WO2016046300A1 - Fluoropolymer composition - Google Patents
Fluoropolymer composition Download PDFInfo
- Publication number
- WO2016046300A1 WO2016046300A1 PCT/EP2015/071940 EP2015071940W WO2016046300A1 WO 2016046300 A1 WO2016046300 A1 WO 2016046300A1 EP 2015071940 W EP2015071940 W EP 2015071940W WO 2016046300 A1 WO2016046300 A1 WO 2016046300A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- phenyl
- substituted
- cycloalkyl
- alkenyl
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 229920002313 fluoropolymer Polymers 0.000 title description 10
- 239000004811 fluoropolymer Substances 0.000 title description 10
- 239000006096 absorbing agent Substances 0.000 claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 15
- 230000004927 fusion Effects 0.000 claims abstract description 13
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920006126 semicrystalline polymer Polymers 0.000 claims abstract description 4
- -1 hydroxylphenyl-triazine compound Chemical class 0.000 claims description 70
- 150000001875 compounds Chemical class 0.000 claims description 57
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 51
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 48
- 125000003342 alkenyl group Chemical group 0.000 claims description 41
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 27
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 25
- 229920001780 ECTFE Polymers 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 125000001624 naphthyl group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 150000001602 bicycloalkyls Chemical group 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 8
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 8
- 125000005293 bicycloalkoxy group Chemical group 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 229920001651 Cyanoacrylate Polymers 0.000 claims description 3
- 238000003490 calendering Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- HTWMTDKMOSSPMU-UHFFFAOYSA-N 1,2-benzoxazin-4-one Chemical class C1=CC=C2C(=O)C=NOC2=C1 HTWMTDKMOSSPMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 230000005855 radiation Effects 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 50
- 238000002834 transmittance Methods 0.000 description 11
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical compound OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- 0 CC([*@@](*)N=**)(C=C1)C=CC(O)=C1c1nc([Al])nc([Al])n1 Chemical compound CC([*@@](*)N=**)(C=C1)C=CC(O)=C1c1nc([Al])nc([Al])n1 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 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 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 description 1
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- BOZYVOUQHUPWQA-UHFFFAOYSA-N 2-(3-hydroxypropylidene)octanoic acid Chemical compound CCCCCCC(C(O)=O)=CCCO BOZYVOUQHUPWQA-UHFFFAOYSA-N 0.000 description 1
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical class OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 1
- HTTGVORJOBRXRJ-UHFFFAOYSA-N 2-(triazin-4-yl)phenol Chemical class OC1=CC=CC=C1C1=CC=NN=N1 HTTGVORJOBRXRJ-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- KHNYNFUTFKJLDD-UHFFFAOYSA-N Benzo[j]fluoranthene Chemical compound C1=CC(C=2C3=CC=CC=C3C=CC=22)=C3C2=CC=CC3=C1 KHNYNFUTFKJLDD-UHFFFAOYSA-N 0.000 description 1
- YBXOKDDFZNIXRE-UHFFFAOYSA-N CC(C=C1)(C=CC(N=C(N)O2)=C1C2=O)I Chemical compound CC(C=C1)(C=CC(N=C(N)O2)=C1C2=O)I YBXOKDDFZNIXRE-UHFFFAOYSA-N 0.000 description 1
- MWCGLPVYZXXJLZ-UHFFFAOYSA-N CCCCCCCC(OC(C(C)Oc(cc1O)ccc1-c1nc(-c(cc2)ccc2-c2ccccc2)nc(-c(cc2)ccc2-c2ccccc2)n1)=O)=C Chemical compound CCCCCCCC(OC(C(C)Oc(cc1O)ccc1-c1nc(-c(cc2)ccc2-c2ccccc2)nc(-c(cc2)ccc2-c2ccccc2)n1)=O)=C MWCGLPVYZXXJLZ-UHFFFAOYSA-N 0.000 description 1
- RAASUWZPTOJQAY-UHFFFAOYSA-N Dibenz[a,c]anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C3=CC=CC=C3C2=C1 RAASUWZPTOJQAY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- HTTLBYITFHMYFK-UHFFFAOYSA-N O=C1OC(c2ccccc2)=Nc2c1cccc2 Chemical compound O=C1OC(c2ccccc2)=Nc2c1cccc2 HTTLBYITFHMYFK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 125000005075 adamantyloxy group Chemical group C12(CC3CC(CC(C1)C3)C2)O* 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- JDPBLCQVGZLACA-UHFFFAOYSA-N benzo[a]perylene Chemical group C1=CC(C=2C3=CC=CC=C3C=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 JDPBLCQVGZLACA-UHFFFAOYSA-N 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- HPNSNYBUADCFDR-UHFFFAOYSA-N chromafenozide Chemical compound CC1=CC(C)=CC(C(=O)N(NC(=O)C=2C(=C3CCCOC3=CC=2)C)C(C)(C)C)=C1 HPNSNYBUADCFDR-UHFFFAOYSA-N 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SIFHTIHFPPIGBL-UHFFFAOYSA-N ctk2i0750 Chemical compound C12=C3C4=CC=CC3=CC=C2C=CC=C1C1=C4CC2=CC=CC=C21 SIFHTIHFPPIGBL-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 1
- 238000009826 distribution 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
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000003993 interaction 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
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 125000002960 margaryl 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])([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
- 125000001421 myristyl 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])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical class C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 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
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000001400 nonyl 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])([H])[H] 0.000 description 1
- 125000002872 norbornadienyl group Chemical group C12=C(C=C(CC1)C2)* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000000913 palmityl 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])([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
- 125000002958 pentadecyl 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])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005327 perimidinyl group Chemical group N1C(=NC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 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
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000004079 stearyl 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])([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])[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 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
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 125000004627 thianthrenyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3SC12)* 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000002889 tridecyl 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])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl 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])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 125000004933 β-carbolinyl group Chemical group C1(=NC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
Definitions
- the invention pertains to a novel fluoropolymer composition advantageously possessing improved UV resistance performances, to a method for its manufacture, to a method for its processing into shaped articles, and to shaped articles manufactured therefrom.
- Exposure to UV light is known to adversely impacts the properties of polymers, including notably decrease of mechanical properties, yellowing, loss of gloss, discolouring, etc...
- stabilisers are conventionally used.
- Stabilizers can be divided in three categories, defined by their mode of action to prevent photo-degradation: 1. Quenchers, which are able to bring back “excited” chromophores (due to photon absorption) to a stable state; 2. Radical scavengers, such as HALS (hindered aromatic amine compounds), which are reactive towards free radicals formed after decomposition of “excited” chromophores (typically through generation of hydroperoxy radicals, and hence hydroperoxides and free radicals, by interaction with oxygen): 3. UV absorbers, which filter out harmful UV radiation, quickly transforming the same into vibrational and rotational energy of the molecule (hence into harmless heat), thus preventing the photodegradation of the polymer.
