WO2024126829A1 - Radiation-curable coating composition, method of coating a substrate and coated substrate - Google Patents
Radiation-curable coating composition, method of coating a substrate and coated substrate Download PDFInfo
- Publication number
- WO2024126829A1 WO2024126829A1 PCT/EP2023/086165 EP2023086165W WO2024126829A1 WO 2024126829 A1 WO2024126829 A1 WO 2024126829A1 EP 2023086165 W EP2023086165 W EP 2023086165W WO 2024126829 A1 WO2024126829 A1 WO 2024126829A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl
- radiation
- coating composition
- monomer
- curable coating
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 72
- 239000000758 substrate Substances 0.000 title claims abstract description 25
- 238000000576 coating method Methods 0.000 title claims description 29
- 239000011248 coating agent Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 76
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 46
- SQEBMLCQNJOCBG-HVHJFMEUSA-N (5s)-3-(hydroxymethyl)-5-methoxy-4-methyl-5-[(e)-2-phenylethenyl]furan-2-one Chemical compound C=1C=CC=CC=1/C=C/[C@]1(OC)OC(=O)C(CO)=C1C SQEBMLCQNJOCBG-HVHJFMEUSA-N 0.000 claims abstract description 29
- FBMORZZOJSDNRQ-UHFFFAOYSA-N Demethoxy,B,HCl-Adriamycin Natural products C1C2C(=C)CCCC2(C)CC2(O)C1=C(C)C(=O)O2 FBMORZZOJSDNRQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- JUTMAMXOAOYKHT-UHFFFAOYSA-N karrikinolide Natural products C1=COC=C2OC(=O)C(C)=C21 JUTMAMXOAOYKHT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 3
- -1 vinyl compound Chemical group 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 25
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000003847 radiation curing Methods 0.000 claims description 6
- 229960000834 vinyl ether Drugs 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 3
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical group COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 claims description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical group CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical group CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical group CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 claims description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical group C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical group C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 2
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical group C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 claims description 2
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical group CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 claims description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical group OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical group C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 claims description 2
- WBZPMFHFKXZDRZ-UHFFFAOYSA-N ethenyl 6,6-dimethylheptanoate Chemical group CC(C)(C)CCCCC(=O)OC=C WBZPMFHFKXZDRZ-UHFFFAOYSA-N 0.000 claims description 2
- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical group CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003844 furanonyl group Chemical group 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical group C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 230000005855 radiation Effects 0.000 description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- DNVMNEBSCNECGO-ZHOBSPGKSA-N 4-[2-[(1r,6r)-1,6-dimethyl-2-methylidenecyclohex-3-en-1-yl]ethyl]-2-hydroxy-2h-furan-5-one Chemical compound C[C@@H]1CC=CC(=C)[C@]1(C)CCC1=CC(O)OC1=O DNVMNEBSCNECGO-ZHOBSPGKSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000005840 aryl radicals Chemical class 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920001567 vinyl ester resin Chemical class 0.000 description 4
- DUAZKLYNTLDKQK-UHFFFAOYSA-N 5-hydroxy-2(5h)-furanone Chemical compound OC1OC(=O)C=C1 DUAZKLYNTLDKQK-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- HRKQHGYEXVCKAX-UHFFFAOYSA-N bis-butenolide Natural products CC(=C/CCC1=CC(=O)OC1)CC2OC(=O)C(=C2)C HRKQHGYEXVCKAX-UHFFFAOYSA-N 0.000 description 3
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- ZLTNEHYKQVLCSE-UHFFFAOYSA-N (5-oxo-2H-furan-2-yl) 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC1OC(=O)C=C1 ZLTNEHYKQVLCSE-UHFFFAOYSA-N 0.000 description 2
- PIQBHASRADDLMR-UHFFFAOYSA-N (5-oxo-2h-furan-4-yl) acetate Chemical compound CC(=O)OC1=CCOC1=O PIQBHASRADDLMR-UHFFFAOYSA-N 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
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- 229920000742 Cotton Polymers 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 125000006528 (C2-C6) alkyl group Chemical group 0.000 description 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005409 aflatoxin Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MJMUPTBJZYLZOS-UHFFFAOYSA-N benzene-1,2,3-tricarboxamide Chemical class NC(=O)C1=CC=CC(C(N)=O)=C1C(N)=O MJMUPTBJZYLZOS-UHFFFAOYSA-N 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- ORZGJQJXBLFGRP-AATRIKPKSA-N bis(ethenyl) (e)-but-2-enedioate Chemical compound C=COC(=O)\C=C\C(=O)OC=C ORZGJQJXBLFGRP-AATRIKPKSA-N 0.000 description 1
- PIPBVABVQJZSAB-UHFFFAOYSA-N bis(ethenyl) benzene-1,2-dicarboxylate Chemical compound C=COC(=O)C1=CC=CC=C1C(=O)OC=C PIPBVABVQJZSAB-UHFFFAOYSA-N 0.000 description 1
- CHQUIOWVSPIVJB-UHFFFAOYSA-N bis(ethenyl) decanedioate Chemical compound C=COC(=O)CCCCCCCCC(=O)OC=C CHQUIOWVSPIVJB-UHFFFAOYSA-N 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- AALXAILNCMAJFZ-UHFFFAOYSA-N bis(ethenyl) propanedioate Chemical compound C=COC(=O)CC(=O)OC=C AALXAILNCMAJFZ-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical compound NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 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
- 238000007598 dipping method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 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
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- BUOCQZKTTPACCW-UHFFFAOYSA-N tert-butyl (5-oxo-2h-furan-2-yl) carbonate Chemical compound CC(C)(C)OC(=O)OC1OC(=O)C=C1 BUOCQZKTTPACCW-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/14—Esters of polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F234/00—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
- C08F234/02—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring in a ring containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
Definitions
- the present invention relates to a radiation-curable coating composition, a method of coating a substrate comprising applying and curing such coating composition, and a coated substrate obtainable by such method.
- Radiation-curable coating compositions containing double bonds that can be activated by actinic radiation are well known in the art.
- Reference herein to actinic radiation is to electromagnetic, ionizing radiation, in particular electron beam radiation, UV light and visible light.
- Radiation-curable coating compositions typically cross-link through radical polymerization of monomers with an ethylenically unsaturated group, such as an acryloyl, methacryloyl, or vinyl group. Examples of such monomers include acrylic acid, methacrylic acid, alkyl esters of (meth)acrylic acid, styrene, alkyl-substituted styrene, vinyl esters, and vinyl ethers. The monomers are usually prepared from petrochemical raw materials.
- Binder polymers at least partly prepared from renewable feedstock are known in the art.
- Alkyd resins for example comprise a relatively high content of fatty acids obtained from vegetable oil.
- a copolymer for use as a protective coating that is prepared by combining a furanone monomer and a vinyl ether monomer in a molar ratio of about one.
- the copolymer may be prepared by photopolymerization or by solution polymerization in the presence of a free-radical initiator.
- Butenolides are ethylenically unsaturated furanoic compounds that can be prepared from carbohydrates, i.e. a renewable feedstock.
- Carbohydrate feedstock such as starch, cellulose or carbohydrate-containing bio-waste can be converted into furfural, hydroxymethylfurfural, or related furan derivatives by dehydration and can then be oxidized into furanones.
- Preparation of alkoxylated furanones is for example described in Chapter II of J.C.
- Poskonin et al. have disclosed in Russian Journal of Organic Chemistry 35 (1999) 721- 726 copolymers prepared by radical polymerization of 5-alkoxy-2(5H)-furanone and styrene, methyl methacrylate, or vinyl acetate. Use of such copolymers for synthesis of physiologically active substances is suggested. Poskonin et al. have further disclosed in Russian Journal of Organic Chemistry 35 (1997) 520-523 oligomers prepared by radical polymerization of 4-acetoxy-2-butenolide (5-acetoxy-2(5H)-furanone) and styrene, methyl methacrylate, or vinyl acetate. Number average molecular weights of from 1860 to 6460 were achieved.
- W02021/084066 describes copolymerization of 5-alkoxy-2(5H)-furanones with selected vinyl ethers or vinyl esters and the use of the resulting copolymers as a binder in a polymer coating composition.
- WO2021/259819 describes a radiation-curable copolymer coating composition comprising a 5-hydroxy or 5-alkoxy-2(5H)-furanone compound and a compound with two or more vinyl ether or vinyl ester groups.
- Trost and Toste have disclosed in J. Am. Chem. Soc. 2003, 125, 3090-3100 two butenolide compounds: 2-tert-Butoxycarbonyloxy-5-oxo-2,5-dihydrofuran and 2- benzoyloxy-5-oxo-2,5-dihydrofuran with application in introducing chirality into synthesis of aflatoxins.
