EP2329958B1 - Heat sensitive recording material with reverse coating - Google Patents
Heat sensitive recording material with reverse coating Download PDFInfo
- Publication number
- EP2329958B1 EP2329958B1 EP20090177677 EP09177677A EP2329958B1 EP 2329958 B1 EP2329958 B1 EP 2329958B1 EP 20090177677 EP20090177677 EP 20090177677 EP 09177677 A EP09177677 A EP 09177677A EP 2329958 B1 EP2329958 B1 EP 2329958B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- sensitive recording
- recording material
- side coating
- material according
- 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.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims description 64
- 239000011248 coating agent Substances 0.000 title claims description 62
- 239000000463 material Substances 0.000 title claims description 45
- 239000010410 layer Substances 0.000 claims description 56
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 50
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 35
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 23
- 239000000049 pigment Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 13
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 18
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000008199 coating composition Substances 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- -1 3-tolylamino Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 231100000489 sensitizer Toxicity 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XAAILNNJDMIMON-UHFFFAOYSA-N 2'-anilino-6'-(dibutylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CCCC)CCCC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 XAAILNNJDMIMON-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000470 constituent Substances 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
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- JWSWULLEVAMIJK-UHFFFAOYSA-N 1-phenylmethoxynaphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1=CC=CC=C1 JWSWULLEVAMIJK-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 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 2
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 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 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- 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 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- 238000000586 desensitisation Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 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 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 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
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-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
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-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
- 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
- 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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 241000294754 Macroptilium atropurpureum Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- IRWGLNFPSKUEMS-UHFFFAOYSA-N n-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)sulfanylacetamide Chemical compound C1=CC(O)=CC=C1SCC(=O)NC1=CC=CC=C1O IRWGLNFPSKUEMS-UHFFFAOYSA-N 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the 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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/36—Backcoats; Back layers
Definitions
- the invention relates to a heat-sensitive recording material having a substrate which carries on its first side at least one heat-sensitive recording layer, which in turn has at least one dye precursor and at least one color acceptor, which react color-forming with one another under the action of heat.
- the substrate carries on its second side opposite the first side a backside coating.
- a heat-sensitive recording material of the type specified above is known from DE-C-38 36 660 known.
- the backside coating can here be formed from water-soluble high polymers, such as starch, gelatin, styrene-maleic anhydride copolymer hydrolysates or polyvinyl alcohol, and from water-insoluble polymers, such as latexes. The polymers are used alone or as a mixture.
- the known backside coating is to prevent that when using the known recording material as a label, in particular plasticizers which are present on a provided with the label sheet can penetrate from the back of the recording layer and thus a weakening or deletion of a possible Effect typeface.
- the barrier layer comprises substantially water-soluble polymer materials such as polyvinyl alcohol, various cellulose ethers, starch, gelatin, casein, and polyvinylpyrrolidone, as well as water-dispersed resins such as polystyrene emulsions.
- the function of the barrier layer is to protect against materials such as oils and plasticizers, which are known to cause the image and / or decolorization of the images developed in the recording layer.
- the backside coating of the known recording material comprises a mixture containing starch, an acrylate copolymer comprising no styrene or vinyl acetate components having a film-forming temperature of less than 5 ° C and preferably less than 2 ° C, and an alkaline catalyst such as calcium carbonate.
- the reverse side of the proposed heat-sensitive recording material should be easy to print in the offset and flexographic printing processes without problems, which means without the occurrence of "mottling” or even "missing dots" in the sense of the present invention.
- thermosensitive recording material with a back coat containing ethylene-vinyl alcohol copolymer (EVOH).
- EVOH ethylene-vinyl alcohol copolymer
- thermosensitive recording material in which the substrate is embedded in a non-claimed, but considered possible embodiment between two ozone-impermeable layers.
- EVOH ethylene-vinyl alcohol copolymer
- the use of ethylene-vinyl alcohol copolymer (EVOH) in a backside coating must be considered as obvious, although the Proposals of this document are not aimed at improving printing possibilities for heat-sensitive recording materials, but at improving their light resistance.
- the at least first backcoat of the heat-sensitive recording material according to the invention comprises in a first embodiment preferably at least 90% by weight, most preferably at least 98% by weight, based in each case on the total weight of the backcoat, of the ethylene-vinyl alcohol copolymer.
- Further constituents of this at least first backside coating are, for example, defoamers and / or agents for stabilizing the color curtain when the coating composition is applied by means of curtain or slide coaters.
- the at least first backcoat layer comprises at least 80% by weight, based on the total weight of this backcoat layer, of the ethylene-vinyl alcohol copolymer and also of the pigment and, with very particular preference, of calcium carbonate.
- the coating weight for the at least first ethylene-vinyl alcohol copolymer-based backcoat layer is preferably in a range of 0.9 to 5.0 g / m 2 , most preferably in a range of 1.5 to 3.5 g / m 2 .
- Particularly suitable brushing compositions for the application of this backcoat coating are, in particular, contactless application devices such as air brushes and curtain coaters or slide coaters, without being limited to these in any way.
- the heat-sensitive recording material according to the invention has, in addition to the first backcoat on the basis of ethylene-vinyl alcohol copolymer on another backside coating, which is then applied to the previously applied back coating with the ethylene-vinyl alcohol copolymer.
- the further backside coating is formed as a pigmented backside coating containing calcium carbonate as a pigment.
- the first backcoat based on ethylene-vinyl alcohol copolymer is that of the second embodiment according to paragraph [0012] which contains at least 80% by weight of the ethylene-ynyl alcohol copolymer and Pigment calcium carbonate has.
- both the calcium carbonate optionally incorporated in the first ethylene vinyl alcohol copolymer backcoat layer and the calcium carbonate of the further backside coating have a respective average particle size (Malvern) in a preferred range of zero , 9 microns to 1.25 microns, most preferably in a range of 1.0 microns to 1.2 microns.
- precipitated calcium carbonate in both the first backcoat on the basis of ethylene-vinyl alcohol copolymer as well as in the other backside coating is considered to be very particularly preferred, with a platelet-like particulate form being advantageous both for a particularly convincing appearance of the rear side of the invention heat-sensitive recording material as well as a good barrier effect of this back has been recognized.
- the further backcoat layer may additionally contain, as pigment, preferably organic, so-called hollow-body pigments. It is then particularly advantageous if the pigment mixture within the further backside coating to 35 to 50 wt.% Or even better to 38 to 45 wt .-% of organic and to 65 to 50 wt .-% or even better to 62 up to 55% by weight Calcium carbonate consists, wherein the wt.% Relate to the total amount of pigment in the further backside coating.
- binder of the further backside coating is considered a combination of (carboxy) methylcellulose and styrene-butadiene latex as preferred, ideally supplemented by corn starch.
- roll-bar coater, knife coater, curtain coater or slide coater or air brush are particularly suitable, knife coater and, in particular, roller coater coating being considered very preferred.
- the basis weight of the further backside coating is preferably between 1 and 20 g / m 2, and more preferably between 3.0 and 8.0 g / m 2 .