- HALS hinderetra aromatic amine compounds
- compounds of this latter class are chromophores that can go back to their stable state after light absorption without creating harmful free radicals (deactivation of the excited state by electronic rearrangement and heat dissipation).
- UV absorber For a UV absorber to be effective in a polymer matrix, it is thus necessary for the UV absorber to absorb UV radiation through a chromophore group present in the molecule more quickly and more efficiently than the chromophores present in the polymer.
- UV absorbers are: a) 2-(2-hydroxyphenyl)-benzotriazoles b) 2-hydroxy-benzophenones c) 2-hydroxyphenyl-triazines d) oxalanilides e) cyanoacrylates.
- copolymers of ethylene with chlorotrifluoroethylene, tetrafluoroethylene or mixtures thereof are well known in the art, in particular for the manufacture of films and protective layers.
- UV absorbers when considering incorporation of UV absorbers into fluoropolymers, other considerations have to be taken into account, including ability of the UV absorber to withstand conditions encountered during processing of the said fluoropolymer, which can be as high as about ⁇ 250°C, as well as the ability for the UV absorbers to homogeneously disperse into the plastic matrix, so as to ensure equally homogeneous protection. Transparency and haze of the films maybe adversely affected due to the poor dispersability of organic UV absorbers in the fluorinated matrix, and UV blocking performances might be equally seriously impacted.
- UV absorbers due to their inherent incompatibility with the fluoropolymer matrix, tend to migrate over time to the surface of films made from fluoropolymer compositions including the same. This phenomenon, referred to in the art as "bleeding" produces a rough and discolored surface which also blocks visible light transmission, and make the film unsuitable in most fields of use.
- US 6444311 SAINT GOBAIN PERFORMANCE PLASTICS 20020903 discloses a multilayer film for coating synthetic environmental surfaces includes an exposed protective layer and an underlying cushioning layer, wherein said protective layer is a layer of a blend comprising a fluorine substituted olefin polymer and an acrylic polymer.
- said protective layer is a layer of a blend comprising a fluorine substituted olefin polymer and an acrylic polymer.
- fluorine-substituted polymers mention is made of ethylene/chlorotrifluoroethylene polymers.
- each of the layers of the multilayer film can contain one or more UV-light absorber; inter alia, Tinuvin(R) 360 benzotriazole compound and Tinuvin(R) 1577FF hydroxyphenyltriazine compound are cited among a very long list of suitable compounds.
- WO WO 2008/083975 ISDIN S.A. 20080717 discloses a light-stabilized composition comprising a polymer, a first light-stabilizing component comprising a heptaazaphernalene group and a second light stabilizer.
- UV absorbers are mentioned about a very large variety of compounds suitable as second stabilizers, including, inter alia , Tinuvin(R) 1577 hydroxyphenyltriazine compound and Tinuvin(R) 360 benzotriazole compound.
- ECTFE and ETFE materials are listed as possible thermoplastic polymers, although all actual working embodiments are based on the use of polypropylene as polymer matrix.
- the invention hereby provides a solution to aforementioned shortfall and provides for a fluoropolymer sulfone polymer composition having improved UV resistance. More precisely, the present invention provides for a composition comprising: - at least one semi-crystalline polymer comprising recurring units derived from ethylene and at least one of chlorotrifluoroethylene (CTFE) and tetrafluoroethylene (TFE), said polymer having a heat of fusion of at most 35 J/g [polymer (A)]; and - at least one organic UV absorber [absorber (UV)] .
- CTFE chlorotrifluoroethylene
- TFE tetrafluoroethylene
- organic UV absorber as above detailed, possessing high absorption capability (high extinction coefficients in UV-VIS region) towards UV light, although having hydrogenated and polar character which make them poorly dispersable in standard ECTFE/ETFE matrices, can be efficiently dispersed in copolymers of ethylene with TFE and/or CTFE delivering outstanding total transmittance, haze but also UV opacity, provided said copolymers have a low crystallinity, that it to say, provided that their heat of fusion is below the above recited boundary.
- Figure 1 is a plot of absorbance as a function of wavelength for three different UV absorbers, namely two absorbers of hydroxyphenyl-triazine type (UV-1, solid line, and UV-2, dotted line), and a UV absorber of benzotriazole type (UV-3, dashed line) (as 10 ppm solution in methylene chloride).
- organic UV absorber is used within the context of the present invention according to its usual meaning, i.e. to designate an organic compound possessing absorption bands in the region ranging from 250 to 400 nm.
- Absorbers (UV) which have been found particularly advantageous within the frame of the present invention are selected from the group consisting of hydroxylphenyl-triazine compounds [compounds (T)], cyanoacrylate compounds [compounds (CN)], benzoxazin-4-one compounds [compounds (BX)], and benzotriazole compounds [compounds (BT)].
- absorber (UV) is at least one hydroxylphenyl-triazine compound [compound (T)] of formula (I): wherein: - Ar a and Ar b , equal to or different from each other, are independently aromatic groups, said aromatic groups possibly comprising one or more than one heteroatom; - R j is a halogen or a hydrocarbon group possibly comprising one or more than one heteroatom; - j is zero or is an integer of 1 to 4, in particular 1 to 2.
- Compound (T) is preferably a compound complying with formula (II): wherein: E 1 and E 2 , equal to or different from each other, is independently a substituted or unsubstituted naphthyl; or a substituted ot unsubstituted aromatic carbocyclic fused ring comprising at least 3 rings, or is a substituted or unsubstituted aromatic hetero ring system comprising one or more rings; or corresponds to the formula (III): R 1 is H, C 1 -C 24 alkyl, C 2 -C 18 alkenyl, C 5 -C 12 cycloalkyl, C 7 -C 15 phenylalkyl, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by C 1 -C 8 alkyl; or OR 3 ; R 2 is H, C 1 -C 18 alkyl; C 2 -C 6 alkenyl; phenyl; phen
- R 11 and R 22 are H.
- R 22 ' that is -OR 3 , especially -OH.
- aromatic carbocyclic fused ring systems comprising at least 3 rings are radicals of anthracene, phenanthrene, fluoranthene, pyrene, chrysene, benzanthracene, dibenzanthracene, benzofluoranthene, benzopyrene, indenopyrene and benzoperylene, preferably phenanthrene, fluoranthene and pyrene, most preferably fluoranthene and pyrene.
- an aromatic carbocyclic fused ring system comprising at least 3 rings means that this ring system comprises at least 3 aromatic rings, in particular at least three aromatic fused rings.
