EP3046778B1 - Thermo transfer films for the dry lacquering of surfaces - Google Patents
Thermo transfer films for the dry lacquering of surfaces Download PDFInfo
- Publication number
- EP3046778B1 EP3046778B1 EP14766739.8A EP14766739A EP3046778B1 EP 3046778 B1 EP3046778 B1 EP 3046778B1 EP 14766739 A EP14766739 A EP 14766739A EP 3046778 B1 EP3046778 B1 EP 3046778B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radiation
- curable
- layer
- thermal transfer
- coating
- 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.)
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- PSMYELRXRQIDAX-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(2-hydroxy-3-tridecoxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 PSMYELRXRQIDAX-UHFFFAOYSA-N 0.000 description 1
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- RPZGFJQDTNFSBG-UHFFFAOYSA-N 2-methylsulfanyl-2-morpholin-4-yl-1-phenylpropan-1-one Chemical compound C=1C=CC=CC=1C(=O)C(C)(SC)N1CCOCC1 RPZGFJQDTNFSBG-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- CCOQPGVQAWPUPE-UHFFFAOYSA-N 4-tert-butylcyclohexan-1-ol Chemical compound CC(C)(C)C1CCC(O)CC1 CCOQPGVQAWPUPE-UHFFFAOYSA-N 0.000 description 1
- 229940091886 4-tert-butylcyclohexanol Drugs 0.000 description 1
- BGFBWRWYROQISE-UHFFFAOYSA-N 5-ethyl-1,3-dioxane-5-methanol Chemical compound CCC1(CO)COCOC1 BGFBWRWYROQISE-UHFFFAOYSA-N 0.000 description 1
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 description 1
- GTNUQXPPSAMOPW-UHFFFAOYSA-N [3-ethoxy-2,4-dimethyl-6-[(oxo-lambda5-phosphanylidyne)methyl]phenyl]-phenylmethanone Chemical compound C(C)OC=1C(=C(C(=CC=1C)C#P=O)C(=O)C1=CC=CC=C1)C GTNUQXPPSAMOPW-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 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
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- QSXQKORYNLKSBB-UHFFFAOYSA-N bis(1,2,2,5,5-pentamethylpiperidin-4-yl) decanedioate Chemical compound CN1C(CC(C(C1)(C)C)OC(CCCCCCCCC(=O)OC1CC(N(CC1(C)C)C)(C)C)=O)(C)C QSXQKORYNLKSBB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- FCSHDIVRCWTZOX-DVTGEIKXSA-N clobetasol Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CCl)(O)[C@@]1(C)C[C@@H]2O FCSHDIVRCWTZOX-DVTGEIKXSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- WFRLANWAASSSFV-FPLPWBNLSA-N palmitoleoyl ethanolamide Chemical compound CCCCCC\C=C/CCCCCCCC(=O)NCCO WFRLANWAASSSFV-FPLPWBNLSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical class OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
-
- 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
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/38242—Contact thermal transfer or sublimation processes characterised by the use of different kinds of energy to effect transfer, e.g. heat and light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/12—Transfer pictures or the like, e.g. decalcomanias
-
- 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
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/38207—Contact thermal transfer or sublimation processes characterised by aspects not provided for in groups B41M5/385 - B41M5/395
- B41M5/38214—Structural details, e.g. multilayer systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/1729—Hot stamping techniques
-
- 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
- B41M2205/06—Printing methods or features related to printing methods; Location or type of the layers relating to melt (thermal) mass transfer
-
- 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
- B41M2205/10—Post-imaging transfer of imaged layer; transfer of the whole imaged layer
-
- 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
- B41M2205/30—Thermal donors, e.g. thermal ribbons
-
- 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
- B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
Definitions
- the present invention relates to thermal transfer films and their use for the dry coating of surfaces.
- the invention also relates to the production of such thermal transfer films and to a process for coating or coating surfaces of articles using the thermal transfer films according to the invention.
- a liquid lacquer is applied to the surface to be coated and then dried, whereby a lacquer layer is formed on the surface.
- the coating is usually carried out in Lackierstra- Shen, wherein for drying regularly longer dry sections are necessary, in which the paint is dried and cured with relatively high energy consumption.
- Such methods are therefore time, energy and also staff-intensive.
- the coating devices of the paint lines must be cleaned, resulting in service life.
- the waste generated when cleaning the machines must be disposed of as special waste.
- thermo transfer foils These films comprise a carrier film on which one or more polymer layers and optionally an adhesive layer are arranged.
- the at least one polymer layer is transferred by means of pressure and / or heat from the carrier film to the surface to be coated.
- the at least one polymer layer on the surface to be coated forms a lacquer layer without having to use organic solvents in the coating process.
- the EP 573676 describes a method of applying a varnish with a paint on a substrate, for example on wood or plastic surfaces, in which a film is used, which applied to a support with release properties decorative layer and applied to the decorative layer partially crosslinked varnish layer having.
- the film is applied with the lacquer layer on the surface to be coated and transferred by pressure and elevated temperature with the decorative layer on the surface, which at the same time comes to a curing of the lacquer layer.
- paints thermally curable coatings are used. Due to the high temperatures required in the process during paint curing, the choice of substrates is severely restricted.
- Thermal transfer films which have a decorative layer arranged on a carrier layer and a heat-activatable adhesive layer arranged on the decorative layer, wherein the carrier layer has a metallic functional layer lying directly on the decorative layer, which facilitates the detachment of the decorative layer from the carrier layer and thus an improved transfer of the To ensure decorative layer on the substrate. Due to the metallization is limited in the decorative layer.
- thermal transfer films which are suitable for the coating of surfaces and which have a base coat layer, a colored decorative layer and an adhesive bonding layer bonded to a carrier film, are based on aqueous coating systems which contain heat-drying aqueous polymer dispersions as binders.
- the surface hardness and abrasion resistance of the resulting coatings are often unsatisfactory. High abrasion resistant coatings can not be obtained with the thermal transfer films described there.
- EP-A-0 210 620 describes methods for producing a textured varnish layer comprising film.
- the EP 2078618 describes thermal transfer films comprising at least one topcoat layer disposed on a carrier film and a thermally activatable adhesive layer, wherein the topcoat layer is preferably based on an aqueous coating composition containing a UV-curable, dispersed polyurethane.
- the thermal transfer foils described there lead to an improved surface hardness in comparison with thermal transfer foils whose lacquer layers are based on heat-drying aqueous polymer dispersions. For some applications, however, this is not satisfactory.
- the use of aqueous coating compositions is associated with increased drying costs in the production of the thermal transfer films.
- the coatings described therein are not always satisfactory in terms of abrasion resistance and surface properties. High abrasion resistant coatings can not be obtained with the thermal transfer films described there.
- thermal transfer films which have at least one lacquer layer arranged on the carrier film and which are based on a non-aqueous radiation-curable, liquid composition which is at least 60% by weight, in particular at least 70% by weight, based on the total weight of the composition containing crosslinkable components selected from organic oligomers having ethylenically unsaturated double bonds and mixtures of these oligomers with monomers having at least one ethylenically unsaturated double bond and having a heat-sealable polymeric adhesive layer (4) containing at least one radiation-curable component contains, are particularly suitable for coating surfaces.
- crosslinkable components selected from organic oligomers having ethylenically unsaturated double bonds and mixtures of these oligomers with monomers having at least one ethylenically unsaturated double bond and having a heat-sealable polymeric adhesive layer (4) containing at least one radiation-curable component contains
- non-aqueous, radiation-curable coating compositions with a high proportion of crosslinkable components allows the targeted adaptation of the thermal transfer film for different substrates, namely for both hard as well as highly elastic substrates.
- the temperature load of the material to be coated during transfer of the lacquer layer (s) on the surface to be coated is comparatively low, since a final curing easily by irradiating the coated surface with high-energy radiation such as UV or electron radiation can be performed and no subsequent annealing is necessary.
- the radiation-curable, liquid compositions used for the preparation of the lacquer layer contain at least 60 wt .-%, in particular at least 70 wt .-%, z. B. 60 to 99 wt .-%, in particular 70 to 95 wt .-%, based on the total weight of the composition, curable components which have ethylenically unsaturated double bonds.
- the constituents are preferably selected such that 1.5 to 8 mol, in particular 2.0 to 7 mol, and especially 2.5 to 6.5 mol, of ethylenically unsaturated double bonds per kg of the coating composition are present in the composition.
- the ethylenically unsaturated double bonds of the curable constituents of the liquid, radiation-curable composition which forms the lacquer layer are preferably in the form of acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular at least 90% or 100%, based on the total amount the ethylenically unsaturated double bonds present in the composition, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups.
- the acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred.
- the curable components of the radiation-curable composition forming the lacquer layer comprise at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds present in the composition, of acrylate groups.
- the liquid, radiation-curable compositions which are used to prepare the lacquer layer contain at least one oligomer which has ethylenically unsaturated double bonds.
- the oligomers preferably have on average a functionality in the range from 1.5 to 10, in particular in the range from 2 to 8.5, ie the number of ethylenically unsaturated double bonds per molecule is on average in the range from 1.5 to 10 and in particular Range from 2 to 8.5.
- Also suitable are mixtures of different oligomers with different Functionality, wherein the average functionality is preferably in the range of 1.5 to 10, in particular in the range of 2 to 8.5.
- the oligomers typically have a linear or branched skeleton which carries on average more than one ethylenically unsaturated double bond, preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular in the form of acrylic or methacrylic groups, wherein the ethylenically unsaturated double bonds may be linked via a linker to the skeleton or are part of the skeleton.
- Suitable oligomers are, in particular, oligomers from the group of polyethers, polyesters, polyurethanes and epoxide-based oligomers. Preference is given to oligomers which have substantially no aromatic structural units and to mixtures of oligomers having aromatic groups and oligomers without aromatic groups.
- the oligomers are selected from polyether (meth) acrylates, i. H. Polyethers having acrylic or methacrylic groups, polyester (meth) acrylates, d. H. Polyesters having acrylic or methacrylic groups, epoxide (meth) acrylates, d. H. Reaction products of polyepoxides with hydroxyl-functionalized acrylic or methacrylic compounds, urethane (meth) acrylates, d. H. Oligomers having a (poly) urethane backbone and acrylic or methacrylic groups, for example, reaction products of polyisocyanates with hydroxyl-functionalized acrylic or methacrylic compounds, and unsaturated polyester resins, d. H. Polyesters having a plurality of preferably present in the polymer backbone ethylenically unsaturated double bonds, for. As condensation products of maleic acid or fumaric acid with aliphatic di- or polyols, and mixtures thereof.
- the oligomers typically have a number average molecular weight of at least 400 g / mol, especially at least 500 g / mol, e.g. B. in the range of 400 to 4000 g / mol and in particular in the range of 500 to 2000 g / mol.
- the monomers typically have molecular weights below 400 g / mol, z. B. in the range of 100 to ⁇ 400 g / mol.
- Suitable polyether (meth) acrylates are, above all, aliphatic polyethers, in particular poly (C 2 -C 4 ) -alkylene ethers, which on average have from 2 to 4 acrylate or methacrylate groups. Examples of these are the Laromer® grades PO33F, LR8863, GPTA, LR8967, LR8962, LR9007 from BASF SE, which in some cases are blends with monomers.
- Suitable polyester (meth) acrylates are, in particular, aliphatic polyesters which on average have from 2 to 6 acrylate or methacrylate groups. Examples of these are the Laromer® grades PE55F, PE56F, PE46T, LR9004, PE9024, PE9045, PE44F, LR8800, LR8907, LR9032, PE9074, PE9079, PE9084 from BASF SE, which in some cases are blends with monomers.
- Suitable polyurethane acrylates are, above all, urethane-containing compounds which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups and which are preferably obtainable by reaction of aromatic or aliphatic di- or oligoisocyanates with hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
- these are the Laromer® grades UA19T, UA9028, UA9030, LR8987, UA9029, UA9033, UA9047, UA9048, UA9050, UA9072, UA9065 and UA9073 from BASF SE, some of which are blends with monomers.
- the radiation-curable, liquid composition forming the lacquer layer comprises at least one oligomer selected from urethane acrylates and polyester acrylates and mixtures thereof, and optionally one or more monomers.
- the radiation-curable, liquid composition which forms the lacquer layer comprises at least one urethane acrylate and optionally one or more monomers.
- the radiation-curable, liquid composition forming the lacquer layer comprises at least one polyester acrylate and optionally one or more monomers.
- the radiation-curable, liquid composition forming the lacquer layer comprises at least one urethane acrylate and at least one polyester acrylate and optionally one or more monomers.
- the radiation-curable, liquid composition forming the lacquer layer comprises at least one aliphatic urethane acrylate and at least one aromatic urethane acrylate or at least two different aliphatic urethane acrylates and optionally one or more monomers.
- the radiation-curable, liquid composition which forms the lacquer layer comprises at least one aliphatic urethane acrylate, at least one aromatic urethane acrylate and at least one polyester acrylate and optionally one or more monomers.
- the crosslinkable constituents of the radiation-curable, liquid composition used to prepare the lacquer layer may contain one or more monomers, which are also referred to as reactive diluents.
- the monomers typically have molecular weights below 400 g / mol, e.g. B. in the range of 100 to ⁇ 400 g / mol.
- Suitable monomers generally have 1 to 6, in particular 2 to 4, ethylenically unsaturated double bonds per molecule.
- the ethylenically unsaturated double bonds are preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular in the form of acrylic or methacrylic groups and especially as acrylate groups.
- Preferred monomers are selected from esters of acrylic acid with monohydric to trihydric, especially dihydric to trihydric, aliphatic or cycloaliphatic alcohols which preferably have 2 to 20 C atoms, for example monoesters of acrylic acid with C 1 -C 20 - Alkanols, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, (5-ethyl-1,3-dioxan-5-yl) methanol, phenoxyethanol, 1,4-butanediol or 4-tert-butylcyclohexanol; Diesters of acrylic acid with ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol or tripropylene glycol; Triesters of acrylic acid with trimethylolpropane or pent
- Suitable monomers are, in particular, trimethylolpropane diacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diarylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 4-t-butylcyclohexyl acrylate, 4-hydroxybutyl acrylate and trimethylolformalmonoacrylate (acrylic acid (5-ethyl-1,3-) dioxan-5-yl) methylester).
- the radiation-curable, liquid composition forming the lacquer layer comprises at least one oligomer, e.g. B. 1, 2 or 3 oligomers, especially at least one, z. B. 1, 2 or 3, the oligomers mentioned as preferred and at least one monomer, for. B. 1, 2 or 3 monomers, especially at least one, z. B. 1, 2 or 3, the monomers mentioned as preferred.
- the oligomer preferably forms the major constituent of the curable components of the composition, ie, the oligomer (s) account for at least 50 wt .-%, in particular at least 60 wt .-%, based on the total amount of oligomer and monomer.
- the weight ratio of oligomer to monomer is in particular in the range from 1: 1 to 20: 1 and especially in the range from 3: 2 to 10: 1.
- the radiation-curable, liquid composition used to prepare the lacquer layer comprises exclusively or almost exclusively, i. H. at least 90% by weight, in particular at least 95% by weight, especially at least 99% by weight, based on the total amount of radiation-curable constituents of the composition, of one or more oligomers, eg. B. 2, 3 or 4 oligomers, in particular 2, 3 or 4 of the oligomers mentioned as preferred.
- the proportion of monomers is at most 10% by weight, in particular not more than 5% by weight, especially not more than 1% by weight or 0% by weight, based on the total amount of radiation-curable constituents of the composition.
- Such compositions preferably contain at least one polyester acrylate and / or polyurethane acrylate and at least one polyether acrylate.
- the radiation-curable, liquid composition used to prepare the lacquer layer generally contains one or more further constituents, such as photoinitiators, inert fillers, abrasives, leveling agents, coloring constituents, in particular color pigments, organic solvents and the like. According to the invention, these constituents do not exceed 40% by weight, in particular not more than 30% by weight, eg. B. 1 to 40 wt .-%, in particular 5 to 30 wt .-%, based on the total weight of the radiation-curable, liquid composition.
- the radiation-curable, liquid composition contains no or not more than 10% by weight, based on its total weight, of non-polymerizable volatiles.
- volatile substances are understood as meaning substances which have a boiling point or an evaporation point below 250 ° C. under atmospheric pressure, for example organic solvents.
- the radiation-curable, liquid composition used to prepare the lacquer layer preferably contains at least one photoinitiator.
- photoinitiators is meant substances which upon irradiation with UV radiation, ie light of wavelength below 420 nm, in particular below 400 nm, decompose to form free radicals and thus trigger a polymerization of the ethylenically unsaturated double bonds.
- the radiation-curable, liquid composition comprises at least one photoinitiator having at least one absorption band, which has a maximum in the range of 220 to 420 nm, in particular in the range of 240 to 400 nm and which is coupled with the initiation of the decay process.
- the nonaqueous, liquid, radiation-curable composition preferably contains at least one photoinitiator which has at least one absorption band with a maximum in the range from 220 to 420 nm, in particular a maximum in the range from 240 to 400 nm.
- Preferred photoinitiators are selected, in particular, from the groups of the alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzoins and acylphosphine oxides.
- the liquid, radiation-curable composition preferably comprises at least one photoinitiator which has an absorption band with a maximum ⁇ max in the range from 230 to 340 nm.
- the non-aqueous, liquid, radiation-curable composition used to prepare the lacquer layer preferably comprises at least two photoinitiators which differ from one another and in which the maxima of the absorption bands differ, preferably by at least 40 nm and in particular by at least 60 nm.
- such a non-aqueous, liquid, radiation-curable composition contains a mixture of at least two mutually different photoinitiators, wherein at least one photoinitiator (hereinafter photoinitiator I) has an absorption band with a maximum ⁇ max in the range of 340 to 420 nm and especially in the range of 360 has up to 420 nm and wherein at least one further photoinitiator (hereinafter photoinitiator II) has an absorption band with a maximum ⁇ max in the range of 220 to 340 and especially in the range of 230 to 320 nm.
- the weight ratio of the total amount of photoinitiators I to the total amount of photoinitiators II is in the range of 2: 1 to 1:20.
- Preferred photoinitiators which have an absorption band having a maximum ⁇ max in the range from 220 to 340 and especially in the range of 230 to 320 nm, the above-mentioned alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic esters, benzophenones, and benzoins.
- Preferred photoinitiators which have an absorption band with a maximum ⁇ max in the range of 340 to 420 nm and especially in the range of 360 to 420 nm are the abovementioned acylphosphine oxides.
- the photoinitiators comprise at least one alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone and at least one acylphosphine oxide and optionally a phenylglyoxalic acid ester and optionally a benzophenone.
- the weight ratio of acylphosphine oxide to alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone is in the range of 2: 1 to 1:20.
- the total amount of photoinitiators is typically in the range of 0.5 to 10% by weight, especially 1 to 5% by weight, based on the total weight of the non-aqueous, liquid, radiation-curable composition.
- nonaqueous, liquid, radiation-curable compositions according to the invention can also be formulated without initiators, in particular when the subsequent curing is carried out by means of electron beams.
- the non-aqueous, liquid, radiation-curable compositions may contain one or more fillers, i. H. solid, non-soluble in the oligomers and the monomers, particulate components.
- these include, in particular aluminum oxides, for example in the form of corundum and silica, such as fumed silica and synthetic, amorphous silica, z. B. precipitated silica.
- the average particle sizes of the fillers can vary over wide ranges and are typically in the range from 1 nm to 100 .mu.m, in particular in the range from 10 nm to 50 .mu.m, depending on the type of filler.
- the total amount of filler will generally not exceed 40% by weight, in particular 30% by weight, based on the total weight of the composition and, if present, is typically in the range from 1 to 39.5% by weight and in particular in the range of 2 to 29 wt .-%.
- the non-aqueous, liquid, radiation-curable compositions contain one or more abrasives.
- Abrasives are fillers which give the lacquer layer increased surface hardness and improved abrasion resistance. These include especially corundum, quartz flour, glass powder, z. As glass flakes and nanoscale silicas.
- non-aqueous, liquid, radiation-curable compositions may contain one or more further additives, for example leveling agents, for.
- leveling agents for.
- siloxane-containing polymers such as polyether siloxane copolymers
- UV stabilizers for. B. sterically hindered amines (so-called HALS stabilizers).
- Table A1 raw material Amount [% by weight] 1) Urethane acrylate, functionality about 2.0 to 6.0 15 - 30 Polyester acrylate, functionality 3.0 to 3.5 5 - 15 Trimethylolpropaneformalmonoacrylat 5 - 15 trimethylolpropane 10 - 20 Dipropyleneglycoldiacrylate 10 - 20 Aliphatic urethane acrylate, functionality 1.5 to 3.5 3 - 15 Alumina (corundum) 20 - 30 Pyrogenic silica 0.1 - 5 phenylglyoxylate 0,5 - 3 acylphosphine 0.2 - 1 alpha-hydroxyalkylphenone 0,5 - 3 1) based on the total weight of the composition raw material Amount [% by weight] 1) Urethane acrylate, functionality about 2.0 to 6.0 20 - 35 Alipha
- the thermal transfer films according to the invention may comprise one or more superposed lacquer layers which, according to the invention, are based on the nonaqueous, liquid, radiation-curable compositions described above.
- the total layer thickness of the lacquer layer, d. H. in the case of several lacquer layers, the sum of all layer thicknesses is typically in the range from 10 to 120 ⁇ m, in particular in the range from 30 to 80 ⁇ m. In the case of one layer, therefore, the layer thickness of the lacquer layer is preferably in the range from 10 to 120 ⁇ m, in particular in the range from 30 to 80 ⁇ m. In the case of several layers, the individual layer thicknesses are typically in the range from 10 to 100 ⁇ m, in particular in the range from 20 to 70 ⁇ m.
- the thermal transfer film according to the invention comprises exactly one lacquer layer arranged on the carrier foil.
- the thermal transfer film according to the invention comprises a coating layer arranged on the carrier film and one or more, for.
- the lacquer layers can be arranged directly on one another.
- a decorative layer can also be provided between two lacquer layers in order to give the article coated with the thermal transfer film a colored design.
- Decorative layers typically have layer thicknesses in the range from 0.5 to 5 ⁇ m, in particular in the range from 0.5 to 2.5 ⁇ m and especially in the range from 1 to 1.5 ⁇ m.
- the thermal transfer films according to the invention have at least one polymeric adhesive layer, in particular exactly one adhesive layer.
- the adhesive layer is arranged either directly on the lacquer layer, or in the case of several lacquer layers directly on the uppermost lacquer layer, or a decorative layer can also be provided between the lacquer layer and the adhesive layer.
- the adhesive layer is heat sealable according to the invention, ie it is not sticky at room temperature and develops its adhesive effect only when heated. It has proved to be advantageous if the adhesive layer contains at least one component which is radiation-curable, ie crosslinked upon exposure to high-energy radiation, for example when irradiated with UV light or electron radiation. This ingredient is organic oligomers or polymers that have ethylenically unsaturated double bonds.
- the heat-sealable adhesive layer according to the invention preferably comprises at least one polymer as the main constituent. The polymer itself may be radiation-curable or blended with one or more radiation-curable oligomers or polymers having ethylenically unsaturated double bonds.
- the polymers which form the main constituent of the heat-sealable adhesive layer are crosslinkable in a preferred embodiment, ie they crosslink upon heating and / or by the action of high-energy radiation, for example when irradiating with UV light and forming covalent bonds between the polymer chains.
- the adhesive layer comprises both oligomeric and / or polymeric components which can be crosslinked by heating, as well as components which are crosslinkable by the action of high-energy radiation. This can be achieved, for example, by the adhesive layer comprising both polymers which crosslink on heating and oligomers or polymers which are crosslinked by the action of high-energy radiation.
- the adhesive layer can also contain so-called dual-cure polymers, ie polymers which crosslink both when exposed to high-energy radiation and when heated.
- the adhesive layer contains at least one water-insoluble polymer, which is usually used for the production of adhesive layers, and which is selected in particular from pure acrylate polymers, styrene acrylate polymers, polyurethanes, in particular polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking, and at least one radiation-curing oligomer or polymer.
- Physically drying polymers are those polymers which, upon drying, form a solid polymer film in which the polymer chains are uncrosslinked.
- Self-crosslinking polymers are those polymers which, upon drying, form a solid polymer film in which the polymer chains are crosslinked.
- self- Polymers have reactive functional groups, for example hydroxyl groups, carboxyl groups, isocyanate groups, blocked isocyanate groups, ketocarbonyl groups or epoxide groups, which can react with one another or with the reactive groups of a crosslinking agent to form covalent bonds.
- the adhesive layer contains at least one water-insoluble polymer which is selected from polyurethanes, in particular polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking, and at least one radiation-curing oligomer or polymer.
- the adhesive layer contains at least one water-insoluble polymer selected from self-crosslinking pure acrylate polymers and self-crosslinking styrene-acrylate polymers, and at least one radiation-curing oligomer or polymer.
- the adhesive layer contains at least one water-insoluble polymer selected from self-crosslinking pure acrylate polymers and self-crosslinking styrene-acrylate polymers and at least one water-insoluble polymer selected from polyurethanes, especially polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking and at least one radiation-curing oligomer or polymer.
- the radiation-curable oligomers and polymers of the adhesive layer are basically those oligomers and polymers which have ethylenically unsaturated double bonds. These double bonds are preferably at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups.
- the acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred.
- at least 90% or 100% of the radiation-curable constituents of the adhesive layer based on the total amount of the ethylenically unsaturated double bonds present in the adhesive layer, comprise acrylate groups.
- the radiation-curable oligomers and polymers of the adhesive layer preferably have on average a functionality in the range of 2 to 20, in particular in the range of 2 to 10, ie the number of ethylenically unsaturated double bonds per molecule is on average in the range of 2 to 20 and in particular in the range of 2 to 10.
- the radiation-curable oligomers and polymers of the adhesive layer are selected from polyether (meth) acrylates, polyester (meth) acrylates, epoxide (meth) acrylates, urethane (meth) acrylates, for example reaction products of polyisocyanates with hydroxyl-functionalized acrylic or methacrylic compounds, and unsaturated polyester resins.
- the radiation-curable oligomers and polymers of the adhesive layer are selected from polyether (meth) acrylates, epoxide (meth) acrylates and urethane (meth) acrylates.
- Suitable polyurethane acrylates are, above all, urethane-containing polymers which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups, in particular polyether urethane arylates, and which are preferably obtainable by reacting isocyanate group-containing polyether urethanes with hydroxyalkyl acrylates or hydroxyalkyl methacrylates , Examples include the Laromer® grades LR 8949, LR 8983 and LR 9005 from BASF SE.