- a hard and chemically resistant cured coating can be obtained by radiation curing, activated by actinic radiation such as visible or UV light or electron beam radiation, of a composition comprising a 5-substituted butenolide monomer and a monomer comprising one or more vinyl groups.
- actinic radiation such as visible or UV light or electron beam radiation
- the coatings formed have properties that make them suitable as protective or decorative coatings.
- the invention provides in a first aspect a radiation-curable coating composition
- a radiation-curable coating composition comprising: a) one or more butenolide monomer A of general formula (I): wherein: n is 0 or an integer of from 1 to 5;
- R 1 is alkyl or aryl
- X is any one of -C(O)-, -C(O)O-, -C(O)NR 2 -, -S(O)-, -S(O 2 )-, -C(O)S-, -C(S)S- and - C(S)NR 2 -; wherein R 2 is hydrogen, alkyl or aryl; or wherein, when n is 0 and X is -C(O)NR 2 - or -C(S)NR 2 -, R 1 and R 2 together with the nitrogen atom through which they are linked form a nitrogen-containing heterocyclic group or nitrogen-containing heteroaryl group; and b) one or more vinyl monomer B comprising one or more vinyl groups wherein at least one vinyl group has a difference in 13 C chemical shift between the a-C and p-C of a vinyl group of at least 25 ppm; wherein at least one monomer of A and B comprises at least two vinyl groups.
- the coating composition it can be formulated without organic solvent or with only a small amount of organic solvent, typically less than 20 wt%.
- the invention provides a method of coating a substrate comprising: providing a substrate applying a coating composition as defined herein to the substrate; and radiation-curing the coating composition to form a cured coating.
- the coating composition and the cured coating formed from it has a relatively high content of furanone, a bio-based material.
- the binder polymer formed upon curing has a polymer backbone with acetal functionality, which advantageously provides possibilities for further crosslinking or modification of the coating, for example with a hydroxyl or thiol functional crosslinker or with a polymer with hydroxyl or thiol functionality.
- the invention provides a coated substrate obtainable by a method according to the second aspect of the invention.
- the radiation-curable coating composition comprises a) one or more butenolide monomer A; and b) one or more vinyl monomer B, wherein at least one monomer of A and B comprises at least two vinyl groups.
- the presence of a monomer having at least two vinyl groups is necessary to act as a cross-linker in the coating composition.
- a butenolide as described herein is equivalent to a furanone.
- a 5-substituted butenolide as described herein is equivalent to a 5-substituted furanone.
- the term one or more with reference to each of A and B means that multiple different monomers of each of A and respectively B may be present in the coating composition.
- a composition may comprise one butenolide monomer A and one vinyl monomer B.
- it may comprise one butenolide monomer A and two vinyl monomers B, which vinyl monomers B are different from each other.
- it may comprise two butenolide monomers A, which butenolide monomers A are different from each other, and one butenolide monomer B.
- a vinyl group has an a-C and p-C determined by proximity to another functional group in the molecule.
- difference in 13 C chemical shift between the a-C and p- C of the vinyl group can be determined from the chemical shift as reported in the Spectral Database for Organic Compounds (https://sdbs.db.aist.go.jp/sdbs/cgi- bin/direct frame top.cgi), managed by the National Institute of Advanced Industrial Science and Technology.
- an alkyl radical may be branched, unbranched, linear or cyclic.
- the alkyl radical may be saturated or unsaturated. It may be substituted or unsubstituted.
- An alkyl radical typically comprises from 1 to 20 carbon atoms, in particular from 1 to 12 carbon atoms, 1 to 6 carbon atoms or 1 to 4 carbon atoms.
- An alkyl radical may comprise from 2 to 20 carbon atoms, in particular from 2 to 12 carbon atoms, 2 to 6 carbon atoms or 2 to 4 carbon atoms.
- An alkyl radical may contain from 1 to 3 carbon atoms, for example 1 , 2 or 3 carbon atoms.
- alkyl radials are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, hexyl, lauryl, oleyl and cyclohexyl.
- cycloalkyl means a cyclic alkyl radical.
- Cyclic heteroalkyl means a cyclic heteroalkyl radical wherein at least one carbon in the cycle is substituted with a heteroatom.
- a heteroatom may be nitrogen, oxygen or another atom other than carbon.
- a cyclic heteroalkyl radical may be a nitrogen-containing cyclic heteroalkyl.
- aryl means an aromatic radical.
- An aryl radical may be substituted or unsubstituted.
- An aryl radical typically contains 6 or 10 carbon atoms.
- An aryl radical may be phenyl or naphthyl, in particular phenyl.
- Heteroaryl means an aryl radical comprising a heteroatom, i.e. an atom other than carbon, in an aromatic ring.
- a heteroaryl radical may be substituted or unsubstituted.
- a heteroaryl radical typically contains from 5 to 12 carbon atoms.
- a typical heteroatom is oxygen or nitrogen.
- the coating composition comprises one or more butenolide monomer A of general formula (I): wherein: n is 0 or an integer of from 1 to 5;
- R 1 is alkyl or aryl
- X is any one of -C(O)-, -C(O)O-, -C(O)NR 2 -, -S(O)-, -S(O 2 )-, -C(O)S-, -C(S)S- and - C(S)NR 2 -; wherein R 2 is hydrogen, alkyl or aryl; or wherein, when n is 0, R 1 and R 2 together with the nitrogen atom through which they are linked form a nitrogen-containing heterocyclic group or nitrogen-containing heteroaryl group.
- n is an integer of from 1 to 5.
- X is any one of -C(O)-, -C(O)O-, -C(O)NR 2 -.
- R 2 is for example hydrogen.
- R 1 may be C2-C6 alkyl or phenyl.
- R 1 is C1-C20 alkyl, C5-C7 cycloalkyl or phenyl.
- R 1 may be C1-C12 alkyl.
- R 1 may be C5-C7 cycloalkyl.
- R 1 may be phenyl.
- R 2 may be hydrogen or C1-C20 alkyl.
- R 2 may be hydrogen or C1-C12 alkyl, for example R 2 may be hydrogen.
- butenolide monomer A is an oligomer obtainable by reacting a multifunctional scaffold having in the range of from 2 to 6 reactive groups with 5-hydroxy-2(5H)-furanone.
- the multifunctional scaffold may for example have from 1 to 40 carbon atoms.
- Suitable multifunctional scaffolds include polyacids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, citric acid, propane- 1 ,2,3-tricarboxylic acid, trimesic acid and the corresponding thioacid, isocyanate and thiocyanate counterparts.
- suitable scaffolds include alkyl carbonate of chloroformate derivatives of polyols such as ethylene glycol, propylene glycol, glycerol, cyclohexanedimethanol or pentaerythritol.
- R 3 is -OR 4 , -OC(O)R 4 or -N(R 5 )C(O)R 4 .
- a vinyl momomer B is a monovinyl ester, a monovinyl ether or a mono N-vinyl compound.
- a vinyl monomer B is n-butyl vinyl ether, iso-butyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, vinyl neodecanoate, vinyl neononanoate, N-vinylpyrrolidone, N-vinyl imidazole, N-vinyl-formamide, N-vinyl-pyrrole or N-vinylcaprolactam.
- a vinyl compound B is a monovinyl ester, a monovinyl ether, a mono N-vinyl compound and/or a (meth)acryloyl monomer with a molecular weight in the range of from 50 to 800 g/mol, more preferably of from 100 to 500 g/mol.
- a vinyl monomer B has at least two vinyl groups.
- R 3 comprises at least one vinyl group.
- R 4 comprises at least one vinyl group or
- R 5 comprises at least one vinyl group or both R 4 and R 5 comprise at least one vinyl group.
- the radiation-curable coating composition may comprise at least two vinyl monomers B. At least one vinyl monomer B may comprise at least two vinyl groups.
- the radiation-curable coating composition may comprise one vinyl monomer B, which is a monovinyl compound and one vinyl monomer B which is a divinyl compound.
- a vinyl monomer B has at least two vinyl groups and is a divinyl ether, a divinyl ester or a di-N-vinyl compound.
- Examples of a vinyl monomer B with at least two vinyl ester groups include malonic acid divinyl ester, adipic acid divinyl ester, fumaric acid divinyl ester, sebacic acid divinyl ester, phthalic acid divinyl ester, and trimellitic acid trivinyl ester.
- Examples of a vinyl monomer B with two or three vinyl ether groups include divinyl ethers or trivinyl ethers of (poly)ethylene glycol or (poly)propylene glycol such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether; butanediol divinyl ether; hexanediol divinyl ether; 1 ,4-cyclohexanedimethanol divinyl ether; and trimethylol propane trivinyl ether.