- both the first backside coating based on ethylene-vinyl alcohol copolymer and the further backside coating can be applied with two, preferably identical, coating units.
- both backcoats wet-on-wet for which, in particular, a curtain coater system or a slide coater is offered.
- the heat-sensitive recording layer of the heat-sensitive recording material according to the invention may likewise include in principle all color acceptors suitable for the possible, in particular the preferred, dye precursors, in particular organic color acceptors.
- the heat-sensitive recording layer has at least one color acceptor selected from the list comprising: 2,2 bis (4-hydroxyphenyl) propane, 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol, 4-hydroxy 4'-isopropoxydiphylsulfone, 4,4'-dihydroxy-diphenylsulfone, 2,4'-dihydroxy-diphenylsulfone, N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) -thio] -acetamide and N- (p-) toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to the following formula (1),
- N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea is known as Pergafast ® 201 from Ciba Specialty Chemicals Inc.
- the recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness.
- Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, Dibenzyl oxalate, benzyl naphthyl ether and diphenyl sulfone, with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 1,2-di (phenoxy) ethane being preferred.
- Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
- water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
- Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer.
- binders for incorporation into the heat-sensitive recording layer.
- polyvinyl alcohol in conjunction with acrylate copolymer as particularly preferred binders, which are incorporated together, based on the total weight of the recording layer, in a range of 12 to 21 wt.% In the heat-sensitive recording layer.
- the coating composition for forming the thermosensitive recording layer may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax.
- slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax.
- the recording layer is, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, which is preferably incorporated in the recording layer in an amount of 10 to 18% by weight, based on the total weight of the recording layer should be considered as preferred.
- the basis weight of the heat-sensitive recording layer is usually between 2.5 and 12 g / m 2, and more preferably between 2.8 and 6.5 g / m 2 .
- a brush for applying the heat-sensitive recording layer in particular, offer a doctor blade and (roll) doctor blade coater, curtain coater and air brush.
- a pigment-containing intermediate layer between the substrate and the heat-sensitive recording layer.
- pigments of the intermediate layer both organic void pigments and inorganic pigments have proven useful, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide, in particular boehmite here.
- such an intermediate layer can make a positive contribution to the leveling of the substrate surface, which reduces the amount of coating color necessarily required for the heat-sensitive recording layer. For this reason, offer to coat the intermediate layer leveling strokes, such as roller coater, doctor blade and (roll) doctor blade coating.
- the pigments of this intermediate layer can absorb the heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording.
- the basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
- the recording material according to the invention may furthermore have a protective layer which is applied to the heat-sensitive recording layer and completely or partially covers it.
- the protective layer takes on a task, as it must also be partially fulfilled by the backside coating, namely on the one hand, the protection of the arranged below her recording layer before organic solvents as well as oils, fats, water and plasticizers.
- paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention.
- a paper web of bleached and ground deciduous and softwood pulps with a basis weight of 130 g / m 2 with the addition of conventional additives in conventional amounts is first prepared on a fourdrinier paper machine as a substrate.
- a mainly calcined kaolin and organic void pigments as pigment mixture, styrene-butadiene latex as binder and starch as co-binder-containing intermediate layer of 8 g / m 2 is applied online within the paper machine with a roller blade coating unit.
- a heat-sensitive recording layer having a basis weight of 4.2 g / m 2 is applied to the pigment-containing intermediate layer by means of a doctor blade coater.
- the coating material used essentially contains the following components: Dye precursors: 3-dibutylamino-6-methyl-7-anilinofluoran, that is ODB-2; color acceptor: N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea, that is Pergafast® 201; sensitizer: Benzylnaphthyl ether, that is BNE; Binder: polyvinyl alcohol; co-binders: Acrylate copolymer; Pigment: Calcium carbonate.
- a protective layer of 2.0 g / m 2 is applied by means of air brush.
- the four coating compositions are now applied to the back of the substrate with a respective basis weight of 2 g / m 2 .
- 0.2 ml of ethanol is applied to the respective dried backcoat of the individual samples corresponding to the two inventive examples 1 and 2 and the two comparative examples 3 and 4 with a pipette. After an exposure time of 1 minute, the ethanol is absorbed and the effect of solvent application on the heat-sensitive recording layer is visually evaluated.
- the heat-sensitive recording layers of the two Inventive Examples 1 and 2 show no thermal reactions at all, the present invention is excellently confirmed in terms of quality.
- Comparative Example 3 there are intense thermal reactions, this backside coating is not at all suitable to develop a far-reaching barrier effect against organic solvents with this order quantity.
- Comparative Example 4 isolated color reaction points are formed on the heat-sensitive recording layer: below these colored dots, the back coat of the coating composition RS4 has cracks and voids due to the too high viscosity of the silanized polyvinyl alcohol. Again, the barrier effect against organic solvents is not convincing, because not without flaws.
- thermosensitive recording material finally expected by the inventors.
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Description
Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial mit einem Substrat, das auf seiner ersten Seite mindestens eine wärmeempfindliche Aufzeichnungsschicht trägt, die ihrerseits mindestens einen Farbstoffvorläufer und mindestens einen Farbakzeptor aufweist, welche unter Einwirkung von Wärme farbbildend miteinander reagieren. Gattungsgemäß trägt das Substrat auf seiner der ersten Seite gegenüberliegenden zweiten Seite eine Rückseitenbeschichtung.The invention relates to a heat-sensitive recording material having a substrate which carries on its first side at least one heat-sensitive recording layer, which in turn has at least one dye precursor and at least one color acceptor, which react color-forming with one another under the action of heat. Generically, the substrate carries on its second side opposite the first side a backside coating.
Ein wärmeempfindliches Aufzeichnungsmaterial der vorstehend angegebenen Art ist aus der
Eine vergleichbare Schutzwirkung erhofft sich dieDE-A-37 20 171 für die rückseitig aufgebrachte Sperrschicht eines vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials, das eine gefärbte Fluorezenzfarbstoffzusammensetzung in seiner Aufzeichnungsschicht aufweist. Die Sperrschicht umfasst im Wesentlichen wasserlösliche Polymermaterialien, wie Polyvinylalkohol, verschiedene Zelluloseether, Stärke, Gelatine, Kasein und Polyvinylpyrolidon sowie in Wasser dispergierte Harze, wie beispielsweise Polystyrolemulsionen. Die Funktion der Sperrschicht besteht im Schutz vor Materialien, wie Öle und Weichmacher, von denen bekannt ist, dass sie zur Ver-und/oder Entfärbung der in der Aufzeichnungsschicht entwickelten Bilder führen können.A comparable protective effect is expected from DE-A-3720171 for the back-coated barrier layer of a proposed thermosensitive recording material having a colored fluorescent dye composition in its recording layer. The barrier layer comprises substantially water-soluble polymer materials such as polyvinyl alcohol, various cellulose ethers, starch, gelatin, casein, and polyvinylpyrrolidone, as well as water-dispersed resins such as polystyrene emulsions. The function of the barrier layer is to protect against materials such as oils and plasticizers, which are known to cause the image and / or decolorization of the images developed in the recording layer.