- aromatic hetero ring systems comprising one or more rings are thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, beta -carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl
- alkyl are branched or unbranched alkyl, e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethyl
- C 5 -C 12 cycloalkyl includes notably cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclodocecyl. Cyclopentyl, cyclohexyl, cyclooctyl and cyclododecyl are preferred.
- Alkenyl includes, within the scope of the definitions given, inter alia allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl and n-octadec-4-enyl.
- Substituted alkyl, cycloalkyl or phenyl radicals may be mono- or poly-substituted and may carry substituents at the binding carbon atom (in the a-position) or at other carbon atoms; if a substituent is bonded by a hetero atom (such as e.g. alkoxy), it is preferably not in the a-position and the substituted alkyl radical comprises 2, especially 3, or more carbon atoms.
- a plurality of substituents is preferably bonded to different carbon atoms.
- Alkyl interrupted by -O-, -NH-, -NR 7 - and/or by -S- may be interrupted by one or more of the mentioned groups, in each case normally one group being inserted into a bond and hetero-hetero bonds, such as, for example, O-O, S-S, NH-NH etc. not occurring; if the interrupted alkyl is, in addition, substituted, the substituents are not normally in the a-position with respect to the hetero atom. If a plurality of interrupting groups of the type -O-, -NH-, -NR 7 - and -S- occurs in a radical, those groups are usually identical.
- Hydroxyalkyl means an alkyl group substituted by at least one hydroxyl group.
- alkoxy, phenoxy, alkenyloxy and cycloalkoxy mean the group -OZ, wherein Z is alkyl, phenyl, alkenyl and cycloalkyl respectively.
- Phenylalkyl comprises within the limits of carbon atoms given, for example, benzyl, a-methylbenzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl; whereby benzyl, a-methylbenzyl and a,a-dimethylbenzyl are preferred.
- Alkylphenyl and alkylphenoxy are alkyl-substituted phenyl and phenoxy, respectively.
- a halogen substituent is -F, -Cl, -Br or -I; -F or -Cl, and especially -Cl, is preferred.
- Haloalkyl is especially chloroalkyl or trifluoromethyl; trifluoromethyl is of particular importance industrially.
- Alkylene is e.g. methylene, ethylene, propylene, butylene, pentylene, hexylene, etc.
- the alkyl chain may also be branched in that case, such as e.g. in isopropylene.
- Cycloalkenyl is e.g. 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2,4-cyclopentadien-1-yl, 2-cyclohexen-1-yl, 2-cyclohepten-1-yl or 2-cyclooctene-1-yl.
- C 6 -C 15 Bicycloalkyl is e.g. bornyl, norbornyl or 2.2.2-bicyclooctyl. Bornyl and norbornyl, and especially bornyl and norborn-2-yl, are preferred.
- C 6 -C 15 Bicycloalkoxy is, for example, bornyloxy or norborn-2-yl-oxy.
- Bicycloalkyl-alkyl or -alkoxy is alkyl or alkoxy substituted by bicycloalkyl, the total number of carbon atoms being 6-15; examples are norbornane-2-methyl and norbornane-2-methoxy.
- C 6 -C 15 Bicycloalkenyl is e.g. norbornenyl or norbornadienyl. Norbornenyl, and especially norborn-5-enyl, is preferred.
- Bicycloalkenyl-alkoxy is alkoxy substituted by bicycloalkenyl, the total number of carbon atoms being 6-15; an example is norborn-5-enyl-2-methoxy.
- C 6 -C 15 -Tricycloalkyl is e.g. 1-adamantyl or 2-adamantyl; 1-adamantyl is preferred.
- C 6 -C 15 -Tricycloalkoxy is e.g. adamantyloxy.
- C 3 -C 12 Heteroaryl is preferably pyridinyl, pyrimidinyl, triazinyl, pyrrolyl, furanyl, thiophenyl or quinolinyl.
- a single compound (T) can be used or mixtures of more than one compound (T) can be equally employed.
- Preferred compounds (T) are compounds complying with any of formulae (T1), (T2) and (T11), as above detailed. These compounds are notably available commercially under trade name TINUVIN® 1600, TINUVIN® 460 and TINUVIN® 1577 UV stabilizer. More particularly, compounds (T1) and (T11) have been proven to behave in an optimum manner when resulting composition has been used for the manufacture of thin films.
- absorber (UV) is at least one cyanoacrylate compound [compound (CN)] of formula (VI): wherein: - Ar a and Ar b , equal to or different from each other, are independently aromatic groups, said aromatic groups possibly comprising one or more than one heteroatom; - R cn is a hydrocarbon group possibly comprising one or more than one heteroatom.
- compound (CN) complies with formula (VII): wherein: - R cn1 is independently C 1 -C 18 alkyl; C 3 -C 6 alkenyl; C 5 -C 12 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -C 11 phenylalkyl; C 7 -C 14 alkylphenyl; or is a group of formula: wherein n is an integer of 1 to 4, and E is a hydrocarbon group, preferably an aliphatic group; - j is zero or an integer of 0 to 4; - each of R j , equal to or different from each other, is independently C 1 -C 18 alkyl; C 3 -C 6 alkenyl; C 5 -C 12 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -C 11 phenylalkyl; C 7 -C 14 alkylpheny
- absorber (UV) is at least one benzoxazin-4-one compound [compounds (BX)] of formula (VIII): wherein: - R BX is independently C 1 -C 18 alkyl; C 3 -C 6 alkenyl; C 5 -C 12 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -C 11 phenylalkyl; C 7 -C 14 alkylphenyl; or is a group of formula: wherein E’ is a hydrocarbon group, preferably an aromatic group, more preferably a phenyl group; - j is zero or an integer of 0 to 4; - each of R j , equal to or different from each other, is independently C 1 -C 18 alkyl; C 3 -C 6 alkenyl; C 5 -C 12 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -C 11
- Compound (BX1) has been found particularly advantageous.
- absorber (UV) is at least one benzotriazole compound [compounds (BT)] of formula (IX): wherein: - R BT is independently H; C 1 -C 18 alkyl; C 3 -C 6 alkenyl; C 5 -C 12 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -C 11 phenylalkyl; C 7 -C 14 alkylphenyl; or is a group of formula: wherein E” is a hydrocarbon group, preferably an aromatic group, more preferably a group of formula: ; - j is zero or an integer of 0 to 4; j’ is zero or an integer of 0 to 3; - each of R j , equal to or different from each other, is independently C 1 -C 18 alkyl; C 3 -C 6 alkenyl; C 5 -C 12 cycloalkyl; phenyl; naphthyl;
- Compound (BT1) is notably commercially available under tradename TINUVIN® 360 benzotriazole UV absorber from BASF.