- divinyl ethers or trivinyl ethers of (poly)ethylene glycol or (poly)propylene glycol such as ethylene glycol divinyl ether, diethylene glyco
- Examples of a vinyl monomer B with at least two N-vinyl groups are N-vinyl substituted polycarboxamides, for example adipamide, succinamide, terephthalamide, isophthalamide, benzene-tricarboxamides.
- Vinyl monomer B may be a compound with a polymeric backbone and two or more vinyl ether groups, for example a polyurethane, polyester-urethane, polyetherurethane, poly(meth)acrylate-urethane, or polyester with two or more vinyl ether groups.
- Such compounds may for example be prepared by reacting an isocyanate with a hydroxyl functional vinyl ether and a hydroxyl functional polyester, polyether or poly(meth)acrylate.
- a polyester with two or more vinyl ether groups can be prepared via a transesterification of a hydroxyl functional vinyl ether with a polyester with two or more ester groups of alcohols with a relatively low boiling point.
- Vinyl monomer B may have a molecular weight in the range of from 100 to 3,000 g/mol. If vinyl monomer B is a compound with a polymeric backbone as described above, the molecular weight may be in the range of from 500 to 3,000 g/mol.
- the weight fraction of monomers comprising at least two vinyl groups in the composition is at most 5 wt.%.
- the molar ratio of furanone moieties to vinyl moieties is in the range of from 1.5: 1.0 to 1.0: 1.5.
- the molar ratio may be of from 1.2 to 1.0 to 1.0 to 1.2.
- Vinyl moieties are present in vinyl monomer B.
- the coating composition does not comprise any compounds with vinyl moieties other than vinyl monomer B.
- the radiation-curable coating composition is free of a compound with two or more acryloyl or methacryloyl groups. The presence of such compound may have a negative effect on film formation.
- the total amount of butenolide monomer A and vinyl monomer B in the radiation- curable coating composition may be in the range of from 70 to 100 wt%, more preferably from 80 to 100 wt%, even more preferably of from 90 to 100 wt%.
- the coating composition is radiation-curable.
- the coating composition may be cured by photoinitiation, i.e. by radiation with visible light or UV light.
- the composition further comprises c) a photo-initiator.
- the photo-initiator may be one photo initiator or a mixture of two or more thereof. Photo-initiators generate free radicals when exposed to radiation energy in the visible light or UV light wavelength range. Any suitable photo-initiator known in the art may be used, depending on the wavelength.
- Suitable photo-initiators include benzoin derivatives, benzile ketales, a-hydroxyalkylphenones, monoacylphosphine oxide (MAPO) and bisacylphosphine oxides (BAPO), such as diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone, bis(2,4,6- trimethylbenzoyl)-phenylphosphineoxide, bis(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentyl-phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl- 1[4-(methylthio)phenyl]-2-morpholono-propan-1-one, a phenyl glyoxylic acid methyl ester. Mixtures of these compounds may also be employed.
- the photo-initiator may be present in an amount of from 0.1 to 10 wt%, for example from 0.5 to 5.0 wt%, based on the total weight of the coating composition.
- the curing of the coating composition may be initiated by electron beam or by gamma radiation.
- the curing of the coating composition may be initiated by electron beam or by gamma radiation.
- no photoinitiator is needed for initiation by electron beam or gamma radiation.
- the coating composition may be a powder coating composition or a liquid coating composition, preferably a liquid coating composition.
- the coating composition preferably is an essentially solvent-free liquid coating composition.
- Reference herein to an essentially solvent-free coating composition is to a coating composition comprising at most 1 wt% of organic solvent, more preferably at most 0.5 wt%, still more preferably 0 wt%.
- the coating composition may comprise some organic solvent to control the viscosity.
- the coating composition comprises at most 30 wt% organic solvent, more preferably at most 20 wt%, even more preferably at most 10 wt%, still more preferably at most 5 wt% or at most 2 wt%.
- Suitable organic solvents are solvents in which butenolide monomer A and vinyl monomer B and the cured polymer dissolve at polymerization conditions.
- the organic solvent may be an oxygenated organic solvent, for example an alcohol, ketone, ester or ether.
- the solvent is a glycol ether, glycol ester or an alkyl acetate, for example 1-methoxy-2-propanol or butyl acetate.
- the coating composition is not a waterborne coating composition, i.e. water is not the liquid medium in which butenolide monomer A and vinyl monomer B are dissolved or dispersed.
- the coating composition may comprise a small amount of water, for example water that is contained in additives comprised in the coating composition.
- the coating composition comprises less than 5 wt% water, more preferably less than 1 wt%.
- the coating composition may comprise further ingredients commonly used in coating compositions such as color pigments, extender pigments, and one or more additives such as for example light stabilizers, other stabilizers, defoaming agents, matting agents, wetting agents, or flow agents.
- additives such as for example light stabilizers, other stabilizers, defoaming agents, matting agents, wetting agents, or flow agents.
- Radiation-curing the coating composition may be by exposing the coating composition to visible light or UV radiation, electron beam radiation, or gamma radiation, to form a cured coating.
- the coating composition may be applied to the substrate by conventional techniques, including spraying, rolling, blade-coating, pouring, brushing or dipping. After evaporation of any organic solvent and/or water, if present, the coating composition results in a coating that is from dust-dry to very tacky. Curing is then induced by means of radiation. Any suitable source of radiation can be used. In particular, radiation curing may be by electron beam radiation, UV radiation or visible light radiation.
- the coating composition further comprises c) a photo-initiator and the coating composition is cured by exposing the coating composition to visible light or UV radiation, for example to visible light with a wavelength in the range of from 400 to 600 nm or to UV radiation with a wavelength in the range of from 200 to 400 nm, in particular to UV radiation with a wavelength in the range of from 280 to 400 nm, or preferably of from 320 to 400 nm (UV-A radiation).
- visible light with a wavelength in the range of from 400 to 600 nm or to UV radiation with a wavelength in the range of from 200 to 400 nm, in particular to UV radiation with a wavelength in the range of from 280 to 400 nm, or preferably of from 320 to 400 nm (UV-A radiation).
- UV radiation Hg lamps, metal halide lamps, xenon lamps, or UV-LED lamps may for example be used. It is preferred to use UV-LED lamps.
- Radiation curing of the coating composition can be done at ambient conditions, e.g. room temperature and atmospheric pressure.
- room temperature is to a temperature in the range of from 15 to 30 °C.
- the curing may be accelerated by post-heating, for example post-heating to a temperature in the range of from 40 to 100 °C, preferably of from 50 to 80 °C.
- the substrate may be any suitable substrate, such as for example wood, polymer, composite, metal, glass, or other mineral substrate.
- the substrate may be a primed or bare substrate.
- the coating composition can be used as a single layer applied directly to the substrate, or in multilayer systems, e.g. as a primer, a basecoat, a clearcoat, or a topcoat.
- the coating composition can be used for various applications, such as coating of wood, electronic appliances, plastic automotive components, food can, or as architectural coating.
- di-functional vinyl compounds was used: diethylene glycol divinyl ether DEGDVE
- N,N'- Dicyclohexylcarbodiimide (1.20 eq., 9.90 g, 48.0 mmol) was dissolved in anhydrous DCM (5 mL) and added dropwise at 0°C over 5 min. After the addition, the ice bath was removed, and the mixture was stirred at room temperature for 1 h. The mixture turned from blue to dark brown with a precipitate. The reaction mixture was filtered on cotton wool, rinsing with DCM, affording a brown solid (urea) and a clear brown filtrate, which was concentrated in vacuo to a dark brown oil.
- DCC N,N'- Dicyclohexylcarbodiimide
- Hydroxy butenolide (1 eq., 5.00 g, 50.0 mmol) was dissolved in dry DCM (25 mL) and cooled to 0°C with an ice bath. This caused hydroxy butenolide to (partially) precipitate.
- Pivalic anhydride (1.2 eq., 12.2 mL, 60.0 mmol) was added, followed by a solution of DMAP (0.1 eq., 610 mg, 5.00 mmol) in dry DCM (2.5 mL). The mixture was first stirred at 0°C for 30 min and was then allowed to warm up to RT, thereby causing full dissolution of the solids. The homogeneous mixture was further stirred at room temperature overnight (20 h in total).
- Hydroxybutenolide (1 eq., 1.00 g, 9.99 mmol) was dissolved in dry DCM (20 mL) and cooled to 0°C with an ice bath. Succinic anhydride (1.6 eq., 1.60 g, 16.0 mmol) was added, followed by a solution of DMAP (0.3 eq., 366 mg, 3.00 mmol) in dry DCM (1 mL). The mixture was first stirred at 0°C, during which it turned from light blue to light green, and was then allowed to warm up to room temperature overnight. In the morning the mixture had darkened even more. Thin layer chromatography (50% AcOEt/hexanes + 1 vol% AcOH, rev.