Die gewünschte rückseitige Bedruckung eines wärmeempfindlichen Aufzeichnungsmaterials im Offset- und Flexodruckverfahren ist Grund für die gestellte Aufgabe in der
Gerade aus der zuletzt gewürdigten Schrift ist es also bekannt, die Rückseite von wärmeempfindlichen Aufzeichnungsmaterialien als Träger für Offset-Bedruckungen zu nutzen. Die aus dem Stand der Technik bekannten Aufzeichnungsmaterialien haben sich, was die Sperrwirkung gegenüber den hierbei zum Einsatz kommenden Chemikalien betrifft, durchaus bewährt. Nachteilig an den bisher bekannten Rückseitenbeschichtungen für wärmeempfindliche Aufzeichnungsmaterialien sind jedoch ganz häufig Verarbeitungsschwierigkeiten beispielsweise durch rheologische Besonderheiten der in der Regel selbstvernetzenden Beschichtungsmassen, die immer wieder zu Defiziten in der Oberflächengüte von der eine Barriere ausbildenden Rückseite von wärmeempfindlichen Aufzeichnungsmaterialien führen. Solche Defizite sind insbesondere eine Orangenhaut-ähnliche Rückseitenoberfläche, die bei einer Bedruckung im Offset- und/oder Flexodruckverfahren zu Ungleichmäßigkeiten im Erscheinungsbild, bekannt als "Mottling", und im schlimmsten Fall zu Druckfehlstellen, so genannten "Missing Dots", führt.Especially from the last acknowledged document, it is thus known to use the back of heat-sensitive recording materials as a carrier for offset printing. The recording materials known from the prior art have proven to be quite effective in terms of the barrier effect with respect to the chemicals used for this purpose. Disadvantages of the hitherto known backside coatings for heat-sensitive recording materials, however, are very often processing difficulties, for example due to rheological peculiarities of the generally self-crosslinking coating compositions, which again and again lead to deficits in the surface quality of the barrier-forming reverse side of heat-sensitive recording materials. Such deficits are, in particular, an orange peel-like back surface which, when printed in offset and / or flexographic printing processes, leads to unevenness in appearance, known as "mottling", and in the worst case to print defects, so-called "missing dots".
Gegenstand der vorliegenden Aufgabe ist es daher, der Öffentlichkeit ein wärmeempfindliches Aufzeichnungsmaterial mit einer Rückseitenbeschichtung zur Verfügung zu stellen, die eine Sperrwirkung gegenüber Weichmachern in selbstklebenden Beschichtungen für Etiketten und insbesondere eine ganz hervorragende Sperrwirkung gegenüber organischen Lösungsmitteln aufweist. Gleichzeitig soll die Rückseite des vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials im Offset- und Flexodruckverfahren ohne Probleme gut zu bedrucken sein, was im Sinne der vorliegenden Erfindung ohne das Auftreten von "Mottling" oder gar von "Missing Dots" heißt.It is therefore an object of the present invention to provide the public with a heat-sensitive recording material having a backcoat which has a blocking effect on plasticizers in self-adhesive coatings for labels and in particular a very outstanding barrier effect to organic solvents. At the same time, the reverse side of the proposed heat-sensitive recording material should be easy to print in the offset and flexographic printing processes without problems, which means without the occurrence of "mottling" or even "missing dots" in the sense of the present invention.
Nach intensiven Überlegungen sahen die Erfinder einen Ansatz darin, ein wärmeempfindliches Aufzeichnungsmaterial mit einer rückseitigen Beschichtung zu versehen, die Ethylen-Vinyl-Alkohol-Copolymer (EVOH) enthält. Der Rückgriff auf Ethylen-Vinyl-Alkohol-Copolymer war für die Erfinder deshalb völlig überraschend, da diese Substanz nie als mögliche Komponente für eine Barriere bildende Rückseitenbeschichtung von wärmeempfindlichen Aufzeichnungsmaterialien angesehen wurde und entsprechende Überlegungen auch nie ernsthaft angestellt wurden.After intensive consideration, the inventors saw an approach to provide a thermosensitive recording material with a back coat containing ethylene-vinyl alcohol copolymer (EVOH). The use of ethylene-vinyl alcohol copolymer was therefore completely surprising for the inventors, since this substance never as a possible component for a barrier-forming backcoat was considered by heat-sensitive recording materials and appropriate considerations were never made serious.
Jedoch ist aus der
In Anbetracht dieses Standes der Technik schlagen die Erfinder ein wärmeempfindliches Aufzeichnungsmaterial mit einem Substrat vor,
- das auf seiner ersten Seite mindestens eine wärmeempfindliche Aufzeichnungsschicht mit mindestens einem Farbstoffvorläufer und mindestens einem Farbakzeptor trägt, wobei Farbstoffvorläufer und Farbakzeptor unter Einwirkung von Wärme farbbildend miteinander reagieren,
- und das auf seiner zweiten Seite mindestens eine erste Rückseitenbeschichtung trägt, die Ethylen-Vinyl-Alkohol-Copolymer (EVOH) enthält,
- which carries on its first side at least one heat-sensitive recording layer having at least one dye precursor and at least one color acceptor, wherein the dye precursor and color acceptor react color-forming with the action of heat,
- and bearing on its second side at least a first backcoat comprising ethylene-vinyl alcohol copolymer (EVOH),
In verschiedenen Versuchen stellte sich jedoch die Überlegenheit der die Erfindung kennzeichnenden Beschichtung heraus. Einerseits verglichen mit einer Beschichtung auf der Basis von üblichem Polyvinylalkohol bildet eine Beschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer eine gegenüber organischen Lösemitteln und Weichmachern wesentlich verbesserte Barrierewirkung. Soll hingegen andererseits eine Barrierebeschichtung beispielsweise auf der Basis von hochmolekularem silanisiertem Polyvinylalkohol ausgebildet werden, spielen die sehr großen Verarbeitungsschwierigkeiten dieses silanisierten Polyvinylalkohols unter anderem in Folge seiner hohen Viskosität eine entscheidende Rolle:
- Wird eine starke wässerige Verdünnung des hochmolekularen Polyvinylalkohols innerhalb der Streichmasse zur Ausbildung der Rückseitenbeschichtung gewählt, ist deren Verarbeitung gut möglich, aber eine zufriedenstellende Abdeckung der Rückseite ist nicht gegeben: es kommt zu unkontrollierbaren Desensibilisierungs- oder Farbreaktionen in der wärmeempfindlichen Aufzeichnungsschicht wegen der von der Rückseite aus eindringenden Lösemittel oder Weichmacher, wenn diese rückseitig aufgebracht werden.