- the polymers, which preferably form the main constituent of the heat-sealable adhesive layer, in the uncrosslinked state have a glass transition temperature Tg, determined by means of differential scanning calorimetry (DSC) according to ASTM D3418 in the range from -60 to 90 ° C., in particular 0 to 90 ° C, and / or it is partially crystalline polymers having a melting point in the range of -60 to 90 ° C, in particular 0 to 90 ° C, determined by DSC is. If the adhesive composition contains a plurality of polymers, these may also have different glass transition temperatures in the uncrosslinked state.
- DSC differential scanning calorimetry
- At least a part, in particular at least 30% by weight of these polymers, based on the total amount of the polymer components of the adhesive composition, in the uncrosslinked state has a glass transition temperature Tg in the range from 0 to 90 ° C., in particular in the range from 20 to 90 ° C have.
- Adhesive compositions for producing heat-sealable polymer layers are familiar to the person skilled in the art and can be obtained commercially or prepared by mixing commercially available adhesive raw materials according to known preparatory formulations. Preference is given to liquid adhesive compositions. In principle, solvent-based adhesives and water-based adhesives are suitable.
- the adhesive layer (4) is preferably based on at least one aqueous polymer dispersion, ie water-based adhesives are used to produce the adhesive layer, ie adhesives which contain the polymers and optionally oligomers in the form of aqueous polymer dispersion. Preference is given to liquid, water-based adhesive compositions containing not more than 10% by weight of volatile, organic, non-polymerizable constituents, such as organic solvents. Suitable polymer dispersions are above all self-crosslinking aqueous polymer dispersions, ie aqueous polymer dispersions containing a reactive dispersed polymer and optionally a crosslinking agent which reacts with the reactive groups of the reactive polymer during drying and / or heating to form bonds.
- self-crosslinking aqueous pure acrylate dispersions self-crosslinking aqueous styrene-acrylate dispersions and self-crosslinking aqueous polyurethane dispersions, in particular aqueous polyetherurethane dispersions and polyesterurethane dispersions.
- Pure acrylate dispersions are understood as meaning aqueous polymer dispersions based on alkyl acrylates and alkyl methacrylates.
- styrene acrylates is meant aqueous polymer dispersions based on styrene, alkyl acrylates and optionally alkyl methacrylates.
- Polyurethane dispersions are understood as meaning aqueous dispersions of polyurethanes, in particular polyetherurethanes and polyesterurethanes.
- the polymers have reactive functional groups, for example hydroxyl groups, carboxyl groups, isocyanate groups, blocked isocyanate groups, ketocarbonyl groups or epoxide groups which can react with the reactive groups of the crosslinking agent to form covalent bonds.
- Suitable crosslinking agents are compounds having at least two reactive groups, for example hydrazide groups, amino groups, hydroxyl groups, epoxide groups, isocyanate groups.
- self-crosslinking aqueous polymer dispersions are the products available under the trade names Luhydran® A 849, Acronal® 849 S, Joncryl® 8330, Joncryl® 8383 from BASF SE and Alberdingk® AC 2742 from Alberdingk Boley GmbH.
- Suitable aqueous polymer dispersions are, above all, UV-crosslinkable polymer dispersions, ie polymer dispersions which comprise a dispersed polymer which has polymerizable ethylenically unsaturated double bonds which are preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular Form of acrylic or methacrylic groups are present, wherein the ethylenic unsaturated double bonds can be linked via a linker to the skeleton or are part of the skeleton.
- UV-crosslinkable aqueous polymer dispersions are aqueous dispersions of polyester acrylates, urethane acrylates and epoxy acrylates, such as those sold by BASF under the trade names Laromer® PE22WN, PE55WN, LR8949, LR8983, LR9005, UA9060, UA9095 and UA9064.
- the aqueous adhesive composition contains, in addition to the polymer of a physically drying or self-crosslinking polymer dispersion, at least one radiation-curable component which is generally selected from the aforementioned polymers and oligomers which have ethylenically unsaturated double bonds and which is preferably also present in dispersed form.
- the radiation-curable oligomers and polymers of the aqueous adhesive composition are, in particular, those oligomers and polymers whose double bonds are at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups available.
- the acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred.
- the radiation-curable oligomers and polymers of the aqueous adhesive composition preferably have on average a functionality in the range of 2 to 20, in particular in the range of 2 to 10, d. H. the number of ethylenically unsaturated double bonds per molecule is on average in the range from 2 to 20 and in particular in the range from 2 to 10. Also suitable are mixtures of different oligomers or polymers with different functionality, the average functionality preferably in the range from 2 to 20, especially in the range of 2 to 10.
- the radiation-curable oligomers and polymers of the aqueous adhesive composition are selected from polyether (meth) acrylates, polyester (meth) acrylates, epoxide (meth) acrylates, urethane (meth) acrylates, and unsaturated polyester resins.
- the radiation-curable oligomers and polymers of the aqueous adhesive composition are selected from polyether (meth) acrylates, epoxide (meth) acrylates and polyurethane (meth) acrylates.
- Suitable polyurethane acrylates are, above all, urethane-containing polymers which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups and which are preferably obtainable by reacting isocyanate-group-containing polyurethanes with hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
- Examples include the Laromer® grades LR 8949, LR 8983 and LR9005 from BASF SE.
- the adhesive compositions used for the preparation of the polymeric adhesive layer may contain the additives customary for this purpose, for example waxes, tackifier resins, defoamers, leveling agents, surfactants, pH adjusting agents, one or more of the aforementioned fillers and UV stabilizers, eg. B. sterically hindered amines (so-called HALS stabilizers).
- additives customary for this purpose for example waxes, tackifier resins, defoamers, leveling agents, surfactants, pH adjusting agents, one or more of the aforementioned fillers and UV stabilizers, eg. B. sterically hindered amines (so-called HALS stabilizers).
- the adhesive composition used to make the polymeric adhesive layer contains a UV-curable polymer, it usually also contains at least one photoinitiator, typically among the aforementioned alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzene derivatives, acylphosphine oxides , Oxime esters, alpha-aminoalkylphenones and benzoins.
- at least one photoinitiator typically among the aforementioned alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzene derivatives, acylphosphine oxides , Oxime esters, alpha-aminoalkylphenones and benzoins.
- Preferred photoinitiators are selected, in particular, from the groups of the alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzoins and acylphosphine oxides.
- the adhesive composition used to make the polymeric adhesive layer contains a UV-curable polymer
- it preferably contains at least one photoinitiator having an absorption band with a maximum ⁇ max in the range of 230 to 340 nm.
- it contains at least two mutually different photoinitiators in which the maxima of the absorption bands differ, preferably by at least 40 nm and in particular at least 60 nm.
- the photoinitiators comprise at least one alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone and at least one acylphosphine oxide and optionally a phenylglyoxalic acid ester and optionally a benzophenone.
- the weight ratio is of acylphosphine oxide to alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone in the range from 2: 1 to 1:20.
- the total amount of photoinitiators is typically in the range from 0.5 to 10% by weight, in particular from 1 to 5% by weight, based on the total weight of the adhesive composition used to make the polymeric adhesive layer.
- Adhesive composition 1 UV-curable, unpigmented
- Adhesive composition 1 30 -70 parts a self-crosslinking aqueous acrylate dispersion (50% strength by weight) 10-50 parts a radiation-curable polyurethane acrylate dispersion (40-50% strength by weight), 5-10 Parts of a hydrophobized fumed silica 5-10 Parts of a nonionic wax dispersion 1,5-3 Parts of a blend of an alpha-hydroxyalkylphenone and benzophenone 0.5-1 Parts of an acylphosphine oxide and optionally the following ingredients 0-20 Parts of water 0.8-1.5 parts a mineral-containing defoamer 0.4-1.2 parts a polyethersiloxane copolymer 0.5-1.0 parts a fluorosurfactant-containing leveling agent 2-4 parts Butyl glycol as a film-forming aid 0.3-0.5 Parts of
- carnauba wax polyethylene wax, a combination of carnauba wax and polyethylene wax or a combination of several polyethylene waxes 1-3 parts a blend of an alpha-hydroxyalkylphenone and benzophenone 0.5-1 parts an acylphosphine oxide and optionally the following ingredients 0.2-1.0 parts a polyethersiloxane copolymer 1-10 parts Hydroxystyrolacrylat copolymer 0.1-5 parts Plasticizer, z. B. triethyl citrate 0,5-5 parts water 0,5-5 parts Butyl glycol as a film-forming aid 0.01-1 parts Base, e.g.
- Hydroxystyrolacrylat copolymer 1-3 parts a blend of an alpha-hydroxyalkylphenone and benzophenone 0.5-1 parts an acylphosphine oxide and optionally the following ingredients 0.1-5 parts Plasticizer, z. B. triethyl citrate 0.2-1.0 parts a polyethersiloxane copolymer 0.2-1.0 parts a defoamer, z. B. a silicone defoamer or a siloxane-free defoamer; 0.3-0.5 parts a flow aid, z. B.
- a fluorosurfactant-containing leveling agent 0,5-5 parts water 0,5-5 parts
- Butyl glycol as a film-forming aid 0.01-1 parts
- Base e.g. As an organic amine 30 -70 parts a polyester urethane dispersion (40% strength by weight) 10-50 parts a radiation-curable aqueous polyether urethane acrylate dispersion (40-50% strength by weight) 1.5-3 parts a blend of an alpha-hydroxyalkylphenone and benzophenone 0.5-1 parts an acylphosphine oxide and optionally the following ingredients 0-20 parts water 0.8-1.5 parts a polysiloxane defoamer 0.4-1.2 parts a polyethersiloxane copolymer 0.5-1.0 parts a fluorosurfactant-containing leveling agent 0.01-0.5 Parts of a polyurethane thickener 15 -60 parts a polyester urethane dispersion (40% strength by weight) 15 -60 parts a self-crosslinking
- lacquer layer (s) and / or the adhesive layer (s) are colored.
- lacquer layer (s) and / or the adhesive layer (s) may contain one or more coloring constituents such as organic and / or inorganic pigments or dyes.
- these pigments are titanium dioxide as a white pigment, furthermore iron oxide pigments such as iron oxide yellow, iron oxide red, iron oxide black, black pigments such as carbon black, phthalocyanine pigments such as heliogen blue or heliogen green, bismuth pigments such as bismuth vanadate yellow and diketopyrrolopyrrole red.
- Metallization effects may also include metal pigments such as iron pigments, pearlescent pigments and aluminum pigments.
- Preferred pigments typically have particle sizes in the range from 0.1 to 100 .mu.m, in particular in the range from 1 to 50 .mu.m.
- Adhesive layers typically have layer thicknesses in the range of 5 to 25 ⁇ m.
- the thermal transfer films according to the invention naturally have at least one carrier foil on which the at least one lacquer layer is arranged.
- the carrier films are usually plastic films made of thermoplastic flexible polymers. In particular, these are polyester films, polyamide films, polypropylene films, films of polyvinyl alcohol or polyesteramide films. Also suitable are so-called coextrudate films, d. H. multilayered films, wherein the plastic material in the individual layers may be different.
- the plastic material which forms the carrier film is predominantly amorphous. Waxed or siliconized papers are also suitable.
- the carrier film (2) has a thickness in the range of 3 to 200 .mu.m, in particular 10 to 100 .mu.m and especially from 20 to 50 microns. Also suitable are thin carrier films with film thicknesses in the range of 3 to 30 microns.
- the surface structure of the carrier film on which the lacquer layer is arranged naturally determines the degree of gloss of the lacquer layer which is obtained in the coating method according to the invention. Smooth surfaces result in shiny or glossy surfaces, whereas rough surfaces can achieve matt effects. It is possible to create coarser structures in the paint surface by a strong structuring of the surface.
- the surface of the carrier film on which the lacquer layer is arranged may have a conventional release layer, which facilitates the detachment of the lacquer layer from the carrier film in the coating method according to the invention.
- thermal transfer films can be carried out in analogy to conventional film coating technologies, as described in the cited prior art, with the difference that in the preparation of the paint layer no heat-drying step is carried out, but by applying the non-aqueous radiation-curable, liquid Composition obtained on the carrier film liquid lacquer layer is at least partially cured by treatment with high-energy radiation such as electron beam or UV radiation.
- the application of the non-aqueous, radiation-curable, liquid composition to the carrier film in step i) of the process according to the invention can be carried out in a manner known per se, for example by knife coating, rolling, casting or spraying. In this way, one obtains a coating of the carrier film with the radiation-curable composition, which can then be cured by treatment with high-energy radiation.
- the order quantity is usually chosen such that a layer thickness results in the above-mentioned ranges.
- the order quantity is in the range of 10 to 120 g / m 2 , in particular in the range of 30 to 80 g / m 2 and in the case of several layers, preferably in the range of 10 to 100 g / m 2 and in particular 20 to 70 g / m 2 .
- step ii) of the method according to the invention the coating obtained in step i) is then at least partially cured by means of high-energy radiation.
- a decorative layer can be applied to the not yet cured or partially cured coating prior to complete curing.
- the adhesive layer may also be applied prior to curing.
- step ii) of the process according to the invention the coating obtained in step i) is only partially cured.
- the layer obtained in step i) is at least partially cured.
- the coating obtained in step i) is irradiated with high-energy radiation.
- the irradiation can be carried out by the carrier foil or by direct irradiation of the coating. Preference is given to direct irradiation.
- the irradiation can be effected by means of electron radiation or with UV light, for example with UV lamps or UV-emitting light-emitting diodes.
- UV radiation is used for curing in step ii).
- UV radiation is used in the wavelength range from 200 to 400 nm.
- medium-pressure mercury lamps or high-pressure mercury lamps for this purpose.
- gallium or iron-doped high-pressure mercury lamps are used.
- the irradiation in step ii) is preferably carried out in such a way that only partial polymerization of the ethylenically unsaturated double bonds contained in the nonaqueous, radiation-curable, liquid composition takes place.
- the radiation density required for this purpose can be determined by the expert by means of routine experiments.
- the irradiation in step ii) takes place at a radiation density in the range from 80 to 2000 J / m 2 , in particular in the range from 110 to 400 J / m 2 .
- the curing in step ii) can be carried out under air atmosphere or under an oxygen-poor atmosphere at residual oxygen concentrations below 2000 ppm, eg. B. at residual oxygen concentrations in the range of 50 to 1000 ppm, take place.
- the curing preferably takes place under air.
- the thermal transfer film according to the invention comprises a plurality of lacquer layers
- the first lacquer layer is at least partially cured by high-energy radiation before the application of the further lacquer layer (s).
- a decorative layer is applied to the lacquer layer prior to the application of the adhesive layer or, in the case of multiple lacquer layers, to the first lacquer layer.
- This decorative layer can be applied in a manner known per se by suitable printing methods, for example by flat, gravure, inkjet or digital printing.
- the lacquer layer is partially cured before applying the decorative layer, wherein the partial curing is preferably carried out only to the extent that just applying the decorative layer is possible.
- the printing inks used to produce the decorative layer can be conventional printing inks or UV-curing printing inks.
- the application of the heat-sealable adhesive layer in step iv) of the method according to the invention can be carried out in a manner known per se.
- a liquid adhesive composition in particular an aqueous adhesive composition in the usual manner, for example, by knife coating, rolling, pouring or spraying on the paint layer or on the decorative layer is usually applied.
- the adhesive layer is dried, for example by heat.
- the application amount of the liquid adhesive composition is usually selected so that, after drying, a layer thickness results in the above ranges.
- the application rate is in the range of 5 to 50 g solids per m 2 , in particular in the range of 5 to 15 g solids per m 2 .
- the following film constructions 1 to 12 can be produced by using the steps given there.
- the film structures 7 to 12 correspond to the film structures 1 to 6 with the difference that a pigment-containing adhesive composition is used.
- the resulting thermal transfer films can then be made up in the usual way, for. B. are wound into rolls.
- the thermal transfer films according to the invention are particularly suitable for the dry coating of surfaces of objects.
- the lacquer layer or the lacquer layers on the surface to be coated of the article hereinafter also referred to as a substrate transferred
- the adhesive layer after irradiation a good bond between the or the paint layers and the substrate causes.
- the use of the thermal transfer films according to the invention is not limited to certain substrates, but they can be very versatile applied to both hard and elastic substrates.
- the substrates can be, for example, articles made of plastic, for example ABS, polycarbonate, melamine, polyester, including glass fiber reinforced Polyester, hard PVC, soft PVC, rubber, wood including exotic natural woods, wood materials, eg. As veneer, MDF, HDF, Feinspan- or multiplex plates, mineral fibers, z. As mineral fiber boards, paper, textile including synthetic leather, metal or plastic-coated materials act.
- the thermal transfer films according to the invention are preferably suitable for smooth, preferably plane or slightly curved surfaces. In principle, however, even more complex structures can be coated in this way.
- the substrates to be coated may be undecorated or already have decorative surfaces.
- thermal transfer films according to the invention it is particularly advantageous to coat exotic natural woods, which often present problems in wet painting, since the contents bleed or adhesion problems are caused.
- the coated using the thermal transfer films of the invention objects, for.
- wood fiber boards, MDF boards or natural wood panels that have been primed using the thermal transfer films of the invention can be readily coated with a conventional UV coating, with no intermediate sanding is required.
- such a primed article can also be dry-coated with a thermal transfer film according to the invention.
- the thermal transfer films according to the invention allow a virtually waste-free coating of articles.
- a change from colorless to color, from dull to glossy can take place very rapidly, without a cleaning step being required between these changes. Drying times are eliminated, and after the coating can be continued directly, z. B. applied a conventional paint job or the coated article to be packaged.
- the carrier film can be peeled off or initially remain as a protective film on the coated surface.
- the use of the thermal transfer films according to the invention permits a dust-free coating.
- the space requirements and personnel costs compared to conventional painting process is much lower.
- the thermal transfer films of the invention provide compared to the known from the prior art thermal transfer films surfaces with particularly high valence, especially high scratch and abrasion resistance.
- surfaces of quality classes AC3 to AC4 can be achieved.
- the surfaces obtained using the thermal transfer films according to the invention regularly show values above 20 N when tested with the Hamberger planer. The surfaces thus obtained regularly meet the requirements of the highest stress group of the furniture standard DIN 68861.
- thermal transfer films according to the invention for coating surfaces of articles is typically carried out in a process which comprises the abovementioned steps a) to d), which are described in more detail below and which are analogous to those described in EP 2078618 A2 described procedure can be performed. On the relevant content of EP 2078618 A2 is hereby incorporated by reference.
- the thermal transfer film of the invention is first applied to the surface of the substrate to be coated and then heat sealed.
- the heat sealing is typically carried out using pressure in suitable presses, wherein the temperature of the press is typically in the range of 100 to 250 ° C, preferably in the range of 160 to 220 ° C.
- the thus coated substrate with high-energy radiation, d. H. irradiated with UV or electron radiation the coating layer cures completely.
- the irradiation may be performed prior to removal of the carrier sheet or subsequently.
- the irradiation can by means of electron radiation, z. B. using gallium radiators or with UV light, for example, with UV lamps or UV-emitting LEDs, done.
- UV radiation is used for curing in step ii).
- UV radiation is used in the wavelength range from 200 to 400 nm.
- medium-pressure mercury lamps or high-pressure mercury lamps for this purpose.
- gallium or iron-doped high-pressure mercury lamps are used.
- the irradiation in step ii) takes place at a radiation density in the range from 40 to 2000 J / m 2 , in particular in the range from 100 to 400 J / m 2 .
- a system for carrying out the method according to the invention comprises at least one commonly used thermal transfer device, which preferably has a cutting device and / or a winding device for the carrier film.
- the equipment may include a first thermal transfer device with which the article is primed and a second thermal transfer device, with which the article is finished, have.
- a conventional thermal transfer device can be constructed as follows: From a film unwinding the wound as a roll thermal transfer film is fed to a heated roller press having at least one driven, heated, optionally rubberized roller, which is optionally adjustable in height.
- the roller press usually has one of the heated roller opposite counter-pressure roller, which may be rubberized. This causes the necessary pressing pressure, whereby the lacquer layer is transferred by means of the adhesive layer to the surface of an object which is guided between the two rollers.
- the counter-pressure roller can be designed so that it causes the separation of the carrier film from the paint layer.
- the separated carrier film can be removed with a cutter or fed to a Folienaufwickelinnate.
- a plate press can be used, which is opened after a predetermined time.
- the coated article with the coated side past a source of high energy radiation, such as an electron gun or UV emitter, exposing the coated side of the article to high energy radiation and achieving final cure.
- a source of high energy radiation such as an electron gun or UV emitter
- the article thus coated is subsequently fed to a collecting device, for example a stacking device.
- the carrier film can be removed with a cutter or fed to a film take-up device.
- the object coated in the thermal transfer device can also be supplied to a further thermal transfer device after removal of the carrier film before or after curing by means of high-energy radiation, in which a further lacquer layer is applied to the coated surface of the article by means of a further thermal transfer film according to the invention.
- a further lacquer layer is applied to the coated surface of the article by means of a further thermal transfer film according to the invention.
- curing with high-energy radiation is carried out as described above.
- a first embodiment of a device for the continuous implementation of the method according to the invention with solid substrates comprises a lay-on conveyor belt, an unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with roller press, as described above, a winding device for the carrier film, a drying channel with UV emitter, a discharge belt and a stacking device.
- the substrates to be coated are placed on the conveyor belt and guided at the desired feed rate through the thermal transfer device.
- the lacquer layer is transferred to the substrate and the carrier foil separated and taken up by the take-up device.
- the lacquer layer is cured in the drying channel.
- the winding station can also be arranged after the drying channel, so that the carrier film initially remains on the substrate and acts there as a protective film.
- a second embodiment of an apparatus for continuously carrying out the method according to the invention with elastic substrates comprises a unwinding station for the substrate, a unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with roller press, as described above, a drying channel with UV lamps and a winding device for the coated substrate.
- the substrate to be coated is guided through the thermal transfer device at the desired feed rate together with the thermal transfer film.
- the thermal transfer film is bonded to the substrate.
- the thus coated substrate is passed through the drying channel, whereby the lacquer layer cures and received by the winding station. After cutting, the carrier film can be removed.
- a third embodiment of a device for continuously carrying out the method according to the invention with solid substrates comprises a conveyor belt, an unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with heated platen press and optionally a take-up device for the carrier film or a cutting device.
- the substrates to be coated are placed on the conveyor belt and fed together with the thermal transfer film in the plate press.
- the press is closed and pressurized with the desired pressure.
- the lacquer layer is transferred to the substrate.
- the substrate is driven out of the press and passed through the drying channel, whereby the lacquer layer cures.
- the carrier film can remain on the substrate and serve as a protective film.
- the carrier film before or after the drying channel be cut with a cutting device.
- a further embodiment of a device for the discontinuous implementation of the method according to the invention with solid substrates comprises a conveyor belt, an unwinding station for wound as a roll thermal transfer film, a cutting device, thermal transfer device with heated platen press and a drying channel with UV lamp.
- the substrate to be coated is placed on the conveyor belt.
- the thermal transfer film is unwound to the desired length, placed with the adhesive layer on the substrate to be coated and cut.
- Substrate and foil are fed into the plate press.
- the press is closed and pressurized with the desired pressure.
- the lacquer layer is transferred to the substrate.
- the coated substrate is driven out of the press and passed through the drying channel, whereby the lacquer layer cures.
- the carrier film can remain on the substrate and serve as a protective film. Alternatively, it is possible to separate the film from the UV channel.
- the adhesive composition 1 was prepared by mixing the ingredients indicated in the following table.
- Adhesive formulation 1 raw material Amount [% by weight] 1) Self-crosslinking aqueous polyacrylate dispersion 1 39.0 Aqueous polyether urethane acrylate dispersion 1 16.4 Polyether emulsion 0.44 Polymeric fluorosurfactant 0.35 carnauba wax dispersion 1.20 Modified polyethylene wax 7.3 Pyrogenic silica 1.5 Synthetic silicic acid 1.3 Micronized polyethylene wax 1.7 polyurethane dispersion 13.0 dimethylpolysiloxane 0.4 Aliphatic epoxy acrylate 6.1 Styrene-acrylate dispersion (50%) 4.4 triethylcitrate 1.75 alpha-hydroxyalkylphenone 1.0 acylphosphine 0.7 benzophenone 0.85 butylglycol 1.0 water 1.0 aminoalcohol 0.17 1) based on the total weight of the composition
- the adhesive formulation 2 was prepared by mixing the constituents indicated in the following table.
- the adhesive formulation 3 was prepared by mixing the constituents indicated in the following table.
- the adhesive formulation 4 was prepared by mixing the constituents indicated in the following table.
- a device was used for the irradiation, in which the coated or printed film with a defined feed rate of a Ga-doped mercury lamps with the power of 120 W / cm was passed.
- Example 1 Film for use as a color lacquer in the furniture sector
- the paint formulation 4 was applied with a layer thickness of 40 g / m 2 .
- the thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
- the UV-curable gravure ink was applied to the gelled lacquer layer.
- the so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
- the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
- Example 2 Film for use as a color lacquer in the furniture sector
- the lacquer formulation 5 having a layer thickness of 70 g / m 2 was applied to an undyed polyethylene terephthalate support film having a layer thickness of 23 ⁇ m.
- the thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
- the UV-curable gravure ink was applied to the gelled lacquer layer.
- the so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
- the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
- Example 3 Film for use as a clearcoat in the furniture sector
- the paint formulation 6 was applied with a layer thickness of 40 g / m 2 .
- the thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
- the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
- Example 4 Film for use as exterior color paint
- the paint formulation 7 was applied with a layer thickness of 45 g / m 2 .
- the thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
- the UV-curable gravure ink was applied to the gelled lacquer layer.
- the so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
- the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
- Example 3 The film of Example 3 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) on a beech wood panel. Subsequently, the thus laminated film was irradiated by Verbeiin the laminated side at a feed rate of 20 m / min to two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film.
- the sample thus obtained was analyzed by ATR-FTIR spectroscopy using an FT-IR spectrometer from Nicolet (Nicolet 380) and a Golden Gate® probe head. Compared to a non-irradiated sample, a significant decrease in the absorption bands characteristic of acrylate groups was observed at 810 cm-1 (> 40%) and 1410 cm-1 (> 30%).
- the film from Example 1 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at a constant contact pressure on an MDF board. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 20 m / min on two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
- Example 1 For comparison purposes, the film of Example 1 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at the same contact pressure on an MDF board, but no subsequent irradiation was made.
- the preparation was carried out in analogy to the preparation of Sample 1, using instead of the film of Example 1, the film of Example 2.
- the preparation was carried out in analogy to the preparation of the comparative sample V1, using instead of the film of Example 1, the film of Example 2.