- the reaction mixture was filtered on a Buchner, rinsing with DCM, leaving a white solid and affording a brown filtrate which was concentrated to a brown murky oil.
- the residue was purified by automatic column chromatography (15 g SiC>2 cartridge, 10-50% AcOEt/pentane over 20 CV), using DCM for liquid injection. Concentration of the collected fraction afforded pure methyl succinyloxy butenolide (163 mg, 0.761 mmol, 76% yield) as a colorless semi-solid.
- the hazy yellowish mixture first became clear yellowish, before turning back to hazy with the precipitation of a solid.
- the slurry then slowly turned brown over time. After 1 h, the ice bath was removed, and the mixture was stirred at room temperature for 1 h.
- the reaction mixture was filtered, rinsing with DCM, affording a white solid (urea) and a clear brown filtrate, which was concentrated in vacuo to a brown solid.
- the residue was purified by automatic column chromatography (25 g SiC>2 cartridge, 0-20% AcOEt/pentane over 20 CV), using solid injection with neutralized silica. Concentration of the collected fraction afforded pure succinyloxy bis-butenolide (532 mg, 1.88 mmol, 75% yield) as a white solid.
- Coating compositions were prepared by combining a butenolide monomer, a monofunctional vinyl monomer and a di-functional monomer (either a butenolide or vinyl monomer) in various ratios as indicated in Table 1 and adding 1-3 mol% (vs. the most abundant compound) bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide (OmniRad 819 or BAPO) as photo-initiator. All compositions were solvent-free compositions.
- a 100 pm wet film of coating composition was drawn on a glass plate using a drawing bar.
- the wet film was cured by irradiating the film with UV light using a IIV-A LED irradiation device with 12 LED lamps emitting UV light with a wavelength of 395 nm and a total irradiance of 21 mW/cm 2 during 5 minutes at a distance of 5 cm. All coatings formed a tack- and defect-free film.
- the dry layer thickness (ISO 2808) of the coatings were measured using the Heidenhain VRZ 402 apparatus calibrated with calibration foil. A spot (10 mm diameter) of curing coating is removed from the glass substrate. The measuring probe was placed on the bare substrate and the measured value was fared, next, three layer thickness measurements are performed. This procedure was performed at three different locations on the substrate (9 measurements in total) and the average value is reported.
- Water resistance (ISO 2812-4:2007 part 4) was measured by placing a droplet of demineralized water on the cured coating and covering it with a watch glass. After 60 minutes, the water droplet was wiped off and the effect on the coating was determined visually on a scale of 0 to 5, wherein 5 means that the water droplet had no visible impact on the coating, and 0 means that the water droplet had a detrimental impact.
- Hk Knoop hardness in kg/mm 2 .
- Tg Glass temperatures
- Q2000 TA Instruments
- DSC Differential Scanning Calorimeter
- a DSC cup filled with 6 +/- 1 mg cured paint chips and an empty DSC reference cup were heated in the DSC in a modulated way (+/- 1°C every 40 seconds) from -80°C to 200°C at 5°C/min in three consecutive runs using Helium (50 ml/min) as purge gas.
- Fourier transformation enabled the separation of the modulated heat flow into a heat capacity component (reversing heat flow) and a kinetic component (non-reversing heat flow) allowing to separate different thermal events occurring at the same time.
- Tg the heat capacity of the material changed rapidly resulting in a strong decrease of the reversing heat flow curve over a certain transfer area.
- the Tg is calculated at the point of inflection (Tg(l)) and at half width (Tg(W)), the Tg(W) measured in the second run is reported.
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Abstract
A radiation-curable coating composition comprising: a) one or more butenolide monomer A of general formula (I) wherein: n is 0 or an integer of from 1 to 5; R1 is alkyl or aryl; X is any one of -C(O)-, -C(O)O-, -C(O)NR2-, -S(O)-, -S(O2)-, -C(O)S-, -C(S)S- and - C(S)NR2-; wherein R2 is hydrogen, alkyl or aryl; or wherein, when n is 0 and X is -C(O)NR2- or -C(S)NR2-, R1 and R2 together with the nitrogen atom through which they are linked form a nitrogen-containing heterocyclic group or nitrogen-containing heteroaryl group; and b) one or more vinyl monomer B comprising one or more vinyl groups wherein at least one vinyl group has a difference in 13C chemical shift between the α-C and β-C of a vinyl group of at least 25 ppm; wherein at least one monomer of A and B comprises at least two vinyl groups; and to coated substrates.
Description
RADIATION-CURABLE COATING COMPOSITION, METHOD OF COATING A SUBSTRATE AND COATED SUBSTRATE
Field of the Invention
The present invention relates to a radiation-curable coating composition, a method of coating a substrate comprising applying and curing such coating composition, and a coated substrate obtainable by such method.
Background of the Invention
Radiation-curable coating compositions containing double bonds that can be activated by actinic radiation, such as UV light or electron beam radiation, are well known in the art. Reference herein to actinic radiation is to electromagnetic, ionizing radiation, in particular electron beam radiation, UV light and visible light. Radiation-curable coating compositions typically cross-link through radical polymerization of monomers with an ethylenically unsaturated group, such as an acryloyl, methacryloyl, or vinyl group. Examples of such monomers include acrylic acid, methacrylic acid, alkyl esters of (meth)acrylic acid, styrene, alkyl-substituted styrene, vinyl esters, and vinyl ethers. The monomers are usually prepared from petrochemical raw materials.
There is an increasing demand for chemical products prepared from renewable feedstock. Binder polymers at least partly prepared from renewable feedstock are known in the art. Alkyd resins for example comprise a relatively high content of fatty acids obtained from vegetable oil.
In US 4,954,593 is disclosed a copolymer for use as a protective coating that is prepared by combining a furanone monomer and a vinyl ether monomer in a molar ratio of about one. The copolymer may be prepared by photopolymerization or by solution polymerization in the presence of a free-radical initiator.
Butenolides are ethylenically unsaturated furanoic compounds that can be prepared from carbohydrates, i.e. a renewable feedstock. Carbohydrate feedstock such as starch, cellulose or carbohydrate-containing bio-waste can be converted into furfural,
hydroxymethylfurfural, or related furan derivatives by dehydration and can then be oxidized into furanones. Preparation of alkoxylated furanones is for example described in Chapter II of J.C. de Jong, Asymmetric Diels-Alder reactions with 5-menthyloxy- 2(5H)-furanones, Thesis University of Groningen, 2006, accessible via https://www.rug.nl/research/portal/en/publications/asymmetric-dielsalder-reactions- With-5menthyloxy25hfuranones(f0ab6c00-8c6c-4ccc-90aa-3ef05f759fa4).html.
Poskonin et al. have disclosed in Russian Journal of Organic Chemistry 35 (1999) 721- 726 copolymers prepared by radical polymerization of 5-alkoxy-2(5H)-furanone and styrene, methyl methacrylate, or vinyl acetate. Use of such copolymers for synthesis of physiologically active substances is suggested. Poskonin et al. have further disclosed in Russian Journal of Organic Chemistry 35 (1997) 520-523 oligomers prepared by radical polymerization of 4-acetoxy-2-butenolide (5-acetoxy-2(5H)-furanone) and styrene, methyl methacrylate, or vinyl acetate. Number average molecular weights of from 1860 to 6460 were achieved.
W02021/084066 describes copolymerization of 5-alkoxy-2(5H)-furanones with selected vinyl ethers or vinyl esters and the use of the resulting copolymers as a binder in a polymer coating composition.
WO2021/259819 describes a radiation-curable copolymer coating composition comprising a 5-hydroxy or 5-alkoxy-2(5H)-furanone compound and a compound with two or more vinyl ether or vinyl ester groups.
Trost and Toste have disclosed in J. Am. Chem. Soc. 2003, 125, 3090-3100 two butenolide compounds: 2-tert-Butoxycarbonyloxy-5-oxo-2,5-dihydrofuran and 2- benzoyloxy-5-oxo-2,5-dihydrofuran with application in introducing chirality into synthesis of aflatoxins.
Parijat Ray et al. “Synthesis of Bioacrylic Polymers from Dihydro-5-hydroxyl furan-2-one (2H-HBO) by Free and Controlled Radical Polymerization”, ACS OMEGA, vol. 3, no. 2, 20 February 2018 (2018-02-20), pages 2040-2048 describes the reaction of dihydro-5- hydroxyl furan-2-one with methacrylic anhydride to form a methacrylic-dihydro-5- hydroxyl furan-2-one monomer. Subsequent homo- and co-polymerisation is carried out.