- Bei einer Reduzierung der wässerigen Verdünnung wird die Streichmasse zur Ausbildung der Rückseitenbeschichtung mehr und mehr zähflüssig: es drohen Beschichtungsfehler, wo es dann erneut zu unkontrollierbaren Desensibilisierungs- oder Farbreaktionen in der wärmeempfindlichen Aufzeichnungsschicht und/oder zu einer schleichenden Verstopfung in den Rohrzuleitungen hin zum Beschichtungsaggregat kommen kann.
- When a strong aqueous dilution of the high molecular weight polyvinyl alcohol is selected within the coating composition to form the backcoat layer, it is well possible to process them, but there is no satisfactory coverage of the back surface: uncontrollable desensitization or color reactions occur in the thermosensitive recording layer because of the back side from penetrating solvent or plasticizer when applied backside.
- With a reduction of the aqueous dilution, the coating composition becomes more viscous for the formation of the backside coating: coating defects threaten where again uncontrollable desensitization or color reactions in the heat-sensitive recording layer and / or creeping clogging in the pipe supply lines to the coating unit can.
Die mindestens erste Rückseitenbeschichtung des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials umfasst in einer ersten Ausführungsvariante bevorzugt zu mindestens 90 Gew.%, ganz besonders bevorzugt zu mindestens 98 Gew.-% - jeweils bezogen auf das Gesamtgewicht der Rückseitenbeschichtung, das Ethylen-Vinyl-Alkohol-Copolymer. Weitere Bestandteile dieser mindestens ersten Rückseitenbeschichtung sind dann beispielsweise Entschäumer und/oder Mittel zur Stabilisierung des Farbvorhangs bei Auftrag der Beschichtungsmasse mittels Curtain- bzw. Slide-Coaters.The at least first backcoat of the heat-sensitive recording material according to the invention comprises in a first embodiment preferably at least 90% by weight, most preferably at least 98% by weight, based in each case on the total weight of the backcoat, of the ethylene-vinyl alcohol copolymer. Further constituents of this at least first backside coating are, for example, defoamers and / or agents for stabilizing the color curtain when the coating composition is applied by means of curtain or slide coaters.
In einer zweiten Ausführungsvariante umfasst die mindestens erste Rückseitenbeschichtung zu mindestens 80 Gew.% - bezogen auf das Gesamtgewicht dieser Rückseitenbeschichtung - das Ethylen-Vinyl-Alkohol-Copolymer sowie femer Pigment und hier ganz besonders bevorzugt Kalziumkarbonat.In a second embodiment variant, the at least first backcoat layer comprises at least 80% by weight, based on the total weight of this backcoat layer, of the ethylene-vinyl alcohol copolymer and also of the pigment and, with very particular preference, of calcium carbonate.
Das Auftragsgewicht für die mindestens erste Rückseitenbeschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer liegt bevorzugt in einem Bereich von 0,9 bis 5,0 g/m2, ganz besonders bevorzugt in einem Bereich von 1,5 bis 3,5 g/m2. Als zum Auftrag dieser Rückseitenbeschichtung besonders geeignete Streichwerke kommen insbesondere kontaktlose Auftragsvorrichtungen wie Luftbürste sowie Curtain- bzw. Slide-Coater in Betracht, ohne darauf in irgendeiner Art und Weise beschränkt zu sein.The coating weight for the at least first ethylene-vinyl alcohol copolymer-based backcoat layer is preferably in a range of 0.9 to 5.0 g / m 2 , most preferably in a range of 1.5 to 3.5 g / m 2 . Particularly suitable brushing compositions for the application of this backcoat coating are, in particular, contactless application devices such as air brushes and curtain coaters or slide coaters, without being limited to these in any way.
Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial weist neben der ersten Rückseitenbeschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer eine weitere Rückseitenbeschichtung auf, die dann auf die zuvor aufgebrachte Rückseitenbeschichtung mit dem Ethylen-Vinyl-Alkohol-Copolymer aufgetragen ist. Die weitere Rückseitenbeschichtung ist dabei als pigmentierte Rückseitenbeschichtung ausgebildet, die Kalziumkarbonat als Pigment enthält.The heat-sensitive recording material according to the invention has, in addition to the first backcoat on the basis of ethylene-vinyl alcohol copolymer on another backside coating, which is then applied to the previously applied back coating with the ethylene-vinyl alcohol copolymer. The further backside coating is formed as a pigmented backside coating containing calcium carbonate as a pigment.
Es gilt als ganz besonders bevorzugt, wenn die erste Rückseitenbeschichtung auf der Basis von Ethyten-Vnyl-Alkohol-Copolymer jene der zweiten Ausführungsvariante gemäß Absatz [0012] ist, die zu mindestens 80 Gew.% das Ethylen-Ynyl-Alkohol-Copolymer sowie als Pigment Kalziumkarbonat aufweist.It is very particularly preferred if the first backcoat based on ethylene-vinyl alcohol copolymer is that of the second embodiment according to paragraph [0012] which contains at least 80% by weight of the ethylene-ynyl alcohol copolymer and Pigment calcium carbonate has.
Es wurde für diesen Fall femer als bevorzugte Ausführungsform erkannt, wenn (a) das Kalziumkarbonat der ersten Rückseitenbeschichtung und (b) das Kalziumkarbonat der weiteren Rückseitenbeschichtung hinsichtlich der jeweiligen Aufbereitungsform und hinsichtlich der jeweiligen physikalischen Merkmale gleich sind. Das soll beispielsweise bedeuten, dass sowohl das Kalziumkarbonat, das optional in der ersten Rückseitenbeschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer eingebunden ist, wie auch das Kalziumkarbonat der weiteren Rückseitenbeschichtung eine jeweilige mittlere Teilchengröße (Malvern) in einem bevorzugten Bereich von 0,9 µm bis 1,25 µm, ganz besonders bevorzugt in einem Bereich von 1,0 µm bis 1,2 µm aufweist.It has also been recognized in this case as a preferred embodiment when (a) the calcium carbonate of the first backside coating and (b) the calcium carbonate of the further backside coating are the same in terms of the particular form of preparation and physical properties. This is intended to mean, for example, that both the calcium carbonate optionally incorporated in the first ethylene vinyl alcohol copolymer backcoat layer and the calcium carbonate of the further backside coating have a respective average particle size (Malvern) in a preferred range of zero , 9 microns to 1.25 microns, most preferably in a range of 1.0 microns to 1.2 microns.
Als ganz besonders bevorzugt gilt überdies der Einsatz von gefälltem Kalziumkarbonat sowohl in der ersten Rückseitenbeschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer wie auch in der weiteren Rückseitenbeschichtung, wobei eine plättchenartige Teilchenform als vorteilhaft sowohl für ein besonders überzeugendes Erscheinungsbild der Rückseite des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterial wie auch für eine gute Barrierewirkung dieser Rückseite erkannt wurde.Moreover, the use of precipitated calcium carbonate in both the first backcoat on the basis of ethylene-vinyl alcohol copolymer as well as in the other backside coating is considered to be very particularly preferred, with a platelet-like particulate form being advantageous both for a particularly convincing appearance of the rear side of the invention heat-sensitive recording material as well as a good barrier effect of this back has been recognized.