- the film from Example 3 was laminated by means of a heated roller (180 ° C, object temperature maximum 50 ° C) at a constant contact pressure on a beech wood panel. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 20 m / min on two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
- Example 3 For comparison purposes, the film of Example 3 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at the same contact pressure on a beech wood panel, but no subsequent irradiation was made.
- the film from Example 43 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at a constant contact pressure on a PVC plate. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 15 m / min at two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
- Example 4 For comparison purposes, the film of Example 4 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at the same contact pressure on a PVC plate, but no subsequent irradiation was made.
- Table P Results of tests P1 - P8 sample UV curing P1 P2 P3 P4 [N] P5 [N] P6 P7 [Umin -1 ] P8 [Umin -1 ] 1 Yes 5 5 5 20 1.2 GT0 nb nb 2 Yes 5 5 5 19 1.0 GT0 620 1600 3 Yes 5 5 5 18 1.1 GT0 nb nb 4 Yes 5 5 5 19 1.3 GT1 nb nb V1 No 4-5 5 5 13 0.7 GT5 nb nb V2 No 4-5 4-5 5 14 0.6 GT4 630 1550 V3 No 4 4 5 13 0.7 GT4 nb nb V4 No 5 5 13 0.7 GT3 nb nb
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Decoration By Transfer Pictures (AREA)
Description
Die vorliegende Erfindung betrifft Thermotransferfolien und deren Verwendung für die Trockenlackierung von Oberflächen. Die Erfindung betrifft auch die Herstellung derartiger Thermotransferfolien sowie ein Verfahren zum Beschichten bzw. Lackieren von Oberflächen von Gegenständen unter Verwendung der erfindungsgemäßen Thermotransferfolien.The present invention relates to thermal transfer films and their use for the dry coating of surfaces. The invention also relates to the production of such thermal transfer films and to a process for coating or coating surfaces of articles using the thermal transfer films according to the invention.
Üblicherweise werden Oberflächen von Gegenständen im Nasslackverfahren beschichtet, d. h. ein flüssiger Lack wird auf die zu beschichtende Oberfläche aufgebracht und anschließend getrocknet, wodurch auf der Oberfläche eine Lackschicht entsteht. Bei einer industriellen Lackierung erfolgt die Lackierung üblicherweise in Lackierstra-ßen, wobei zur Trocknung regelmäßig längere Trockenstrecken notwendig sind, bei denen der Lack mit vergleichsweise hohem Energieaufwand getrocknet und ausgehärtet wird. Derartige Verfahren sind daher zeit-, energie- und zudem personalintensiv. Zudem müssen nach Beendigung der Lackierung die Beschichtungsvorrichtungen der Lackierstraßen gereinigt werden, was zu Standzeiten führt. Zudem muss der beim Reinigen der Maschinen entstehende Abfall als Sondermüll beseitigt werden. Einige Zweikomponenten-Lacke haben eine begrenzte Verarbeitungsdauer, und nicht verbrauchte Reste müssen ebenfalls als Sondermüll entsorgt werden.Usually surfaces of articles are coated by wet coating, d. H. a liquid lacquer is applied to the surface to be coated and then dried, whereby a lacquer layer is formed on the surface. In an industrial coating, the coating is usually carried out in Lackierstra- Shen, wherein for drying regularly longer dry sections are necessary, in which the paint is dried and cured with relatively high energy consumption. Such methods are therefore time, energy and also staff-intensive. In addition, after completion of the painting, the coating devices of the paint lines must be cleaned, resulting in service life. In addition, the waste generated when cleaning the machines must be disposed of as special waste. Some two-component paints have a limited processing time, and unused residues must also be disposed of as hazardous waste.
Verschiedentlich wurde über Beschichtungs- bzw. Lackiertechniken berichtet, bei denen eine oder mehrere Lackschichten mittels Heißprägefolien, auch als Thermotransferfolien bezeichnet, auf die zu beschichtende Oberfläche übertragen werden. Diese Folien umfassen eine Trägerfolie, auf der eine oder mehrere Polymerschichten und gegebenenfalls eine Klebeschicht angeordnet sind. Beim Beschichten wird die wenigstens eine Polymerschicht mittels Druck und/oder Wärme von der Trägerfolie auf die zu beschichtende Oberfläche übertragen. Auf diese Weise bildet die wenigstens eine Polymerschicht auf der zu beschichtenden Oberfläche eine Lackschicht, ohne dass bei dem Beschichtungsvorgang organische Lösungsmittel eingesetzt werden müssen. Durch Kombination von Dekor- und Lackschichten können unterschiedlichste Gestaltungen der Oberfläche in einfachster Weise reproduzierbar erzielt werden.There have been various reports of coating techniques in which one or more coats of paint are transferred to the surface to be coated by means of hot stamping foils, also referred to as thermal transfer foils. These films comprise a carrier film on which one or more polymer layers and optionally an adhesive layer are arranged. During coating, the at least one polymer layer is transferred by means of pressure and / or heat from the carrier film to the surface to be coated. In this way, the at least one polymer layer on the surface to be coated forms a lacquer layer without having to use organic solvents in the coating process. By combining decorative and lacquer layers, the most varied designs of the surface can be reproducibly achieved in the simplest possible way.
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Es wurde überraschenderweise gefunden, dass Thermotransferfolien, die wenigstens eine auf der Trägerfolie angeordnete Lackschicht aufweisen, welche auf einer nicht-wässrigen strahlungshärtbaren, flüssigen Zusammensetzung basiert, die wenigstens 60 Gew.-%, insbesondere wenigstens 70 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, vernetzbare Bestandteile enthält, die ausgewählt sind unter organischen Oligomeren, die ethylenisch ungesättigte Doppelbindungen aufweisen und Gemischen dieser Oligomere mit Monomeren, die wenigstens eine ethylenisch ungesättigte Doppelbindung aufweisen, und die eine heißsiegelbare polymere Klebeschicht (4) aufweisen, welche wenigstens einen strahlungshärtbaren Bestandteil enthält, in besonderer Weise zur Beschichtung von Oberflächen geeignet sind. So führt die Verwendung derartiger Thermotransferfolien zu besonders widerstandsfähigen Oberflächen die besonders gut auf den beschichteten Untergründen haften. Zudem erlaubt der Einsatz nicht-wässriger, strahlungshärtbarer Beschichtungszusammensetzungen mit einem hohen Anteil an vernetzbaren Bestandteilen die gezielte Anpassung der Thermotransferfolie für unterschiedliche Untergründe, nämlich sowohl für harte wie auch für hochelastische Untergründe. Im Unterschied zu Thermotransferfolien mit Lackschichten auf Basis thermisch härtbarer Beschichtungsmittel ist die Temperaturbelastung des zu beschichtenden Materials beim Transfer der Lackschicht(en) auf die zu beschichtende Oberfläche vergleichsweise gering, da eine Endhärtung in leichter Weise durch Bestrahlen der beschichteten Oberfläche mit energiereicher Strahlung wie UV- oder Elektronenstrahlung durchgeführt werden kann und keine nachträgliche Temperung notwendig ist.It has surprisingly been found that thermal transfer films which have at least one lacquer layer arranged on the carrier film and which are based on a non-aqueous radiation-curable, liquid composition which is at least 60% by weight, in particular at least 70% by weight, based on the total weight of the composition containing crosslinkable components selected from organic oligomers having ethylenically unsaturated double bonds and mixtures of these oligomers with monomers having at least one ethylenically unsaturated double bond and having a heat-sealable polymeric adhesive layer (4) containing at least one radiation-curable component contains, are particularly suitable for coating surfaces. Thus, the use of such thermal transfer films to particularly resistant surfaces adhere particularly well to the coated substrates. In addition, the use of non-aqueous, radiation-curable coating compositions with a high proportion of crosslinkable components allows the targeted adaptation of the thermal transfer film for different substrates, namely for both hard as well as highly elastic substrates. In contrast to thermal transfer films with lacquer layers based on thermally curable coating materials, the temperature load of the material to be coated during transfer of the lacquer layer (s) on the surface to be coated is comparatively low, since a final curing easily by irradiating the coated surface with high-energy radiation such as UV or electron radiation can be performed and no subsequent annealing is necessary.
Aufgrund der Verwendung flüssiger Zusammensetzungen mit einem hohen Anteil an vernetzbaren Bestandteilen, welche durch energiereiche Strahlung, insbesondere durch UV-Strahlung ausgehärtet werden, können zudem lange Trocknungszeiten bei der Herstellung der Thermotransferfolien entfallen, so dass deren Herstellung sehr effizient durchgeführt werden kann.Due to the use of liquid compositions having a high proportion of crosslinkable constituents which are cured by high-energy radiation, in particular by UV radiation, moreover, long drying times in the production of the thermal transfer films can be dispensed with, so that their production can be carried out very efficiently.
Dementsprechend betrifft ein erster Gegenstand der vorliegenden Erfindung eine Thermotransferfolie (1), umfassend:
- a) eine Trägerfolie (2),
- b) wenigstens eine, z. B. ein, zwei oder drei, unmittelbar auf der Trägerfolie (2) angeordnete Lackschicht(en) (3),
- c) wenigstens eine, insbesondere genau eine heißsiegelbare, polymere Klebeschicht (4),
- i. das Aufbringen der nicht-wässrigen, strahlungshärtbaren, flüssigen Zusammensetzung, wobei man eine durch energiereiche Strahlung härtbare Beschichtung erhält;
- ii. Bestrahlung der in Schritt i. erhaltenen härtbaren Beschichtung mit energiereicher Strahlung, insbesondere mit UV-Licht, wobei man die Lackschicht (3) erhält;
- iii. gegebenenfalls Aufbringen einer Dekorschicht auf die härtbare Beschichtung oder auf die Lackschicht (3); und
- iv. Aufbringen der heißsiegelbaren, polymeren Klebeschicht (4).
Gegenstand der Erfindung ist auch ein Verfahren zum Beschichten von Oberflächen von Gegenständen, umfassend die folgenden Schritte:
- a) Aufbringen der erfindungsgemäßen Thermotransferfolie (1) mit der Klebeschicht auf die zu beschichtende Oberfläche;
- b) Heißsiegeln der Transferfolie, wobei man eine mit der Transferfolie beschichtete Oberfläche erhält;
- c) Bestrahlung der mit der Transferfolie beschichteten Oberfläche mit energiereicher Strahlung, insbesondere mit UV- oder Elektronenstrahlung, speziell mit UV-Strahlung; und
- d) gegebenenfalls Ablösen der Trägerfolie (2).
- a) a carrier film (2),
- b) at least one, z. B. one, two or three, directly on the carrier film (2) arranged lacquer layer (s) (3),
- c) at least one, in particular precisely heat-sealable, polymeric adhesive layer (4),
- i. applying the non-aqueous, radiation curable, liquid composition to obtain a high energy radiation curable coating;
- ii. Irradiation of the in step i. obtained curable coating with high-energy radiation, in particular with UV light, to obtain the lacquer layer (3);
- iii. optionally applying a decorative layer on the curable coating or on the lacquer layer (3); and
- iv. Applying the heat-sealable polymeric adhesive layer (4).
The invention also provides a process for coating surfaces of objects, comprising the following steps:
- a) applying the thermal transfer film (1) according to the invention with the adhesive layer to the surface to be coated;
- b) heat-sealing the transfer film to obtain a surface coated with the transfer film;
- c) irradiation of the surface coated with the transfer film with high-energy radiation, in particular with UV or electron radiation, especially with UV radiation; and
- d) optionally detaching the carrier film (2).
Die zur Herstellung der Lackschicht verwendeten strahlungshärtbaren, flüssigen Zusammensetzungen enthalten wenigstens 60 Gew.-%, insbesondere wenigstens 70 Gew.-%, z. B. 60 bis 99 Gew.-%, insbesondere 70 bis 95 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, härtbare Bestandteile, welche ethylenisch ungesättigte Doppelbindungen aufweisen. Hierbei werden die Bestandteile vorzugsweise so ausgewählt, dass in der Zusammensetzung 1,5 bis 8 mol, insbesondere 2,0 bis 7 mol und speziell 2,5 bis 6,5 mol ethylenisch ungesättigte Doppelbindungen pro kg der Beschichtungszusammensetzung vorliegen.The radiation-curable, liquid compositions used for the preparation of the lacquer layer contain at least 60 wt .-%, in particular at least 70 wt .-%, z. B. 60 to 99 wt .-%, in particular 70 to 95 wt .-%, based on the total weight of the composition, curable components which have ethylenically unsaturated double bonds. In this case, the constituents are preferably selected such that 1.5 to 8 mol, in particular 2.0 to 7 mol, and especially 2.5 to 6.5 mol, of ethylenically unsaturated double bonds per kg of the coating composition are present in the composition.
Die ethylenisch ungesättigten Doppelbindungen der härtbaren Bestandteile der flüssigen, strahlungshärtbaren Zusammensetzung, welche die Lackschicht bildet, liegen vorzugsweise in Form von Acrylgruppen, Methacrylgruppen, Allylgruppen, Fumarsäuregruppen, Maleinsäuregruppen und/oder Maleinsäureanhydridgruppen, insbesondere zu wenigstens 90 % oder 100 %, bezogen auf die Gesamtmenge der in der Zusammensetzung enthaltenen ethylenisch ungesättigten Doppelbindungen, in Form Acryl- oder Methacrylgruppen und speziell in Form von Acrylgruppen vor. Die Acryl- und Methacrylgruppen können in Form von (Meth)Acrylamid- oder (Meth)Acrylat-gruppen vorliegen, wobei Letzteres bevorzugt ist. Insbesondere weisen die härtbaren Bestandteile der strahlungshärtbaren Zusammensetzung welche die Lackschicht bildet, zu wenigstens 90 % oder 100 %, bezogen auf die Gesamtmenge der in der Zusammensetzung enthaltenen ethylenisch ungesättigten Doppelbindungen, Acrylatgruppen auf.The ethylenically unsaturated double bonds of the curable constituents of the liquid, radiation-curable composition which forms the lacquer layer are preferably in the form of acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular at least 90% or 100%, based on the total amount the ethylenically unsaturated double bonds present in the composition, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups. The acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred. In particular, the curable components of the radiation-curable composition forming the lacquer layer comprise at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds present in the composition, of acrylate groups.
Erfindungsgemäß enthalten die flüssigen, strahlungshärtbaren Zusammensetzungen, welche zur Herstellung der Lackschicht eingesetzt werden, wenigstens ein Oligomer, das ethylenisch ungesättigte Doppelbindungen aufweist. Die Oligomere weisen vorzugsweise im Mittel eine Funktionalität im Bereich von 1,5 bis 10, insbesondere im Bereich von 2 bis 8,5 auf, d. h. die Anzahl ethylenisch ungesättigter Doppelbindungen pro Molekül liegt im Mittel im Bereich von 1,5 bis 10 und insbesondere im Bereich von 2 bis 8,5. Geeignet sind auch Gemische verschiedener Oligomere mit unterschiedlicher Funktionalität, wobei die mittlere Funktionalität vorzugsweise im Bereich von 1,5 bis 10, insbesondere im Bereich von 2 bis 8,5 liegt.According to the invention, the liquid, radiation-curable compositions which are used to prepare the lacquer layer contain at least one oligomer which has ethylenically unsaturated double bonds. The oligomers preferably have on average a functionality in the range from 1.5 to 10, in particular in the range from 2 to 8.5, ie the number of ethylenically unsaturated double bonds per molecule is on average in the range from 1.5 to 10 and in particular Range from 2 to 8.5. Also suitable are mixtures of different oligomers with different Functionality, wherein the average functionality is preferably in the range of 1.5 to 10, in particular in the range of 2 to 8.5.
Die Oligomere weisen typischerweise ein lineares oder verzweigtes Grundgerüst auf, das im Mittel mehr als eine ethylenisch ungesättigte Doppelbindung trägt, vorzugsweise in Form der vorgenannten Acrylgruppen, Methacrylgruppen, Allylgruppen, Fumarsäuregruppen, Maleinsäuregruppen und/oder Maleinsäureanhydridgruppen, insbesondere in Form von Acryl- oder Methacrylgruppen, wobei die ethylenisch ungesättigten Doppelbindungen über einen Linker an das Grundgerüst gebunden sein können oder Bestandteil des Grundgerüsts sind. Geeignete Oligomere sind vor allem Oligomere aus der Gruppe der Polyether, Polyester, Polyurethane und Epoxid-basierte Oligomere. Bevorzugt sind Oligomere, die im Wesentlichen keine aromatischen Struktureinheiten aufweisen sowie Gemische von Oligomeren mit aromatischen Gruppen und Oligomeren ohne aromatische Gruppen.The oligomers typically have a linear or branched skeleton which carries on average more than one ethylenically unsaturated double bond, preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular in the form of acrylic or methacrylic groups, wherein the ethylenically unsaturated double bonds may be linked via a linker to the skeleton or are part of the skeleton. Suitable oligomers are, in particular, oligomers from the group of polyethers, polyesters, polyurethanes and epoxide-based oligomers. Preference is given to oligomers which have substantially no aromatic structural units and to mixtures of oligomers having aromatic groups and oligomers without aromatic groups.
Insbesondere sind die Oligomere ausgewählt unter Polyether(meth)acrylaten, d. h. Polyether mit Acryl- oder Methacrylgruppen, Polyester(meth)acrylaten, d. h. Polyester mit Acryl- oder Methacrylgruppen, Epoxid(meth)acrylaten, d. h. Reaktionsprodukte von Polyepoxiden mit hydroxyl-funktionalisierten Acryl- oder Methacrylverbindungen, Urethan(meth)acrylaten, d. h. Oligomere, die ein (Poly)urethangerüst und Acryl- oder Methacrylgruppen aufweisen, beispielsweise Umsetzungsprodukte von Polyisocyanaten mit hydroxyl-funktionalisierten Acryl- oder Methacrylverbindungen, und ungesättigten Polyesterharzen, d. h. Polyester, die mehrere vorzugsweise im Polymergerüst vorliegende ethylenisch ungesättigte Doppelbindungen aufweisen, z. B. Kondensationsprodukte von Maleinsäure oder Fumarsäure mit aliphatischen Di- oder Polyolen, und deren Gemischen.In particular, the oligomers are selected from polyether (meth) acrylates, i. H. Polyethers having acrylic or methacrylic groups, polyester (meth) acrylates, d. H. Polyesters having acrylic or methacrylic groups, epoxide (meth) acrylates, d. H. Reaction products of polyepoxides with hydroxyl-functionalized acrylic or methacrylic compounds, urethane (meth) acrylates, d. H. Oligomers having a (poly) urethane backbone and acrylic or methacrylic groups, for example, reaction products of polyisocyanates with hydroxyl-functionalized acrylic or methacrylic compounds, and unsaturated polyester resins, d. H. Polyesters having a plurality of preferably present in the polymer backbone ethylenically unsaturated double bonds, for. As condensation products of maleic acid or fumaric acid with aliphatic di- or polyols, and mixtures thereof.
Im Unterschied zu den Monomeren, welche ebenfalls in diesen härtbaren Zusammensetzungen enthalten sein können, weisen die Oligomere typischerweise ein Molekulargewicht (Zahlenmittel) von wenigstens 400 g/mol, insbesondere wenigstens 500 g/mol, z. B. im Bereich von 400 bis 4000 g/mol und insbesondere im Bereich von 500 bis 2000 g/mol auf. Die Monomere weisen demgegenüber typischerweise Molekulargewichte unterhalb 400 g/mol, z. B. im Bereich von 100 bis < 400 g/mol auf.Unlike the monomers which may also be included in these curable compositions, the oligomers typically have a number average molecular weight of at least 400 g / mol, especially at least 500 g / mol, e.g. B. in the range of 400 to 4000 g / mol and in particular in the range of 500 to 2000 g / mol. In contrast, the monomers typically have molecular weights below 400 g / mol, z. B. in the range of 100 to <400 g / mol.
Geeignete Polyether(meth)acrylate sind vor allem aliphatische Polyether, insbesondere Poly(C2-C4)-alkylenether, die im Mittel 2 bis 4 Acrylat- oder Methacrylat-Gruppen aufweisen. Beispiele hierfür sind die Laromer®-Typen PO33F, LR8863, GPTA, LR8967, LR8962, LR9007 der BASF SE, bei denen es sich teilweise um Abmischungen mit Monomeren handelt.Suitable polyether (meth) acrylates are, above all, aliphatic polyethers, in particular poly (C 2 -C 4 ) -alkylene ethers, which on average have from 2 to 4 acrylate or methacrylate groups. Examples of these are the Laromer® grades PO33F, LR8863, GPTA, LR8967, LR8962, LR9007 from BASF SE, which in some cases are blends with monomers.
Geeignete Polyester(meth)acrylate sind vor allem aliphatische Polyester, die im Mittel 2 bis 6 Acrylat- oder Methacrylat-Gruppen aufweisen. Beispiele hierfür sind die Laromer®-Typen PE55F, PE56F, PE46T, LR9004, PE9024, PE9045, PE44F, LR8800, LR8907, LR9032, PE9074, PE9079, PE9084 der BASF SE, bei denen es sich teilweise um Abmischungen mit Monomeren handelt.Suitable polyester (meth) acrylates are, in particular, aliphatic polyesters which on average have from 2 to 6 acrylate or methacrylate groups. Examples of these are the Laromer® grades PE55F, PE56F, PE46T, LR9004, PE9024, PE9045, PE44F, LR8800, LR8907, LR9032, PE9074, PE9079, PE9084 from BASF SE, which in some cases are blends with monomers.
Geeignete Polyurethanacrylate sind vor allem Urethangruppen-haltige Verbindungen, die im Mittel 2 bis 10, insbesondere 2 bis 8,5 Acrylat- oder Methacrylat-Gruppen aufweisen und die vorzugsweise durch Umsetzung aromatischer oder aliphatischer Di- oder Oligoisocyanate mit Hydroxyalkylacrylaten oder Hydroxylalkylmethacrylaten erhältlich sind. Beispiele hierfür sind die Laromer®-Typen UA19T, UA9028, UA9030, LR8987, UA9029, UA9033, UA9047, UA9048, UA9050, UA9072, UA9065 und UA9073 der BASF SE, bei denen es sich teilweise um Abmischungen mit Monomeren handelt.Suitable polyurethane acrylates are, above all, urethane-containing compounds which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups and which are preferably obtainable by reaction of aromatic or aliphatic di- or oligoisocyanates with hydroxyalkyl acrylates or hydroxyalkyl methacrylates. Examples of these are the Laromer® grades UA19T, UA9028, UA9030, LR8987, UA9029, UA9033, UA9047, UA9048, UA9050, UA9072, UA9065 and UA9073 from BASF SE, some of which are blends with monomers.
In bevorzugten Ausführungsformen der Erfindung umfasst die strahlungshärtbare, flüssige Zusammensetzung welche die Lackschicht bildet, wenigstens ein Oligomer, das unter Urethanacrylaten und Polyesteracrylaten und deren Mischungen ausgewählt ist sowie gegebenenfalls ein oder mehrere Monomere.In preferred embodiments of the invention, the radiation-curable, liquid composition forming the lacquer layer comprises at least one oligomer selected from urethane acrylates and polyester acrylates and mixtures thereof, and optionally one or more monomers.
In besonderen Ausführungsformen der Erfindung umfasst die strahlungshärtbare, flüssige Zusammensetzung welche die Lackschicht bildet, wenigstens ein Urethanacrylat und gegebenenfalls ein oder mehrere Monomere.In particular embodiments of the invention, the radiation-curable, liquid composition which forms the lacquer layer comprises at least one urethane acrylate and optionally one or more monomers.
In anderen besonderen Ausführungsformen der Erfindung umfasst die strahlungshärtbare, flüssige Zusammensetzung welche die Lackschicht bildet, wenigstens ein Poylesteracrylat und gegebenenfalls ein oder mehrere Monomere.In other particular embodiments of the invention, the radiation-curable, liquid composition forming the lacquer layer comprises at least one polyester acrylate and optionally one or more monomers.
In speziellen Ausführungsformen der Erfindung umfasst die strahlungshärtbare, flüssige Zusammensetzung welche die Lackschicht bildet, wenigstens ein Urethanacrylat und wenigstens ein Polyesteracrylat und gegebenenfalls ein oder mehrere Monomere.In specific embodiments of the invention, the radiation-curable, liquid composition forming the lacquer layer comprises at least one urethane acrylate and at least one polyester acrylate and optionally one or more monomers.
In weiteren speziellen Ausführungsformen der Erfindung umfasst die strahlungshärtbare, flüssige Zusammensetzung welche die Lackschicht bildet, wenigstens ein aliphatisches Urethanacrylat und wenigstens ein aromatisches Urethancrylat oder wenigstens zwei verschiedene aliphatische Urethanacrylate und gegebenenfalls ein oder mehrere Monomere.In further specific embodiments of the invention, the radiation-curable, liquid composition forming the lacquer layer comprises at least one aliphatic urethane acrylate and at least one aromatic urethane acrylate or at least two different aliphatic urethane acrylates and optionally one or more monomers.
In weiteren speziellen Ausführungsformen der Erfindung umfasst die strahlungshärtbare, flüssige Zusammensetzung welche die Lackschicht bildet, wenigstens ein aliphatisches Urethanacrylat, wenigstens ein aromatisches Urethanacrylat und wenigstens ein Polyesteracrylat und gegebenenfalls ein oder mehrere Monomere.In further specific embodiments of the invention, the radiation-curable, liquid composition which forms the lacquer layer comprises at least one aliphatic urethane acrylate, at least one aromatic urethane acrylate and at least one polyester acrylate and optionally one or more monomers.
Neben den ethylenisch ungesättigte Doppelbindungen aufweisenden Oligomeren können die vernetzbaren Bestandteile der strahlungshärtbaren, flüssigen Zusammensetzung welche zur Herstellung der Lackschicht eingesetzt wird, ein oder mehrere Monomere enthalten, die auch als Reaktivverdünner bezeichnet werden. Die Monomere weisen typischerweise Molekulargewichte unterhalb 400 g/mol, z. B. im Bereich von 100 bis < 400 g/mol auf. Geeignete Monomere weisen in der Regel 1 bis 6, insbesondere 2 bis 4 ethylenisch ungesättigte Doppelbindungen pro Molekül auf. Die ethylenisch ungesättigten Doppelbindungen liegen dabei vorzugsweise in Form der vorgenannten Acrylgruppen, Methacrylgruppen, Allylgruppen, Fumarsäuregruppen, Maleinsäuregruppen und/oder Maleinsäureanhydridgruppen, insbesondere in Form von Acryl- oder Methacrylgruppen und speziell als Acrylatgruppen vor.In addition to the oligomers having ethylenically unsaturated double bonds, the crosslinkable constituents of the radiation-curable, liquid composition used to prepare the lacquer layer may contain one or more monomers, which are also referred to as reactive diluents. The monomers typically have molecular weights below 400 g / mol, e.g. B. in the range of 100 to <400 g / mol. Suitable monomers generally have 1 to 6, in particular 2 to 4, ethylenically unsaturated double bonds per molecule. The ethylenically unsaturated double bonds are preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular in the form of acrylic or methacrylic groups and especially as acrylate groups.