There is a need for radiation-curable coating compositions that can at least partially be obtained from renewable feedstock.
Summary of the Invention
It has now been found that a hard and chemically resistant cured coating can be obtained by radiation curing, activated by actinic radiation such as visible or UV light or electron beam radiation, of a composition comprising a 5-substituted butenolide monomer and a monomer comprising one or more vinyl groups. The coatings formed have properties that make them suitable as protective or decorative coatings.
Accordingly, the invention provides in a first aspect a radiation-curable coating composition comprising: a) one or more butenolide monomer A of general formula (I):
wherein: n is 0 or an integer of from 1 to 5;
R1 is alkyl or aryl;
X is any one of -C(O)-, -C(O)O-, -C(O)NR2-, -S(O)-, -S(O2)-, -C(O)S-, -C(S)S- and - C(S)NR2-; wherein R2 is hydrogen, alkyl or aryl; or wherein, when n is 0 and X is -C(O)NR2- or -C(S)NR2-, R1 and R2 together with the nitrogen atom through which they are linked form a nitrogen-containing heterocyclic
group or nitrogen-containing heteroaryl group; and b) one or more vinyl monomer B comprising one or more vinyl groups wherein at least one vinyl group has a difference in 13C chemical shift between the a-C and p-C of a vinyl group of at least 25 ppm; wherein at least one monomer of A and B comprises at least two vinyl groups.
It is an advantage of the coating composition that it can be formulated without organic solvent or with only a small amount of organic solvent, typically less than 20 wt%.
In a second aspect, the invention provides a method of coating a substrate comprising: providing a substrate applying a coating composition as defined herein to the substrate; and radiation-curing the coating composition to form a cured coating.
The coating composition and the cured coating formed from it has a relatively high content of furanone, a bio-based material.
The binder polymer formed upon curing has a polymer backbone with acetal functionality, which advantageously provides possibilities for further crosslinking or modification of the coating, for example with a hydroxyl or thiol functional crosslinker or with a polymer with hydroxyl or thiol functionality.
In a third aspect, the invention provides a coated substrate obtainable by a method according to the second aspect of the invention.
Detailed Description
The radiation-curable coating composition comprises a) one or more butenolide monomer A; and b) one or more vinyl monomer B, wherein at least one monomer of A and B comprises at least two vinyl groups. The presence of a monomer having at least two vinyl groups is necessary to act as a cross-linker in the coating composition.
A butenolide as described herein is equivalent to a furanone. A 5-substituted butenolide as described herein is equivalent to a 5-substituted furanone.
As used herein the term one or more with reference to each of A and B means that multiple different monomers of each of A and respectively B may be present in the coating composition. For example a composition may comprise one butenolide monomer A and one vinyl monomer B. Alternatively, it may comprise one butenolide monomer A and two vinyl monomers B, which vinyl monomers B are different from each other. Alternatively, it may comprise two butenolide monomers A, which butenolide monomers A are different from each other, and one butenolide monomer B.
A vinyl group has an a-C and p-C determined by proximity to another functional group in the molecule. As used herein difference in 13C chemical shift between the a-C and p- C of the vinyl group can be determined from the chemical shift as reported in the Spectral Database for Organic Compounds (https://sdbs.db.aist.go.jp/sdbs/cgi- bin/direct frame top.cgi), managed by the National Institute of Advanced Industrial Science and Technology.
As used herein an alkyl radical may be branched, unbranched, linear or cyclic. The alkyl radical may be saturated or unsaturated. It may be substituted or unsubstituted. An alkyl radical typically comprises from 1 to 20 carbon atoms, in particular from 1 to 12 carbon atoms, 1 to 6 carbon atoms or 1 to 4 carbon atoms. An alkyl radical may comprise from 2 to 20 carbon atoms, in particular from 2 to 12 carbon atoms, 2 to 6 carbon atoms or 2 to 4 carbon atoms. An alkyl radical may contain from 1 to 3 carbon atoms, for example 1 , 2 or 3 carbon atoms. Examples of alkyl radials are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, hexyl, lauryl, oleyl and cyclohexyl.
As used herein, cycloalkyl means a cyclic alkyl radical. Cyclic heteroalkyl means a cyclic heteroalkyl radical wherein at least one carbon in the cycle is substituted with a heteroatom. A heteroatom may be nitrogen, oxygen or another atom other than carbon. A cyclic heteroalkyl radical may be a nitrogen-containing cyclic heteroalkyl.
As used herein aryl means an aromatic radical. An aryl radical may be substituted or unsubstituted. An aryl radical typically contains 6 or 10 carbon atoms. An aryl radical may be phenyl or naphthyl, in particular phenyl. Heteroaryl means an aryl radical comprising a heteroatom, i.e. an atom other than carbon, in an aromatic ring. A
heteroaryl radical may be substituted or unsubstituted. A heteroaryl radical typically contains from 5 to 12 carbon atoms. A typical heteroatom is oxygen or nitrogen.
The coating composition comprises one or more butenolide monomer A of general formula (I):
wherein: n is 0 or an integer of from 1 to 5;
R1 is alkyl or aryl;
X is any one of -C(O)-, -C(O)O-, -C(O)NR2-, -S(O)-, -S(O2)-, -C(O)S-, -C(S)S- and - C(S)NR2-; wherein R2 is hydrogen, alkyl or aryl; or wherein, when n is 0, R1 and R2 together with the nitrogen atom through which they are linked form a nitrogen-containing heterocyclic group or nitrogen-containing heteroaryl group.
In one embodiment for at least one butenolide monomer A, n=0; and wherein at least one vinyl monomer B comprises at least two vinyl groups.
In one embodiment which comprises at least two butenolide monomers A, for at least one butenolide monomer A, n is an integer of from 1 to 5.
In one embodiment X is any one of -C(O)-, -C(O)O-, -C(O)NR2-. In this embodiment R2 is for example hydrogen. Alternatively, when X is -C(O)-, R1 may be C2-C6 alkyl or phenyl.
In one embodiment R1 is C1-C20 alkyl, C5-C7 cycloalkyl or phenyl. In one embodiment, R1 may be C1-C12 alkyl. In another embodiment, R1 may be C5-C7 cycloalkyl. In another embodiment R1 may be phenyl.
In one embodiment, R2 may be hydrogen or C1-C20 alkyl. In particular, R2 may be hydrogen or C1-C12 alkyl, for example R2 may be hydrogen.
If n is an integer with a value in the range of from 1 to 5, butenolide monomer A is an oligomer obtainable by reacting a multifunctional scaffold having in the range of from 2 to 6 reactive groups with 5-hydroxy-2(5H)-furanone. The multifunctional scaffold may for example have from 1 to 40 carbon atoms.
Examples of suitable multifunctional scaffolds include polyacids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, citric acid, propane- 1 ,2,3-tricarboxylic acid, trimesic acid and the corresponding thioacid, isocyanate and thiocyanate counterparts. Other examples of suitable scaffolds include alkyl carbonate of chloroformate derivatives of polyols such as ethylene glycol, propylene glycol, glycerol, cyclohexanedimethanol or pentaerythritol.
In one embodiment a vinyl monomer B is a vinyl compound of general formula (II) R3CH=CH2 (II); wherein R3 is any one of:
-OR4, -OC(O)R4, -N(R5)C(O)R4, -N(R5)C(O)OR4, -NR5C(S)R4, -NR5C(S)OR4, - NR5C(S)SR4 and -SC(S)SR4; wherein R4 is alkyl or aryl, and wherein R5 is hydrogen, alkyl or aryl, or wherein R4 and R5 together with the atoms through which they are linked form a nitrogen-containing heterocyclic group or nitrogen-containing heteroaryl group.
In one embodiment R3 is -OR4, -OC(O)R4 or -N(R5)C(O)R4.
In one embodiment a vinyl momomer B is a monovinyl ester, a monovinyl ether or a mono N-vinyl compound.
In one embodiment a vinyl monomer B is n-butyl vinyl ether, iso-butyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, vinyl neodecanoate, vinyl neononanoate, N-vinylpyrrolidone, N-vinyl imidazole, N-vinyl-formamide, N-vinyl-pyrrole or N-vinylcaprolactam.
In one embodiment, a vinyl compound B is a monovinyl ester, a monovinyl ether, a mono N-vinyl compound and/or a (meth)acryloyl monomer with a molecular weight in the range of from 50 to 800 g/mol, more preferably of from 100 to 500 g/mol.
