WO2022037950A1 - Systèmes d'agents de revêtement, constitués d'un revêtement de base et d'un revêtement supérieur, et produit semi-fini à base de ceux-ci et production associée - Google Patents
Systèmes d'agents de revêtement, constitués d'un revêtement de base et d'un revêtement supérieur, et produit semi-fini à base de ceux-ci et production associée Download PDFInfo
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- WO2022037950A1 WO2022037950A1 PCT/EP2021/071830 EP2021071830W WO2022037950A1 WO 2022037950 A1 WO2022037950 A1 WO 2022037950A1 EP 2021071830 W EP2021071830 W EP 2021071830W WO 2022037950 A1 WO2022037950 A1 WO 2022037950A1
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- aliphatic
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- polycarbonate
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 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
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003015 aliphatic polyurethane dispersion Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 101150059062 apln gene Proteins 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008269 hand cream Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- SMUVTFSHWISULV-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.COC(=O)C(C)=C SMUVTFSHWISULV-UHFFFAOYSA-N 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UQMZDGOZAWEVRF-UHFFFAOYSA-N prop-2-enoyloxymethyl prop-2-enoate Chemical compound C=CC(=O)OCOC(=O)C=C UQMZDGOZAWEVRF-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
- B29C37/0032—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied upon the mould surface before introducing the moulding compound, e.g. applying a gelcoat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
- B29C2037/0042—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied in solid sheet form, e.g. as meltable sheet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1679—Making multilayered or multicoloured articles applying surface layers onto injection-moulded substrates inside the mould cavity, e.g. in-mould coating [IMC]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Definitions
- WO 2005/118689 A1 discloses an analogous composite layered sheet or film in which the radiation-curable composition additionally contains acid groups. Both applications describe the top layer as non-adhesive, a higher blocking resistance, such as is required for rolling the film around a core, is not achieved. The possibility of winding up the composite films into rolls before radiation curing of the cover layer is therefore not mentioned either.
- B2) comprises at least one organic (co)solvent
- the at least one thermoplastic polymer has an average molecular weight Mw of at least 100,000 g/mol and preferably an average molecular weight Mw of at least 250,000 g/mol , determined according to DIN EN/ISO 16014-1, whereby the chromatographic conditions were selected according to DIN 55762-1 (2016).
- A3 at least one photoinitiator in a content of >0.1% by weight to ⁇ 10% by weight of the solids content of the composition (ZA), and
- Polymethyl methacrylate is understood to mean, in particular, polymethyl methacrylate homopolymer and copolymers based on methyl methacrylate with a methyl methacrylate proportion of more than 70% by weight.
- Such polymethyl methacrylates are available, for example, under the trade names Degalan®, Degacryl®, Plexyglas®, Acrylite® (Rohm), Altuglas, Oroglas (Arkema), Elvacite®, Colacryl®, Lucite® (Lucite) and others under names Acrylglas, Conacryl, Deglas, Diakon, Friacryl, Hesaglas, Limacryl, PerClax and Vitroflex available.
- PMMA homopolymers and/or copolymers of 70% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 30% by weight methyl acrylate are preferred.
- PMMA homopolymers and copolymers of 90% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 10% by weight methyl acrylate are particularly preferred.
- the Vicat softening point VET (ISO 306) can be in the range of at least 90°C, preferably from >100°C to ⁇ 115°C.
- PMMA homopolymers and copolymers with an average molar weight Mw of at least 100,000 g/mol and very particularly preferably with an average molar weight Mw of at least 250,000 g/mol.
- the at least one thermoplastic polymer has an average molecular weight Mw of at least 100,000 g/mol and preferably an average molecular weight Mw of at least 250,000 g/mol, determined according to DIN EN / ISO 16014-1 (chromatographic conditions according to DIN 55762-1 (2016)) or according to DIN EN/ISO 16014-5 (2019).
- bi- to hexafunctional acrylic and/or methacrylic monomers preferably suitable esters of the polyhydroxy compounds mentioned are glycol diacrylate and dimethacrylate, butanediol diacrylate or dimethacrylate, dimethylolpropane diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, divinylbenzene, trimethylolpropane triacrylate or trimethacrylate, glycerol triacrylate or trimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate, Dipentaerythritol penta/hexaacrylate (DPHA), 1,2,3,4-butanetetraol tetraacrylate or tetramethacrylate, tetramethylolethane tetraacrylate or tetramethacrylate, 2,2-dihydroxypropanediol-1,3-tetraacrylate or
- At least one photoinitiator in a content of >0.1% by weight to ⁇ 10% by weight of the solids fraction of the composition (ZA) is used as component A3) of the composition (ZA).