Bevorzugte Monomere sind ausgewählt unter Estern der Acrylsäure mit 1- bis 6-wertigen, insbesondere 2- bis 4-wertigen aliphatischen oder cycloaliphatischen Alkoholen, die vorzugsweise 2 bis 20 C-Atome aufweisen, wie beispielsweise Monoester der Acrylsäure mit C1-C20-Alkanolen, Benzylalkohol, Furfurylalkohol, Tetrahydrofurfurylalkohol, (5-Ethyl-1,3-dioxan-5-yl)methanol, Phenoxyethanol, 1,4-Butandiol oder 4-tert.-Butylcyclohexanol; Diester der Acrylsäure mit Ethylenglykol, 1,3-Propandiol, 1,2-Propandiol, 1,4-Butandiol, 1,6-Hexandiol, Diethylenglykol, Triethylenglykol, Dipropylenglykol oder Tripropylenglykol; Triester der Acrylsäure mit Trimethylolpropan oder Pentaerythrit sowie die Tetraester der Acrylsäure mit Pentaerythrit. Beispiele für geeignete Monomere sind vor allem Trimethylolpropandiacrylat, Trimethylolpropantriacrylat, Ethylenglykoldiacrylat, Butandioldiacrylat, Hexandioldiacrylat, Dipropylenglykoldiacrylat, Tripropylenglykoldiacarylat, Phenoxyethylacrylat, Furfurylacrylat, Tetrahydrofurfurylacrylat, 4-t-Butylcyclohexylacrylat, 4-Hydroxybutylacrylat und Trimethylolformalmonoacrylat (Acrylsäure-(5-ethyl-1,3-dioxan-5-yl)methylester).Preferred monomers are selected from esters of acrylic acid with monohydric to trihydric, especially dihydric to trihydric, aliphatic or cycloaliphatic alcohols which preferably have 2 to 20 C atoms, for example monoesters of acrylic acid with C 1 -C 20 - Alkanols, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, (5-ethyl-1,3-dioxan-5-yl) methanol, phenoxyethanol, 1,4-butanediol or 4-tert-butylcyclohexanol; Diesters of acrylic acid with ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol or tripropylene glycol; Triesters of acrylic acid with trimethylolpropane or pentaerythritol and the tetraesters of acrylic acid with pentaerythritol. Examples of suitable monomers are, in particular, trimethylolpropane diacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diarylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 4-t-butylcyclohexyl acrylate, 4-hydroxybutyl acrylate and trimethylolformalmonoacrylate (acrylic acid (5-ethyl-1,3-) dioxan-5-yl) methylester).
In bevorzugten Ausführungsformen der Erfindung umfasst die strahlungshärtbare, flüssige Zusammensetzung welche die Lackschicht bildet, wenigstens ein Oligomer, z. B. 1, 2 oder 3 Oligomere, insbesondere wenigstens eines, z. B. 1, 2 oder 3, der als bevorzugt genannten Oligomere und wenigstens ein Monomer, z. B. 1, 2 oder 3 Monomere, insbesondere wenigstens eines, z. B. 1, 2 oder 3, der als bevorzugt genannten Monomere. In diesen Zusammensetzungen bildet das Oligomer vorzugsweise den Hauptbestandteil der härtbaren Bestandteile der Zusammensetzung, d. h. das bzw. die Oligomere machen wenigstens 50 Gew.-%, insbesondere wenigstens 60 Gew.-%, bezogen auf die Gesamtmenge an Oligomer und Monomer aus. Das Gewichtsverhältnis von Oligomer zu Monomer liegt insbesondere im Bereich von 1 : 1 bis 20 : 1 und speziell im Bereich von 3 : 2 bis 10 : 1.In preferred embodiments of the invention, the radiation-curable, liquid composition forming the lacquer layer comprises at least one oligomer, e.g. B. 1, 2 or 3 oligomers, especially at least one, z. B. 1, 2 or 3, the oligomers mentioned as preferred and at least one monomer, for. B. 1, 2 or 3 monomers, especially at least one, z. B. 1, 2 or 3, the monomers mentioned as preferred. In these compositions, the oligomer preferably forms the major constituent of the curable components of the composition, ie, the oligomer (s) account for at least 50 wt .-%, in particular at least 60 wt .-%, based on the total amount of oligomer and monomer. The weight ratio of oligomer to monomer is in particular in the range from 1: 1 to 20: 1 and especially in the range from 3: 2 to 10: 1.
In anderen, ebenfalls bevorzugten Ausführungsformen der Erfindung umfasst die strahlungshärtbare, flüssige Zusammensetzung, welche zur Herstellung der Lackschicht eingesetzt wird, ausschließlich oder nahezu ausschließlich, d. h. wenigstens 90 Gew.-%, insbesondere wenigstens 95 Gew.-%, speziell wenigstens 99 Gew.-%, bezogen auf die Gesamtmenge an strahlungshärtbaren Bestandteilen der Zusammensetzung, ein oder mehrere Oligomere, z. B. 2, 3 oder 4 Oligomere, insbesondere 2, 3 oder 4 der als bevorzugt genannten Oligomere. Der Anteil der Monomere liegt dann dementsprechend bei maximal 10 Gew.-%, insbesondere maximal 5 Gew.-%, speziell maximal 1 Gew.-% oder bei 0 Gew.-%, bezogen auf die Gesamtmenge an strahlungshärtbaren Bestandteilen der Zusammensetzung. Bevorzugt enthalten solche Zusammensetzungen wenigstens ein Polyesteracrylat und/oder Polyurethanacrylat und wenigstens ein Polyetheracrylat.In other, likewise preferred embodiments of the invention, the radiation-curable, liquid composition used to prepare the lacquer layer comprises exclusively or almost exclusively, i. H. at least 90% by weight, in particular at least 95% by weight, especially at least 99% by weight, based on the total amount of radiation-curable constituents of the composition, of one or more oligomers, eg. B. 2, 3 or 4 oligomers, in particular 2, 3 or 4 of the oligomers mentioned as preferred. Accordingly, the proportion of monomers is at most 10% by weight, in particular not more than 5% by weight, especially not more than 1% by weight or 0% by weight, based on the total amount of radiation-curable constituents of the composition. Such compositions preferably contain at least one polyester acrylate and / or polyurethane acrylate and at least one polyether acrylate.
Neben den härtbaren Bestandteilen enthält die strahlungshärtbare, flüssige Zusammensetzung, welche zur Herstellung der Lackschicht eingesetzt wird, in der Regel einen oder mehrere weitere Bestandteile, wie Photoinitiatoren, inerte Füllstoffe, Abrasive, Verlaufshilfsmittel, farbgebende Bestandteile, insbesondere Farbpigmente, organische Lösungsmittel und dergleichen. Erfindungsgemäß machen diese Bestandteile nicht mehr als 40 Gew.-%, insbesondere nicht mehr als 30 Gew.-%, z. B. 1 bis 40 Gew.-%, insbesondere 5 bis 30 Gew.-%, bezogen auf das Gesamtgewicht der strahlungshärtbaren, flüssigen Zusammensetzung aus. Vorzugsweise enthält die strahlungshärtbare, flüssige Zusammensetzung keine oder nicht mehr als 10 Gew.-%, bezogen auf ihr Gesamtgewicht, an nicht polymerisierbaren flüchtigen Bestandteilen. Hierbei versteht man unter flüchtigen Bestandteilen solche Substanzen, die einen Siedepunkt bzw. einen Verdampfungspunkt unterhalb 250 °C bei Normaldruck aufweisen, beispielsweise organische Lösungsmittel.In addition to the curable constituents, the radiation-curable, liquid composition used to prepare the lacquer layer generally contains one or more further constituents, such as photoinitiators, inert fillers, abrasives, leveling agents, coloring constituents, in particular color pigments, organic solvents and the like. According to the invention, these constituents do not exceed 40% by weight, in particular not more than 30% by weight, eg. B. 1 to 40 wt .-%, in particular 5 to 30 wt .-%, based on the total weight of the radiation-curable, liquid composition. Preferably, the radiation-curable, liquid composition contains no or not more than 10% by weight, based on its total weight, of non-polymerizable volatiles. In this context, volatile substances are understood as meaning substances which have a boiling point or an evaporation point below 250 ° C. under atmospheric pressure, for example organic solvents.
Bevorzugt enthält die strahlungshärtbare, flüssige Zusammensetzung, welche zur Herstellung der Lackschicht eingesetzt wird, wenigstens einen Photoinitiator. Unter Photoinitiatoren versteht man Substanzen, die bei Bestrahlung mit UV-Strahlung, d. h. Licht der Wellenlänge unterhalb 420 nm, insbesondere unterhalb 400 nm unter Bildung von Radikalen zerfallen und so eine Polymerisation der ethylenisch ungesättigten Doppelbindungen auslösen. Bevorzugt enthält die strahlungshärtbare, flüssige Zusammensetzung wenigstens einen Photoinitiator, der wenigstens eine Absorptionsbande aufweist, die im Bereich von 220 bis 420 nm, insbesondere im Bereich von 240 bis 400 nm ein Maximum aufweist und die mit der Initiierung des Zerfallsprozesses gekoppelt ist. Vorzugsweise enthält die nicht-wässrige, flüssige, strahlungshärtbare Zusammensetzung wenigstens einen Photoinitiator, der wenigstens eine Absorptionsbande mit einem Maximum im Bereich von 220 bis 420 nm, insbesondere einem Maximum im Bereich von 240 bis 400 nm aufweist.The radiation-curable, liquid composition used to prepare the lacquer layer preferably contains at least one photoinitiator. By "photoinitiators" is meant substances which upon irradiation with UV radiation, ie light of wavelength below 420 nm, in particular below 400 nm, decompose to form free radicals and thus trigger a polymerization of the ethylenically unsaturated double bonds. Preferably, the radiation-curable, liquid composition comprises at least one photoinitiator having at least one absorption band, which has a maximum in the range of 220 to 420 nm, in particular in the range of 240 to 400 nm and which is coupled with the initiation of the decay process. The nonaqueous, liquid, radiation-curable composition preferably contains at least one photoinitiator which has at least one absorption band with a maximum in the range from 220 to 420 nm, in particular a maximum in the range from 240 to 400 nm.
- alpha-Hydroxyalkylphenone und alpha-Dialkoxyacetophenone wie 1-Hydroxycyclohexylphenylketon, 2-Hydroxy-2-methyl-1-phenyl-1-propanon, 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-on, 2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanon oder 2,2-Dimethoxy-1 -phenylethanon;alpha-hydroxyalkylphenones and alpha-dialkoxyacetophenones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl} -2-methylpropan-1-one, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone or 2,2-dimethoxy-1-phenylethanone;
- Phenylglyoxalsäureester wie Phenylglyoxalsäuremethylester;Phenylglyoxalic acid esters, such as phenylglyoxalic acid methyl ester;
- Benzophenone wie Benzophenon, 2-Hydroxybenzophenon, 3-Hydroxybenzophenon, 4-Hydroxybenzophenon, 2-Methylbenzophenon, 3-Methylbenzophenon, 4-Methylbenzophenon, 2,4-Dimethylbenzophenon, 3,4-Dimethylbenzophenon, 2,5-Dimethylbenzophenon, 4-Benzoylbiphenyl, oder 4-Methoxybenzophenon;Benzophenones such as benzophenone, 2-hydroxybenzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4-dimethylbenzophenone, 3,4-dimethylbenzophenone, 2,5-dimethylbenzophenone, 4-benzoylbiphenyl, or 4-methoxybenzophenone;
- Benzilderivate wie Benzil, 4,4'-Dimethylbenzil und Benzildimethylketal;Benzil derivatives such as benzil, 4,4'-dimethylbenzil and benzil dimethyl ketal;
- Benzoine wie Benzoin, Benzoinethylether, Benzoinisopropylether und Benzoinmethylether;Benzoins such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin methyl ether;
- Acylphosphinoxide wie 2,4,6-Trimethylbenzoyl-diphenylphosphinoxid, Ethoxy(phenyl)phosphoryl-(2,4,6-trimethylphenyl)methanon sowie Bis(2,4,6-trimethylbenzoyl)phenylphosphinoxid;Acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethoxy (phenyl) phosphoryl- (2,4,6-trimethylphenyl) -methanone, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
- Titanocene wie das unter der Bezeichnung Irgacure® 784 von der BASF SE vertriebene Produkt,Titanocenes such as the product sold under the name Irgacure® 784 by BASF SE,
- Oximester wie die unter der Bezeichnung Irgacure® OXE01 und OXE02 von der BASF SE vertriebene Produkt,Oxime esters such as the product sold under the name Irgacure® OXE01 and OXE02 by BASF SE,
- alpha-Aminoalkylphenone wie 2-Methyl-1-[4(methylthio)phenyl-2-morpholinopropan-1-on, 2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanon oder 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1 -butanon.alpha-aminoalkylphenones such as 2-methyl-1- [4 (methylthio) phenyl-2-morpholinopropan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -1-butanone or 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone.
Bevorzugte Photoinitiatoren sind vor allem ausgewählt aus den Gruppen der alpha-Hydroxyalkylphenone, alpha-Dialkoxyacetophenone, Phenylglyoxalsäureester, Benzophenone, Benzoine und Acylphosphinoxide.Preferred photoinitiators are selected, in particular, from the groups of the alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzoins and acylphosphine oxides.
Vorzugsweise enthält die flüssige, strahlungshärtbare Zusammensetzung wenigstens einen Photoinitiator, der eine Absorptionsbande mit einem Maximum λmax im Bereich von 230 bis 340 nm aufweist.The liquid, radiation-curable composition preferably comprises at least one photoinitiator which has an absorption band with a maximum λ max in the range from 230 to 340 nm.
Bevorzugt enthält die nicht-wässrige, flüssige, strahlungshärtbare Zusammensetzung, welche zur Herstellung der Lackschicht eingesetzt wird, wenigstens zwei voneinander verschiedene Photoinitiatoren, bei denen sich die Maxima der Absorptionsbanden unterscheiden, vorzugsweise um wenigstens 40 nm und insbesondere um wenigstens 60 nm.The non-aqueous, liquid, radiation-curable composition used to prepare the lacquer layer preferably comprises at least two photoinitiators which differ from one another and in which the maxima of the absorption bands differ, preferably by at least 40 nm and in particular by at least 60 nm.
Insbesondere enthält eine derartige nicht-wässrige, flüssige, strahlungshärtbare Zusammensetzung ein Gemisch wenigstens zwei voneinander verschiedener Photoinitiatoren, wobei wenigstens ein Photoinitiator (im Folgenden Photoinitiator I) eine Absorptionsbande mit einem Maximum λmax im Bereich von 340 bis 420 nm und speziell im Bereich von 360 bis 420 nm aufweist und wobei wenigstens ein weiterer Photoinitiator (im Folgenden Photoinitiator II) eine Absorptionsbande mit einem Maximum λmax im Bereich von 220 bis 340 und speziell im Bereich von 230 bis 320 nm aufweist. Vorzugsweise liegt das Gewichtsverhältnis der Gesamtmenge an Photoinitiatoren I zur Gesamtmenge an Photoinitiatoren II im Bereich von 2 : 1 bis 1 : 20.In particular, such a non-aqueous, liquid, radiation-curable composition contains a mixture of at least two mutually different photoinitiators, wherein at least one photoinitiator (hereinafter photoinitiator I) has an absorption band with a maximum λ max in the range of 340 to 420 nm and especially in the range of 360 has up to 420 nm and wherein at least one further photoinitiator (hereinafter photoinitiator II) has an absorption band with a maximum λ max in the range of 220 to 340 and especially in the range of 230 to 320 nm. Preferably, the weight ratio of the total amount of photoinitiators I to the total amount of photoinitiators II is in the range of 2: 1 to 1:20.
Bevorzugte Photoinitiatoren, die eine Absorptionsbande mit einem Maximum λmax im Bereich von 220 bis 340 und speziell im Bereich von 230 bis 320 nm aufweisen, sind die vorgenannten alpha-Hydroxyalkylphenone, alpha-Dialkoxyacetophenone, Phenylglyoxalsäureester, Benzophenone und Benzoine.Preferred photoinitiators which have an absorption band having a maximum λ max in the range from 220 to 340 and especially in the range of 230 to 320 nm, the above-mentioned alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic esters, benzophenones, and benzoins.
Bevorzugte Photoinitiatoren, die eine Absorptionsbande mit einem Maximum λmax im Bereich 340 bis 420 nm und speziell im Bereich von 360 bis 420 nm aufweisen, sind die vorgenannten Acylphosphinoxide.Preferred photoinitiators which have an absorption band with a maximum λ max in the range of 340 to 420 nm and especially in the range of 360 to 420 nm are the abovementioned acylphosphine oxides.
In bevorzugten Ausführungsformen umfassen die Photoinitiatoren wenigstens ein alpha-Hydroxyalkylphenon oder alpha-Dialkoxyacetophenon und wenigstens ein Acylphosphinoxid sowie gegebenenfalls einen Phenylglyoxalsäureester und gegebenenfalls ein Benzophenon. Vorzugsweise liegt das Gewichtsverhältnis von Acylphosphinoxid zu alpha-Hydroxyalkylphenon bzw. alpha-Dialkoxyacetophenon im Bereich von 2 : 1 bis 1 : 20.In preferred embodiments, the photoinitiators comprise at least one alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone and at least one acylphosphine oxide and optionally a phenylglyoxalic acid ester and optionally a benzophenone. Preferably, the weight ratio of acylphosphine oxide to alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone is in the range of 2: 1 to 1:20.
Die Gesamtmenge an Photoinitiatoren liegt typischerweise im Bereich von 0,5 bis 10 Gew.-%, insbesondere 1 bis 5 Gew.-%, bezogen auf das Gesamtgewicht der nicht-wässrigen, flüssigen, strahlungshärtbaren Zusammensetzung.The total amount of photoinitiators is typically in the range of 0.5 to 10% by weight, especially 1 to 5% by weight, based on the total weight of the non-aqueous, liquid, radiation-curable composition.
Die erfindungsgemäßen, nicht-wässrigen, flüssigen, strahlungshärtbaren Zusammensetzungen können auch initiatorfrei formuliert werden, insbesondere dann, wenn die anschließende Härtung mittels Elektronenstrahlen erfolgt.The nonaqueous, liquid, radiation-curable compositions according to the invention can also be formulated without initiators, in particular when the subsequent curing is carried out by means of electron beams.
Weiterhin können die nicht-wässrigen, flüssigen, strahlungshärtbaren Zusammensetzungen einen oder mehrere Füllstoffe, d. h. feste, in den Oligomeren und den Monomeren nicht lösliche, partikelförmige Bestandteile enthalten. Hierzu zählen vor allem Aluminiumoxide, beispielsweise in Form von Korund sowie Siliziumdioxid, wie pyrogene Kieselsäure und synthetische, amorphe Kieselsäure, z. B. Fällungskieselsäure. Die mittleren Partikelgrößen der Füllstoffe (Gewichtsmittel) können über weite Bereiche variieren und liegen typischerweise im Bereich von 1 nm bis 100 µm, insbesondere im Bereich von 10 nm bis 50 µm, je nach Art des Füllstoffs. Die Gesamtmenge an Füllstoff wird in der Regel 40 Gew.-%, insbesondere 30 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung nicht überschreiten und liegt, sofern enthalten, typischerweise im Bereich von 1 bis 39,5 Gew.-% und insbesondere im Bereich von 2 bis 29 Gew.-%.Furthermore, the non-aqueous, liquid, radiation-curable compositions may contain one or more fillers, i. H. solid, non-soluble in the oligomers and the monomers, particulate components. These include, in particular aluminum oxides, for example in the form of corundum and silica, such as fumed silica and synthetic, amorphous silica, z. B. precipitated silica. The average particle sizes of the fillers (weight average) can vary over wide ranges and are typically in the range from 1 nm to 100 .mu.m, in particular in the range from 10 nm to 50 .mu.m, depending on the type of filler. The total amount of filler will generally not exceed 40% by weight, in particular 30% by weight, based on the total weight of the composition and, if present, is typically in the range from 1 to 39.5% by weight and in particular in the range of 2 to 29 wt .-%.
Vorzugsweise enthalten die nicht-wässrigen, flüssigen, strahlungshärtbaren Zusammensetzungen einen oder mehrere Abrasive. Abrasive sind Füllstoffe, welche der Lackschicht eine erhöhte Oberflächenhärte und eine verbesserte Abriebfestigkeit verleihen. Hierzu zählen vor allem Korund, Quarzmehle, Glaspulver, z. B. Glasflakes und nanoskalige Kieselsäuren.Preferably, the non-aqueous, liquid, radiation-curable compositions contain one or more abrasives. Abrasives are fillers which give the lacquer layer increased surface hardness and improved abrasion resistance. These include especially corundum, quartz flour, glass powder, z. As glass flakes and nanoscale silicas.
Daneben können die nicht-wässrigen, flüssigen, strahlungshärtbaren Zusammensetzungen einen oder mehrere weitere Additive enthalten, beispielsweise Verlaufshilfsmittel, z. B. siloxanhaltige Polymere wie Polyethersiloxancopolymere, sowie UV-Stabilisatoren, z. B. sterisch gehinderte Amine (so genannte HALS-Stabilisatoren).In addition, the non-aqueous, liquid, radiation-curable compositions may contain one or more further additives, for example leveling agents, for. B. siloxane-containing polymers such as polyether siloxane copolymers, as well as UV stabilizers, for. B. sterically hindered amines (so-called HALS stabilizers).
Typische Zusammensetzungen der nicht-wässrigen, flüssigen, strahlungshärtbaren Zusammensetzungen, welche zur Herstellung der Lackschicht eingesetzt werden, sind in den folgenden Tabellen A1, A2 und A3 angegeben.
Die erfindungsgemäßen Thermotransferfolien können eine oder mehrere übereinander angeordnete Lackschichten aufweisen, die erfindungsgemäß auf den zuvor beschriebenen nicht-wässrigen, flüssigen, strahlungshärtbaren Zusammensetzungen basieren.The thermal transfer films according to the invention may comprise one or more superposed lacquer layers which, according to the invention, are based on the nonaqueous, liquid, radiation-curable compositions described above.
Die Gesamtschichtdicke der Lackschicht, d. h. bei mehreren Lackschichten die Summe aller Schichtdicken, liegt typischerweise im Bereich von 10 bis 120 µm, insbesondere im Bereich von 30 bis 80 µm. Bei einer Schicht liegt daher die Schichtdicke der Lackschicht vorzugsweise im Bereich von 10 bis 120 µm, insbesondere im Bereich von 30 bis 80 µm. Bei mehreren Schichten liegen die einzelnen Schichtdicken typischerweise im Bereich von 10 bis 100 µm, insbesondere im Bereich von 20 bis 70 µm.The total layer thickness of the lacquer layer, d. H. in the case of several lacquer layers, the sum of all layer thicknesses is typically in the range from 10 to 120 μm, in particular in the range from 30 to 80 μm. In the case of one layer, therefore, the layer thickness of the lacquer layer is preferably in the range from 10 to 120 μm, in particular in the range from 30 to 80 μm. In the case of several layers, the individual layer thicknesses are typically in the range from 10 to 100 μm, in particular in the range from 20 to 70 μm.
In einer ersten Ausführungsform der Erfindung umfasst die erfindungsgemäße Thermotransferfolie genau eine auf der Trägerfolie angeordnete Lackschicht.In a first embodiment of the invention, the thermal transfer film according to the invention comprises exactly one lacquer layer arranged on the carrier foil.
In einer weiteren Ausführungsform umfasst die erfindungsgemäße Thermotransferfolie eine auf der Trägerfolie angeordnete Lackschicht sowie eine oder mehrere, z. B. eine oder zwei weitere, Lackschichten, die auf den zuvor beschriebenen nicht-wässrigen, flüssigen, strahlungshärtbaren Zusammensetzungen basieren. Die Lackschichten können unmittelbar aufeinander angeordnet sein. Zwischen zwei Lackschichten kann auch eine Dekorschicht vorgesehen sein, um dem mit der Thermotransferfolie beschichteten Gegenstand eine farbige Gestaltung zu verleihen.In a further embodiment, the thermal transfer film according to the invention comprises a coating layer arranged on the carrier film and one or more, for. One or two further paint layers based on the non-aqueous, liquid, radiation-curable compositions described above. The lacquer layers can be arranged directly on one another. A decorative layer can also be provided between two lacquer layers in order to give the article coated with the thermal transfer film a colored design.
Dekorschichten weisen typischerweise Schichtdicken im Bereich von 0,5 bis 5 µm, insbesondere im Bereich von 0,5 bis 2,5 µm und speziell im Bereich von 1 bis 1,5 µm auf.Decorative layers typically have layer thicknesses in the range from 0.5 to 5 μm, in particular in the range from 0.5 to 2.5 μm and especially in the range from 1 to 1.5 μm.
Weiterhin weisen die erfindungsgemäßen Thermotransferfolien wenigstens eine polymere Klebeschicht, insbesondere genau eine Klebeschicht auf. Die Klebeschicht ist entweder unmittelbar auf der Lackschicht, bzw. bei mehreren Lackschichten unmittelbar auf der obersten Lackschicht angeordnet, oder zwischen der Lackschicht und der Klebeschicht kann auch eine Dekorschicht vorgesehen sein.Furthermore, the thermal transfer films according to the invention have at least one polymeric adhesive layer, in particular exactly one adhesive layer. The adhesive layer is arranged either directly on the lacquer layer, or in the case of several lacquer layers directly on the uppermost lacquer layer, or a decorative layer can also be provided between the lacquer layer and the adhesive layer.
Die Klebeschicht ist erfindungsgemäß heißsiegelbar, d. h. sie ist bei Raumtemperatur nicht klebrig und entfaltet erst beim Erwärmen ihre Klebewirkung. Hierbei hat es sich als vorteilhaft erwiesen, wenn die Klebeschicht wenigstens einen Bestandteil enthält, der strahlungshärtbar ist, d.h. bei Einwirkung energiereicher Strahlung, beispielsweise beim Bestrahlen mit UV-Licht oder Elektronenstrahlung, vernetzt. Bei diesem Bestandteil handelt es sich um organische Oligomere oder Polymere, die ethylenisch ungesättigte Doppelbindungen aufweisen.