In one embodiment a vinyl monomer B has at least two vinyl groups. In the vinyl monomer of formula (II), R3 comprises at least one vinyl group. For example, R4 comprises at least one vinyl group or R5 comprises at least one vinyl group or both R4 and R5 comprise at least one vinyl group.
The radiation-curable coating composition may comprise at least two vinyl monomers B. At least one vinyl monomer B may comprise at least two vinyl groups. For example, the radiation-curable coating composition may comprise one vinyl monomer B, which is a monovinyl compound and one vinyl monomer B which is a divinyl compound.
In one embodiment a vinyl monomer B has at least two vinyl groups and is a divinyl ether, a divinyl ester or a di-N-vinyl compound.
Examples of a vinyl monomer B with at least two vinyl ester groups include malonic acid divinyl ester, adipic acid divinyl ester, fumaric acid divinyl ester, sebacic acid divinyl ester, phthalic acid divinyl ester, and trimellitic acid trivinyl ester.
Examples of a vinyl monomer B with two or three vinyl ether groups include divinyl ethers or trivinyl ethers of (poly)ethylene glycol or (poly)propylene glycol such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether; butanediol divinyl ether; hexanediol divinyl ether; 1 ,4-cyclohexanedimethanol divinyl ether; and trimethylol propane trivinyl ether.
Examples of a vinyl monomer B with at least two N-vinyl groups are N-vinyl substituted polycarboxamides, for example adipamide, succinamide, terephthalamide, isophthalamide, benzene-tricarboxamides.
Vinyl monomer B may be a compound with a polymeric backbone and two or more vinyl ether groups, for example a polyurethane, polyester-urethane, polyetherurethane, poly(meth)acrylate-urethane, or polyester with two or more vinyl ether groups. Such compounds may for example be prepared by reacting an isocyanate with a hydroxyl functional vinyl ether and a hydroxyl functional polyester, polyether or poly(meth)acrylate. A polyester with two or more vinyl ether groups can be prepared via a transesterification of a hydroxyl functional vinyl ether with a polyester with two or more ester groups of alcohols with a relatively low boiling point. By using in the coating composition such compound with a polymeric backbone, the properties of the cured coating, in particular mechanical properties, can be tuned by the choice of the backbone.
Vinyl monomer B may have a molecular weight in the range of from 100 to 3,000 g/mol. If vinyl monomer B is a compound with a polymeric backbone as described above, the molecular weight may be in the range of from 500 to 3,000 g/mol.
In one embodiment, the weight fraction of monomers comprising at least two vinyl groups in the composition is at most 5 wt.%.
In one embodiment, the molar ratio of furanone moieties to vinyl moieties is in the range of from 1.5: 1.0 to 1.0: 1.5. For example the molar ratio may be of from 1.2 to 1.0 to 1.0 to 1.2. Vinyl moieties are present in vinyl monomer B. In one embodiment, the coating composition does not comprise any compounds with vinyl moieties other than vinyl monomer B.
In one embodiment, the radiation-curable coating composition is free of a compound with two or more acryloyl or methacryloyl groups. The presence of such compound may have a negative effect on film formation.
The total amount of butenolide monomer A and vinyl monomer B in the radiation- curable coating composition may be in the range of from 70 to 100 wt%, more preferably from 80 to 100 wt%, even more preferably of from 90 to 100 wt%.
The coating composition is radiation-curable. The coating composition may be cured by photoinitiation, i.e. by radiation with visible light or UV light. In one embodiment, the composition further comprises c) a photo-initiator.
The photo-initiator may be one photo initiator or a mixture of two or more thereof. Photo-initiators generate free radicals when exposed to radiation energy in the visible light or UV light wavelength range. Any suitable photo-initiator known in the art may be used, depending on the wavelength. Suitable photo-initiators include benzoin derivatives, benzile ketales, a-hydroxyalkylphenones, monoacylphosphine oxide (MAPO) and bisacylphosphine oxides (BAPO), such as diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone, bis(2,4,6- trimethylbenzoyl)-phenylphosphineoxide, bis(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentyl-phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl- 1[4-(methylthio)phenyl]-2-morpholono-propan-1-one, a phenyl glyoxylic acid methyl ester. Mixtures of these compounds may also be employed.
The photo-initiator may be present in an amount of from 0.1 to 10 wt%, for example from 0.5 to 5.0 wt%, based on the total weight of the coating composition.
Alternatively, the curing of the coating composition may be initiated by electron beam or by gamma radiation. For initiation by electron beam or gamma radiation, no photoinitiator is needed.
The coating composition may be a powder coating composition or a liquid coating composition, preferably a liquid coating composition. The coating composition preferably is an essentially solvent-free liquid coating composition. Reference herein to an essentially solvent-free coating composition is to a coating composition comprising at most 1 wt% of organic solvent, more preferably at most 0.5 wt%, still more preferably 0 wt%.
In case the viscosity of butenolide monomer A and vinyl monomer B is undesirably high the coating composition may comprise some organic solvent to control the viscosity. Preferably, the coating composition comprises at most 30 wt% organic solvent, more preferably at most 20 wt%, even more preferably at most 10 wt%, still more preferably at most 5 wt% or at most 2 wt%.
Suitable organic solvents are solvents in which butenolide monomer A and vinyl monomer B and the cured polymer dissolve at polymerization conditions. The organic solvent may be an oxygenated organic solvent, for example an alcohol, ketone, ester or ether. In particular, the solvent is a glycol ether, glycol ester or an alkyl acetate, for example 1-methoxy-2-propanol or butyl acetate.
The coating composition is not a waterborne coating composition, i.e. water is not the liquid medium in which butenolide monomer A and vinyl monomer B are dissolved or dispersed. The coating composition may comprise a small amount of water, for example water that is contained in additives comprised in the coating composition. In one embodiment, the coating composition comprises less than 5 wt% water, more preferably less than 1 wt%.
The coating composition may comprise further ingredients commonly used in coating compositions such as color pigments, extender pigments, and one or more additives such as for example light stabilizers, other stabilizers, defoaming agents, matting agents, wetting agents, or flow agents.
Radiation-curing the coating composition may be by exposing the coating composition to visible light or UV radiation, electron beam radiation, or gamma radiation, to form a cured coating.
The coating composition may be applied to the substrate by conventional techniques, including spraying, rolling, blade-coating, pouring, brushing or dipping. After evaporation of any organic solvent and/or water, if present, the coating composition results in a coating that is from dust-dry to very tacky. Curing is then induced by means of radiation. Any suitable source of radiation can be used. In particular, radiation curing may be by electron beam radiation, UV radiation or visible light radiation.
In one embodiment, the coating composition further comprises c) a photo-initiator and the coating composition is cured by exposing the coating composition to visible light or UV radiation, for example to visible light with a wavelength in the range of from 400 to 600 nm or to UV radiation with a wavelength in the range of from 200 to 400 nm, in particular to UV radiation with a wavelength in the range of from 280 to 400 nm, or preferably of from 320 to 400 nm (UV-A radiation).
For UV radiation, Hg lamps, metal halide lamps, xenon lamps, or UV-LED lamps may for example be used. It is preferred to use UV-LED lamps.
Radiation curing of the coating composition can be done at ambient conditions, e.g. room temperature and atmospheric pressure. Reference herein to room temperature is to a temperature in the range of from 15 to 30 °C. The curing may be accelerated by post-heating, for example post-heating to a temperature in the range of from 40 to 100 °C, preferably of from 50 to 80 °C.
The substrate may be any suitable substrate, such as for example wood, polymer, composite, metal, glass, or other mineral substrate. The substrate may be a primed or bare substrate.
The coating composition can be used as a single layer applied directly to the substrate, or in multilayer systems, e.g. as a primer, a basecoat, a clearcoat, or a topcoat. The coating composition can be used for various applications, such as coating of wood, electronic appliances, plastic automotive components, food can, or as architectural coating.
The invention is further illustrated by means of the following non-limiting examples.