- the OMNIRAD (formerly IRGACURE®)® types from IGM Resins are used as photoinitiators, such as the types OMNIRAD® 184, OMNIRAD® 500, OMNIRAD® 1173, OMNIRAD®2959, OMNIRAD® 745, OMNIRAD® 651, OMNIRAD® 369 , OMNIRAD® 907, OMNIRAD® 1000, OMNIRAD® 1300, OMNIRAD® 819, OMNIRAD® 819DW, OMNIRAD® 2022, OMNIRAD® 2100, OMNIRAD® 784, OMNIRAD® 250, OMNIRAD® MBF, OMNIRAD® 1173, OMNIRAD® TPO ® 4265 is used.
- the other UV photoinitiators are used, e.g. EsacureTM One (also IGM Resins).
- the polyol component b) is selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyesteramides, polyethers, polythioethers, polycarbonates, polyacetals, polyolefins or polysiloxanes and mixtures of at least two of these.
- suitable aliphatic polyether polyols are polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide and polytetrahydrofuran (pTHF 1000, pTHF 2000, BASF SE, Ludwigshafen, DE).
- Tertiary amines which are particularly suitable and preferred for salt formation are, for example, triethylamine, dimethylcyclohexylamine and ethyldiisopropylamine.
- Other amines can also be used for salt formation, such as ammonia, diethanolamine, triethanolamine, dimethylethanolamine, methyldiethanolamine, aminomethylpropanol and also mixtures of the amines mentioned and other amines. It makes sense for these amines to be added only after the isocyanate groups have largely reacted.
- the solution of the water-dispersible polyurethane prepolymer in the vinyl monomer can be prepared by adding one or more other aliphatic polymerizates to the prepolymer or, which is preferred, by preparing the prepolymer in the presence of one or more vinyl monomers.
- suitable monomers are ethylenically unsaturated hydrocarbons, esters and ethers, especially esters of acrylic acid and methacrylic acid, esters and ethers of vinyl alcohol and styrene.
- esters and ethers especially esters of acrylic acid and methacrylic acid, esters and ethers of vinyl alcohol and styrene.
- Specific examples include butadiene, isoprene, styrene, substituted styrenes, the (Cl-6) lower alkyl esters of acrylic, methacrylic and maleic acid, vinyl acetate, butyrate, acrylate and methacrylate, acrylonitrile, allyl methacrylate, vinyl methyl, - propyl and butyl ether, divinyl ether, divinyl sulfide, vinyl chloride, vinylidene chloride, hexanediol diacrylate, trimethylolpropane triacrylate, and the like. Free acids should
- Surface-modified nanoparticles are optionally introduced during or after the production of the at least one aliphatic polyurethane-polyurea. This can be done by simply stirring in the particles. However, it is also conceivable to use increased dispersing energy, for example by means of ultrasound, jet dispersing or high-speed stirrers based on the rotor-stator principle. Simple mechanical stirring is preferred.
- Suitable organic (co)solvents B2) are butyl glycol, propylene glycol, propylene glycol mono-n-butyl ether, or diethylene glycol monoethyl ether.
- compositions (ZA) and the composition (ZB) can be produced in a simple manner.
- the components are mixed with one another at room temperature in compliance with the usual working instructions and are thereby homogenized.
- the thermoplastic polymer is first completely dissolved in the solvent at room temperature or at elevated temperatures.
- the other obligatory and optionally the optional components are then added to the solution, which has been cooled to room temperature, either in the absence of solvent(s) and mixed together by stirring, or in the presence of solvent(s), for example in the solvent(s) and also through Stir mixed together.
- the photoinitiator is preferably first dissolved in the solvent or solvents and then the other components are added.
- a further purification by means of filtration preferably by means of fine filtration, then takes place.
- Film insert molding in the context of the present invention is a process in which the layer structure according to the invention is three-dimensionally deformed, for example thermally, and then the layer structure is back-coated or back-injected with the thermoplastic polymer on the side facing away from the film.
- the coating can already include a drying process.
- the coating on the surface of the layer structure is preferably cured by means of actinic radiation, preferably UV radiation.
- Drying follows the application of the coating agent.
- work is carried out in particular with elevated temperatures in ovens and with moving and optionally also dehumidified air such as, for example, in convection ovens or by means of jet dryers and thermal radiation such as IR and/or NIR. Furthermore, microwaves can be used. It is possible and advantageous to combine several of these drying processes.
- the drying of the coating in steps (c and e) preferably comprises flashing off at room temperature and/or elevated temperature, such as preferably at 20-200° C., particularly preferably at 40-120° C.
- After the coating has dried it is block-resistant, so that the coated thermoplastic polymer layer C, in particular the coated film, can be laminated, printed and/or thermally deformed.