Neben Kalziumkarbonat kann die weitere Rückseitenbeschichtung als Pigment zusätzlich bevorzugt organische, so genannte Hohlkörperpigmente enthalten. Es gilt dann als besonders vorteilhaft, wenn die Pigmentmischung innerhalb der weiteren Rückseitenbeschichtung zu 35 bis 50 Gew.% bzw. noch besser zu 38 bis 45 Gew.-% aus organischem und zu 65 bis 50 Gew.-% bzw. noch besser zu 62 bis 55 Gew.-% aus Kalziumkarbonat besteht, wobei sich die Gew.% auf den Gesamtanteil an Pigment in der weiteren Rückseitenbeschichtung beziehen.In addition to calcium carbonate, the further backcoat layer may additionally contain, as pigment, preferably organic, so-called hollow-body pigments. It is then particularly advantageous if the pigment mixture within the further backside coating to 35 to 50 wt.% Or even better to 38 to 45 wt .-% of organic and to 65 to 50 wt .-% or even better to 62 up to 55% by weight Calcium carbonate consists, wherein the wt.% Relate to the total amount of pigment in the further backside coating.
Als Bindemittel der weiteren Rückseitenbeschichtung gilt eine Kombination aus (Carboxy-) Methylcellulose und Styrol-Butadien-Latex als bevorzugt, idealerweise ergänzt durch Maisstärke.As a binder of the further backside coating is considered a combination of (carboxy) methylcellulose and styrene-butadiene latex as preferred, ideally supplemented by corn starch.
Zum Auftrag der weiteren Rückseitenbeschichtung bieten sich insbesondere Rollrakelstreichwerk, Messerstreichwerk, Curtain- bzw. Slide-Coater oder Luftbürste an, wobei Messerstreichwerk und insbesonders Rollrakelstreichwerk als ganz bevorzugt gelten. Die flächenbezogene Masse der weiteren Rückseitenbeschichtung liegt bevorzugt zwischen 1 und 20 g/m2 und noch besser zwischen 3,0 und 8,0 g/m2.For the application of the further backside coating, roll-bar coater, knife coater, curtain coater or slide coater or air brush are particularly suitable, knife coater and, in particular, roller coater coating being considered very preferred. The basis weight of the further backside coating is preferably between 1 and 20 g / m 2, and more preferably between 3.0 and 8.0 g / m 2 .
In einer bevorzugten Ausführung können sowohl die erste Rückseitenbeschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer wie auch die weitere Rückseitenbeschichtung mit zwei bevorzugt gleichen Streichwerken aufgebracht werden. Insbesondere ist es dann möglich, beide Rückseitenbeschichtungen nass-in-nass aufzutragen, wofür sich insbesondere ein Curtain-Coater System oder ein Slide-Coater anbietet.In a preferred embodiment, both the first backside coating based on ethylene-vinyl alcohol copolymer and the further backside coating can be applied with two, preferably identical, coating units. In particular, it is then possible to apply both backcoats wet-on-wet, for which, in particular, a curtain coater system or a slide coater is offered.
Hinsichtlich der wärmeempfindlichen Aufzeichnungsschicht erkannten die Erfinder mit Bezug auf die gestellte Aufgabe, dass die Aufzeichnungsschicht zunächst grundsätzlich alle bekannten Farbstoffvorläufer beinhalten kann, wobei auch Kombinationen mehrerer Farbstoffvorläufer möglich sind. Als Farbstoffvorläufer sind insbesondere bevorzugt:
- 6'-(dipentylamino)-3'-methyl-2'-(phenylamino)-spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one sowie
- Spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one-6'-(diethylamino)-3'-methyl-2'-(3-tolylamino)
- 3-diethylamino-6-methyl-7-Anilinofluoran,
- 3-dibutylamino-6-methyl-7-Anilinofluoran,
- 3-(N-methyl-N-propyl)amino-6-methyl-7-Anilinofluoran,
- 3-(N-ethyl-N-isoamyl)amino-6-methyl-7-Anilinofluoran,
- 3-(N-methyl-N-cyclohexyl)amino-6-methyl-7-Anilinofluoran,
- 3-(N-ethyl-N-tolyl)amino-6-methyl-7-Anilinofluoran und
- 3-(N-ethyl-N-tetrahydrofuryl)-amino-6-methyl-7-Anilinofluoran.
- 6 '- (dipentylamino) -3'-methyl-2' - (phenylamino) -spiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one and
- Spiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one 6' - (diethylamino) -3'-methyl-2 '- (3-tolylamino)
- 3-diethylamino-6-methyl-7-anilinofluoran,
- 3-dibutylamino-6-methyl-7-anilinofluoran,
- 3- (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran,
- 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran,
- 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran,
- 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran and
- 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluoran.
Die wärmeempfindliche Aufzeichnungsschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials kann genauso auch grundsätzlich alle zu den möglichen wie insbesondere zu den bevorzugt aufgeführten Farbstoffvorläufern im einzelnen passenden Farbakzeptoren, insbesondere organische Farbakzeptoren beinhalten. Bevorzugt weist die wärmeempfindliche Aufzeichnungsschicht mindestens einen Farbakzeptor auf, ausgesucht aus der Liste, umfassend: 2,2 bis (4-hydroxyphenyl)-Propan, 4-[(4-(1-methylethoxy)phenyl)sulfonyl]-Phenol, 4-hydroxy-4'-isopropoxydiphylsulfon, 4,4'-Dihydroxy-Diphenylsulfon, 2,4'-Dihydroxy-Diphenylsulfon, N-(2-hydroxyphenyl)-2-[(4-hydroxyphenyl)thio]-Acetamid sowie N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-hamstoff gemäß der folgenden Formel (1), wobei die beiden CH3-Endmoleküle in der Literatur auch häufig weggelassen werden:
N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß obiger Formel (1) ist bekannt als Pergafast® 201 der Firma CIBA Speciality Chemicals Inc.N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea according to the above formula (1) is known as Pergafast ® 201 from Ciba Specialty Chemicals Inc.
Die Aufzeichnungsschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials kann zur Erhöhung der thermischen Ansprechempfindlichkeit bevorzugt auch Sensibilisatoren mit einem Schmelzpunkt idealerweise von 60°C bis 180°C, besonders bevorzugt mit einem Schmelzpunkt von 80°C bis 140°C, enthalten. Derartige Sensibilisatoren sind beispielsweise: Benzyl-p-benzyloxy-benzoat, Stearamid, N-Methylolstearamid, p-Benzylbiphenyl, 1,2-Di(phenoxy)-ethan, 1,2-Di(m-methylphenoxy)ethan, m-Terphenyl, Dibenzyloxalat, Benzyl-naphthylether und Diphenylsulfon, wobei Benzylnaphthylether, Diphenylsulfon, 1,2-Di(m-methylphenoxy)ethan und 1,2-Di(phenoxy)-ethan als bevorzugt gelten.The recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness. Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, Dibenzyl oxalate, benzyl naphthyl ether and diphenyl sulfone, with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 1,2-di (phenoxy) ethane being preferred.