The following butenolide compounds were used:
5-methoxy-2(5H)-furanone (Methoxy butenolide) MeOBut
5-acetoxy-2(5H)-furanone (Acetoxy butenolide) AcOBut
5-isobutyroxy-2(5H)-furanone (Isobutyroxy butenolide) iBrOBut
5-pivaloyloxy-2(5H)-furanone (Pivaloyloxy butenolide) PivOBut
5-succinyloxy-2(5H)-furanone methyl ester (Succinyloxy butenolide methyl ester) MeOSuccOBut
The following mono-functional vinyl compounds were used: ethylene glycol vinyl ether EGVE
/V-vinylpyrrolidone NVP
The following di-functional butenolide compound was used:
Bis(5-oxo-2,5-dihydrofuran-2-yl) succinate (Succinyloxy bis-butenolide) SuccOBut2
The following di-functional vinyl compounds was used: diethylene glycol divinyl ether DEGDVE
Preparation of butenolide monomers
Methoxy butenolide
5-methoxy-2(5H)-furanone
Chemical Formula: C5H5O3
Molecular Weight: 114.1000
This product and its synthesis were previously described in: Hermens et al., Sci. Adv. 2020; 6: eabe0026. 5-Hydroxy-2(5H)-furanone (100.0 g, 1 mol) was dissolved in 500 mL dry methanol and heated at reflux for 20 h. The conversion was followed by 1H NMR until all 5-hydroxy-2(5H)-furanone was consumed. The solvent was evaporated under reduced pressure and the crude was distilled under reduced pressure (70 °C, 1.0x1 O'2 mbar) yielding 5-methoxy-2(5H)-furanone (86.5 g, 0.76 mol, 76%) as a slightly yellow oil.
Acetoxy butenolide
5-oxo-2 , 5-d i hyd rof uran-2-y I acetate
Chemical Formula: C6H5O4
Molecular Weight: 142.1100
This product and its synthesis were previously described in: G.C. Resende, E.S. Alvarenga, J.C.G. Galindo, F.A. Macias, J. Braz. Chem. Soc. 2012, 23 (12), 2266-2270. In a flask under N2 atmosphere, hydroxy butenolide (1 eq., 500 mg, 5.00 mmol, grey solid) was dissolved in dry DCM (25 mL) and cooled to 0°C with an ice bath. Acetic anhydride (1.6 eq., 754 (1 L, 7.99 mmol) was added, followed by a solution of DMAP (0.3 eq., 183 mg, 1.50 mmol) in dry DCM (1.5 mL). The mixture was stirred at 0°C for 1 h and then allowed to warm up to RT. TLC (25% AcOEt/hexanes, rev. KMnO4) showed formation of a new product at Rf = 0.37. The clear solution was washed with water (25 mL). After phase separation, the aqueous layer was further extracted with DCM (25 mL). The combined organic extracts were dried with sodium sulfate, filtered on cotton and concentrated under reduced pressure. The residue was purified by automatic column chromatography (15g SiO2 cartridge, 10 — 40% AcOEt/pentane over 20 column volume (CV), using DCM for liquid injection. Concentration of the collected fraction afforded pure acetoxy butenolide as a colorless liquid (506 mg, 3.56 mmol, 71 % yield).
Isobutyroxy butenolide
5-isobutyroxy-2(5H)-furanone
(5-oxo-2,5-dihydrofuran-2-yl isobutyrate)
Chemical Formula: C8H10O4 Molecular Weight: 170.1640
In a flask under N2 atmosphere, hydroxy butenolide (90 wt% pure, 1.50 eq., 6.67 g, 4.00 mmol) was dissolved in anhydrous DCM (40 mL, [acid] = 1 M). Isobutyric acid (1.00 eq., 3.70 mL, 40.0 mmol) and DMAP (5 mol%, 244 mg, 2.00 mmol) were added. The clear mixture (blue due to hydroxy butenolide) was cooled to 0°C with an ice bath. N,N'- Dicyclohexylcarbodiimide (DCC) (1.20 eq., 9.90 g, 48.0 mmol) was dissolved in anhydrous DCM (5 mL) and added dropwise at 0°C over 5 min. After the addition, the ice bath was removed, and the mixture was stirred at room temperature for 1 h. The mixture turned from blue to dark brown with a precipitate. The reaction mixture was filtered on cotton wool, rinsing with DCM, affording a brown solid (urea) and a clear brown filtrate, which was concentrated in vacuo to a dark brown oil. The crude residue was purified by automatic column chromatography (80 g SiO2 cartridge, 5-30% AcOEt/pentane over 15 CV), using DCM for liquid injection. Concentration of the
collected fraction afforded pure isobutyroxy butenolide as a yellow oil (4.84 g, 28.4 mmol,
71% yield).
Pivaloyloxy butenolide
5-pivaloyloxy-2(5H)-furanone
(5-oxo-2, 5-di hydrofuran-2-yl pivalate)
Chemical Formula: C9H12O4 Molecular Weight: 184.1910
Hydroxy butenolide (1 eq., 5.00 g, 50.0 mmol) was dissolved in dry DCM (25 mL) and cooled to 0°C with an ice bath. This caused hydroxy butenolide to (partially) precipitate. Pivalic anhydride (1.2 eq., 12.2 mL, 60.0 mmol) was added, followed by a solution of DMAP (0.1 eq., 610 mg, 5.00 mmol) in dry DCM (2.5 mL). The mixture was first stirred at 0°C for 30 min and was then allowed to warm up to RT, thereby causing full dissolution of the solids. The homogeneous mixture was further stirred at room temperature overnight (20 h in total). Over the course of the reaction, the initially blue mixture turned to dark green/brown. The reaction mixture was concentrated. The residue was purified by automatic column chromatography (80 g SiO2 cartridge, 5-30% AcOEt/pentane over 15 CV), using DCM for liquid injection. Concentration of the collected fraction afforded pure pivaloyloxy butenolide as a pale-yellow oil (6.74 g, 36.6 mmol, 73% yield).
Succinyloxy butenolide 4-oxo-4-((5-oxo-2,5-dihydrofuran-2-yl)oxy)butanoic acid Chemical Formula: CsHsOe Molecular Weight: 200.1460
Hydroxybutenolide (1 eq., 1.00 g, 9.99 mmol) was dissolved in dry DCM (20 mL) and cooled to 0°C with an ice bath. Succinic anhydride (1.6 eq., 1.60 g, 16.0 mmol) was added, followed by a solution of DMAP (0.3 eq., 366 mg, 3.00 mmol) in dry DCM (1 mL). The mixture was first stirred at 0°C, during which it turned from light blue to light green, and was then allowed to warm up to room temperature overnight. In the morning the mixture had darkened even more. Thin layer chromatography (50% AcOEt/hexanes + 1 vol% AcOH, rev. KMnCL) showed formation of a new, polar spot at Rf = 0.25. The reaction mixture was concentrated. The residue was purified by automatic column
chromatography (40 g SiC>2 cartridge, 10-60% AcOEt/pentane over 25 CV, then 60-100% over 5 CV), using DCM as solvent for liquid injection and adding 1 vol% AcOH in AcOEt. Concentration of the collected fraction afforded succinyloxy butenolide as a white solid (1.37 g) which still contained traces of succinic anhydride. Another purification by column chromatography (25 g SiC>2 cartridge, 10-60% AcOEt/pentane over 25 CV, then 60 — 100% over 5 CV), using solid injection (adsorbed in SiCh) and adding 1 vol% AcOH in AcOEt, afforded pure succinyloxy butenolide (1.13 g, 5.63 mmol, 56% yield) as a white solid.
Succinyloxy butenolide methyl ester
5-succinyloxy-2(5H)-furanone methyl ester
(methyl (5-oxo-2,5-dihydrofuran-2-yl) succinate) Chemical Formula: C9H10O6 Molecular Weight: 214.1730
In a flask under N2 atmosphere, succinyloxy butenolide (1.00 eq., 200 mg, 1.00 mmol) was dissolved in anhydrous DCM (5 mL, [SM] = 0.2 M). Methanol (3.00 eq., 121 pL, 3.00 mmol) and DMAP (5 mol%, 6 mg, 0.05 mmol) were added. The hazy mixture was cooled to 0°C with an ice bath. DCC (1.10 eq., 227 mg, 1.10 mmol) was added at once at 0°C. The mixture was stirred at 0°C for 30 min and then at room temperature for 30 min.
The reaction mixture was filtered on a Buchner, rinsing with DCM, leaving a white solid and affording a brown filtrate which was concentrated to a brown murky oil. The residue was purified by automatic column chromatography (15 g SiC>2 cartridge, 10-50% AcOEt/pentane over 20 CV), using DCM for liquid injection. Concentration of the collected fraction afforded pure methyl succinyloxy butenolide (163 mg, 0.761 mmol, 76% yield) as a colorless semi-solid.
Succinyloxy bis-butenolide
Bis(5-oxo-2,5-dihydrofuran-2-yl) succinate
Chemical formula: C12H10O8 Molecular Weight: 282.2040
In a flask under N2 atmosphere, succinyloxy butenolide (1.00 eq., 500 mg, 2.50 mmol)
and hydroxy butenolide (2.00 eq., 500 mg, 5.00 mmol) were dissolved in anhydrous DCM (20 mL, [SM] = 0.125 M). DMAP (5 mol%, 15 mg, 0.13 mmol) was added. The clear mixture was cooled to 0°C with an ice bath. DCC (1.20 eq., 618 mg, 3.00 mmol) was dissolved in anhydrous DCM (2 mL) and added dropwise at 0°C over 5 min. During the addition, the hazy yellowish mixture first became clear yellowish, before turning back to hazy with the precipitation of a solid. The slurry then slowly turned brown over time. After 1 h, the ice bath was removed, and the mixture was stirred at room temperature for 1 h.