Vorzugsweise umfasst die erfindungsgemäße heißsiegelbare Klebeschicht wenigstens ein Polymer als Hauptbestandteil. Das Polymer kann selber strahlungshärtbar sein oder mit einem oder mehreren strahlungshärtbaren Oligomeren oder Polymeren abgemischt sein, die ethylenisch ungesättigte Doppelbindungen aufweisen.
Die Polymere, welche den Hauptbestandteil der heißsiegelbaren Klebeschicht bilden, sind in einer bevorzugten Ausführungsform vernetzbar, d. h. sie vernetzen beim Erwärmen und/oder durch Einwirkung energiereicher Strahlung, beispielsweise beim Bestrahlen mit UV-Licht und Ausbildung kovalenter Bindungen zwischen den Polymerketten.
Insbesondere hat es sich als vorteilhaft erwiesen, wenn die Klebeschicht sowohl oligomere und/oder polymere Bestandteile umfasst, die durch Erwärmen vernetzbar sind, als auch Bestandteile, die durch Einwirkung energiereicher Strahlung vernetzbar sind. Dies kann beispielsweise dadurch erreicht werden, dass die Klebeschicht sowohl Polymere, welche beim Erwärmen vernetzen, als auch Oligomere oder Polymere umfasst, welche durch Einwirkung energiereicher Strahlung vernetzt werden. Die Klebeschicht kann auch sogenannte Dual-Cure-Polymere enthalten, d. h. Polymere, die sowohl beim Einwirken von energiereicher Strahlung als auch beim Erhitzen vernetzen.
In einer bevorzugten Ausführungsform enthält die Klebschicht wenigstens ein wasserunlösliches Polymer, das üblicherweise zur Herstellung von Klebstoffschichten eingesetzt wird, und das insbesondere unter Reinacrylat-Polymeren, Styrolacrylat-Polymeren, Polyurethanen, insbesondere Polyesterurethanen und Polyetherurethanen, ausgewählt ist und das physikalisch trocknend oder selbstvernetzendes ist, sowie wenigstens ein strahlungshärtendes Oligomer oder Polymer.The adhesive layer is heat sealable according to the invention, ie it is not sticky at room temperature and develops its adhesive effect only when heated. It has proved to be advantageous if the adhesive layer contains at least one component which is radiation-curable, ie crosslinked upon exposure to high-energy radiation, for example when irradiated with UV light or electron radiation. This ingredient is organic oligomers or polymers that have ethylenically unsaturated double bonds.
The heat-sealable adhesive layer according to the invention preferably comprises at least one polymer as the main constituent. The polymer itself may be radiation-curable or blended with one or more radiation-curable oligomers or polymers having ethylenically unsaturated double bonds.
The polymers which form the main constituent of the heat-sealable adhesive layer are crosslinkable in a preferred embodiment, ie they crosslink upon heating and / or by the action of high-energy radiation, for example when irradiating with UV light and forming covalent bonds between the polymer chains.
In particular, it has proven to be advantageous if the adhesive layer comprises both oligomeric and / or polymeric components which can be crosslinked by heating, as well as components which are crosslinkable by the action of high-energy radiation. This can be achieved, for example, by the adhesive layer comprising both polymers which crosslink on heating and oligomers or polymers which are crosslinked by the action of high-energy radiation. The adhesive layer can also contain so-called dual-cure polymers, ie polymers which crosslink both when exposed to high-energy radiation and when heated.
In a preferred embodiment, the adhesive layer contains at least one water-insoluble polymer, which is usually used for the production of adhesive layers, and which is selected in particular from pure acrylate polymers, styrene acrylate polymers, polyurethanes, in particular polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking, and at least one radiation-curing oligomer or polymer.
Physikalisch trocknende Polymere sind solche Polymere, die beim Trocknen einen festen Polymerfilm bilden, in dem die Polymerketten unvernetzt vorliegen. Selbstvernetzende Polymere sind solche Polymere, die beim Trocknen einen festen Polymerfilm bilden, in dem die Polymerketten vernetzt vorliegen. Selbstvernetzende Polymere weisen reaktive funktionelle Gruppen auf, beispielsweise Hydroxylgruppen, Carboxylgruppen, Isocyanatgruppen, blockierte Isocyanatgruppen, Ketocarbonylgruppen oder Epoxidgruppen, die untereinander oder mit den reaktiven Gruppen eines Vernetzungsmittels unter Ausbildung kovalenter Bindungen reagieren können.Physically drying polymers are those polymers which, upon drying, form a solid polymer film in which the polymer chains are uncrosslinked. Self-crosslinking polymers are those polymers which, upon drying, form a solid polymer film in which the polymer chains are crosslinked. self- Polymers have reactive functional groups, for example hydroxyl groups, carboxyl groups, isocyanate groups, blocked isocyanate groups, ketocarbonyl groups or epoxide groups, which can react with one another or with the reactive groups of a crosslinking agent to form covalent bonds.
In einer besonders bevorzugten Ausführungsform enthält die Klebschicht wenigstens ein wasserunlösliches Polymer, das unter Polyurethanen, insbesondere Polyesterurethanen und Polyetherurethanen, ausgewählt ist und das physikalisch trocknend oder selbstvernetzendes ist, sowie wenigstens ein strahlungshärtendes Oligomer oder Polymer.In a particularly preferred embodiment, the adhesive layer contains at least one water-insoluble polymer which is selected from polyurethanes, in particular polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking, and at least one radiation-curing oligomer or polymer.
In einer ebenfalls besonders bevorzugten Ausführungsform enthält die Klebschicht wenigstens ein wasserunlösliches Polymer, das unter selbstvernetzenden Reinacrylat-Polymeren und selbstvernetzenden Styrolacrylat-Polymeren ausgewählt ist, sowie wenigstens ein strahlungshärtendes Oligomer oder Polymer.In a likewise particularly preferred embodiment, the adhesive layer contains at least one water-insoluble polymer selected from self-crosslinking pure acrylate polymers and self-crosslinking styrene-acrylate polymers, and at least one radiation-curing oligomer or polymer.
In einer ebenfalls besonders bevorzugten Ausführungsform enthält die Klebschicht wenigstens ein wasserunlösliches Polymer, das unter selbstvernetzenden Reinacrylat-Polymeren und selbstvernetzenden Styrolacrylat-Polymeren ausgewählt ist und wenigstens ein wasserunlösliches Polymer, das unter Polyurethanen, insbesondere Polyesterurethanen und Polyetherurethanen, ausgewählt ist und das physikalisch trocknend oder selbstvernetzendes ist, sowie wenigstens ein strahlungshärtendes Oligomer oder Polymer.In a further particularly preferred embodiment, the adhesive layer contains at least one water-insoluble polymer selected from self-crosslinking pure acrylate polymers and self-crosslinking styrene-acrylate polymers and at least one water-insoluble polymer selected from polyurethanes, especially polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking and at least one radiation-curing oligomer or polymer.
Bei den strahlungshärtbaren Oligomeren und Polymeren der Klebeschicht handelt es sich grundsätzlich um solche Oligomere und Polymere, die ethylenisch ungesättigte Doppelbindungen aufweisen. Diese Doppelbindungen liegen vorzugsweise zu wenigstens 90 % oder 100 %, bezogen auf die Gesamtmenge der ethylenisch ungesättigten Doppelbindungen, in Form Acryl- oder Methacrylgruppen und speziell in Form von Acrylgruppen vor. Die Acryl- und Methacrylgruppen können in Form von (Meth)Acrylamid- oder (Meth)Acrylat-gruppen vorliegen, wobei Letzteres bevorzugt ist. Insbesondere weisen die strahlungshärtbaren Bestandteile der Klebeschicht, zu wenigstens 90 % oder 100 %, bezogen auf die Gesamtmenge der in der Klebeschicht enthaltenen ethylenisch ungesättigten Doppelbindungen, Acrylatgruppen auf.The radiation-curable oligomers and polymers of the adhesive layer are basically those oligomers and polymers which have ethylenically unsaturated double bonds. These double bonds are preferably at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups. The acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred. In particular, at least 90% or 100% of the radiation-curable constituents of the adhesive layer, based on the total amount of the ethylenically unsaturated double bonds present in the adhesive layer, comprise acrylate groups.
Die strahlungshärtbaren Oligomere und Polymere der Klebeschicht weisen vorzugsweise im Mittel eine Funktionalität im Bereich von 2bis 20, insbesondere im Bereich von 2 bis 10 auf, d. h. die Anzahl ethylenisch ungesättigter Doppelbindungen pro Molekül liegt im Mittel im Bereich von 2 bis 20 und insbesondere im Bereich von 2 bis 10.The radiation-curable oligomers and polymers of the adhesive layer preferably have on average a functionality in the range of 2 to 20, in particular in the range of 2 to 10, ie the number of ethylenically unsaturated double bonds per molecule is on average in the range of 2 to 20 and in particular in the range of 2 to 10.
Geeignet sind auch Gemische verschiedener Oligomere bzw. Polymere mit unterschiedlicher Funktionalität, wobei die mittlere Funktionalität vorzugsweise im Bereich von 2 bis 20, insbesondere im Bereich von 2 bis 10 liegt.
Insbesondere sind die strahlungshärtbaren Oligomere und Polymere der Klebeschicht ausgewählt unter Polyether(meth)acrylaten, Polyester(meth)acrylaten, Epoxid(meth)acrylaten, Urethan(meth)acrylaten, beispielsweise Umsetzungsprodukte von Polyisocyanaten mit hydroxyl-funktionalisierten Acryl- oder Methacrylverbindungen, und ungesättigten Polyesterharzen.Also suitable are mixtures of different oligomers or polymers with different functionality, the average functionality preferably being in the range from 2 to 20, in particular in the range from 2 to 10.
In particular, the radiation-curable oligomers and polymers of the adhesive layer are selected from polyether (meth) acrylates, polyester (meth) acrylates, epoxide (meth) acrylates, urethane (meth) acrylates, for example reaction products of polyisocyanates with hydroxyl-functionalized acrylic or methacrylic compounds, and unsaturated polyester resins.
Speziell sind die strahlungshärtbaren Oligomere und Polymere der Klebeschicht ausgewählt unter Polyether(meth)acrylaten, Epoxid(meth)acrylaten und Urethan(meth)acrylaten.
Geeignete Polyurethanacrylate sind vor allem Urethangruppen-haltige Polymere, die im Mittel 2 bis 10, insbesondere 2 bis 8,5 Acrylat- oder Methacrylat-Gruppen aufweisen, insbesondere Polyetherurethanarylate, und die vorzugsweise durch Umsetzung Isocyanat-Gruppen enthaltender Polyetherurethane mit Hydroxyalkylacrylaten oder Hydroxylalkylmethacrylaten erhältlich sind. Beispiele hierfür sind die Laromer®-Typen LR 8949, LR 8983 und LR 9005 der BASF SE.
Ferner hat es sich als vorteilhaft erwiesen, wenn die Polymere, welche vorzugsweise den Hauptbestandteil der heißsiegelbaren Klebeschicht bilden, im unvernetzten Zustand eine Glasübergangstemperatur Tg, bestimmt mittels Dynamischer Differenzkalorimetrie (DSC) nach ASTM D3418 im Bereich von -60 bis 90 °C, insbesondere 0 bis 90°C, aufweisen und/oder es sich um teilkristalline Polymere mit einem Schmelzpunkt im Bereich von -60 bis 90 °C, insbesondere 0 bis 90°C, bestimmt mittels DSC, handelt. Sofern Klebstoffzusammensetzung mehrere Polymere enthält, können diese im unvernetzten Zustand auch unterschiedliche Glasübergangstemperaturen aufweisen. Es ist dann bevorzugt, dass wenigstens ein Teil, insbesondere wenigstens 30 Gew.-% dieser Polymere, bezogen auf die Gesamtmenge der Polymerbestandteile der Klebstoffzusammensetzung, im unvernetzten Zustand eine Glasübergangstemperatur Tg im Bereich von 0 bis 90°C, insbesondere im Bereich von 20 bis 90°C aufweisen. Klebstoffzusammensetzungen zur Herstellung heißsiegelbarer Polymerschichten sind dem Fachmann geläufig und können kommerziell erworben oder durch Abmischen kommerziell verfügbarer Klebrohstoffe nach bekannten Richtrezepturen hergestellt werden. Bevorzugt sind flüssige Klebstoffzusammensetzungen. Geeignet sind grundsätzlich lösungsmittelbasierte Klebstoffe wie auch wasserbasierte Klebstoffe.Specifically, the radiation-curable oligomers and polymers of the adhesive layer are selected from polyether (meth) acrylates, epoxide (meth) acrylates and urethane (meth) acrylates.
Suitable polyurethane acrylates are, above all, urethane-containing polymers which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups, in particular polyether urethane arylates, and which are preferably obtainable by reacting isocyanate group-containing polyether urethanes with hydroxyalkyl acrylates or hydroxyalkyl methacrylates , Examples include the Laromer® grades LR 8949, LR 8983 and LR 9005 from BASF SE.
Furthermore, it has proved to be advantageous if the polymers, which preferably form the main constituent of the heat-sealable adhesive layer, in the uncrosslinked state have a glass transition temperature Tg, determined by means of differential scanning calorimetry (DSC) according to ASTM D3418 in the range from -60 to 90 ° C., in particular 0 to 90 ° C, and / or it is partially crystalline polymers having a melting point in the range of -60 to 90 ° C, in particular 0 to 90 ° C, determined by DSC is. If the adhesive composition contains a plurality of polymers, these may also have different glass transition temperatures in the uncrosslinked state. It is then preferred that at least a part, in particular at least 30% by weight of these polymers, based on the total amount of the polymer components of the adhesive composition, in the uncrosslinked state has a glass transition temperature Tg in the range from 0 to 90 ° C., in particular in the range from 20 to 90 ° C have. Adhesive compositions for producing heat-sealable polymer layers are familiar to the person skilled in the art and can be obtained commercially or prepared by mixing commercially available adhesive raw materials according to known preparatory formulations. Preference is given to liquid adhesive compositions. In principle, solvent-based adhesives and water-based adhesives are suitable.
Vorzugsweise basiert die Klebeschicht (4) auf wenigstens einer wässrigen Polymerdispersion, d. h. zur Herstellung der Klebeschicht werden wasserbasierte Klebstoffe eingesetzt, d. h. Klebstoffe, welche die Polymere und gegebenenfalls Oligomere in Form wässriger Polymerdispersion enthalten. Bevorzugt sind flüssige, wasserbasierte Klebstoffzusammensetzungen, die nicht mehr als 10 Gew.-% flüchtige, organische, nicht polymerisierbare Bestandteile wie organische Lösungsmittel enthalten.
Geeignete Polymerdispersionen sind vor allem selbstvernetzende wässrige Polymerdispersionen, d. h. wässrige Polymerdispersionen, welche ein reaktives dispergiertes Polymer und gegebenenfalls ein Vernetzungsmittel enthalten, das mit den reaktiven Gruppen des reaktiven Polymers beim Trocknen und/oder Erwärmen unter Bindungsbildung reagiert. Geeignet sind vor allem selbstvernetzende wässrige Reinacrylatdispersionen, selbstvernetzende wässrige Styrolacrylatdispersionen und selbstvernetzende wässrige Polyurethandispersionen, insbesondere wässrige Polyetherurethandispersionen und Polyesterurethandispersionen.The adhesive layer (4) is preferably based on at least one aqueous polymer dispersion, ie water-based adhesives are used to produce the adhesive layer, ie adhesives which contain the polymers and optionally oligomers in the form of aqueous polymer dispersion. Preference is given to liquid, water-based adhesive compositions containing not more than 10% by weight of volatile, organic, non-polymerizable constituents, such as organic solvents.
Suitable polymer dispersions are above all self-crosslinking aqueous polymer dispersions, ie aqueous polymer dispersions containing a reactive dispersed polymer and optionally a crosslinking agent which reacts with the reactive groups of the reactive polymer during drying and / or heating to form bonds. Especially suitable are self-crosslinking aqueous pure acrylate dispersions, self-crosslinking aqueous styrene-acrylate dispersions and self-crosslinking aqueous polyurethane dispersions, in particular aqueous polyetherurethane dispersions and polyesterurethane dispersions.
Unter Reinacrylatdispersionen versteht man wässrige Polymerdispersionen auf Basis von Alkylacrylaten und Alkylmethacrylaten. Unter Styrolacrylaten versteht man wässrige Polymerdispersionen auf Basis von Styrol, Alkylacrylaten und gegebenenfalls Alkylmethacrylaten. Unter Polyurethandispersionen versteht man wässrige Dispersionen von Polyurethanen, insbesondere Polyetherurethanen und Polyesterurethanen.Pure acrylate dispersions are understood as meaning aqueous polymer dispersions based on alkyl acrylates and alkyl methacrylates. By styrene acrylates is meant aqueous polymer dispersions based on styrene, alkyl acrylates and optionally alkyl methacrylates. Polyurethane dispersions are understood as meaning aqueous dispersions of polyurethanes, in particular polyetherurethanes and polyesterurethanes.
In den selbstvernetzenden wässrigen Polymerdispersionen weisen die Polymere reaktive funktionelle Gruppen auf, beispielsweise Hydroxylgruppen, Carboxylgruppen, Isocyanatgruppen, blockierte Isocyanatgruppen, Ketocarbonylgruppen oder Epoxidgruppen, die mit den reaktiven Gruppen des Vernetzungsmittels unter Ausbildung kovalenter Bindungen reagieren können. Geeignete Vernetzungsmittel sind Verbindungen mit wenigstens zwei reaktiven Gruppen, beispielsweise Hydrazidgruppen, Aminogruppen, Hydroxylgruppen, Epoxidgruppen, Isocyanatgruppen. Beispiele für selbstvernetzende wässrige Polymerdispersionen sind die unter den Handelsbezeichnungen Luhydran® A 849, Acronal® 849 S, Joncryl® 8330, Joncryl® 8383 der BASF SE und Alberdingk® AC 2742 der Fa. Alberdingk Boley GmbH erhältlichen Produkte.In the self-crosslinking aqueous polymer dispersions, the polymers have reactive functional groups, for example hydroxyl groups, carboxyl groups, isocyanate groups, blocked isocyanate groups, ketocarbonyl groups or epoxide groups which can react with the reactive groups of the crosslinking agent to form covalent bonds. Suitable crosslinking agents are compounds having at least two reactive groups, for example hydrazide groups, amino groups, hydroxyl groups, epoxide groups, isocyanate groups. Examples of self-crosslinking aqueous polymer dispersions are the products available under the trade names Luhydran® A 849, Acronal® 849 S, Joncryl® 8330, Joncryl® 8383 from BASF SE and Alberdingk® AC 2742 from Alberdingk Boley GmbH.
Geeignete wässrige Polymerdispersionen sind vor allem auch UV-vernetzbare Polymerdispersionen, d. h. Polymerdispersionen, welche ein dispergiertes Polymer enthalten, das polymerisierbare ethylenisch ungesättigte Doppelbindungen aufweist, die vorzugsweise in Form der vorgenannten Acrylgruppen, Methacrylgruppen, Allylgruppen, Fumarsäuregruppen, Maleinsäuregruppen und/oder Maleinsäureanhydridgruppen, insbesondere in Form von Acryl- oder Methacrylgruppen vorliegen, wobei die ethylenisch ungesättigten Doppelbindungen über einen Linker an das Grundgerüst gebunden sein können oder Bestandteil des Grundgerüsts sind. Beispiele für geeignete UV-vernetzbare wässrige Polymerdispersionen sind wässrige Dispersionen von Polyesteracrylaten, Urethanacrylaten und Epoxidacrylaten, wie sie beispielsweise von der BASF unter den Handelsbezeichnungen Laromer® PE22WN, PE55WN, LR8949, LR8983, LR9005, UA9060, UA9095 und UA9064 vertrieben werden.Suitable aqueous polymer dispersions are, above all, UV-crosslinkable polymer dispersions, ie polymer dispersions which comprise a dispersed polymer which has polymerizable ethylenically unsaturated double bonds which are preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular Form of acrylic or methacrylic groups are present, wherein the ethylenic unsaturated double bonds can be linked via a linker to the skeleton or are part of the skeleton. Examples of suitable UV-crosslinkable aqueous polymer dispersions are aqueous dispersions of polyester acrylates, urethane acrylates and epoxy acrylates, such as those sold by BASF under the trade names Laromer® PE22WN, PE55WN, LR8949, LR8983, LR9005, UA9060, UA9095 and UA9064.
Erfindungsgemäß enthält die wässrige Klebstoffzusammensetzung neben dem Polymer einer physikalisch trocknenden oder selbstvernetzenden Polymerdispersion wenigstens einen strahlungshärtbaren Bestandteil, der in der Regel unter den vorgenannten Polymeren und Oligomeren ausgewählt ist, welche ethylenisch ungesättigte Doppelbindungen aufweisen und der vorzugsweise ebenfalls in dispergierter Form vorliegt.According to the invention, the aqueous adhesive composition contains, in addition to the polymer of a physically drying or self-crosslinking polymer dispersion, at least one radiation-curable component which is generally selected from the aforementioned polymers and oligomers which have ethylenically unsaturated double bonds and which is preferably also present in dispersed form.
Bei dem strahlungshärtbaren Oligomeren und Polymeren der wässrigen Klebstoffzusammensetzug handelt es sich insbesondere um solche Oligomere und Polymere, eren Doppelbindungen zu wenigstens 90 % oder 100 %, bezogen auf die Gesamtmenge der ethylenisch ungesättigten Doppelbindungen, in Form Acryl- oder Methacrylgruppen und speziell in Form von Acrylgruppen vorliegen. Die Acryl- und Methacrylgruppen können in Form von (Meth)Acrylamid- oder (Meth)Acrylat-gruppen vorliegen, wobei Letzteres bevorzugt ist.The radiation-curable oligomers and polymers of the aqueous adhesive composition are, in particular, those oligomers and polymers whose double bonds are at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups available. The acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred.
Die strahlungshärtbaren Oligomere und Polymere der wässrigen Klebstoffzusammensetzung weisen vorzugsweise im Mittel eine Funktionalität im Bereich von 2bis 20, insbesondere im Bereich von 2 bis 10 auf, d. h. die Anzahl ethylenisch ungesättigter Doppelbindungen pro Molekül liegt im Mittel im Bereich von 2 bis 20 und insbesondere im Bereich von 2 bis 10. Geeignet sind auch Gemische verschiedener Oligomere bzw. Polymere mit unterschiedlicher Funktionalität, wobei die mittlere Funktionalität vorzugsweise im Bereich von 2 bis 20, insbesondere im Bereich von 2 bis 10 liegt.The radiation-curable oligomers and polymers of the aqueous adhesive composition preferably have on average a functionality in the range of 2 to 20, in particular in the range of 2 to 10, d. H. the number of ethylenically unsaturated double bonds per molecule is on average in the range from 2 to 20 and in particular in the range from 2 to 10. Also suitable are mixtures of different oligomers or polymers with different functionality, the average functionality preferably in the range from 2 to 20, especially in the range of 2 to 10.
Insbesondere sind die strahlungshärtbaren Oligomere und Polymere der wässrigen Klebstoffzusammensetzung ausgewählt unter Polyether(meth)acrylaten, Polyester(meth)acrylaten, Epoxid(meth)acrylaten, Urethan(meth)acrylaten, und ungesättigten Polyesterharzen.In particular, the radiation-curable oligomers and polymers of the aqueous adhesive composition are selected from polyether (meth) acrylates, polyester (meth) acrylates, epoxide (meth) acrylates, urethane (meth) acrylates, and unsaturated polyester resins.
Speziell sind die strahlungshärtbaren Oligomere und Polymere der wässrigen Klebstoffzusammensetzung ausgewählt unter Polyether(meth)acrylaten, Epoxid(meth)acrylaten und Polyurethan(meth)acrylaten.Specifically, the radiation-curable oligomers and polymers of the aqueous adhesive composition are selected from polyether (meth) acrylates, epoxide (meth) acrylates and polyurethane (meth) acrylates.
Geeignete Polyurethanacrylate sind vor allem Urethangruppen-haltige Polymere, die im Mittel 2 bis 10, insbesondere 2 bis 8,5 Acrylat- oder Methacrylat-Gruppen aufweisen und die vorzugsweise durch Umsetzung Isocyanat-Gruppen enthaltender Polyurethane mit Hydroxyalkylacrylaten oder Hydroxylalkylmethacrylaten erhältlich sind. Beispiele hierfür sind die Laromer®-Typen LR 8949, LR 8983 und LR9005 der BASF SE.Suitable polyurethane acrylates are, above all, urethane-containing polymers which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups and which are preferably obtainable by reacting isocyanate-group-containing polyurethanes with hydroxyalkyl acrylates or hydroxyalkyl methacrylates. Examples include the Laromer® grades LR 8949, LR 8983 and LR9005 from BASF SE.
Geeignet sind vor allem auch Gemische wenigstens zwei verschiedener wässriger Polymerdispersionen, insbesondere Gemische wenigstens einer wässrigen UV-vernetzbaren Polymerdispersion, z. B. einer wässrigen Urethanacrylatdispersion und/oder einer wässrigen Epoxyacrylatdispersion, und wenigstens einer selbstvernetzenden wässrigen Polymerdispersion, z. B. einer selbstvernetzenden wässrigen Reinacrylat-, Styrolacrylat- oder Polyurethandispersion.Particularly suitable are also mixtures of at least two different aqueous polymer dispersions, in particular mixtures of at least one aqueous UV-crosslinkable polymer dispersion, for. An aqueous urethane acrylate dispersion and / or an aqueous epoxy acrylate dispersion, and at least one self-crosslinking aqueous polymer dispersion, e.g. B. a self-crosslinking aqueous pure acrylate, styrene acrylate or polyurethane dispersion.
Die zur Herstellung der polymeren Klebschicht verwendeten Klebstoffzusammensetzungen können die hierfür üblichen Zusätze enthalten, beispielsweise Wachse, Klebharze, Entschäumer, Verlaufshilfsmittel, Tenside, Mittel zur Einstellung des pH-Werts, einen oder mehrere der vorgenannten Füllstoffe sowie UV-Stabilisatoren, z. B. sterisch gehinderte Amine (so genannte HALS-Stabilisatoren).The adhesive compositions used for the preparation of the polymeric adhesive layer may contain the additives customary for this purpose, for example waxes, tackifier resins, defoamers, leveling agents, surfactants, pH adjusting agents, one or more of the aforementioned fillers and UV stabilizers, eg. B. sterically hindered amines (so-called HALS stabilizers).