Als weiterer und ganz besonders bevorzugter Sensibilisator gilt femer 2-(2H-benzotriazol-2-yl)-p-cresol gemäß der folgenden Formel (2):
2-(2H-benzotriazol-2-yl)-p-cresol gemäß Formel (2), erhältlich als Tinuvin® der Firma CIBA Speciality Chemicals Inc., kann als alleiniger Sensibilisator oder in Kombination mit den in Absatz [0025] genannten Sensibilisatoren in der Aufzeichnungsschicht des erfindungsgemäßen Aufzeichnungsmaterials eingesetzt werden.2- (2H-benzotriazol-2-yl) -p-cresol in accordance with formula (2), available as Tinuvin ® from Ciba Specialty Chemicals Inc., may be used as the sole sensitizer or in combination with those mentioned in paragraph [0025] sensitizers in the recording layer of the recording material according to the invention are used.
Geeignete Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht sind beispielsweise wasserlösliche Bindemittel wie Stärke, Hydroxyethylzellulose, Methylzellulose, Carboxymethylzellulose, Gelatine, Kasein, Polyvinylalkohole, modifizierte Polyvinylalkohole, Natriumpolyacrylate, Acrylamid-Acrylat-Copolymere, Acrylamid-Acrylat-Methacrylat-Terpolymere, Alkalisalze von Styrol-Maleinsäureanhydrid-Copolymeren oder Ethylen-Maleinsäureanhydrid-Copolymeren, die allein oder in Kombination untereinander eingesetzt werden können; auch wasserunlösliche Latexbinder wie Styrol-Butadien-Copolymere, Acrylnitril-Butadien-Copolymere und Methyl-Acrylat-Butadien-Copolymere bieten sich als Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht an. Im Sinne der vorliegenden Erfindung gelten Polyvinylalkohol in Verbindung mit Acrylat-Copolymer als besonders bevorzugte Bindemittel, die zusammen, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in einem Bereich von 12 bis 21 Gew.% in die wärmeempfindliche Aufzeichnungsschicht eingebunden sind.Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene. Maleic anhydride copolymers or ethylene-maleic anhydride copolymers which may be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer. For the purposes of the present invention are polyvinyl alcohol in conjunction with acrylate copolymer as particularly preferred binders, which are incorporated together, based on the total weight of the recording layer, in a range of 12 to 21 wt.% In the heat-sensitive recording layer.
Zur Vermeidung des Klebens an einem Thermokopf und zur Vermeidung einer übermäßigen Abnutzung des Thermokopfes kann die Beschichtungsmasse zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht weiterhin Gleit- und Trennmittel enthalten wie Metallsalze höherer Fettsäuren, zum Beispiel Zinkstearat, Kalziumstearat und Wachse, wie zum Beispiel Paraffin, oxidiertes Paraffin, Polyethylen, Polyethylenoxid, Stearamide und Kastorwachs. Weitere Bestandteile der Aufzeichnungsschicht sind beispielsweise Pigmente, bevorzugt anorganische Pigmente wie beispielsweise Aluminium(hydr)oxid, Kieselsäure und Kalziumkarbonat, wobei hier insbesondere Kalziumkarbonat, das bevorzugt in einer Menge von 10 bis 18 Gew.%, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in die Aufzeichnungsschicht eingebunden sein soll, als bevorzugt gilt.To avoid sticking to a thermal head and avoiding excessive wear of the thermal head, the coating composition for forming the thermosensitive recording layer may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax. Other ingredients The recording layer is, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, which is preferably incorporated in the recording layer in an amount of 10 to 18% by weight, based on the total weight of the recording layer should be considered as preferred.
Die flächenbezogene Masse der wärmeempfindlichen Aufzeichnungsschicht liegt gewöhnlich zwischen 2,5 und 12 g/m2 und besonders bevorzugt zwischen 2,8 und 6,5 g/m2. Als Streichwerk zum Auftrag der wärmeempfindlichen Aufzeichnungsschicht bieten sich insbesondere Streichmesser- und (Roll-) Rakelstreichwerk, Curtain-Coater und Luftbürste an.The basis weight of the heat-sensitive recording layer is usually between 2.5 and 12 g / m 2, and more preferably between 2.8 and 6.5 g / m 2 . As a brush for applying the heat-sensitive recording layer, in particular, offer a doctor blade and (roll) doctor blade coater, curtain coater and air brush.
Als weiterhin bevorzugt gilt die Ausbildung einer pigmenthaltigen Zwischenschicht zwischen dem Substrat und der wärmeempfindlichen Aufzeichnungsschicht. Als Pigmente der Zwischenschicht haben sich sowohl organische Hohlraum-Pigmente wie auch anorganische Pigmente bewährt, letztere bevorzugt ausgewählt aus der Gruppe, umfassend natürliches wie kalziniertes Kaolin, Siliziumoxid und hier besonders Bentonit, Kalziumkarbonat sowie Aluminiumhydroxid und hier besonders Böhmit. Eine solche Zwischenschicht kann zum einen einen positiven Beitrag zur Egalisierung der Substratoberfläche leisten, womit sich die Menge an notwendigerweise aufzubringender Streichfarbe für die wärmeempfindliche Aufzeichnungsschicht reduziert. Aus diesem Grund bieten sich zum Auftrag der Zwischenschicht egalisierende Streichwerke an, wie beispielsweise Walzenstreichwerke, Streichmesser- und (Roll-) Rakelstreichwerke. Zum anderen können die Pigmente dieser Zwischenschicht die durch Hitzeeinwirkung verflüssigten Wachsbestandteile der wärmeempfindlichen Aufzeichnungsschicht bei der Schriftbildausbildung aufnehmen und begünstigen so eine sichere und schnelle Funktionsweise der wärmeinduzierten Aufzeichnung. Die flächenbezogene Masse der pigmentierten Zwischenschicht liegt bevorzugt zwischen 5 und 20 g/m2 und noch besser zwischen 7 und 11 g/m2.Further preferred is the formation of a pigment-containing intermediate layer between the substrate and the heat-sensitive recording layer. As pigments of the intermediate layer, both organic void pigments and inorganic pigments have proven useful, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide, in particular boehmite here. On the one hand, such an intermediate layer can make a positive contribution to the leveling of the substrate surface, which reduces the amount of coating color necessarily required for the heat-sensitive recording layer. For this reason, offer to coat the intermediate layer leveling strokes, such as roller coater, doctor blade and (roll) doctor blade coating. On the other hand, the pigments of this intermediate layer can absorb the heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording. The basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
Das erfindungsgemäße Aufzeichnungsmaterial kann femer eine Schutzschicht aufweisen, die auf die wärmeempfindliche Aufzeichnungsschicht aufgetragen ist und diese ganz oder teilweise abdeckt. Die Schutzschicht nimmt dabei eine Aufgabe wahr, wie sie auch teilweise von der Rückseitenbeschichtung erfüllt werden muss, nämlich zum einen den Schutz der unter ihr angeordneten Aufzeichnungsschicht vor organischen Lösungsmitteln wie auch vor Ölen, Fetten, Wasser und Weichmacher.The recording material according to the invention may furthermore have a protective layer which is applied to the heat-sensitive recording layer and completely or partially covers it. The protective layer takes on a task, as it must also be partially fulfilled by the backside coating, namely on the one hand, the protection of the arranged below her recording layer before organic solvents as well as oils, fats, water and plasticizers.