- the amount of absorber (UV) used in the inventive composition is not particularly limited, provided that the same is used in an effective amount for delivering the expected UV resistance; one of ordinary skills in the art will be able to determine by routine experiments optimized amounts. Generally, nevertheless, the amount of absorber (UV) will be of at least 0.001, preferably at least 0.01, more preferably at least 0.1 weight parts per 100 weight parts of polymer (A).
- the amount of absorber (UV) will be generally of at most 10, preferably at least 8, more preferably at least 5 weight parts per 100 weight parts of polymer (A).
- the heat of fusion of polymer (A) is determined by Differential Scanning Calorimetry (DSC) at a heating rate of 10°C/min, according to ASTM D 3418.
- Polymer (A) possesses a heat of fusion of at most 35 J/g, preferably of at most 30 J/g, more preferably of at most 25 J/g.
- polymer (A) is essential for polymer (A) of being a semi-crystalline polymer, i.e. a polymer having a detectable melting point when determined according to ASTM D 3418. Without lower limit for heat of fusion being critical, it is nevertheless understood that polymer (A) will generally possess a heat of fusion of at least 1 J/g, preferably of at least 2 J/g, more preferably of at least 5 J/g.
- polymers (A) which are preferred for the purpose of the invention are indeed those comprising an amount of recurring units derived from ethylene of less than 50 % moles, preferably of less than 48 % moles, more preferably of less than 45 % moles, with respect to the total number of moles of recurring units, as they enable achieving improved properties due to the fluoromonomer components.
- Polymer (A) of the composition of the invention typically comprises: (a) from 30 to 48%, preferably from 35 to 45 % by moles of recurring units derived from ethylene (E); (b) from 52 to 70%, preferably from 55 to 65% by moles of recurring units derived from chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) or mixture thereof; and (c) from 0 to 5%, preferably from 0 to 2.5 % by moles, based on the total amount of monomers (a) and (b), of recurring units derived from one or more fluorinated and/or hydrogenated comonomer(s), with respect to the total number of moles of recurring units.
- CTFE chlorotrifluoroethylene
- TFE tetrafluoroethylene
- the said comonomer (c) is a hydrogenated comonomer selected from the group of the (meth)acrylic monomers. More preferably the hydrogenated comonomer is selected from the group of the hydroxyalkylacrylate comonomers, such as hydroxyethylacrylate, hydroxypropylacrylate and (hydroxy)ethylhexylacrylate, and alkyl acrylate comomnomers, such as n–butyl acrylate.
- ECTFE copolymers i.e. copolymers of ethylene and CTFE and optionally a third monomer (comonomer (c)), as above detailed, are preferred.
- ECTFE polymers suitable in the composition of the invention typically possess a melting temperature not exceeding 210°C, preferably not exceeding 200°C, even not exceeding 198°C, preferably not exceeding 195°C, more preferably not exceeding 193°C, even more preferably not exceeding 190°C.
- the ECTFE polymer has a melting temperature of advantageously at least 120°C, preferably of at least 130°C, still preferably of at least 140°C, more preferably of at least 145°C, even more preferably of at least 150°C.
- the melting temperature is determined by Differential Scanning Calorimetry (DSC) at a heating rate of 10°C/min, according to ASTM D 3418.
- ECTFE polymers which have been found to give particularly good results are those consisting essentially of : (a) from 35 to 47% by moles, with respect to the total number of moles of recurring units, of recurring units derived from ethylene (E); (b) from 53 to 65% by moles, with respect to the total number of moles of recurring units, of recurring units derived from chlorotrifluoroethylene (CTFE).
- the melt flow rate of the ECTFE polymer ranges generally from 0.01 to 75 g/10 min, preferably from 0.1 to 50 g/10 min, more preferably from 0.5 to 30 g/10 min.
- Another aspect of the present invention is a method for manufacturing the composition, as above detailed.
- the method of the invention advantageously comprises mixing at least the said polymer (A) and the organic UV absorber [absorber (UV)].
- Other optional ingredients may be equally mixed in the method of the invention for finally providing for the composition as above detailed.
- the polymer (A) is generally provided in the method of the invention under the form of a powder or under the form of pellets.
- the expression “powder” has to be understood as possessing the usual meaning, i.e. under the form of loose discrete particles of material.
- the method generally comprises mixing the said ingredients by blending in the molten state (melt blending); conventional melt compounding devices, such as co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc-pack processors and various other types of extrusion equipment can be used.
- melt compounding devices such as co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc-pack processors and various other types of extrusion equipment can be used.
- extruders more preferably twin screw extruders can be used.
- the design of the compounding screw e.g. flight pitch and width, clearance, length as well as operating conditions will be advantageously chosen so that sufficient heat and mechanical energy is provided to advantageously fully melt the polymer (A) and advantageously obtain a homogeneous distribution of the different ingredients. It is hence advantageously possible to obtain strand extrudates of the composition of the invention. Such strand extrudates can be chopped by means e.g. of a rotating cutting knife after some cooling time on a conveyer with water spray, so as to provide the composition under the form of pellets or beads, which can be further can processed for the manufacture of shaped articles.
- the method may additionally comprise, prior to the melt blending, a preliminary step of dry blending a powder of polymer (A) in the solid state with the absorber (UV).
- the dry blending as detailed above is carried out by using high intensity mixers, such as notably Henschel-type mixers and ribbon mixers.
- the polymer composition (C) is notably very well suited for the manufacture of articles useful in a wide variety of end uses.
- composition of the invention is particularly suitable for being used for manufacturing films, sheets, coatings or other finished articles.
- Still another object of the invention is the use of the polymer composition of the invention for manufacturing films.
- composition of the invention will be preferably processed under the form of a film by cast extrusion or hot blown extrusion techniques, optionally with mono- or bi-axial orientation.
- a technique particularly adapted to the manufacture of films of the composition of the invention involve extruding the composition, as above detailed, in the molten state through a die having elongated shape so as to obtain an extruded tape and casting/calendering said extruded tape so as to obtain a film.
- Tape can be calendered into a film by passing through appropriate rolls, which can be maintained at appropriate temperatures, and whose speed can be adjusted so as to achieve the required thickness.
- Films made from the composition of the invention are preferably transparent films, i.e. films having a total transmittance of more than 80 %, preferably more than 85 %, even more preferably more than 92 % when determined on films having a thickness of about 50 ⁇ m, when measured according to ASTM D 1003 standard in air.
- Total transmittance and haze can also be determined according to ASTM D1003 standard in water, e.g; by placing the film in a quartz cuvette filled with deionized water.
- total transmittance of films obtained from the inventive composition if generally of more than 85 %, more preferably of more than 90%, even more preferably of more than 94 %.
