image density (optical density, o.D.) was measured with a Macbeth densitometer RD-914, by Gretag.
- the recording sheet is pressed against a series of thermostated metallic dies at different temperatures with a contact pressure of 0.2 kg / cm 2 and a contact time of 5 seconds (TP 3000QM thermal tester,
- the image density (optical density) of the images thus obtained is measured with a Macbeth densitometer RD-914 from Gretag.
- the static starting point is by definition the lowest temperature at which an optical density of 0.2 is reached.
- a sheet of recording paper is cut into three identical strips.
- a stripe is dynamically recorded and the image density determined according to the method of (2).
- the other two strips are in the unprinted (white) state for 4 weeks a climate of 60 ° C and 50% rel. Exposed to humidity.
- a plasticizer-containing cling film (PVC film with 20-25% dioctyl adipate) was brought into contact with wrinkles and trapped air, wound into a roll and left at room temperature for 16 hours (20-22 ° C) stored. After removal of the film, the image density (o. D.) was measured and
- Detector Sample preparation: From the paper sample, 2 circular surfaces are punched out and weighed with a punching iron. The paper samples are extracted with 3 ml of acetonitrile (HPLC grade) in an ultrasonic bath for 30 min. And the extract is filtered through a PTFE syringe filter (0.45 ⁇ m).
- Acetonitrile THF: H 2 O (450: 89: 200 parts by wt.) Eluted with acetonitrile gradient.
- Quantitative analysis of the chromatograms takes place via the area comparison of the sample peaks assigned over tr times with a calibration straight line determined via the reference patterns.
- the measurement error in the HPLC quantification is ⁇ 2%.
- Table 3 summarizes the evaluation of synthetic paper (Yupo® FP680) as the carrier, Table 4, the evaluation of the recording materials made with a prepainted carrier paper together.
- FEI is FEIO
- FEII is FEI
- the heat-sensitive recording material according to the invention shows
- the recorded image of the heat-sensitive recording materials according to the invention with the color developer according to the invention has a max.
- Print density which corresponds to the print density of the comparative samples (max oD values from Tables 3, 4), is stable under the conditions of artificial aging and scarcely fades after exposure to hydrophobic agents (adhesives, plasticizers), comparable to the performance of the known ones phenolic developing agents (Tables 3, 4).
- Heat-sensitive recording materials according to the present invention (static starting point, Tables 3, 4) is comparable or higher than in the comparative papers even when using
- the heat-sensitive recording material of the present invention shows a slight drop in writing performance after four weeks of unprinted storage under extreme storage conditions
- thermosensitive recording materials with each other or with known non-phenolic developers lead to no disadvantages in terms of surface whiteness or starting temperature and can be advantageously used to specifically improve performance characteristics and / or to control the economics of the color development system of the heat-sensitive recording material according to the invention.
- the production method according to the invention makes it possible, in particular a heat-sensitive recording material of high quality in all important application-related matters, to be economical
- heat-sensitive recording material according to the invention is to make all important properties optimally.