Auch wenn nicht auf Papier als Substrat beschränkt, ist Papier das Substrat, die sich am Markt auch mit Blick auf die gute Umweltverträglichkeit wegen der guten Recyclingfähigkeit durchgesetzt hat und die im Sinne der Erfindung bevorzugt ist.Although not limited to paper as a substrate, paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention.
Die in Beschreibung und Patentansprüchen gemachten Angaben zur flächenbezogenen Masse, zu Gew.% (Gewichts-%), zu Gew.-Teilen (Gewichts-Teilen) und zu Komponentenverhältnissen beziehen sich, soweit nicht ausdrücklich anders vermerkt, jeweils auf das "atro"-Gewicht, d.h. absolut trockene Gewichtsteile. Die Abkürzung "lutro" steht für lufttrocken, und bedeutet, sofern genutzt, dass die so gekennzeichneten Komponenten in ihrer handelsüblichen Lieferform beschrieben werden.The information given in the description and claims relating to the basis weight,% by weight (% by weight), parts by weight (parts by weight) and component ratios, unless expressly stated otherwise, refers to the "atro" in each case. Weight, ie absolutely dry parts by weight. The abbreviation "lutro" stands for air-dry, and means, if used, that the so marked components are described in their commercial delivery form.
Die Erfindung wird anhand der nachfolgenden erfindungsgemäßen Beispiele 1 und 2 sowie der beiden Vergleichsbeispiele 3 und 4 weiter verdeutlicht:The invention is further illustrated by the following inventive examples 1 and 2 and the two comparative examples 3 and 4:
Zu diesem Zweck wird zunächst auf einer Langsieb-Papiermaschine als Substrat eine Papierbahn aus gebleichten und gemahlenen Laub- und Nadelholzzellstoffen mit einer flächenbezogenen Masse von 130 g/m2 unter Zusatz üblicher Zuschlagstoffe in üblichen Mengen hergestellt. Frontseitig wird online innerhalb der Papiermaschine mit einem Rollrakel-Streichwerk eine hauptsächlich kalziniertes Kaolin und organische Hohlraum-Pigmente als Pigmentmischung, Styrolbutadienlatex als Bindemittel und Stärke als Cobinder aufweisende Zwischenschicht von 8 g/m2 aufgebracht.For this purpose, a paper web of bleached and ground deciduous and softwood pulps with a basis weight of 130 g / m 2 with the addition of conventional additives in conventional amounts is first prepared on a fourdrinier paper machine as a substrate. On the front side, a mainly calcined kaolin and organic void pigments as pigment mixture, styrene-butadiene latex as binder and starch as co-binder-containing intermediate layer of 8 g / m 2 is applied online within the paper machine with a roller blade coating unit.
Unter Verwendung einer Mehrkopf-Streichmaschine wird auf die pigmenthaltige Zwischenschicht mittels Rollrakel-Streicheinrichtung eine wärmeempfindliche Aufzeichnungsschicht mit einer flächenbezogenen Masse von 4,2 g/m2 aufgetragen. Die dabei zum Einsatz kommende Streichmasse enthält im wesentlichen die folgenden Komponenten:
Auf die wärmeempfindliche Aufzeichnungsschicht wird mittels Luftbürste eine Schutzschicht von 2,0 g/m2 aufgetragen.On the heat-sensitive recording layer, a protective layer of 2.0 g / m 2 is applied by means of air brush.
Zur Ausbildung der erfindungsgemäßen und vergleichenden Beispiele werden vier verschiedene Streichmassen für eine rückseitige Beaufschlagung des Substrates vorbereitet:
- ■ Streichmasse RS1(für Beispiel1) enthält zu 99,5 Gew.-% Ethylen-Vinyl-Alkohol-Copolymer (EVOH), genauer Exceval HR 3010 (Kuraray), weitere Bestandteile sind in erster Linie Entschäumer.
- ■ Streichmasse RS2(für Beispiel 2) enthält zu 89,5 Gew.% Ethylen-Vinyl-Alkohol-Copolymer (EVOH), zu 10 Gew.% gefälltes Kalziumkarbonat mit einer mittleren Teilchengröße (Malvern) von 1,10 µm sowie zu 0,5 Gew.% weitere Bestandteile, das sind in erster Linie Entschäumer.
- ■ Streichmasse RS3(für Vergleichs beispiel 3) enthält zu 99,5 Gew.-% üblichen Polyvinylalkohol, genauer Gohsenol NM 11 (Nippon Gohsei), weitere Bestandteile sind in erster Linie Entschäumer.
- ■ Streichmasse RS4(für vergleichsbeispiel 4) enthält zu 99,5 Gew.-% silanisierten Polyvinylalkohol, genauer R 1130 (Kuraray), weitere Bestandteile sind in erster Linie Entschäumer.
- ■ Slip compound RS1 (for example 1 ) contains 99.5% by weight of ethylene-vinyl alcohol copolymer (EVOH), more precisely Exceval HR 3010 (Kuraray), other constituents are primarily defoamers.
- Coating slip RS2 (for Example 2) contains 89.5% by weight ethylene-vinyl alcohol copolymer (EVOH), 10% by weight precipitated calcium carbonate having a mean particle size (Malvern) of 1.10 μm and 0, 5% by weight of other ingredients, these are primarily defoamers.
- ■ Slip compound RS3 (for comparison example 3) contains 99.5% by weight of conventional polyvinyl alcohol, more specifically Gohsenol NM 11 (Nippon Gohsei), other constituents are primarily defoamers.
- Coating compound RS4 ( for Comparative Example 4) contains 99.5% by weight of silanized polyvinyl alcohol, more precisely R 1130 (Kuraray), further components are primarily defoamers.
Die vier Streichmassen werden zum beabsichtigten Auftrag mittels Luftbürste auf einen Feststoffgehalt von 12 % mit Wasser verdünnt. Anschließend werden die jeweiligen Viskositäten der Streichmassen nach Brookfield (Spindel 3 / 100 rpm / 23 °C) bestimmt, es ergeben sich die Messwerte:
- ■ Streichmasse RS1: 750,
- ■ Streichmasse RS2: 870,
- ■ Streichmasse RS3: 690,
- ■ Streichmasse RS4: 2780 (Fraktionsbildung, kein sauberes Verstreichen möglich).
- ■ coating RS1: 750,
- ■ coating RS2: 870,
- ■ coating RS3: 690,
- ■ Coating weight RS4: 2780 (formation of fractions, no clean spreading possible).