- films made from the composition of the invention are preferably such that in transmission, the scattering of light responsible for the reduction of contrast of images viewed through it is limited.
- films obtained from the composition of the invention have values of Haze of less than 15, preferably of less than 10 %, even more preferably of less than 7 %, when determined on films having a thickness of about 50 ⁇ m, when measured according to ASTM D 1003 standard in air.
- the films obtained from the inventive compositions when haze is measured in water, as above detailed for total transmittance, it is generally preferred for the films obtained from the inventive compositions to possess a haze of less than 12 %, more preferably of less than 8 %, even more preferably of less than 5 %.
- the film of the invention can be advantageously assembled in a multilayer structure.
- Multilayer structures comprising the film of the invention, as above detailed, and at least one additional layer adhered thereto, are still objects of the present invention.
- the multilayer assemblies as above detailed are particularly suitable for being used as protective films for photovoltaic modules, as films for transportation, for industrial and food packaging, for pharmaceutical storage and packaging, as architectural membranes or capstocks.
- the film obtained from the composition of the invention as above detailed, and/or of the multilayer assembly comprising the same, as above specified, as protective films for photovoltaic modules, as films for transportation, for industrial and food packaging, for pharmaceutical storage and packaging, as architectural membranes or capstocks.
- ECTFE-c is a 50/50 mole% ethylene/chlorotrifluoroethylene (E/CTFE) copolymer commercially available under trade name HALAR ® 500 having a melting point (T m2 ) of 242°C and a heat of fusion ( ⁇ H 2f ) of 42 J/g and a MFI of 18 g/10min (275°C/2.16 kg).
- ECTFE 1 is a 41/59 mole% E/CTFE copolymer having a melting point (T m2 ) of 180°C, a heat of fusion ( ⁇ H 2f ) of about 18 J/g and a MFI of 1.4 g/10min (230°C/2.16 kg).
- Tinuvin ® 1600 is a hydroxyphenyl triazine UV absorber of formula (T1), as above detailed, from BASF.
- Tinuvin ® 1577 is a hydroxyphenyl triazine UV absorber of formula (T11) from BASF.
- Tinuvin ® 360 is a benzotriazole UV absorber of formula (BT1), as above detailed, from BASF.
- compositions of the invention The polymer, under the form of powder, and the organic UV absorber particles were pre-mixed in a rapid mixer equipped with a three stages paddles mixer so as to obtain a homogeneous powder mixture having required weight ratio between mentioned ingredients. Powder mixture was then processed by extrusion in a double screw conical extruder (Brabender), equipped with 4 temperature zones and a 3 mm 2 holes die. Processing set points were set as follows, for ECTFE-c (Table 1) and ECTFE-1 (Table 2), respectively:
- Screws speed was set at 20 rpm, with a torque of 15%, so as to yield a throughput rate of about 4.6 kg/h, and a melt extrudate temperature of 274°C.
- Screws speed was set at 20 rpm, with a torque of 40%, so as to yield a throughput rate of about 4.7 kg/h, and a melt extrudate temperature of 244°C.
- Extruded strands were cooled in a water bath, dried, calibrated and cut in a pelletizer.
- the die used was a flat-die 100 mm wide having a die gap of 500 ⁇ m.
- molten tape was casted on a three subsequent chill rolls, whose speed was adapted so as to obtain a film thickness of about 50 ⁇ m.
- Conditions are summarized in Table 3.
- Haze data further corroborate the findings evidences in transmittance spectra; when the organic UV blocker is used in a standard ECTFE matrix (see Ex. 2C), a substantial loss in haze is detected, hence corresponding to a film which promote light scattering.
- a polymer (A) as above described, possessing a heat of fusion of at most 35 J/g, haze is maintained at values similar to haze of films of " neat " polymer, hence demonstrating that the UV blocker is not detrimentally affecting transparency and/or causing scattering phenomena.
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Abstract
The invention pertains to a polymer composition possessing improved resistance towards degradation and discolouring phenomena induced by UV radiation, said composition comprising at least one semi-crystalline polymer comprising recurring units derived from ethylene and at least one of chlorotrifluoroethylene (CTFE) and tetrafluoroethylene (TFE), said polymer having a heat of fusion of at most 35 J/g [polymer (A)]; and at least one organic UV absorber [absorber (UV)].
Description
This application claims priority to European application No. 14186119.5 filed on September 24th, 2014, the whole content of this application being incorporated herein by reference for all purposes.
The invention pertains to a novel fluoropolymer composition advantageously possessing improved UV resistance performances, to a method for its manufacture, to a method for its processing into shaped articles, and to shaped articles manufactured therefrom.
Exposure to UV light is known to adversely impacts the properties of polymers, including notably decrease of mechanical properties, yellowing, loss of gloss, discolouring, etc…
These effects are particularly observed when films of polymer materials are exposed to solar radiation for prolonged time, hence cumulating a significant amount of radiation energy in UV domain.
To avoid, or at least limit, the detrimental impact of UV radiation on polymeric materials, stabilisers are conventionally used.
Stabilizers can be divided in three categories, defined by their mode of action to prevent photo-degradation:
1. Quenchers, which are able to bring back “excited” chromophores (due to photon absorption) to a stable state;
2. Radical scavengers, such as HALS (hindered aromatic amine compounds), which are reactive towards free radicals formed after decomposition of “excited” chromophores (typically through generation of hydroperoxy radicals, and hence hydroperoxides and free radicals, by interaction with oxygen):
3. UV absorbers, which filter out harmful UV radiation, quickly transforming the same into vibrational and rotational energy of the molecule (hence into harmless heat), thus preventing the photodegradation of the polymer.
1. Quenchers, which are able to bring back “excited” chromophores (due to photon absorption) to a stable state;
2. Radical scavengers, such as HALS (hindered aromatic amine compounds), which are reactive towards free radicals formed after decomposition of “excited” chromophores (typically through generation of hydroperoxy radicals, and hence hydroperoxides and free radicals, by interaction with oxygen):
3. UV absorbers, which filter out harmful UV radiation, quickly transforming the same into vibrational and rotational energy of the molecule (hence into harmless heat), thus preventing the photodegradation of the polymer.
In other terms, compounds of this latter class are chromophores that can go back to their stable state after light absorption without creating harmful free radicals (deactivation of the excited state by electronic rearrangement and heat dissipation).
For a UV absorber to be effective in a polymer matrix, it is thus necessary for the UV absorber to absorb UV radiation through a chromophore group present in the molecule more quickly and more efficiently than the chromophores present in the polymer.