- shaping is preferred, since the shape for a three-dimensional plastic part produced using the film insert molding process can be predetermined simply by shaping a coated film.
- the emitters can be installed immovably, so that the item to be irradiated is moved past the radiation source by means of a mechanical device, or the emitters can be movable, and the item to be irradiated does not change its location during curing.
- the radiation dose usually sufficient for crosslinking in UV curing is in the range from >80 mJ/cm 2 to ⁇ 5000 mJ/cm 2 .
- the layered structure according to the invention can be used, for example, to produce molded bodies which have structural elements with very small radii of curvature. After curing, the top layer A and the adhesion promoter layer B have good abrasion resistance and chemical resistance.
- Figure 4 shows the comparison of the test results of the formation of microcracks in paints on thermoplastic films using light microscopy (table microscope, 10x magnification): a) component after back-injection, which is OK (because there are no micro-cracks) and b) component after back-injection, which is not in order is (since micro cracks on edge / corner).
- a layer structure according to the invention ABSC
- Fig. 4a compared to the existing prior art (not according to the invention, single-layer acrylate-based paint according to Table 3, Example A), Fig. 4b) after deformation, UV - Hardening and back-molding with polycarbonate (Makrolon®) evaluated as indicated in the example section.
- Bayhydrol® UH XP2648 aliphatic, polyether-polycarbonatediol containing anionic
- JonCryl® HYB6340 araliphatic, polyether-polyesterdiol-containing anionic polyurethane-polyacrylate dispersion, solvent-free (BASF SE, Ludwigshafen a. Rh., DE)
- EsacureTM One: functional 1-hydroxyalkyl aryl ketone photoinitiator
- Makrofol® DE 1-1 Polycarbonate film (Covestro Deutschland AG, Leverkusen, DE)
- a flat test specimen was prepared from the coated film previously cured by actinic radiation and fixed on a glass plate.
- the pencil hardness was determined using the Wolf-Wilbum pencil hardness tester from BYK-Gardner and pencils from Cretacolor. Here, based on ISO 15184, the designation of the pencil was specified which, in the test arrangement, caused no surface damage at a pressure of 500 g at an angle of 45°.
- the PUR/PAC hybrid dispersion B1) (eg NeoPacTM E-123) was initially taken and the solvent mixture was added with stirring (1000 rpm) within 5 min. Thereafter, the respective additives, as indicated in Table 1 for formulation examples 1 to 13 (in the case of example 11: BYK 346 etc.), were added stepwise with stirring (500 rpm) with a subsequent stirring time of 5 minutes. The pH was determined and adjusted to a pH of 7.9-8.2 with stirring (500 rpm) by adding N,N-dimethylethylamine in portions. With further stirring (500 rpm), the Levasil® CC 401 was added within 10 minutes and stirred for a further 20 minutes.
- Steps 4 to 7 represent the processing that has been carried out of the layer systems according to the invention and relevant comparative samples, which are required for a final evaluation of the features in terms of application technology (step 8).
- the expert processing of the layer systems in the so-called film insert molding process (FIM) is a prerequisite for the comparative evaluation of the different layer systems.
- HVAC Panel TCF Internal Test Tool
- the UV curing of the coating according to the invention was carried out using an evo 7 dr high-pressure mercury vapor lamp (ssr engineering GmbH, Lippstadt, Germany).
- the system was equipped with dichroic reflectors and quartz discs and had a specific power of 160 W/cm.
- the surface temperature during UV curing should reach > 60 °C.
- the information on the UV dose was determined using a Lightbug ILT 490 (International Light Technologies Inc., Peabody MA, USA).
- the data on the surface temperature were determined using temperature test strips from the RS brand (order number 285-936; RS Components GmbH, Bad Hersfeld, Germany).
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
La présente invention concerne une structure stratifiée comprenant au moins l'une des couches suivantes directement successives qui sont collées par adhésion l'une à l'autre dans l'ordre suivant : couche de revêtement - couche favorisant l'adhésion - couche de polymère thermoplastique ; un kit-de-pièces ; un procédé de production de la structure stratifiée selon l'invention ; un procédé de moulage par insert de film pour produire un moulage ; des produits comprenant la structure stratifiée selon l'invention ; et l'utilisation de la structure stratifiée selon l'invention.
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EP20191519.6 | 2020-08-18 | ||
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PCT/EP2021/071830 WO2022037950A1 (fr) | 2020-08-18 | 2021-08-05 | Systèmes d'agents de revêtement, constitués d'un revêtement de base et d'un revêtement supérieur, et produit semi-fini à base de ceux-ci et production associée |
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