Sofern die zur Herstellung der polymeren Klebschicht verwendete Klebstoffzusammensetzung ein durch UV-Strahlung härtbares Polymer enthält, enthält sie in der Regel auch wenigstens einen Photoinitiator, der in der Regel unter den vorgenannten alpha-Hydroxyalkylphenonen, alpha-Dialkoxyacetophenonen, Phenylglyoxalsäureestern, Benzophenonen, Benzilderivaten, Acylphosphinoxiden, Oximestern, alpha-Aminoalkylphenonen und Benzoinen ausgewählt ist. Bevorzugte Photoinitiatoren sind vor allem ausgewählt aus den Gruppen der alpha-Hydroxyalkylphenone, alpha-Dialkoxyacetophenone, Phenylglyoxalsäureester, Benzophenone, Benzoine und Acylphosphinoxide.If the adhesive composition used to make the polymeric adhesive layer contains a UV-curable polymer, it usually also contains at least one photoinitiator, typically among the aforementioned alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzene derivatives, acylphosphine oxides , Oxime esters, alpha-aminoalkylphenones and benzoins. Preferred photoinitiators are selected, in particular, from the groups of the alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzoins and acylphosphine oxides.
Sofern die zur Herstellung der polymeren Klebschicht verwendete Klebstoffzusammensetzung ein durch UV-Strahlung härtbares Polymer enthält, enthält sie vorzugsweise wenigstens einen Photoinitiator, der eine Absorptionsbande mit einem Maximum λmax im Bereich von 230 bis 340 nm aufweist. Insbesondere enthält sie wenigstens zwei voneinander verschiedene Photoinitiatoren, bei denen sich die Maxima der Absorptionsbanden unterscheiden, vorzugsweise um wenigstens 40 nm und insbesondere wenigstens 60 nm. In besonders bevorzugten Ausführungsformen umfassen die Photoinitiatoren wenigstens ein alpha-Hydroxyalkylphenon oder alpha-Dialkoxyacetophenon und wenigstens ein Acylphosphinoxid sowie gegebenenfalls einen Phenylglyoxalsäureester und gegebenenfalls ein Benzophenon. Vorzugsweise liegt das Gewichtsverhältnis von Acylphosphinoxid zu alpha-Hydroxyalkylphenon bzw. alpha-Dialkoxyacetophenon im Bereich von 2 : 1 bis 1 : 20. Die Gesamtmenge an Photoinitiatoren liegt typischerweise im Bereich von 0,5 bis 10 Gew.-%, insbesondere 1 bis 5 Gew.-%, bezogen auf das Gesamtgewicht der zur Herstellung der polymeren Klebschicht verwendeten Klebstoffzusammensetzung.When the adhesive composition used to make the polymeric adhesive layer contains a UV-curable polymer, it preferably contains at least one photoinitiator having an absorption band with a maximum λ max in the range of 230 to 340 nm. In particular, it contains at least two mutually different photoinitiators in which the maxima of the absorption bands differ, preferably by at least 40 nm and in particular at least 60 nm. In particularly preferred embodiments, the photoinitiators comprise at least one alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone and at least one acylphosphine oxide and optionally a phenylglyoxalic acid ester and optionally a benzophenone. Preferably, the weight ratio is of acylphosphine oxide to alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone in the range from 2: 1 to 1:20. The total amount of photoinitiators is typically in the range from 0.5 to 10% by weight, in particular from 1 to 5% by weight, based on the total weight of the adhesive composition used to make the polymeric adhesive layer.
Beispiele für typische Klebstoffzusammensetzungen sind die im Folgenden angegebenen Zusammensetzungen, wobei alle Teile als Gewichtsprozente, bezogen auf das Gesamtgewicht der Zusammensetzung zu verstehen sind:
Ferner kann es gewünscht sein, dass die Klebeschicht(en) und/oder die Lackschicht(en) farbig ausgestaltet sind. Zu diesem Zweck können Lackschicht(en) und/oder die Klebeschicht(en) ein oder mehrere farbgebende Bestandteile wie organische und/oder anorganische Pigmente oder Farbstoffe enthalten. Beispiele für diese Pigmente sind Titandioxid als weißes Pigment, weiterhin Eisenoxid-Pigmente wie Eisenoxidgelb, Eisenoxidrot, Eisenoxidschwarz, Schwarzpigmente wie Ruß, Phthalocyaninpigmente wie Heliogenblau oder Heliogengrün, Bismutpigmente wie Bismutvanadatgelb und Diketopyrrolopyrrolrot. Für Metallisierungseffekte können auch Metallpigmente wie Eisenpigmente, Perlglanzpigmente und Aluminiumpigmente enthalten sein. Bevorzugte Pigmente weisen typischerweise Partikelgrößen im Bereich von 0,1 bis 100 µm, insbesondere im Bereich von 1 bis 50 µm auf.Furthermore, it may be desired that the adhesive layer (s) and / or the lacquer layer (s) are colored. For this purpose, lacquer layer (s) and / or the adhesive layer (s) may contain one or more coloring constituents such as organic and / or inorganic pigments or dyes. Examples of these pigments are titanium dioxide as a white pigment, furthermore iron oxide pigments such as iron oxide yellow, iron oxide red, iron oxide black, black pigments such as carbon black, phthalocyanine pigments such as heliogen blue or heliogen green, bismuth pigments such as bismuth vanadate yellow and diketopyrrolopyrrole red. Metallization effects may also include metal pigments such as iron pigments, pearlescent pigments and aluminum pigments. Preferred pigments typically have particle sizes in the range from 0.1 to 100 .mu.m, in particular in the range from 1 to 50 .mu.m.
Klebeschichten weisen typischerweise Schichtdicken im Bereich von 5 bis 25 µm auf.Adhesive layers typically have layer thicknesses in the range of 5 to 25 μm.
Die erfindungsgemäßen Thermotransferfolien weisen naturgemäß wenigstens eine Trägerfolie auf, auf der die wenigstens eine Lackschicht angeordnet ist. Bei den Trägerfolien handelt es sich in der Regel um Kunststofffolien aus thermoplastischen flexiblen Polymeren. Insbesondere handelt es sich um Polyesterfolien, Polyamidfolien, Polypropylenfolien, Folien aus Polyvinylalkohol oder Polyesteramidfolien. Geeignet sind auch so genannte Koextrudat-Folien, d. h. aus mehreren Schichten bestehende Folien, wobei das Kunststoffmaterial in den einzelnen Schichten verschieden sein kann. Vorzugsweise ist das Kunststoffmaterial, welches die Trägerfolie bildet, überwiegend amorph. Geeignet sind auch gewachste oder silikonisierte Papiere. Vorzugsweise weist die Trägerfolie (2) eine Dicke im Bereich von 3 bis 200 µm, insbesondere 10 bis 100 µm und speziell von 20 bis 50 µm auf. Geeignet sind auch dünne Trägerfolien mit Folienstärken im Bereich von 3 bis 30 µm.The thermal transfer films according to the invention naturally have at least one carrier foil on which the at least one lacquer layer is arranged. The carrier films are usually plastic films made of thermoplastic flexible polymers. In particular, these are polyester films, polyamide films, polypropylene films, films of polyvinyl alcohol or polyesteramide films. Also suitable are so-called coextrudate films, d. H. multilayered films, wherein the plastic material in the individual layers may be different. Preferably, the plastic material which forms the carrier film is predominantly amorphous. Waxed or siliconized papers are also suitable. Preferably, the carrier film (2) has a thickness in the range of 3 to 200 .mu.m, in particular 10 to 100 .mu.m and especially from 20 to 50 microns. Also suitable are thin carrier films with film thicknesses in the range of 3 to 30 microns.
Die Oberflächenstruktur der Trägerfolie, auf welcher die Lackschicht angeordnet ist, bestimmt naturgemäß den Glanzgrad der Lackschicht, welche bei dem erfindungsgemäßen Beschichtungsverfahren erhalten wird. Glatte Oberflächen führen zu glänzenden oder hochglänzenden Oberflächen, wohingegen durch raue Oberflächen Matteffekte erreicht werden können. Es ist möglich, durch eine starke Strukturierung der Oberfläche auch gröbere Strukturen in der Lackoberfläche zu erzeugen.The surface structure of the carrier film on which the lacquer layer is arranged naturally determines the degree of gloss of the lacquer layer which is obtained in the coating method according to the invention. Smooth surfaces result in shiny or glossy surfaces, whereas rough surfaces can achieve matt effects. It is possible to create coarser structures in the paint surface by a strong structuring of the surface.
Die Oberfläche der Trägerfolie, auf welcher die Lackschicht angeordnet ist, kann eine übliche Releaseschicht aufweisen, welche das Ablösen der Lackschicht von der Trägerfolie bei dem erfindungsgemäßen Beschichtungsverfahren erleichtert.The surface of the carrier film on which the lacquer layer is arranged may have a conventional release layer, which facilitates the detachment of the lacquer layer from the carrier film in the coating method according to the invention.
Die Herstellung der Thermotransferfolien kann in Analogie zu üblichen Folienbeschichtungstechnologien erfolgen, wie sie auch im eingangs zitierten Stand der Technik beschrieben werden, mit dem Unterschied, dass bei der Herstellung der Lackschicht kein Wärmetrocknungsschritt vorgenommen wird, sondern die durch Aufbringen der nicht-wässrigen strahlungshärtbaren, flüssigen Zusammensetzung auf die Trägerfolie erhaltene flüssige Lackschicht durch Behandlung mit energiereicher Strahlung wie Elektronenstrahlung oder UV-Strahlung wenigstens teilweise ausgehärtet wird.The production of the thermal transfer films can be carried out in analogy to conventional film coating technologies, as described in the cited prior art, with the difference that in the preparation of the paint layer no heat-drying step is carried out, but by applying the non-aqueous radiation-curable, liquid Composition obtained on the carrier film liquid lacquer layer is at least partially cured by treatment with high-energy radiation such as electron beam or UV radiation.
Das Aufbringen der nicht-wässrigen, strahlungshärtbaren, flüssigen Zusammensetzung auf die Trägerfolie in Schritt i) des erfindungsgemäßen Verfahrens kann in an sich bekannter Weise erfolgen, beispielsweise durch Rakeln, Walzen, Gießen oder Sprühen. Auf diese Weise erhält man eine Beschichtung der Trägerfolie mit der strahlungshärtbaren Zusammensetzung, die dann durch Behandlung mit energiereicher Strahlung ausgehärtet werden kann. Die Auftragsmenge wird in der Regel so gewählt, dass eine Schichtdicke in den oben genannten Bereichen resultiert. In der Regel liegt die Auftragsmenge im Bereich von 10 bis 120 g/m2, insbesondere im Bereich von 30 bis 80 g/m2 und bei mehreren Schichten vorzugsweise im Bereich von 10 bis 100 g/m2 und insbesondere 20 bis 70 g/m2.The application of the non-aqueous, radiation-curable, liquid composition to the carrier film in step i) of the process according to the invention can be carried out in a manner known per se, for example by knife coating, rolling, casting or spraying. In this way, one obtains a coating of the carrier film with the radiation-curable composition, which can then be cured by treatment with high-energy radiation. The order quantity is usually chosen such that a layer thickness results in the above-mentioned ranges. As a rule, the order quantity is in the range of 10 to 120 g / m 2 , in particular in the range of 30 to 80 g / m 2 and in the case of several layers, preferably in the range of 10 to 100 g / m 2 and in particular 20 to 70 g / m 2 .
In Schritt ii) des erfindungsgemäßen Verfahrens wird dann die in Schritt i) erhaltene Beschichtung mittels energiereicher Strahlung wenigstens teilweise ausgehärtet. Gegebenenfalls kann vor dem vollständigen Aushärten eine Dekorschicht auf die noch nicht ausgehärtete bzw. teilausgehärtete Beschichtung aufgebracht werden. Gegebenenfalls kann die Klebeschicht ebenfalls vor dem Aushärten aufgebracht werden. Vorzugsweise wird in Schritt ii) des erfindungsgemäßen Verfahrens die in Schritt i) erhaltene Beschichtung nur teilweise ausgehärtet. Vorzugsweise wird man jedoch vor dem Aufbringen der heißsiegelbaren, polymeren Klebeschicht und vor dem optionalen Aufbringen der Dekorschicht die in Schritt i) erhaltene Schicht wenigstens teilweise aushärten.In step ii) of the method according to the invention, the coating obtained in step i) is then at least partially cured by means of high-energy radiation. Optionally, a decorative layer can be applied to the not yet cured or partially cured coating prior to complete curing. Optionally, the adhesive layer may also be applied prior to curing. Preferably, in step ii) of the process according to the invention, the coating obtained in step i) is only partially cured. Preferably, however, prior to the application of the heat-sealable, polymeric adhesive layer and before the optional application of the decorative layer, the layer obtained in step i) is at least partially cured.
Zum Härten in Schritt ii) wird die in Schritt i) erhaltene Beschichtung mit energiereicher Strahlung bestrahlt. Die Bestrahlung kann durch die Trägerfolie oder durch unmittelbares Bestrahlen der Beschichtung erfolgen. Bevorzugt ist die unmittelbare Bestrahlung.For hardening in step ii), the coating obtained in step i) is irradiated with high-energy radiation. The irradiation can be carried out by the carrier foil or by direct irradiation of the coating. Preference is given to direct irradiation.
Die Bestrahlung kann mittels Elektronenstrahlung oder mit UV-Licht, beispielsweise mit UV-Lampen oder UV-Strahlung emittierenden Leuchtdioden erfolgen. Vorzugsweise wird UV-Strahlung zur Härtung in Schritt ii) eingesetzt. Insbesondere verwendet man UV-Strahlung im Wellenlängenbereich von 200 bis 400 nm. Bevorzugt verwendet man hierfür Quecksilbermitteldruck- oder Quecksilberhochdrucklampen. In vielen Fällen werden Gallium- oder Eisen-dotierte Quecksilberhochdruckstrahler eingesetzt.The irradiation can be effected by means of electron radiation or with UV light, for example with UV lamps or UV-emitting light-emitting diodes. Preferably, UV radiation is used for curing in step ii). In particular, UV radiation is used in the wavelength range from 200 to 400 nm. Preference is given to using medium-pressure mercury lamps or high-pressure mercury lamps for this purpose. In many cases, gallium or iron-doped high-pressure mercury lamps are used.
Vorzugsweise führt man die Bestrahlung in Schritt ii) so durch, dass nur eine teilweise Polymerisation der in der nicht-wässrigen, strahlungshärtbaren, flüssigen Zusammensetzung enthaltenen ethylenisch ungesättigten Doppelbindungen erfolgt. Die hierfür erforderliche Strahlungsdichte kann der Fachmann durch Routineexperimente ermitteln.The irradiation in step ii) is preferably carried out in such a way that only partial polymerization of the ethylenically unsaturated double bonds contained in the nonaqueous, radiation-curable, liquid composition takes place. The radiation density required for this purpose can be determined by the expert by means of routine experiments.
Typischerweise erfolgt die Bestrahlung in Schritt ii) bei einer Strahlungsdichte im Bereich von 80 bis 2000 J/m2, insbesondere im Bereich von 110 bis 400 J/m2.Typically, the irradiation in step ii) takes place at a radiation density in the range from 80 to 2000 J / m 2 , in particular in the range from 110 to 400 J / m 2 .
Die Härtung in Schritt ii) kann unter Luftatmosphäre oder unter einer sauerstoffarmen Atmosphäre bei Restsauerstoffkonzentrationen unterhalb 2000 ppm, z. B. bei Restsauerstoffkonzentrationen im Bereich von 50 bis 1000 ppm, erfolgen. Bevorzugt erfolgt die Härtung unter Luft.The curing in step ii) can be carried out under air atmosphere or under an oxygen-poor atmosphere at residual oxygen concentrations below 2000 ppm, eg. B. at residual oxygen concentrations in the range of 50 to 1000 ppm, take place. The curing preferably takes place under air.
Sofern die erfindungsgemäße Thermotransferfolie mehrere Lackschichten aufweist, kann man die einzelnen Lackschichten beispielsweise im flüssig-flüssig-Auftrag aufbringen, d. h. die zweite Lackschicht und etwaige weitere Lackschichten werden auf die noch flüssige erste Beschichtung vor dem Aushärten aufgebracht. Vorzugsweise wird jedoch die erste Lackschicht vor dem Aufbringen der weiteren Lackschicht(en) wenigstens teilweise durch energiereiche Strahlung ausgehärtet.If the thermal transfer film according to the invention comprises a plurality of lacquer layers, it is possible to apply the individual lacquer layers, for example, in a liquid-liquid order, ie. H. the second lacquer layer and any further lacquer layers are applied to the still liquid first coating before curing. Preferably, however, the first lacquer layer is at least partially cured by high-energy radiation before the application of the further lacquer layer (s).
Gegebenenfalls wird auf die Lackschicht vor dem Aufbringen der Klebeschicht oder im Falle mehrerer Lackschichten auch auf die erste Lackschicht, eine Dekorschicht aufgebracht. Diese Dekorschicht kann in an sich bekannter Weise durch geeignete Druckverfahren, beispielsweise durch Flach-, Tief-, Inkjet- oder Digitaldruck, aufgebracht werden. Vorzugsweise wird die Lackschicht vor dem Aufbringen der Dekorschicht teilweise ausgehärtet, wobei man die teilweise Härtung vorzugsweise nur soweit durchführt, dass gerade noch ein Aufbringen der Dekorschicht möglich ist. Bei den zur Herstellung der Dekorschicht verwendeten Druckfarben kann es sich um konventionelle Druckfarben oder um UV-härtende Druckfarben handeln.Optionally, a decorative layer is applied to the lacquer layer prior to the application of the adhesive layer or, in the case of multiple lacquer layers, to the first lacquer layer. This decorative layer can be applied in a manner known per se by suitable printing methods, for example by flat, gravure, inkjet or digital printing. Preferably, the lacquer layer is partially cured before applying the decorative layer, wherein the partial curing is preferably carried out only to the extent that just applying the decorative layer is possible. The printing inks used to produce the decorative layer can be conventional printing inks or UV-curing printing inks.
Das Aufbringen der heißsiegelbaren Klebeschicht in Schritt iv) des erfindungsgemäßen Verfahrens kann in an sich bekannter Weise erfolgen. Hierzu wird man in der Regel eine flüssige Klebstoffzusammensetzung, insbesondere eine wässrige Klebstoffzusammensetzung in üblicher Weise, beispielsweise durch Rakeln, Walzen, Gießen oder Sprühen auf die Lackschicht bzw. auf die Dekorschicht aufbringen. Anschließend wird die Klebstoffschicht getrocknet, beispielsweise durch Wärme. Die Auftragsmenge der flüssigen Klebstoffzusammensetzung wird in der Regel so gewählt, dass nach dem Trocknen eine Schichtdicke in den oben genannten Bereichen resultiert. In der Regel liegt die Auftragsmenge im Bereich von 5 bis 50 g Feststoff pro m2, insbesondere im Bereich von 5 bis 15 g Feststoff pro m2.The application of the heat-sealable adhesive layer in step iv) of the method according to the invention can be carried out in a manner known per se. For this purpose, a liquid adhesive composition, in particular an aqueous adhesive composition in the usual manner, for example, by knife coating, rolling, pouring or spraying on the paint layer or on the decorative layer is usually applied. Subsequently, the adhesive layer is dried, for example by heat. The application amount of the liquid adhesive composition is usually selected so that, after drying, a layer thickness results in the above ranges. In general, the application rate is in the range of 5 to 50 g solids per m 2 , in particular in the range of 5 to 15 g solids per m 2 .
Beispielsweise können mit dem erfindungsgemäßen Verfahren die folgenden Folienaufbauten 1 bis 12 durch Anwendung der dort angegebenen Schritte hergestellt werden. Hierbei entsprechen die Folienaufbauten 7 bis 12 den Folienaufbauten 1 bis 6 mit dem Unterschied, dass eine pigmenthaltige Klebstoffzusammensetzung eingesetzt wird.For example, with the method according to the invention, the following film constructions 1 to 12 can be produced by using the steps given there. Here, the film structures 7 to 12 correspond to the film structures 1 to 6 with the difference that a pigment-containing adhesive composition is used.
- 1. Bereitstellen einer Trägerfolie;1. providing a carrier film;
- 2. Beschichtung der Trägerfolie mit einer flüssigen, strahlungshärtbaren, abrasivfreien, farblosen Zusammensetzung;2. coating the carrier film with a liquid, radiation-curable, abrasion-free, colorless composition;
- 3. Teilhärtung der Lackschicht mittels UV-Strahlung;Partial hardening of the lacquer layer by means of UV radiation;
- 4. Aufbringen einer wasserbasierten, pigmentfreien Klebstoffzusammensetzung mit strahlungshärtbaren Bestandteilen;4. applying a water-based, pigment-free adhesive composition with radiation-curable constituents;
- 5. Luft-Wärmetrocknung.5. Air heat drying.
- 1. Bereitstellen einer Trägerfolie;1. providing a carrier film;
- 2. Beschichtung der Trägerfolie mit einer flüssigen, strahlungshärtbaren, abrasivfreien Zusammensetzung;2. coating the carrier film with a liquid, radiation-curable, abrasive-free composition;
- 3. Teilhärtung der Lackschicht mittels UV-Strahlung;Partial hardening of the lacquer layer by means of UV radiation;
- 4. Aufbringen einer Dekorschicht mittels Tiefdruck oder Digitaldruck unter Verwendung einer UV-härtbaren Druckfarbe;4. application of a decorative layer by gravure or digital printing using a UV-curable ink;
- 5. Trocknung der Dekorschicht mittels UV-Strahlung;5. drying of the decorative layer by means of UV radiation;
- 6. Aufbringen einer wasserbasierten, pigmentfreien Klebstoffzusammensetzung mit strahlungshärtbaren Bestandteilen auf die Dekorschicht;6. applying a water-based, pigment-free adhesive composition having radiation-curable constituents to the decorative layer;
- 7. Luft-Wärmetrocknung.7. Air heat drying.
- 1. Bereitstellen einer Trägerfolie;1. providing a carrier film;
- 2. Beschichtung der Trägerfolie mit einer flüssigen, strahlungshärtbaren, abrasivfreien, Farbpigment-haltigen Zusammensetzung;2. coating the carrier film with a liquid, radiation-curable, abrasive-free, color pigment-containing composition;
- 3. Teilhärtung der farbigen Lackschicht mittels UV-Strahlung;Partial hardening of the colored lacquer layer by means of UV radiation;
- 4. Aufbringen einer wasserbasierten, pigmentfreien Klebstoffzusammensetzung mit strahlungshärtbaren Bestandteilen auf die Lackschicht;4. applying a water-based, pigment-free adhesive composition having radiation-curable constituents to the lacquer layer;
- 5. Luft-Wärmetrocknung.5. Air heat drying.
- 1. Bereitstellen einer Trägerfolie;1. providing a carrier film;
- 2. Beschichtung der Trägerfolie mit einer flüssigen, strahlungshärtbaren, Korundhaltigen Zusammensetzung;2. coating the carrier film with a liquid, radiation-curable, corundum-containing composition;
- 3. Trocknung der farbigen Lackschicht mittels UV-Strahlung;3. Drying of the colored lacquer layer by means of UV radiation;
- 4. Aufbringen einer wasserbasierten, pigmentfreien Klebstoffzusammensetzung mit strahlungshärtbaren Bestandteilen auf die Lackschicht;4. applying a water-based, pigment-free adhesive composition having radiation-curable constituents to the lacquer layer;
- 5. Luft-Wärmetrocknung.5. Air heat drying.
- 1. Bereitstellen einer Trägerfolie;1. providing a carrier film;
- 2. Beschichtung der Trägerfolie mit einer flüssigen, strahlungshärtbaren, Korundhaltigen Zusammensetzung;2. coating the carrier film with a liquid, radiation-curable, corundum-containing composition;
- 3. Teilhärtung der Lackschicht mittels UV-Strahlung;Partial hardening of the lacquer layer by means of UV radiation;
- 4. Aufbringen einer Dekorschicht mittels Tiefdruck oder Digitaldruck unter Verwendung einer UV-härtbaren Druckfarbe;4. application of a decorative layer by gravure or digital printing using a UV-curable ink;
- 5. Trocknung der Dekorschicht mittels UV-Strahlung;5. drying of the decorative layer by means of UV radiation;
- 6. Aufbringen einer wasserbasierten, pigmentfreien Klebstoffzusammensetzung mit strahlungshärtbaren Bestandteilen auf die Dekorschicht;6. applying a water-based, pigment-free adhesive composition having radiation-curable constituents to the decorative layer;
- 7. Luft-Wärmetrocknung.7. Air-heat drying.
- 1. Bereitstellen einer Trägerfolie;1. providing a carrier film;
- 2. Beschichtung der Trägerfolie mit einer flüssigen, strahlungshärtbaren, abrasivhaltigen, Farbpigment-haltigen Zusammensetzung;2. coating the carrier film with a liquid, radiation-curable, abrasive-containing, color pigment-containing composition;
- 3. Teilhärtung der farbigen Lackschicht mittels UV-Strahlung;Partial hardening of the colored lacquer layer by means of UV radiation;
- 4. Aufbringen einer wasserbasierten, pigmentfreien Klebstoffzusammensetzung mit strahlungshärtbaren Bestandteilen auf die Lackschicht;4. applying a water-based, pigment-free adhesive composition having radiation-curable constituents to the lacquer layer;
- 5. Luft-Wärmetrocknung.5. Air heat drying.
Die so erhaltenen Thermotransferfolien können anschließend in üblicher Weise konfektioniert werden, z. B. zu Rollen aufgewickelt werden.The resulting thermal transfer films can then be made up in the usual way, for. B. are wound into rolls.
Die erfindungsgemäßen Thermotransferfolien eignen sich in besonderer Weise zum Trockenlackieren von Oberflächen von Gegenständen. Hierbei werden, wie bereits eingangs beschrieben, mittels Anwendung von Wärme und/oder Druck die Lackschicht bzw. die Lackschichten auf die zu beschichtende Oberfläche des Gegenstands, im Folgenden auch als Substrat bezeichnet, übertragen, wobei die Klebeschicht nach dem Bestrahlen einen guten Haftverbund zwischen der bzw. den Lackschichten und dem Substrat bewirkt. Die Verwendung der erfindungsgemäßen Thermotransferfolien ist nicht auf bestimmte Substrate beschränkt, sondern sie können sehr vielseitig sowohl bei harten wie auch bei elastischen Substraten angewendet werden.The thermal transfer films according to the invention are particularly suitable for the dry coating of surfaces of objects. Here, as already described above, by application of heat and / or pressure, the lacquer layer or the lacquer layers on the surface to be coated of the article, hereinafter also referred to as a substrate transferred, the adhesive layer after irradiation a good bond between the or the paint layers and the substrate causes. The use of the thermal transfer films according to the invention is not limited to certain substrates, but they can be very versatile applied to both hard and elastic substrates.