The most important UV absorbers are:
a) 2-(2-hydroxyphenyl)-benzotriazoles
b) 2-hydroxy-benzophenones
c) 2-hydroxyphenyl-triazines
d) oxalanilides
e) cyanoacrylates.
a) 2-(2-hydroxyphenyl)-benzotriazoles
b) 2-hydroxy-benzophenones
c) 2-hydroxyphenyl-triazines
d) oxalanilides
e) cyanoacrylates.
On the other side, copolymers of ethylene with chlorotrifluoroethylene, tetrafluoroethylene or mixtures thereof are well known in the art, in particular for the manufacture of films and protective layers.
In this field, weatherability, stain resistance and transparency are often considered as valuable properties for a protective film; this is particularly true when these protective films are intended to be used as agricultural films, as protective sheeting for photovoltaic cells, as packaging materials and the like.
In all these fields of use, it has been found particularly advantageous to introduce in the polymer matrix suitable compounds which substantially prevent penetration of ultra-violet light, without affecting penetration of visible light. This is notably valuable when films thereof are intended for use in architectural applications, e.g. as roof tensioned covers.
Nevertheless, when considering incorporation of UV absorbers into fluoropolymers, other considerations have to be taken into account, including ability of the UV absorber to withstand conditions encountered during processing of the said fluoropolymer, which can be as high as about ~250°C, as well as the ability for the UV absorbers to homogeneously disperse into the plastic matrix, so as to ensure equally homogeneous protection. Transparency and haze of the films maybe adversely affected due to the poor dispersability of organic UV absorbers in the fluorinated matrix, and UV blocking performances might be equally seriously impacted.
Furthermore, UV absorbers, due to their inherent incompatibility with the fluoropolymer matrix, tend to migrate over time to the surface of films made from fluoropolymer compositions including the same. This phenomenon, referred to in the art as "bleeding" produces a rough and discolored surface which also blocks visible light transmission, and make the film unsuitable in most fields of use.
Within this frame, US 6444311 SAINT GOBAIN PERFORMANCE PLASTICS 20020903 discloses a multilayer film for coating synthetic environmental surfaces includes an exposed protective layer and an underlying cushioning layer, wherein said protective layer is a layer of a blend comprising a fluorine substituted olefin polymer and an acrylic polymer. In a long list of fluorine-substituted polymers, mention is made of ethylene/chlorotrifluoroethylene polymers. Furthermore, this document teaches that each of the layers of the multilayer film can contain one or more UV-light absorber; inter alia, Tinuvin(R) 360 benzotriazole compound and Tinuvin(R) 1577FF hydroxyphenyltriazine compound are cited among a very long list of suitable compounds.
Despite these generic and accidental teachings of combinations of UV absorbers and fluoropolymers like ETFE and ECTFE, the choice of an appropriate UV absorber for fluoropolymers, and more particularly for ECTFE and ETFE polymers remains a critical task, as presently no suitable solution is indeed available in the art for efficient homogeneous dispersion of organic UV absorbers in ECTFE/ETFE matrices, and for avoiding “bleeding” phenomena, so as to ensure effective and long-lasting stabilization against degradation induced by UV and VIS radiation.
The invention hereby provides a solution to aforementioned shortfall and provides for a fluoropolymer sulfone polymer composition having improved UV resistance. More precisely, the present invention provides for a composition comprising:
- at least one semi-crystalline polymer comprising recurring units derived from ethylene and at least one of chlorotrifluoroethylene (CTFE) and tetrafluoroethylene (TFE), said polymer having a heat of fusion of at most 35 J/g [polymer (A)]; and
- at least one organic UV absorber [absorber (UV)] .
- at least one semi-crystalline polymer comprising recurring units derived from ethylene and at least one of chlorotrifluoroethylene (CTFE) and tetrafluoroethylene (TFE), said polymer having a heat of fusion of at most 35 J/g [polymer (A)]; and
- at least one organic UV absorber [absorber (UV)] .
The Applicant has surprisingly found that organic UV absorber, as above detailed, possessing high absorption capability (high extinction coefficients in UV-VIS region) towards UV light, although having hydrogenated and polar character which make them poorly dispersable in standard ECTFE/ETFE matrices, can be efficiently dispersed in copolymers of ethylene with TFE and/or CTFE delivering outstanding total transmittance, haze but also UV opacity, provided said copolymers have a low crystallinity, that it to say, provided that their heat of fusion is below the above recited boundary.
Figure 1 is a plot of absorbance as a function of wavelength for three different UV absorbers, namely two absorbers of hydroxyphenyl-triazine type (UV-1, solid line, and UV-2, dotted line), and a UV absorber of benzotriazole type (UV-3, dashed line) (as 10 ppm solution in methylene chloride).
Figures 2 to 7 are the graphs of UV-Visible transmittance (in %) as a function of wavelength (in nm) from 190 nm to 1100 nm, measured with a Perkin-Elmer lambda 6 spectrophotometer, for films from examples 1C (= figure 2), 2C (= figure 3), 3C (= figure 4), 4 (= figure 5) and 5 (= figure 6), and 6 (= figure 7 ).
The expression “organic UV absorber” is used within the context of the present invention according to its usual meaning, i.e. to designate an organic compound possessing absorption bands in the region ranging from 250 to 400 nm.
Absorbers (UV) which have been found particularly advantageous within the frame of the present invention are selected from the group consisting of hydroxylphenyl-triazine compounds [compounds (T)], cyanoacrylate compounds [compounds (CN)], benzoxazin-4-one compounds [compounds (BX)], and benzotriazole compounds [compounds (BT)].
According to certain embodiments, absorber (UV) is at least one hydroxylphenyl-triazine compound [compound (T)] of formula (I): 
wherein:
- Ara and Arb, equal to or different from each other, are independently aromatic groups, said aromatic groups possibly comprising one or more than one heteroatom;
- Rj is a halogen or a hydrocarbon group possibly comprising one or more than one heteroatom;
- j is zero or is an integer of 1 to 4, in particular 1 to 2.
- Ara and Arb, equal to or different from each other, are independently aromatic groups, said aromatic groups possibly comprising one or more than one heteroatom;
- Rj is a halogen or a hydrocarbon group possibly comprising one or more than one heteroatom;
- j is zero or is an integer of 1 to 4, in particular 1 to 2.