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- Inorganic Chemistry (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102015104306.8A DE102015104306B4 (de) | 2015-03-23 | 2015-03-23 | Wärmeempfindliches Aufzeichnungsmaterial |
PCT/DE2016/100101 WO2016150428A1 (de) | 2015-03-23 | 2016-03-07 | Wärmeempfindliches aufzeichnungsmaterial |
Publications (2)
Publication Number | Publication Date |
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EP3274184A1 true EP3274184A1 (de) | 2018-01-31 |
EP3274184B1 EP3274184B1 (de) | 2021-05-05 |
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EP16717087.7A Active EP3274184B1 (de) | 2015-03-23 | 2016-03-07 | Wärmeempfindliches aufzeichnungsmaterial |
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US (1) | US10265985B2 (de) |
EP (1) | EP3274184B1 (de) |
JP (1) | JP6709227B2 (de) |
KR (1) | KR102012459B1 (de) |
CN (1) | CN107454874B (de) |
BR (1) | BR112017020441B1 (de) |
DE (1) | DE102015104306B4 (de) |
ES (1) | ES2883073T3 (de) |
WO (1) | WO2016150428A1 (de) |
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KR20180133244A (ko) | 2016-02-16 | 2018-12-13 | 더 유니버서티 어브 퀸슬랜드 | 설포닐유레아 및 관련 화합물 및 이의 용도 |
EP3523134A1 (de) | 2016-10-07 | 2019-08-14 | Mitsubishi HiTec Paper Europe GmbH | Wärmeempfindliches aufzeichnungsmaterial |
EP3305538A1 (de) | 2016-10-07 | 2018-04-11 | Mitsubishi HiTec Paper Europe GmbH | Wärmeempfindliches aufzeichnungsmaterial |
DE102017102702B4 (de) * | 2017-02-10 | 2019-09-12 | Papierfabrik August Koehler Se | Wärmeempfindliches Aufzeichnungsmaterial |
DE102018102177A1 (de) * | 2018-01-31 | 2019-08-01 | Mitsubishi Hitec Paper Europe Gmbh | Beschichtungszusammensetzung, wärmeempfindliche Aufzeichnungsschicht, wärmeempfindliches Aufzeichnungsmaterial sowie entsprechende Verwendungen und Verfahren |
DE102018102180A1 (de) | 2018-01-31 | 2019-08-01 | Mitsubishi Hitec Paper Europe Gmbh | Wärmeempfindliches Aufzeichnungsmaterial |
DE102018133168B4 (de) * | 2018-12-20 | 2021-02-18 | Papierfabrik August Koehler Se | Wärmeempfindliches Aufzeichnungsmaterial |
KR102004118B1 (ko) * | 2019-01-16 | 2019-07-25 | 최영규 | 감열지 제조방법 및 이로부터 제조된 감열지 |
DE102019126220A1 (de) | 2019-09-27 | 2021-04-01 | Mitsubishi Hitec Paper Europe Gmbh | Wärmeempfindliches Aufzeichnungsmaterial, umfassend phenolfreie organische Farbentwickler |
EP3957488A1 (de) | 2020-08-19 | 2022-02-23 | Mitsubishi HiTec Paper Europe GmbH | Wärmeempfindliches aufzeichnungsmaterial sowie wärmeempfindliche aufzeichnungsschicht und beschichtungszusammensetzung zu seiner herstellung, entsprechende verwendungen und verfahren |
DE102023104323A1 (de) | 2022-02-22 | 2023-08-24 | Mitsubishi Hitec Paper Europe Gmbh | Beschichtung für ein umweltfreundliches wärmeempfindliches Aufzeichnungsmaterial |
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-
2015
- 2015-03-23 DE DE102015104306.8A patent/DE102015104306B4/de not_active Expired - Fee Related
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2016
- 2016-03-07 JP JP2017546887A patent/JP6709227B2/ja active Active
- 2016-03-07 KR KR1020177030452A patent/KR102012459B1/ko active IP Right Grant
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- 2016-03-07 WO PCT/DE2016/100101 patent/WO2016150428A1/de active Application Filing
- 2016-03-07 EP EP16717087.7A patent/EP3274184B1/de active Active
- 2016-03-07 US US15/560,060 patent/US10265985B2/en active Active
- 2016-03-07 ES ES16717087T patent/ES2883073T3/es active Active
- 2016-03-07 BR BR112017020441-0A patent/BR112017020441B1/pt active IP Right Grant
Also Published As
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KR102012459B1 (ko) | 2019-10-21 |
ES2883073T3 (es) | 2021-12-03 |
JP2018513794A (ja) | 2018-05-31 |
US10265985B2 (en) | 2019-04-23 |
EP3274184B1 (de) | 2021-05-05 |
KR20170129257A (ko) | 2017-11-24 |
DE102015104306A1 (de) | 2016-09-29 |
BR112017020441A2 (pt) | 2018-07-03 |
WO2016150428A1 (de) | 2016-09-29 |
CN107454874B (zh) | 2019-06-14 |
JP6709227B2 (ja) | 2020-06-10 |
BR112017020441B1 (pt) | 2022-07-26 |
CN107454874A (zh) | 2017-12-08 |
DE102015104306B4 (de) | 2018-05-03 |
US20180079243A1 (en) | 2018-03-22 |
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