Bei den Substraten kann es sich beispielsweise um Gegenstände aus Kunststoff, beispielsweise aus ABS, Polycarbonat, Melamin, Polyester, einschließlich glasfaserverstärkter Polyester, Hart-PVC, Weich-PVC, Gummi, Holz einschließlich exotischer Naturhölzer, Holzwerkstoffen, z. B. Furnier, MDF-, HDF-, Feinspan- oder Multiplexplatten, Mineralfasern, z. B. Mineralfaserplatten, Papier, Textil einschließlich Kunstleder, Metall oder Kunststoff-beschichteten Materialien, handeln. Vorzugsweise eignen sich die erfindungsgemäßen Thermotransferfolien für glatte, vorzugsweise plane oder leicht gewölbte Oberflächen. Grundsätzlich lassen sich jedoch auch komplexere Strukturen auf diese Weise beschichten. Die zu beschichtenden Substrate können undekoriert sein oder bereits Dekoroberflächen aufweisen. Besonders vorteilhaft lassen sich unter Verwendung der erfindungsgemäßen Thermotransferfolien exotische Naturhölzer beschichten, die vielfach Probleme bei der Nasslackierung bereiten, da die Inhaltsstoffe ausbluten oder Adhäsionsprobleme verursacht werden. Die unter Verwendung der erfindungsgemäßen Thermotransferfolien beschichteten Gegenstände, z. B. Holzfaserplatten, MDF-Platten oder Naturholzplatten, die unter Verwendung der erfindungsgemäßen Thermotransferfolien grundiert wurden, können ohne Weiteres mit einem konventionellen UV-Lack weiter beschichtet werden, wobei kein Zwischenschliff erforderlich ist. Alternativ kann ein so grundierter Gegenstand auch mit einer erfindungsgemäßen Thermotransferfolie trockenbeschichtet werden.The substrates can be, for example, articles made of plastic, for example ABS, polycarbonate, melamine, polyester, including glass fiber reinforced Polyester, hard PVC, soft PVC, rubber, wood including exotic natural woods, wood materials, eg. As veneer, MDF, HDF, Feinspan- or multiplex plates, mineral fibers, z. As mineral fiber boards, paper, textile including synthetic leather, metal or plastic-coated materials act. The thermal transfer films according to the invention are preferably suitable for smooth, preferably plane or slightly curved surfaces. In principle, however, even more complex structures can be coated in this way. The substrates to be coated may be undecorated or already have decorative surfaces. Using the thermal transfer films according to the invention, it is particularly advantageous to coat exotic natural woods, which often present problems in wet painting, since the contents bleed or adhesion problems are caused. The coated using the thermal transfer films of the invention objects, for. As wood fiber boards, MDF boards or natural wood panels that have been primed using the thermal transfer films of the invention can be readily coated with a conventional UV coating, with no intermediate sanding is required. Alternatively, such a primed article can also be dry-coated with a thermal transfer film according to the invention.
Die erfindungsgemäßen Thermotransferfolien erlauben eine nahezu abfallfreie Beschichtung von Gegenständen. Bei der industriellen Fertigung kann ein Wechsel von farblos auf farbig, von matt auf glänzend, sehr rasch erfolgen, ohne dass zwischen diesem Wechsel ein Reinigungsschritt erforderlich ist. Trockenzeiten entfallen, und nach der Beschichtung kann unmittelbar weitergearbeitet werden, z. B. ein konventioneller Lackauftrag aufgebracht oder der beschichtete Gegenstand verpackt werden. Die Trägerfolie kann abgelöst oder zunächst als Schutzfolie auf der beschichteten Oberfläche verbleiben. Im Vergleich zu konventionellen Lackierverfahren erlaubt die Verwendung der erfindungsgemäßen Thermotransferfolien eine staubfreie Lackierung. Zudem ist der Platzbedarf und Personalaufwand im Vergleich zu konventionellen Lackierverfahren sehr viel geringer.The thermal transfer films according to the invention allow a virtually waste-free coating of articles. In industrial production, a change from colorless to color, from dull to glossy, can take place very rapidly, without a cleaning step being required between these changes. Drying times are eliminated, and after the coating can be continued directly, z. B. applied a conventional paint job or the coated article to be packaged. The carrier film can be peeled off or initially remain as a protective film on the coated surface. In comparison to conventional painting processes, the use of the thermal transfer films according to the invention permits a dust-free coating. In addition, the space requirements and personnel costs compared to conventional painting process is much lower.
Die erfindungsgemäßen Thermotransferfolien liefern im Vergleich zu den aus dem Stand der Technik bekannten Thermotransferfolien Oberflächen mit besonders hoher Wertigkeit, insbesondere hohen Kratz- und Abriebfestigkeiten. So lassen sich beispielweise Oberflächen der Güteklassen AC3 bis AC4 (DIN EN 13329) erreichen. Die unter Verwendung der erfindungsgemäßen Thermotransferfolien erhaltenen Oberflächen weisen bei Prüfung mit dem Hamberger Hobel regelmäßig Werte über 20 N auf. Die so erhaltenen Oberflächen erfüllen regelmäßig die Erfordernisse der höchsten Beanspruchungsgruppe der Möbelnorm DIN 68861.The thermal transfer films of the invention provide compared to the known from the prior art thermal transfer films surfaces with particularly high valence, especially high scratch and abrasion resistance. For example, surfaces of quality classes AC3 to AC4 (DIN EN 13329) can be achieved. The surfaces obtained using the thermal transfer films according to the invention regularly show values above 20 N when tested with the Hamberger planer. The surfaces thus obtained regularly meet the requirements of the highest stress group of the furniture standard DIN 68861.
Die Verwendung der erfindungsgemäßen Thermotransferfolien zur Beschichtung von Oberflächen von Gegenständen erfolgt typischerweise in einem Verfahren, welches die zuvor genannten Schritte a) bis d) umfasst, die im Folgenden näher beschrieben werden und die in Analogie zu der in
Hierbei wird zunächst die erfindungsgemäße Thermotransferfolie auf die Oberfläche des zu beschichtenden Substrats aufgebracht und anschließend heißgesiegelt. Das Heißsiegeln erfolgt typischerweise unter Anwendung von Druck in geeigneten Pressen, wobei die Temperatur der Presse typischerweise im Bereich von 100 bis 250 °C, bevorzugt im Bereich von 160 bis 220 °C liegt. Bevorzugt sind Walzenpressen, da auf diese Weise nur ein kurzer Kontakt erforderlich ist, so dass die Objekttemperatur hierbei einen Wert von 70 °C, insbesondere von 60 °C nicht überschreitet. Auf diese Weise können auch hitzeempfindliche Substrate beschichtet werden.Here, the thermal transfer film of the invention is first applied to the surface of the substrate to be coated and then heat sealed. The heat sealing is typically carried out using pressure in suitable presses, wherein the temperature of the press is typically in the range of 100 to 250 ° C, preferably in the range of 160 to 220 ° C. Preference is given to roller presses, since in this way only a short contact is required, so that the object temperature in this case does not exceed a value of 70 ° C, in particular of 60 ° C. In this way, heat-sensitive substrates can be coated.
Anschließend wird das so beschichtete Substrat mit energiereicher Strahlung, d. h. mit UV- oder Elektronenstrahlung, bestrahlt, wobei die Lackschicht vollständig aushärtet. Die Bestrahlung kann vor Entfernen der Trägerfolie oder im Anschluss daran durchgeführt werden. Für eine Reihe von Anwendungen ist es von Vorteil, die Bestrahlung vor Entfernen der Trägerfolie durchzuführen, da dann die Trägerfolie als Schutzfolie auf dem beschichteten Substrat verbleibt.Subsequently, the thus coated substrate with high-energy radiation, d. H. irradiated with UV or electron radiation, the coating layer cures completely. The irradiation may be performed prior to removal of the carrier sheet or subsequently. For a number of applications, it is advantageous to carry out the irradiation before removing the carrier film, since then the carrier film remains as a protective film on the coated substrate.
Die Bestrahlung kann mittels Elektronenstrahlung, z. B. unter Verwendung von Gallium-Strahlern oder mit UV-Licht, beispielsweise mit UV-Lampen oder UV-Strahlung emittierenden Leuchtdioden, erfolgen. Vorzugsweise wird UV-Strahlung zur Härtung in Schritt ii) eingesetzt. Insbesondere verwendet man UV-Strahlung im Wellenlängenbereich von 200 bis 400 nm. Bevorzugt verwendet man hierfür Quecksilbermitteldruck- oder Quecksilberhochdrucklampen. In vielen Fällen werden Gallium- oder Eisen-dotierte Quecksilberhochdruckstrahler eingesetzt.The irradiation can by means of electron radiation, z. B. using gallium radiators or with UV light, for example, with UV lamps or UV-emitting LEDs, done. Preferably, UV radiation is used for curing in step ii). In particular, UV radiation is used in the wavelength range from 200 to 400 nm. Preference is given to using medium-pressure mercury lamps or high-pressure mercury lamps for this purpose. In many cases, gallium or iron-doped high-pressure mercury lamps are used.
Typischerweise erfolgt die Bestrahlung in Schritt ii) bei einer Strahlungsdichte im Bereich von 40 bis 2000 J/m2, insbesondere im Bereich von 100 bis 400 J/m2.Typically, the irradiation in step ii) takes place at a radiation density in the range from 40 to 2000 J / m 2 , in particular in the range from 100 to 400 J / m 2 .
Eine Anlage zur Durchführung des erfindungsgemäßen Verfahrens umfasst mindestens eine üblicherweise verwendete Thermotransfervorrichtung, die vorzugsweise eine Abschneidevorrichtung und/oder eine Aufwickelvorrichtung für die Trägerfolie aufweist. In Abhängigkeit des beabsichtigten Verwendungszwecks des fertig lackierten Gegenstands kann die Anlage eine erste Thermotransfervorrichtung, mit der der Gegenstand grundiert wird und eine zweite Thermotransfervorrichtung, mit der der Gegenstand endlackiert wird, aufweisen.A system for carrying out the method according to the invention comprises at least one commonly used thermal transfer device, which preferably has a cutting device and / or a winding device for the carrier film. Depending on the intended use of the finished painted article, the equipment may include a first thermal transfer device with which the article is primed and a second thermal transfer device, with which the article is finished, have.
Eine übliche Thermotransfervorrichtung kann folgendermaßen aufgebaut sein: Von einer Folienabwickeleinrichtung wird die als Rolle aufgewickelte Thermotransferfolie zu einer beheizten Walzenpresse geführt, die wenigstens eine angetriebene, beheizte, gegebenenfalls gummierte Walze aufweist, die gegebenenfalls höhenverstellbar ist. Die Walzenpresse weist in der Regel eine der beheizten Walze gegenüberliegende Gegendruckwalze auf, die gummiert sein kann. Diese bewirkt den notwendigen Pressdruck, wodurch die Lackschicht mittels der Klebeschicht auf die Oberfläche eines Gegenstands übertragen wird, der zwischen den beiden Walzen geführt wird. Die Gegendruckwalze kann so ausgestaltet sein, dass sie die Trennung der Trägerfolie von der Lackschicht bewirkt. Die abgetrennte Trägerfolie kann mit einer Abschneidevorrichtung entfernt oder einer Folienaufwickeleinrichtung zugeleitet werden. Anstelle einer Walzenpresse kann auch eine Plattenpresse eingesetzt werden, die nach einer vorbestimmten Zeit geöffnet wird.A conventional thermal transfer device can be constructed as follows: From a film unwinding the wound as a roll thermal transfer film is fed to a heated roller press having at least one driven, heated, optionally rubberized roller, which is optionally adjustable in height. The roller press usually has one of the heated roller opposite counter-pressure roller, which may be rubberized. This causes the necessary pressing pressure, whereby the lacquer layer is transferred by means of the adhesive layer to the surface of an object which is guided between the two rollers. The counter-pressure roller can be designed so that it causes the separation of the carrier film from the paint layer. The separated carrier film can be removed with a cutter or fed to a Folienaufwickeleinrichtung. Instead of a roll press, a plate press can be used, which is opened after a predetermined time.
Anschließend wird der beschichtete Gegenstand mit der beschichteten Seite an einer Quelle für energiereiche Strahlung, beispielsweise einem Elektronenstrahler oder einem UV-Strahler, vorbeigeführt, wodurch die beschichtete Seite des Gegenstands energiereicher Strahlung ausgesetzt wird und die Endhärtung erreicht wird. Der so beschichtete Gegenstand wird anschließend einer Sammelvorrichtung, beispielsweise einer Abstapelvorrichtung, zugeführt. Vor oder nach dem Bestrahlen kann die Trägerfolie mit einer Abschneidevorrichtung entfernt werden oder einer Folienaufwickeleinrichtung zugeleitet werden.Subsequently, the coated article with the coated side past a source of high energy radiation, such as an electron gun or UV emitter, exposing the coated side of the article to high energy radiation and achieving final cure. The article thus coated is subsequently fed to a collecting device, for example a stacking device. Before or after the irradiation, the carrier film can be removed with a cutter or fed to a film take-up device.
Der in der Thermotransfervorrichtung beschichtete Gegenstand kann nach Ablösen der Trägerfolie vor oder nach der Härtung mittels energiereicher Strahlung auch einer weiteren Thermotransfervorrichtung zugeführt werden, bei der mittels einer weiteren erfindungsgemäßen Thermotransferfolie eine weitere Lackschicht auf die beschichtete Oberfläche des Gegenstands aufgebracht wird. Vorzugsweise erfolgt im Anschluss an das Aufbringen der weiteren Lackschicht eine Härtung mit energiereicher Strahlung wie zuvor beschrieben.The object coated in the thermal transfer device can also be supplied to a further thermal transfer device after removal of the carrier film before or after curing by means of high-energy radiation, in which a further lacquer layer is applied to the coated surface of the article by means of a further thermal transfer film according to the invention. Preferably, following the application of the further lacquer layer, curing with high-energy radiation is carried out as described above.
Eine erste Ausgestaltung einer Vorrichtung zur kontinuierlichen Durchführung des erfindungsgemäßen Verfahrens mit festen Substraten weist ein Auflege-Transportband, eine Abwickelstation für die als Rolle aufgewickelte Thermotransferfolie, eine Thermotransfervorrichtung mit Walzenpresse, wie zuvor beschrieben, eine Aufwickelvorrichtung für die Trägerfolie, einen Trockenkanal mit UV-Strahler, ein Auslaufband und eine Abstapeleinrichtung auf.A first embodiment of a device for the continuous implementation of the method according to the invention with solid substrates comprises a lay-on conveyor belt, an unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with roller press, as described above, a winding device for the carrier film, a drying channel with UV emitter, a discharge belt and a stacking device.
Die zu beschichtenden Substrate, vorzugsweise Platten, werden auf das Transportband gelegt und mit dem gewünschten Vorschub durch die Thermotransfervorrichtung geführt. Hierbei wird die Lackschicht auf das Substrat übertragen und die Trägerfolie abgetrennt und von der Aufwickelvorrichtung aufgenommen. Anschließend wird die Lackschicht im Trockenkanal ausgehärtet. Die Aufwickelstation kann auch nach dem Trockenkanal angeordnet sein, so dass die Trägerfolie zunächst auf dem Substrat verbleibt und dort als Schutzfolie wirkt.The substrates to be coated, preferably plates, are placed on the conveyor belt and guided at the desired feed rate through the thermal transfer device. In this case, the lacquer layer is transferred to the substrate and the carrier foil separated and taken up by the take-up device. Subsequently, the lacquer layer is cured in the drying channel. The winding station can also be arranged after the drying channel, so that the carrier film initially remains on the substrate and acts there as a protective film.
Eine zweite Ausgestaltung einer Vorrichtung zur kontinuierlichen Durchführung des erfindungsgemäßen Verfahrens mit elastischen Substraten weist eine Abwickelstation für das Substrat, eine Abwickelstation für die als Rolle aufgewickelte Thermotransferfolie, eine Thermotransfervorrichtung mit Walzenpresse, wie zuvor beschrieben, einen Trockenkanal mit UV-Strahler und eine Aufwickelvorrichtung für das beschichtete Substrat auf.A second embodiment of an apparatus for continuously carrying out the method according to the invention with elastic substrates comprises a unwinding station for the substrate, a unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with roller press, as described above, a drying channel with UV lamps and a winding device for the coated substrate.
Das zu beschichtende Substrat wird zusammen mit der Thermotransferfolie mit dem gewünschten Vorschub durch die Thermotransfervorrichtung geführt. Hierbei wird die Thermotransferfolie mit dem Substrat verbunden. Anschließend wird das so beschichtete Substrat durch den Trockenkanal geführt, wodurch die Lackschicht aushärtet und von der Aufwickelstation aufgenommen. Nach dem Zuschnitt kann die Trägerfolie entfernt werden.The substrate to be coated is guided through the thermal transfer device at the desired feed rate together with the thermal transfer film. Here, the thermal transfer film is bonded to the substrate. Subsequently, the thus coated substrate is passed through the drying channel, whereby the lacquer layer cures and received by the winding station. After cutting, the carrier film can be removed.
Eine dritte Ausgestaltung einer Vorrichtung zur kontinuierlichen Durchführung des erfindungsgemäßen Verfahrens mit festen Substraten weist ein Transportband, eine Abwickelstation für die als Rolle aufgewickelte Thermotransferfolie, eine Thermotransfervorrichtung mit beheizter Plattenpresse und gegebenenfalls eine Aufwickelvorrichtung für die Trägerfolie oder eine Schneidvorrichtung auf.A third embodiment of a device for continuously carrying out the method according to the invention with solid substrates comprises a conveyor belt, an unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with heated platen press and optionally a take-up device for the carrier film or a cutting device.
Die zu beschichtenden Substrate, vorzugsweise Platten, werden auf das Transportband gelegt und zusammen mit der Thermotransferfolie in die Plattenpresse geführt. Die Presse wird verschlossen und mit dem gewünschten Druck beaufschlagt. Hierbei wird die Lackschicht auf das Substrat übertragen. Nach Öffnen der Presse wird das Substrat aus der Presse gefahren und durch den Trockenkanal geleitet, wodurch die Lackschicht aushärtet. Hierbei kann die Trägerfolie auf dem Substrat verbleiben und als Schutzfolie dienen. In diesem Fall kann die Trägerfolie vor oder nach dem Trockenkanal mit einer Schneidvorrichtung gekappt werden. Alternativ ist es möglich, die Folie als Ganzes vor dem UV-Kanal abzutrennen und der Aufwickelvorrichtung zuzuführen.The substrates to be coated, preferably plates, are placed on the conveyor belt and fed together with the thermal transfer film in the plate press. The press is closed and pressurized with the desired pressure. In this case, the lacquer layer is transferred to the substrate. After opening the press, the substrate is driven out of the press and passed through the drying channel, whereby the lacquer layer cures. In this case, the carrier film can remain on the substrate and serve as a protective film. In this case, the carrier film before or after the drying channel be cut with a cutting device. Alternatively, it is possible to separate the film as a whole in front of the UV channel and supply it to the take-up device.
Eine weitere Ausgestaltung einer Vorrichtung zur diskontinuierlichen Durchführung des erfindungsgemäßen Verfahrens mit festen Substraten weist ein Transportband, eine Abwickelstation für die als Rolle aufgewickelte Thermotransferfolie, eine Schneidvorrichtung, Thermotransfervorrichtung mit beheizter Plattenpresse und einen Trockenkanal mit UV-Strahler auf.A further embodiment of a device for the discontinuous implementation of the method according to the invention with solid substrates comprises a conveyor belt, an unwinding station for wound as a roll thermal transfer film, a cutting device, thermal transfer device with heated platen press and a drying channel with UV lamp.
Das zu beschichtende Substrat wird auf das Transportband gelegt. Die Thermotransferfolie wird in der gewünschten Länge abgewickelt, mit der Klebeschicht auf dem zu beschichtenden Substrat platziert und abgeschnitten. Substrat und Folie werden in die Plattenpresse geführt. Die Presse wird verschlossen und mit dem gewünschten Druck beaufschlagt. Hierbei wird die Lackschicht auf das Substrat übertragen. Nach Öffnen der Presse wird das beschichtete Substrat aus der Presse gefahren und durch den Trockenkanal geleitet, wodurch die Lackschicht aushärtet. Hierbei kann die Trägerfolie auf dem Substrat verbleiben und als Schutzfolie dienen. Alternativ ist es möglich, die Folie vor dem UV-Kanal abzutrennen.The substrate to be coated is placed on the conveyor belt. The thermal transfer film is unwound to the desired length, placed with the adhesive layer on the substrate to be coated and cut. Substrate and foil are fed into the plate press. The press is closed and pressurized with the desired pressure. In this case, the lacquer layer is transferred to the substrate. After opening the press, the coated substrate is driven out of the press and passed through the drying channel, whereby the lacquer layer cures. In this case, the carrier film can remain on the substrate and serve as a protective film. Alternatively, it is possible to separate the film from the UV channel.
Wegen weiterer Details hierzu wird insbesondere auf die Figuren 2 bis 6 der
Die folgenden Beispiele dienen der Erläuterung der Erfindung:The following examples serve to illustrate the invention:
- Urethanacrylat, verdünnt mit 35 Gew.-% Dipropylenglykoldiacrylat, Funktionalität 2,0: Laromer® UA9065 der BASF SEUrethane acrylate diluted with 35% by weight of dipropylene glycol diacrylate, functionality 2.0: Laromer® UA9065 from BASF SE
- Aliphatisches Urethanacrylat 1, verdünnt mit 35 Gew.-% Dipropylenglykoldiacrylat: Laromer® UA19T der BASF SEAliphatic urethane acrylate 1 diluted with 35% by weight of dipropylene glycol diacrylate: Laromer® UA19T from BASF SE
- Aliphatisches Urethanacrylat 2, verdünnt mit 30 Gew.-% Trimethylolpropanformal-Monoacrylat, Funktionalität 1,7: Laromer® UA9033 der BASF SEAliphatic urethane acrylate 2 diluted with 30% by weight of trimethylolpropane formal monoacrylate, functionality 1.7: Laromer® UA9033 from BASF SE
- Aliphatisches Urethanacrylat 3, verdünnt mit 30 Gew.-% Hexandioldiacrylat: Laromer® LR 8987 der BASF SEAliphatic urethane acrylate 3, diluted with 30% by weight of hexanediol diacrylate: Laromer® LR 8987 from BASF SE
- Polyesteracrylat 1, Funktionalität 3,3, Hydroxylzahl 70: Laromer® PE9084 der BASF SEPolyester acrylate 1, functionality 3.3, hydroxyl number 70: Laromer® PE9084 from BASF SE
- Polyesteracrylat 2, Funktionalität 3,2, Hydroxylzahl 50: Laromer® PE9074 der BASF SEPolyester acrylate 2, functionality 3.2, hydroxyl number 50: Laromer® PE9074 from BASF SE
- Polyesteracrylat 3, Funktionalität 3,1, Hydroxylzahl 70: Laromer® PE55F der BASF SEPolyester acrylate 3, functionality 3.1, hydroxyl number 70: Laromer® PE55F from BASF SE
- Polyesteracrylat 4, Funktionalität 2,5, Hydroxylzahl 60, abgemischt mit 20 Gew.-% Tripropylenglykoldiacrylat: Laromer® PE9045 der BASF SEPolyester acrylate 4, functionality 2.5, hydroxyl number 60, blended with 20% by weight of tripropylene glycol diacrylate: Laromer® PE9045 from BASF SE
- Phenoxyethylacrylat: Laromer® POEA der BASF SEPhenoxyethyl acrylate: Laromer® POEA from BASF SE
- Trimethylolpropanformal-Monoacrylat: Laromer® LR8887 der BASF SETrimethylolpropane Formal Monoacrylate: Laromer® LR8887 from BASF SE
- Trimethylolpropantriacrylat: Laromer® TMPTA der BASF SETrimethylolpropane triacrylate: Laromer® TMPTA from BASF SE
- Dipropylenglykoldiacrylat (DPGDA)Dipropylene glycol diacrylate (DPGDA)
- Pyrogene Kieselsäure: ACE Matt TS 100 der Fa. Evonik Industries AGPyrogenic silica: ACE Matt TS 100 from Evonik Industries AG
- Mattierungsmittel auf Basis von Kieselsäure (Syloid ED 80)Matting agent based on silica (Syloid ED 80)
- Aluminiumoxid: Alodur ZWSK F320/280 der Fa. TreibacherAluminum oxide: Alodur ZWSK F320 / 280 from Treibacher
- Korund 1: Alodur F280 der Fa. TreibacherCorundum 1: Alodur F280 Fa. Treibacher
- Korund 2: Alodur F320 der Fa. TreibacherCorundum 2: Alodur F320 Fa. Treibacher
- Synthetische Kieselsäure: Syloid® RAD 2005 der Fa. GraceSynthetic silicic acid: Syloid® RAD 2005 from Grace
- Synthetische, organisch modifizierte Kieselsäure: Gasil® UV 70CSynthetic, organically modified silicic acid: Gasil® UV 70C
- Polyethersiloxan: Tego Glide 435 der Fa. Evonik Industries AGPolyethersiloxane: Tego Glide 435 from Evonik Industries AG
- Entlüfterkonzentrat: Tego Airex 920 der Fa. EvonikDeaerator concentrate: Tego Airex 920 from Evonik
- alpha-Hydroxyalkylphenon: Irgacure® 184 der BASF SEalpha-hydroxyalkylphenone: Irgacure® 184 from BASF SE
- Acylphosphinoxid: Irgacure® 2100 der BASF SEAcylphosphine oxide: Irgacure® 2100 from BASF SE
- Phenylglyoxylat: Irgacure® MBF der BASF SEPhenylglyoxylate: Irgacure® MBF from BASF SE
- Triazin-basierter UV-Absorber: Gemisch aus 2-[4-[(2-Hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin und 2-[4-[(2-Hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin.Triazine-based UV absorber: Mixture of 2- [4 - [(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5 triazine and 2- [4 - [(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.