Compound (T) is preferably a compound complying with formula (II):
wherein:
E1 and E2 , equal to or different from each other, is independently a substituted or unsubstituted naphthyl; or a substituted ot unsubstituted aromatic carbocyclic fused ring comprising at least 3 rings, or is a substituted or unsubstituted aromatic hetero ring system comprising one or more rings; or corresponds to the formula (III):
R1 is H, C1-C24 alkyl, C2-C18 alkenyl, C5-C12 cycloalkyl, C7-C15 phenylalkyl, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by C1-C8 alkyl; or OR3;
R2 is H, C1-C18 alkyl; C2-C6 alkenyl; phenyl; phenyl substituted by C1-C8 alkyl or by C1-C8 alkoxy; C7-C11 phenylalkyl; C5-C12 cycloalkyl; COOR4; CN; NH2, NHR7, -N(R7)(R8), NH-CO-R5; halogen; C1-C18haloalkyl; C1-C18alkoxy; -S-R3 or -O-R3;
R3 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COOR4, -O-CO-R5, -O-CO-O-R6, -CO-NH2, -CO-NHR7, -CO-N(R7)(R8), CN, NH2, NHR7, -N(R7)(R8), -NH-CO-R5, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-R5; -CO-R9 or -SO2-R10; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy; or -A, -CH2-CH(XA)-CH2-O-R12; -CR13R13'-(CH2)m-X-A; -CH2-CH(OA)-R14; -CH2-CH(OH)-CH2-XA; a group of formula (IV) or (V):
-CR15R15'-C(-CH2)-R15”; -CR13R13'-(CH2)m-CO-X-A; -CR13R13'-(CH2)m-CO-O-CR15R15'-C(-CH2)-R15” or -CO-O-CR15R15'-C(-CH2)-R15”;
A is -CO-CR16-CH-R17;
R4 is independently C1-C18 alkyl; C3-C18 alkenyl; C7-C11 phenylalkyl; C5-C12 cycloalkyl; or C3-C50 alkyl that is interrupted by one or more of -O-, -NH-, -NR7- and -S- and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy; or C2-C12 hydroxyalkyl;
R5 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COOR4; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COOR4; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;
R6 is independently C1-C18 alkyl; C3-C18 alkenyl; phenyl; C7-C11 phenylalkyl; or C5-C12 cycloalkyl;
R7 and R8 are independently C1-C12 alkyl; C3-C12 alkoxyalkyl; C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;
R9 is independently C1-C18 alkyl; C2-C18 alkenyl; phenyl; C5-C12 cycloalkyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl, C6-C15 bicycloalkyl-alkyl, C6-C15 bicycloalkenyl, or C6-C15 tricycloalkyl;
R10 is independently C1-C12 alkyl; phenyl; naphthyl or C7-C14 alkylphenyl;
R11 and R22 are independently H; C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy;
R12 is independently C1-C18 alkyl; C3-C18 alkenyl; phenyl; phenyl substituted by one to three of the radicals C1-C8 alkyl, C1-C8 alkoxy, C3-C8 alkenyloxy, halogen and trifluoromethyl; C7-C11-phenylalkyl; C5-C12 cycloalkyl; C6-C15 tricycloalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkyl-alkyl; C6-C15 bicycloalkenyl-alkyl; -CO-R5; or C3-C50 alkyl that is interrupted by one or more of -O-, -NH-, -NR7- and -S- and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy;
R13 and R13' are independently H; C1-C18 alkyl; or phenyl;
R14 is independently C1-C18 alkyl; C3-C12 alkoxyalkyl; phenyl; or phenyl-C1-C4 alkyl;
R15, R15' and R15” are independently H or CH3;
R16 is independently H; -CH2-COO-R4; C1-C4 alkyl; or CN;
R17 is independently H; -COOR4; C1-C17alkyl; or phenyl;
R22' has one of the meanings of R11; or is NH2, NHR7, NH-CO-R5; -S-R3, -N(R7)(R8) or OR3;
X is independently -NH-; -NR7-; -O-; -NH-(CH2)p-NH-; or -O-(CH2)q-NH-; and the indices are as follows: m is a number from 0 to 19; n is a number from 1 to 8; p is a number from 0 to 4; and q is a number from 2 to 4.
E1 and E2 , equal to or different from each other, is independently a substituted or unsubstituted naphthyl; or a substituted ot unsubstituted aromatic carbocyclic fused ring comprising at least 3 rings, or is a substituted or unsubstituted aromatic hetero ring system comprising one or more rings; or corresponds to the formula (III):
R1 is H, C1-C24 alkyl, C2-C18 alkenyl, C5-C12 cycloalkyl, C7-C15 phenylalkyl, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by C1-C8 alkyl; or OR3;
R2 is H, C1-C18 alkyl; C2-C6 alkenyl; phenyl; phenyl substituted by C1-C8 alkyl or by C1-C8 alkoxy; C7-C11 phenylalkyl; C5-C12 cycloalkyl; COOR4; CN; NH2, NHR7, -N(R7)(R8), NH-CO-R5; halogen; C1-C18haloalkyl; C1-C18alkoxy; -S-R3 or -O-R3;
R3 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COOR4, -O-CO-R5, -O-CO-O-R6, -CO-NH2, -CO-NHR7, -CO-N(R7)(R8), CN, NH2, NHR7, -N(R7)(R8), -NH-CO-R5, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-R5; -CO-R9 or -SO2-R10; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy; or -A, -CH2-CH(XA)-CH2-O-R12; -CR13R13'-(CH2)m-X-A; -CH2-CH(OA)-R14; -CH2-CH(OH)-CH2-XA; a group of formula (IV) or (V):
A is -CO-CR16-CH-R17;
R4 is independently C1-C18 alkyl; C3-C18 alkenyl; C7-C11 phenylalkyl; C5-C12 cycloalkyl; or C3-C50 alkyl that is interrupted by one or more of -O-, -NH-, -NR7- and -S- and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy; or C2-C12 hydroxyalkyl;
R5 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COOR4; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COOR4; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;
R6 is independently C1-C18 alkyl; C3-C18 alkenyl; phenyl; C7-C11 phenylalkyl; or C5-C12 cycloalkyl;
R7 and R8 are independently C1-C12 alkyl; C3-C12 alkoxyalkyl; C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;
R9 is independently C1-C18 alkyl; C2-C18 alkenyl; phenyl; C5-C12 cycloalkyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl, C6-C15 bicycloalkyl-alkyl, C6-C15 bicycloalkenyl, or C6-C15 tricycloalkyl;
R10 is independently C1-C12 alkyl; phenyl; naphthyl or C7-C14 alkylphenyl;
R11 and R22 are independently H; C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy;
R12 is independently C1-C18 alkyl; C3-C18 alkenyl; phenyl; phenyl substituted by one to three of the radicals C1-C8 alkyl, C1-C8 alkoxy, C3-C8 alkenyloxy, halogen and trifluoromethyl; C7-C11-phenylalkyl; C5-C12 cycloalkyl; C6-C15 tricycloalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkyl-alkyl; C6-C15 bicycloalkenyl-alkyl; -CO-R5; or C3-C50 alkyl that is interrupted by one or more of -O-, -NH-, -NR7- and -S- and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy;
R13 and R13' are independently H; C1-C18 alkyl; or phenyl;
R14 is independently C1-C18 alkyl; C3-C12 alkoxyalkyl; phenyl; or phenyl-C1-C4 alkyl;
R15, R15' and R15” are independently H or CH3;
R16 is independently H; -CH2-COO-R4; C1-C4 alkyl; or CN;
R17 is independently H; -COOR4; C1-C17alkyl; or phenyl;
R22' has one of the meanings of R11; or is NH2, NHR7, NH-CO-R5; -S-R3, -N(R7)(R8) or OR3;
X is independently -NH-; -NR7-; -O-; -NH-(CH2)p-NH-; or -O-(CH2)q-NH-; and the indices are as follows: m is a number from 0 to 19; n is a number from 1 to 8; p is a number from 0 to 4; and q is a number from 2 to 4.