The reaction mixture was filtered, rinsing with DCM, affording a white solid (urea) and a clear brown filtrate, which was concentrated in vacuo to a brown solid. The residue was purified by automatic column chromatography (25 g SiC>2 cartridge, 0-20% AcOEt/pentane over 20 CV), using solid injection with neutralized silica. Concentration of the collected fraction afforded pure succinyloxy bis-butenolide (532 mg, 1.88 mmol, 75% yield) as a white solid.
Examples 1 to 13 and Comparative Example A
Coating compositions were prepared by combining a butenolide monomer, a monofunctional vinyl monomer and a di-functional monomer (either a butenolide or vinyl monomer) in various ratios as indicated in Table 1 and adding 1-3 mol% (vs. the most abundant compound) bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide (OmniRad 819 or BAPO) as photo-initiator. All compositions were solvent-free compositions.
A 100 pm wet film of coating composition was drawn on a glass plate using a drawing bar. The wet film was cured by irradiating the film with UV light using a IIV-A LED irradiation device with 12 LED lamps emitting UV light with a wavelength of 395 nm and a total irradiance of 21 mW/cm2 during 5 minutes at a distance of 5 cm. All coatings formed a tack- and defect-free film.
The UV-cured coatings thus obtained were tested as described below for water resistance, solvent resistance and for hardness, after 4 days of storing at 23 °C and 50 % relative humidity. Results are indicated in Table 1.
Dry layer thickness (DFT)
The dry layer thickness (ISO 2808) of the coatings were measured using the Heidenhain VRZ 402 apparatus calibrated with calibration foil. A spot (10 mm diameter) of curing coating is removed from the glass substrate. The measuring probe was placed on the bare substrate and the measured value was fared, next, three layer thickness measurements are performed. This procedure was performed at three different locations on the substrate (9 measurements in total) and the average value is reported.
Solvent resistance (methyl ethyl ketone)
MEK double rub resistances were measured by rubbing the coating back and forth (5 cm) with a cloth soaked in 2-butanone (MEK) applying 10 N downward pressure. The number of double rubs (= 1x back and 1x forth) until the coating failure (dissolution) were counted with a maximum for 200 double rubs. At >200 double rub resistance the film appearance was described (e.g. dulling, staining, or any other change in appearance).
Water resistance
Water resistance (ISO 2812-4:2007 part 4) was measured by placing a droplet of demineralized water on the cured coating and covering it with a watch glass. After 60 minutes, the water droplet was wiped off and the effect on the coating was determined visually on a scale of 0 to 5, wherein 5 means that the water droplet had no visible impact on the coating, and 0 means that the water droplet had a detrimental impact.
Hardness (Knoop)
Knoop hardness’s (related to ASTM D1474, method A) were measured using the Fischerscope HM 2000 Xyp equipment calibrated using poly(methyl methacrylate) (PMMA). The indentation hardness was determined by measuring the indentation depth after applying a 98 mN (10 gram) load for 18 seconds using a diamond pyramidal shaped indenter (longitudinal angles: 172°30' and transverse angles: 130°) to the dried coating. Five consecutive measurements on different predefined spots were performed making sure the indentation depth does not exceed 75% of the coating thickness. The Knoop hardness was calculated by:
Hk = ~^
C x d2
Where:
Hk = Knoop hardness in kg/mm2.
P = load applied on the indenter in kg.
C = indenter correction constant: 65.438. d = indentation depth in mm.
Glass transition temperature (Tg)
Glass temperatures (Tg) were measured with a Q2000 (TA Instruments) Differential Scanning Calorimeter (DSC). A DSC cup filled with 6 +/- 1 mg cured paint chips and an empty DSC reference cup were heated in the DSC in a modulated way (+/- 1°C every 40 seconds) from -80°C to 200°C at 5°C/min in three consecutive runs using Helium (50 ml/min) as purge gas. Fourier transformation enabled the separation of the modulated heat flow into a heat capacity component (reversing heat flow) and a kinetic component (non-reversing heat flow) allowing to separate different thermal events occurring at the same time.
At the materials Tg (observed in the reversing heat flow curve) the heat capacity of the material changed rapidly resulting in a strong decrease of the reversing heat flow curve over a certain transfer area. The Tg is calculated at the point of inflection (Tg(l)) and at half width (Tg(W)), the Tg(W) measured in the second run is reported.
Claims
CLAIMS A radiation-curable coating composition comprising: a) one or more butenolide monomer A of general formula (I):
wherein: n is 0 or an integer of from 1 to 5;
R1 is alkyl or aryl;
X is any one of -C(O)-, -C(O)O-, -C(O)NR2-, -S(O)-, -S(O2)-, -C(O)S-, -C(S)S- and -C(S)NR2-; wherein R2 is hydrogen, alkyl or aryl; or wherein, when n is 0 and X is -C(O)NR2- or -C(S)NR2-, R1 and R2 together with the nitrogen atom through which they are linked form a nitrogen-containing heterocyclic group or nitrogen-containing heteroaryl group; and b) one or more vinyl monomer B comprising one or more vinyl groups wherein at least one vinyl group has a difference in 13C chemical shift between the a-C and p-C of a vinyl group of at least 25 ppm; wherein at least one monomer of A and B comprises at least two vinyl groups; and wherein the difference in 13C chemical shift between the a-C and p-C of the vinyl group is determined from the chemical shift reported in the Spectral Database for Organic Compounds (https://sdbs.db.aist.go.jp/sdbs/cqi- bin/direct frame top.cqi), managed by the National Institute of Advanced Industrial Science and Technology.
A radiation-curable coating composition according claim 1 , wherein for at least one butenolide monomer A, n=0; and wherein at least one vinyl monomer B comprises at least two vinyl groups. A radiation-curable coating composition according to claim 1 or claim 2, which comprises at least two butenolide monomers A, wherein for at least one butenolide monomer A, n is an integer of from 1 to 5. A radiation-curable coating composition according to any one of claims 1 to 3, wherein the weight fraction of monomers comprising at least two vinyl groups in the composition is at most 5 wt.%. A radiation-curable coating composition according to any one of claims 1 to 4, wherein X is any one of -C(O)-, -C(O)O-, -C(O)NR2-. A radiation-curable coating composition according to any one of claims 1 to 5, wherein R1 is C1-C20 alkyl, C5-C7 cycloalkyl or phenyl. A radiation-curable coating composition according to any one of claims 1 to 6, wherein a vinyl monomer B is a vinyl compound of general formula (II)
R3CH=CH2 (II); wherein R3 is any one of:
-OR4, -OC(O)R4, -N(R5)C(O)R4, -N(R5)C(O)OR4, -NR5C(S)R4, -NR5C(S)OR4, - NR5C(S)SR4 and -SC(S)SR4; wherein R4 is alkyl or aryl, and wherein R5 is hydrogen, alkyl or aryl, or wherein R4 and R5 together with the atoms through which they are linked form a nitrogen-containing heterocyclic group or nitrogen-containing heteroaryl group. A radiation-curable coating composition according to claim 7, wherein R3 is - OR4, -OC(O)R4 or -N(R5)C(O)R4.
A radiation-curable composition according to any one of claims 1 to 8, wherein a vinyl momomer B is a monovinyl ester, a monovinyl ether or a mono N-vinyl compound. A radiation-curable coating composition according to claim 9, wherein a vinyl monomer B is n-butyl vinyl ether, iso-butyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, vinyl neodecanoate, vinyl neononanoate, N-vinylpyrrolidone, N-vinyl imidazole, N-vinyl-formamide, N-vinyl-pyrrole, N-vinylcaprolactam or a mixture of two or more thereof. A radiation-curable coating composition according to any one of claims 1 to 10, wherein a vinyl monomer B has at least two vinyl groups and which is a divinyl ether, a divinyl ester or a di-N-vinyl compound. A radiation-curable coating composition according to any one of claims 1 to 11, wherein the molar ratio of furanone moieties to vinyl moieties is in the range of from 1.5: 1.0 to 1.0: 1.5. A radiation-curable coating composition according to any one of claims 1 to 12, wherein the composition further comprises c) a photo-initiator. A method of coating a substrate comprising: providing a substrate; applying a coating composition as defined in any one of the preceding claims to the substrate; and radiation-curing the coating composition to form a cured coating. A coated substrate obtainable by a method according to claim 14.
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