Zur Ausbildung der erfindungsgemäßen Beispiele 1 und 2 sowie der beiden Vergleichsbeispiele 3 und 4 werden die vier Streichmassen nunmehr rückseitig auf das Substrat mit einer jeweiligen flächenbezogenen Masse von 2 g/m2 aufgetragen.To form the inventive examples 1 and 2 and the two comparative examples 3 and 4, the four coating compositions are now applied to the back of the substrate with a respective basis weight of 2 g / m 2 .
Zur Beurteilung der erwünschten Sperrwirkung gegenüber organischen Lösemitteln wird auf die jeweilige getrocknete Rückseitenbeschichtung der einzelnen Proben entsprechend der beiden erfindungsgemäßen Beispiele 1 und 2 sowie der beiden Vergleichsbeispiele 3 und 4 mit einer Pipette 0,2 ml Ethanol aufgegeben. Nach einer Einwirkzeit von 1 Minute ist das Ethanol aufgesaugt und die Auswirkung des Lösemittelauftrags auf die wärmeempfindliche Aufzeichnungsschicht wird visuell beurteilt.To assess the desired barrier effect with respect to organic solvents, 0.2 ml of ethanol is applied to the respective dried backcoat of the individual samples corresponding to the two inventive examples 1 and 2 and the two comparative examples 3 and 4 with a pipette. After an exposure time of 1 minute, the ethanol is absorbed and the effect of solvent application on the heat-sensitive recording layer is visually evaluated.
Die wärmeempfindlichen Aufzeichnungsschichten der beiden erfindungsgemäßen Beispiele 1 und 2 zeigen überhaupt keine Thermoreaktionen, die vorliegende Erfindung wird hinsichtlich ihrer Güte hervorragend bestätigt. Bei dem Vergleichsbeispiel 3 zeigen sich intensive Thermoreaktionen, diese Rückseitenbeschichtung ist überhaupt nicht geeignet, eine weitreichende Barrierewirkung gegenüber organischen Lösemitteln mit dieser Auftragsmenge zu entfalten. Bei dem Vergleichsbeispiel 4 ergeben sich vereinzelte Farbreaktionspunkte auf der wärmeempfindlichen Aufzeichnungsschicht: unterhalb dieser farbigen Punkte weist die Rückseitenbeschichtung aus der Streichmasse RS4 Risse und Fehlstellen infolge der zu hohen Viskosität des silanisierten Polyvinylalkohols auf. Auch hier ist die Barrierewirkung gegenüber organischen Lösemitteln nicht überzeugend, weil nicht ohne Fehlstellen.The heat-sensitive recording layers of the two Inventive Examples 1 and 2 show no thermal reactions at all, the present invention is excellently confirmed in terms of quality. In Comparative Example 3, there are intense thermal reactions, this backside coating is not at all suitable to develop a far-reaching barrier effect against organic solvents with this order quantity. In Comparative Example 4, isolated color reaction points are formed on the heat-sensitive recording layer: below these colored dots, the back coat of the coating composition RS4 has cracks and voids due to the too high viscosity of the silanized polyvinyl alcohol. Again, the barrier effect against organic solvents is not convincing, because not without flaws.
Damit kann die schließlich seitens der Erfinder erwartete Überlegenheit des vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials bestätigt werden.Thus, the superiority of the proposed thermosensitive recording material finally expected by the inventors can be confirmed.
Claims (13)
- Heat-sensitive recording material having a substrate- which on its first side bears at least one heat-sensitive recording layer having at least one dye precursor and at least one colour acceptor, the dye precursor and colour acceptor reacting with one another under the action of heat to form colour,- and which on its second side bears at least one first rear-side coating which comprises ethylene vinyl alcohol copolymer (EVOH),characterised in that the heat-sensitive recording material has a further rear-side coating applied on top of the previously applied first rear-side coating, the further rear-side coating comprising calcium carbonate.
- Heat-sensitive recording material according to claim 1, characterised in that the at least first rear-side coating comprises at least 80 % by weight ethylene vinyl alcohol copolymer.
- Heat-sensitive recording material according to one of claims 1 or 2, characterised in that the at least first rear-side coating comprises a pigment.
- Heat-sensitive recording material according to claim 3, characterised in that the at least first rear-side coating comprises, as pigment, calcium carbonate.
- Heat-sensitive recording material according to claim 4, characterised in that the average particle size of the calcium carbonate contained in the rear-side coating that comprises ethylene vinyl alcohol copolymer (EVOH) is in a range from 0.9 µm to 1.25 µm.
- Heat-sensitive recording material according to one of claims 1 to 5, characterised in that the average particle size of the calcium carbonate in the further rear-side coating is in a range from 0.9 µm to 1.25 µm.
- Heat-sensitive recording material according to one of claims 1 to 6, characterised in that the calcium carbonate contained in the rear-side coating that comprises ethylene vinyl alcohol copolymer (EVOH) and the calcium carbonate in the further rear-side coating are the same in respect of their respective preparation form and in respect of their respective physical features.
- Heat-sensitive recording material according to one of claims 1 to 7, characterised in that the calcium carbonate of the further rear-side coating is precipitated.
- Heat-sensitive recording material according to one of claims 1 to 8, characterised in that the further rear-side coating also comprises as pigment, in addition to calcium carbonate, organic hollow pigments.
- Heat-sensitive recording material according to claim 1, characterised in that the at least first rear-side coating comprises at least 90 %, by weight, ethylene vinyl alcohol copolymer.
- Heat-sensitive recording material according to claim 1, characterised in that the at least first rear-side coating comprises at least 98 %, by weight, ethylene vinyl alcohol copolymer.
- Heat-sensitive recording material according to one of claims 1 to 11, characterised in that the heat-sensitive recording material has a pigment-containing intermediate layer located between the substrate and heat-sensitive recording layer.
- Heat-sensitive recording material according to one of claims 1 to 12, characterised in that the heat-sensitive recording material has a protective layer covering the heat-sensitive recording layer.
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| SE500916C2 (en) | 1986-06-16 | 1994-10-03 | Ricoh Kk | Thermosensitive recording material with recording layer containing fluorescence dye composition |
| JP2528905B2 (en) | 1987-10-27 | 1996-08-28 | 三菱製紙株式会社 | Method for manufacturing thermosensitive recording medium |
| JPH04364983A (en) * | 1991-06-12 | 1992-12-17 | Oji Paper Co Ltd | Thermal recording body |
| JPH1024657A (en) * | 1996-05-10 | 1998-01-27 | Mitsubishi Paper Mills Ltd | Thermal recording material and its production |
| DE59800342D1 (en) | 1997-09-12 | 2000-12-21 | Mitsubishi Hitec Paper Flensbu | HEAT-SENSITIVE RECORDING SHEET WITH A BACK COATING CONTAINS STRENGTH, AN ACRYLATE COPOLYMER AND AN ALKALINE CATALYST |
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