- UV-Stabilisator (HALS): Gemisch aus Bis-(1,2,2,5,5-pentamethyl-4-piperidyl)sebacat 1-(Methyl)-8-(1,2,2,5,5-pentamethyl-4-piperidyl)sebacatUV stabilizer (HALS): mixture of bis (1,2,2,5,5-pentamethyl-4-piperidyl) sebacate 1- (methyl) -8- (1,2,2,5,5-pentamethyl) 4-piperidyl) sebacate
Aus den oben genannten Rohstoffen wurden die folgenden strahlungshärtbaren Lackformulierungen 1 bis 7 durch Vermischen hergestellt:
- Selbstvernetzende, wässrige Polyacrylat-Dispersion 1 (50 gew.-%ig): Acronal® A849S der BASF SESelf-crosslinking, aqueous polyacrylate dispersion 1 (50% strength by weight): Acronal® A849S from BASF SE
- Selbstvernetzende, wässrige Mehrphasen- Polyacrylat-Dispersion 2 (48 gew.-%ig), Mindestfilmbildetemperatur 50°C;Self-crosslinking, aqueous multiphase polyacrylate dispersion 2 (48% by weight), minimum film-forming temperature 50 ° C .;
- Wässrige Polyesterurethandispersion, 40 gew.-%ig, Glasübergangstemperatur < -50°C;Aqueous polyester urethane dispersion, 40% strength by weight, glass transition temperature <-50 ° C .;
- Wässrige Polyetherurethanacrylat-Dispersion 1 (40 gew.-%ig): Laromer® LR9005 der BASF SEAqueous polyether urethane acrylate dispersion 1 (40% strength by weight): Laromer® LR9005 from BASF SE
- Wässrige Polyetherurethanacrylat-Dispersion 2 (40 gew.-%ig): Syntholux® 1014 W der Synthopol ChemieAqueous polyether urethane acrylate dispersion 2 (40% strength by weight): Syntholux® 1014 W from Synthopol Chemie
- Aliphatisches Epoxyacrylat: Laromer® LR 8765 der BASF SEAliphatic epoxy acrylate: Laromer® LR 8765 from BASF SE
- Polyethersiloxan-Emulsion: Tego® Wet 270 der Fa. Evonik Industries AGPolyethersiloxane emulsion: Tego® Wet 270 from Evonik Industries AG
- Polymeres Fluortensid: Tego® Twin der Fa. Evonik Industries AGPolymeric fluorosurfactant: Tego® Twin from Evonik Industries AG
- Benetzungsadditiv 1: Siloxan-Gemini-TensidWetting additive 1: siloxane-gemini-surfactant
- Benetzungsadditiv 2: PolyethersiloxanWetting additive 2: polyethersiloxane
- Carnaubawachsdispersion: CA 30 der Fa. Münzing Liquid Technologies GmbHCarnauba wax dispersion: CA 30 from Münzing Liquid Technologies GmbH
- Modifiziertes Polyethylenwachs, wässrige Dispersion: Aquamat® 270 der Fa. Byk Chemie GmbHModified polyethylene wax, aqueous dispersion: Aquamat® 270 from Byk Chemie GmbH
- Pyrogene Kieselsäure: ACE Matt TS 100, Fa. Evonik Industries AGPyrogenic silica: ACE Matt TS 100, Evonik Industries AG
- Mikronisiertes Polyethylenwachs: Aquaflour® 400 der Fa. Byk Chemie GmbHMicronized polyethylene wax: Aquaflour® 400 from Byk Chemie GmbH
- Synthetische Kieselsäure: Sylysia der Fa. Finma ChemieSynthetic silicic acid: Sylysia from the company Finma Chemie
- Wässrige Polyurethan-Dispersion : Ecrothan 90 der Ecronova Polymer GmbHAqueous polyurethane dispersion: Ecrothan 90 from Ecronova Polymer GmbH
- Dimethylpolysiloxan: Tego® Glide 482 der Fa. Evonik Industries AGDimethylpolysiloxane: Tego® Glide 482 from Evonik Industries AG
- Styrol-Acrylat-Copolymer: Acronal® S 813 der BASF SEStyrene-acrylate copolymer: Acronal® S 813 from BASF SE
- Triethylcitrat: Citrofol Al der Jungbunzlauer GmbHTriethyl citrate: Citrofol Al from Jungbunzlauer GmbH
- alpha-Hydroxyalkylphenon: lrgacure® 184alpha-hydroxyalkylphenone: Irgacure® 184
- Acylphosphinoxid: Irgacure® 2100Acyl phosphine oxide: Irgacure® 2100
- Bisacylphosphinoxid: Irgacure® 819 DWBisacylphosphine oxide: Irgacure® 819 DW
- Gemisch aus Benzophenon und 1-Hydroxycyclohexylphenylketon;Mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone;
- Entschäumer: Siliconbasierte Emulsion;Defoamer: silicone-based emulsion;
- Verdicker: Wässrige Verdickerlösung (Vocaflex)Thickener: Aqueous thickener solution (Vocaflex)
- Wässrige Titandioxidpaste: Luconyl® white 0022 der BASF SEAqueous titanium dioxide paste: Luconyl® white 0022 from BASF SE
Die Herstellung der Klebstoffzusammensetzung 1 erfolgte durch Vermischen der in der folgenden Tabelle angegebenen Bestandteile.
Die Herstellung der Klebstoffformulierung 2 erfolgte durch Vermischen der in der folgenden Tabelle angegebenen Bestandteile.
Die Herstellung der Klebstoffformulierung 3 erfolgte durch Vermischen der in der folgenden Tabelle angegebenen Bestandteile.
Die Herstellung der Klebstoffformulierung 4 erfolgte durch Vermischen der in der folgenden Tabelle angegebenen Bestandteile.
In den folgenden Beispielen wurde zur Bestrahlung eine Vorrichtung eingesetzt, bei der die beschichtete bzw. bedruckte Folie mit definierter Vorschubgeschwindigkeit an einer Ga-dotierten Quecksilberstrahler mit der Leistung von 120 W/cm vorbeigeführt wurde.In the following examples, a device was used for the irradiation, in which the coated or printed film with a defined feed rate of a Ga-doped mercury lamps with the power of 120 W / cm was passed.
Für die Folien der Beispiele 1, 2 und 3 wurde eine UV-härtbare Tiefdruckfarbe auf Basis eines Epoxidacrylats eingesetzt.For the films of Examples 1, 2 and 3, a UV-curable gravure ink based on an epoxy acrylate was used.
Auf eine ungefärbte Polyethylenterephthalat-Trägerfolie mit einer Schichtdicke von 23 µm wurde die Lackformulierung 4 mit einer Schichtdicke von 40 g/m2 aufgebracht. Die so beschichtete Folie wurde zur Gelierung der Lackschicht mit einer Vorschubgeschwindigkeit von 30 m/min an dem Ga-dotierten Quecksilberstrahler vorbeiführt.On a non-colored polyethylene terephthalate support film with a layer thickness of 23 microns, the paint formulation 4 was applied with a layer thickness of 40 g / m 2 . The thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
Anschließend wurde die UV-härtbare Tiefdruckfarbe auf die gelierte Lackschicht aufgebracht. Die so bedruckte Folie wurde zur Härtung mit einer Vorschubgeschwindigkeit von 30 m/min erneut an dem Ga-dotierten Quecksilberstrahler vorbeiführt.Subsequently, the UV-curable gravure ink was applied to the gelled lacquer layer. The so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
Dann wurde die Klebstoffformulierung 3 mit einer Schichtdicke von 15 g/m2 auf die bedruckte Lackschicht aufgebracht und thermisch getrocknet.Then the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
Auf eine ungefärbte Polyethylenterephthalat-Trägerfolie mit einer Schichtdicke von 23 µm wurde die Lackformulierung 5 mit einer Schichtdicke von 70 g/m2 aufgebracht. Die so beschichtete Folie wurde zur Gelierung der Lackschicht mit einer Vorschubgeschwindigkeit von 30 m/min an dem Ga-dotierten Quecksilberstrahler vorbeiführt.The lacquer formulation 5 having a layer thickness of 70 g / m 2 was applied to an undyed polyethylene terephthalate support film having a layer thickness of 23 μm. The thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
Anschließend wurde die UV-härtbare Tiefdruckfarbe auf die gelierte Lackschicht aufgebracht. Die so bedruckte Folie wurde zur Härtung mit einer Vorschubgeschwindigkeit von 30 m/min erneut an dem Ga-dotierten Quecksilberstrahler vorbeiführt.Subsequently, the UV-curable gravure ink was applied to the gelled lacquer layer. The so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
Dann wurde die Klebstoffformulierung 3 mit einer Schichtdicke von 15 g/m2 auf die bedruckte Lackschicht aufgebracht und thermisch getrocknet.Then the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
Auf eine ungefärbte Polyethylenterephthalat-Trägerfolie mit einer Schichtdicke von 23 µm wurde die Lackformulierung 6 mit einer Schichtdicke von 40 g/m2 aufgebracht. Die so beschichtete Folie wurde zur Gelierung der Lackschicht mit einer Vorschubgeschwindigkeit von 30 m/min an dem Ga-dotierten Quecksilberstrahler vorbeiführt.On a non-colored polyethylene terephthalate support film with a layer thickness of 23 microns, the paint formulation 6 was applied with a layer thickness of 40 g / m 2 . The thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
Dann wurde die Klebstoffformulierung 3 mit einer Schichtdicke von 15 g/m2 auf die bedruckte Lackschicht aufgebracht und thermisch getrocknet.Then the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
Auf eine ungefärbte Polyethylenterephthalat-Trägerfolie mit einer Schichtdicke von 23 µm wurde die Lackformulierung 7 mit einer Schichtdicke von 45 g/m2 aufgebracht. Die so beschichtete Folie wurde zur Gelierung der Lackschicht mit einer Vorschubgeschwindigkeit von 30 m/min an dem Ga-dotierten Quecksilberstrahler vorbeiführt.On an undyed polyethylene terephthalate support film with a layer thickness of 23 microns, the paint formulation 7 was applied with a layer thickness of 45 g / m 2 . The thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
Anschließend wurde die UV-härtbare Tiefdruckfarbe auf die gelierte Lackschicht aufgebracht. Die so bedruckte Folie wurde zur Härtung mit einer Vorschubgeschwindigkeit von 30 m/min erneut an dem Ga-dotierten Quecksilberstrahler vorbeiführt.Subsequently, the UV-curable gravure ink was applied to the gelled lacquer layer. The so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
Dann wurde die Klebstoffformulierung 3 mit einer Schichtdicke von 15 g/m2 auf die bedruckte Lackschicht aufgebracht und thermisch getrocknet.Then the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
Die Folie aus Beispiel 3 wurde mittels einer beheizten Walze (180°C, Objekttemperatur maximal 50°C) auf eine Buchenholzplatte kaschiert. Anschließend wurde die so kaschierte Folie durch Verbeiführen der kaschierten Seite mit einer Vorschubgeschwindigkeit von 20 m/min an zwei UV-Strahlern (Quecksilberstrahler und Ga-dotierter Quecksilberstrahler) mit jeweils einer Leistung von 120 W/cm durch die Folie bestrahlt.The film of Example 3 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) on a beech wood panel. Subsequently, the thus laminated film was irradiated by Verbeiführen the laminated side at a feed rate of 20 m / min to two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film.
Die so erhaltene Probe wurde mittels ATR-FTIR-Spektroskopie unter Verwendung eines FT-IR Spektrometers der Fa. Nicolet (Nicolet 380) und eines Golden Gate® Probenkopfs untersucht. Im Vergleich zu einer nicht bestrahlten Probe war ein signifikanter Rückgang der für Acrylat-Gruppen charakteristischen Absorbtionsbanden bei 810 cm-1 (> 40 %) und 1410 cm-1 (> 30 %) zu erkennen.The sample thus obtained was analyzed by ATR-FTIR spectroscopy using an FT-IR spectrometer from Nicolet (Nicolet 380) and a Golden Gate® probe head. Compared to a non-irradiated sample, a significant decrease in the absorption bands characteristic of acrylate groups was observed at 810 cm-1 (> 40%) and 1410 cm-1 (> 30%).
Es wurden die folgenden Prüfungen vorgenommen:
- P1: Beständigkeit gegen Wassereinwirkung (24 h) nach DIN 68861-1:2011-01. Die Bewertung erfolgte auf einer Skala von 1 (schlecht) bis 5 (gut).
- P2: Beständigkeit gegen Ethanoleinwirkung (6 h) nach DIN 68861-1:2011-01. Die Bewertung erfolgte auf einer Skala von 1 (schlecht) bis 5 (gut).
- P3: Beständigkeit gegen Einwirkung von Ethylacetat (10 s) nach DIN 68861-1:2011-01. Die Bewertung erfolgte auf einer Skala von 1 (schlecht) bis 5 (gut).
- P4: Prüfung mit dem Hamberger Hobel: Hierzu wird ein münzähnlicher Prüfkörper in vorgegebenem Winkel mit variabler Kraft über die zu prüfende Oberfläche gezogen. Das Prüfgerät erlaubt eine stufenlose Einstellung der applizierten Kraft. Angegeben wird die Kraft in Newton bei der gerade noch keine Beschädigung der Oberfläche zu erkennen ist.
- P5: Kratzbeständigkeit im Diamant-Test nach EN 438-2:205. Angegeben ist der Zahlenwert der höchsten angewendeten Kraft, die keinen durchgehenden Oberflächenkratzer hinterlässt.
- P6: Der Gitterschnitttest erfolgte nach DIN EN ISO 2409:2013. Die Bewertung erfolgte auf einer Skala von GT 0 (gute Haftung) bis GT 5 (sehr starkes Abplatzen der Beschichtung).
- P7: Abriebbeständigkeit nach der Falling Sand Methode nach DIN EN 14354:2005-03
- P8: Abriebbeständigkeit nach der S24-Methode nach DIN 13329:2013-12
- P1: Resistance to water (24 h) according to DIN 68861-1: 2011-01. The rating was on a scale of 1 (poor) to 5 (good).
- P2: Resistance to ethanol (6 h) according to DIN 68861-1: 2011-01. The rating was on a scale of 1 (poor) to 5 (good).
- P3: Resistance to ethyl acetate (10 s) according to DIN 68861-1: 2011-01. The rating was on a scale of 1 (poor) to 5 (good).
- P4: Testing with the Hamberger planer: For this purpose, a coin-like test specimen is drawn at a predetermined angle with variable force over the surface to be tested. The tester allows a stepless adjustment of the applied force. Indicated is the force in Newton at the just no damage to the surface can be seen.
- P5: Scratch resistance in the diamond test according to EN 438-2: 205. Given is the numerical value of the highest applied force, which leaves no continuous surface scratch.
- P6: The cross-cut test was carried out according to DIN EN ISO 2409: 2013. The evaluation was carried out on a scale of GT 0 (good adhesion) to GT 5 (very strong flaking of the coating).
- P7: Abrasion resistance according to the Falling Sand method according to DIN EN 14354: 2005-03
- P8: Abrasion resistance according to the S24 method according to DIN 13329: 2013-12
Die Ergebnisse der Prüfungen P1 - P8 sind in der Tabelle P zusammengefasst.The results of tests P1-P8 are summarized in Table P.
Die Folie aus Beispiel 1 wurde mittels einer beheizten Walze (180°C, Objekttemperatur maximal 50°C) bei konstantem Anpressdruck auf eine MDF-Platte kaschiert. Anschließend wurde die so kaschierte Platte durch Vorbeiführen der kaschierten Seite mit einer Vorschubgeschwindigkeit von 20 m/min an zwei UV-Strahlern (Quecksilberstrahler und Ga-dotierter Quecksilberstrahler) mit jeweils einer Leistung von 120 W/cm durch die Folie bestrahlt. Anschließend wurde die Trägerfolie entfernt.The film from Example 1 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at a constant contact pressure on an MDF board. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 20 m / min on two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
Zu Vergleichszwecken wurde die Folie aus Beispiel 1 mittels einer beheizten Walze (180°C, Objekttemperatur maximal 50°C) bei dem gleichen Anpressdruck auf eine MDF-Platte kaschiert, wobei jedoch keine anschließende Bestrahlung vorgenommen wurde.For comparison purposes, the film of Example 1 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at the same contact pressure on an MDF board, but no subsequent irradiation was made.
Die Herstellung erfolgte in Analogie zur Herstellung der Probe 1, wobei man anstelle der Folie aus Beispiel 1 die Folie aus Beispiel 2 verwendete.The preparation was carried out in analogy to the preparation of Sample 1, using instead of the film of Example 1, the film of Example 2.
Die Herstellung erfolgte in Analogie zur Herstellung der Vergleichsprobe V1, wobei man anstelle der Folie aus Beispiel 1 die Folie aus Beispiel 2 verwendete.The preparation was carried out in analogy to the preparation of the comparative sample V1, using instead of the film of Example 1, the film of Example 2.
Die Folie aus Beispiel 3 wurde mittels einer beheizten Walze (180°C, Objekttemperatur maximal 50°C) bei konstantem Anpressdruck auf eine Buchenholzplatte kaschiert. Anschließend wurde die so kaschierte Platte durch Vorbeiführen der kaschierten Seite mit einer Vorschubgeschwindigkeit von 20 m/min an zwei UV-Strahlern (Quecksilberstrahler und Ga-dotierter Quecksilberstrahler) mit jeweils einer Leistung von 120 W/cm durch die Folie bestrahlt. Anschließend wurde die Trägerfolie entfernt.The film from Example 3 was laminated by means of a heated roller (180 ° C, object temperature maximum 50 ° C) at a constant contact pressure on a beech wood panel. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 20 m / min on two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
Zu Vergleichszwecken wurde die Folie aus Beispiel 3 mittels einer beheizten Walze (180°C, Objekttemperatur maximal 50°C) bei dem gleichen Anpressdruck auf eine Buchenholzplatte kaschiert, wobei jedoch keine anschließende Bestrahlung vorgenommen wurde.For comparison purposes, the film of Example 3 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at the same contact pressure on a beech wood panel, but no subsequent irradiation was made.
Die Folie aus Beispiel 43 wurde mittels einer beheizten Walze (180°C, Objekttemperatur maximal 50°C) bei konstantem Anpressdruck auf eine PVC-Platte kaschiert. Anschließend wurde die so kaschierte Platte durch Vorbeiführen der kaschierten Seite mit einer Vorschubgeschwindigkeit von 15 m/min an zwei UV-Strahlern (Quecksilberstrahler und Ga-dotierter Quecksilberstrahler) mit jeweils einer Leistung von 120 W/cm durch die Folie bestrahlt. Anschließend wurde die Trägerfolie entfernt.The film from Example 43 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at a constant contact pressure on a PVC plate. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 15 m / min at two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
Zu Vergleichszwecken wurde die Folie aus Beispiel 4 mittels einer beheizten Walze (180°C, Objekttemperatur maximal 50°C) bei dem gleichen Anpressdruck auf eine PVC-Platte kaschiert, wobei jedoch keine anschließende Bestrahlung vorgenommen wurde.
Die Ergebnisse zeigen, dass eine gute Haftung nur dann erreicht werden kann, wenn die Klebschicht einen strahlungshärtbaren Bestandteil enthält, der durch Bestrahlung mit UV-Strahlung nach dem Kaschieren vernetzt wird.The results show that good adhesion can only be achieved if the adhesive layer contains a radiation-curable component which is crosslinked by irradiation with UV radiation after lamination.
Claims (16)
- A thermal transfer foil (1) comprising:a) a backing foil (2),b) at least one layer (3) of coating material arranged on the backing foil (2),c) at least one heat-sealable, polymeric adhesive layer (4),where the layer of coating material is based on a non-aqueous, radiation-curable, liquid composition which comprises at least 60% by weight, based on the total weight of the composition, of curable constituents selected from organic oligomers which have ethylenically unsaturated double bonds and mixtures of said oligomers with monomers which have at least one ethylenically unsaturated double bond,
and where the heat-sealable polymeric adhesive layer (4) comprises at least one radiation-curable constituent which is selected from oligomers and polymers which have ethylenically unsaturated double bonds. - The thermal transfer foil according to claim 1, wherein the radiation-curable composition which forms the layer of coating material comprises from 1.5 to 8 mols of ethylenically unsaturated double bonds per kg of the composition.
- The thermal transfer foil according to any of the preceding claims, wherein the oligomers in the radiation-curable composition which forms the layer of coating material have an average of from 1.5 to 10, in particular from 2 to 8, ethylenically unsaturated double bonds per molecule.
- The thermal transfer foil according to any of the preceding claims, wherein the ethylenically unsaturated double bonds in the oligomers and in the monomers of the radiation-curable composition which forms the layer of coating material take the form of acrylic or methacrylic groups.
- The thermal transfer foil according to any of the preceding claims, wherein the oligomers of the radiation-curable composition which forms the layer of coating material are selected from the following: polyether (meth)acrylates, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, unsaturated polyester resins, and mixtures of these.
- The thermal transfer foil according to any of the preceding claims, wherein the radiation-curable liquid composition comprises at least one photoinitiator which has an absorption band with a maximum λmax in the range from 220 to 420 nm.
- The thermal transfer foil according to any of the preceding claims, wherein the thickness of the layer (3) of coating material is from 10 to 120 µm.
- The thermal transfer foil according to any of the preceding claims, which has a decorative layer between the layer (3) of coating material and the adhesive layer (4).
- The thermal transfer foil according to any of the preceding claims, wherein the adhesive layer (4) is based on at least one aqueous polymer dispersion which comprises a UV-radiation-curable oligomer or polymer in dispersed form.
- The thermal transfer foil according to claim 9, where the UV-radiation-curable polymer is a polyurethane acrylate, in particular a polyether urethane acrylate.
- The thermal transfer foil according to any of the preceding claims, wherein the adhesive layer (4) is based on at least two aqueous polymer dispersions, where at least one polymer dispersion comprises a UV-radiation-curable polymer in dispersed form, and where at least one other polymer dispersion comprises a self-crosslinking polymer in dispersed form.
- A process for the production of a thermal transfer foil according to any of the preceding claims, comprising:i. the application of the non-aqueous, radiation-curable, liquid composition, where a coating curable by high-energy radiation is obtained;ii. irradiation, by high-energy radiation, of the curable coating obtained in step i., where the layer (3) of coating material is obtained;iii. optionally application of a decorative layer to the curable coating or to the layer (3) of coating material; andiv. application of the heat-sealable, polymeric adhesive layer (4).
- The process according to claim 12, where the irradiation of the coating curable by high-energy radiation takes place before the application of the adhesive layer and before the optional application of the decorative layer.
- The process according to claim 12 or 13, where the manner of irradiation of the coating curable by high-energy radiation is such as to cause only partial polymerization of the ethylenically unsaturated double bonds comprised in the non-aqueous, radiation-curable, liquid composition.
- A process for the coating of surfaces of articles, comprising the following steps:a) application of the thermal transfer foil (1) according to any of claims 1 to 11 with the adhesive layer to the surface to be coated;b) heat-sealing of the transfer foil, where a surface coated with the transfer foil is obtained;c) irradiation, with UV radiation or electron beams, of the surface coated with the transfer foil;d) optionally release of the backing foil (2).
- The use of thermal transfer foils according to any of claims 1 to 11 for the dry coating of articles.
Priority Applications (4)
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SI201430640T SI3046778T1 (en) | 2013-09-18 | 2014-09-18 | Thermo transfer films for the dry lacquering of surfaces |
PL14766739.8T PL3046778T5 (en) | 2013-09-18 | 2014-09-18 | Thermo transfer films for the dry lacquering of surfaces |
EP14766739.8A EP3046778B2 (en) | 2013-09-18 | 2014-09-18 | Thermo transfer films for the dry lacquering of surfaces |
NO14766739A NO3046778T3 (en) | 2013-09-18 | 2014-09-18 |
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EP13185007 | 2013-09-18 | ||
PCT/EP2014/069895 WO2015040113A1 (en) | 2013-09-18 | 2014-09-18 | Heat transfer films for the dry coating of surfaces |
EP14766739.8A EP3046778B2 (en) | 2013-09-18 | 2014-09-18 | Thermo transfer films for the dry lacquering of surfaces |
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US10106643B2 (en) | 2015-03-31 | 2018-10-23 | 3M Innovative Properties Company | Dual-cure nanostructure transfer film |
US20170057268A1 (en) * | 2015-09-01 | 2017-03-02 | Jerry Surber | Process for Producing Printed Wooden Plaques and Trophies |
DE102015117261A1 (en) * | 2015-10-09 | 2017-04-13 | Weilburger Graphics GmbH | Glue, use of certain printing units and processes exclusively for cold foil finishing |
EP3500535B1 (en) * | 2016-08-19 | 2020-06-24 | Xylo Technologies AG | Coated panel and method for manufacturing a coated panel |
FI4034368T3 (en) * | 2019-09-25 | 2024-02-08 | Basf Coatings Gmbh | Method for transferring an embossed structure to the surface of a coating, and composite employable as embossing mold |
WO2022040513A1 (en) * | 2020-08-20 | 2022-02-24 | Wayne State University | Coating compositions and methods |
DE102020128927A1 (en) | 2020-11-03 | 2022-05-05 | Aluminium Féron GmbH & Co. KG | Transfer film for furniture |
DE102021000890A1 (en) * | 2021-02-19 | 2022-08-25 | Giesecke+Devrient Currency Technology Gmbh | Security element and method for its manufacture |
CN115449326B (en) * | 2022-10-11 | 2023-05-19 | 东莞市德聚胶接技术有限公司 | Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof |
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- 2014-09-18 CN CN201480051191.2A patent/CN105555545B/en active Active
- 2014-09-18 DK DK14766739.8T patent/DK3046778T4/en active
- 2014-09-18 WO PCT/EP2014/069895 patent/WO2015040113A1/en active Application Filing
- 2014-09-18 EP EP14766739.8A patent/EP3046778B2/en active Active
- 2014-09-18 JP JP2016543400A patent/JP6581589B2/en active Active
- 2014-09-18 RU RU2016114693A patent/RU2674190C2/en active
- 2014-09-18 SI SI201430640T patent/SI3046778T1/en unknown
- 2014-09-18 PL PL14766739.8T patent/PL3046778T5/en unknown
- 2014-09-18 NO NO14766739A patent/NO3046778T3/no unknown
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Also Published As
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US10710388B2 (en) | 2020-07-14 |
RU2674190C2 (en) | 2018-12-05 |
PT3046778T (en) | 2018-03-22 |
NO3046778T3 (en) | 2018-05-19 |
SI3046778T1 (en) | 2018-04-30 |
WO2015040113A1 (en) | 2015-03-26 |
CN105555545B (en) | 2020-03-03 |
ES2663451T5 (en) | 2022-12-07 |
RU2016114693A3 (en) | 2018-05-31 |
PL3046778T3 (en) | 2018-08-31 |
US20160297226A1 (en) | 2016-10-13 |
DK3046778T3 (en) | 2018-04-09 |
US20190315144A1 (en) | 2019-10-17 |
RU2016114693A (en) | 2017-10-20 |
DK3046778T4 (en) | 2022-11-14 |
JP2016538165A (en) | 2016-12-08 |
EP3046778B2 (en) | 2022-08-17 |
PL3046778T5 (en) | 2023-01-09 |
EP3046778A1 (en) | 2016-07-27 |
JP6581589B2 (en) | 2019-09-25 |
ES2663451T3 (en) | 2018-04-12 |
CN105555545A (en) | 2016-05-04 |
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