Preferably R11 and R22 are H.
Of interest is R22' that is -OR3, especially -OH.
Examples of aromatic carbocyclic fused ring systems comprising at least 3 rings are radicals of anthracene, phenanthrene, fluoranthene, pyrene, chrysene, benzanthracene, dibenzanthracene, benzofluoranthene, benzopyrene, indenopyrene and benzoperylene, preferably phenanthrene, fluoranthene and pyrene, most preferably fluoranthene and pyrene.
For instance, an aromatic carbocyclic fused ring system comprising at least 3 rings means that this ring system comprises at least 3 aromatic rings, in particular at least three aromatic fused rings.
Examples of aromatic hetero ring systems comprising one or more rings are thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, beta -carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl and phenoxazinyl.
Within the scope of the definitions given, alkyl are branched or unbranched alkyl, e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
For example C5-C12cycloalkyl includes notably cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclodocecyl. Cyclopentyl, cyclohexyl, cyclooctyl and cyclododecyl are preferred.
Alkenyl includes, within the scope of the definitions given, inter alia allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl and n-octadec-4-enyl.
Substituted alkyl, cycloalkyl or phenyl radicals may be mono- or poly-substituted and may carry substituents at the binding carbon atom (in the a-position) or at other carbon atoms; if a substituent is bonded by a hetero atom (such as e.g. alkoxy), it is preferably not in the a-position and the substituted alkyl radical comprises 2, especially 3, or more carbon atoms. A plurality of substituents is preferably bonded to different carbon atoms.
Alkyl interrupted by -O-, -NH-, -NR7- and/or by -S- may be interrupted by one or more of the mentioned groups, in each case normally one group being inserted into a bond and hetero-hetero bonds, such as, for example, O-O, S-S, NH-NH etc. not occurring; if the interrupted alkyl is, in addition, substituted, the substituents are not normally in the a-position with respect to the hetero atom. If a plurality of interrupting groups of the type -O-, -NH-, -NR7- and -S- occurs in a radical, those groups are usually identical.
Hydroxyalkyl means an alkyl group substituted by at least one hydroxyl group.
For instance alkoxy, phenoxy, alkenyloxy and cycloalkoxy mean the group -OZ, wherein Z is alkyl, phenyl, alkenyl and cycloalkyl respectively.
Phenylalkyl comprises within the limits of carbon atoms given, for example, benzyl, a-methylbenzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl; whereby benzyl, a-methylbenzyl and a,a-dimethylbenzyl are preferred.
Alkylphenyl and alkylphenoxy are alkyl-substituted phenyl and phenoxy, respectively.
A halogen substituent is -F, -Cl, -Br or -I; -F or -Cl, and especially -Cl, is preferred. Haloalkyl is especially chloroalkyl or trifluoromethyl; trifluoromethyl is of particular importance industrially.
Alkylene is e.g. methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. The alkyl chain may also be branched in that case, such as e.g. in isopropylene.
C4-C12 Cycloalkenyl is e.g. 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2,4-cyclopentadien-1-yl, 2-cyclohexen-1-yl, 2-cyclohepten-1-yl or 2-cyclooctene-1-yl.
C6-C15 Bicycloalkyl is e.g. bornyl, norbornyl or 2.2.2-bicyclooctyl. Bornyl and norbornyl, and especially bornyl and norborn-2-yl, are preferred.
C6-C15 Bicycloalkoxy is, for example, bornyloxy or norborn-2-yl-oxy.
C6-C15 Bicycloalkyl-alkyl or -alkoxy is alkyl or alkoxy substituted by bicycloalkyl, the total number of carbon atoms being 6-15; examples are norbornane-2-methyl and norbornane-2-methoxy.
C6-C15 Bicycloalkenyl is e.g. norbornenyl or norbornadienyl. Norbornenyl, and especially norborn-5-enyl, is preferred.
C6-C15 Bicycloalkenyl-alkoxy is alkoxy substituted by bicycloalkenyl, the total number of carbon atoms being 6-15; an example is norborn-5-enyl-2-methoxy.
C6-C15-Tricycloalkyl is e.g. 1-adamantyl or 2-adamantyl; 1-adamantyl is preferred.
C6-C15-Tricycloalkoxy is e.g. adamantyloxy.
C3-C12 Heteroaryl is preferably pyridinyl, pyrimidinyl, triazinyl, pyrrolyl, furanyl, thiophenyl or quinolinyl.
Among compounds (T) which can be used in the context of the present invention, mention can be notably made of compounds complying with any of formulae below: 
with m being an integer of 1 to 20, preferably a mixture of 11 and 12; 
A single compound (T) can be used or mixtures of more than one compound (T) can be equally employed.
Preferred compounds (T) are compounds complying with any of formulae (T1), (T2) and (T11), as above detailed. These compounds are notably available commercially under trade name TINUVIN® 1600, TINUVIN® 460 and TINUVIN® 1577 UV stabilizer. More particularly, compounds (T1) and (T11) have been proven to behave in an optimum manner when resulting composition has been used for the manufacture of thin films.
According to certain embodiments, absorber (UV) is at least one cyanoacrylate compound [compound (CN)] of formula (VI): 
wherein:
- Ara and Arb, equal to or different from each other, are independently aromatic groups, said aromatic groups possibly comprising one or more than one heteroatom;
- Rcn is a hydrocarbon group possibly comprising one or more than one heteroatom.
- Ara and Arb, equal to or different from each other, are independently aromatic groups, said aromatic groups possibly comprising one or more than one heteroatom;
- Rcn is a hydrocarbon group possibly comprising one or more than one heteroatom.
Preferably, compound (CN) complies with formula (VII): 
wherein:
- Rcn1 is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:
wherein n is an integer of 1 to 4, and E is a hydrocarbon group, preferably an aliphatic group;
- j is zero or an integer of 0 to 4;
- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:
- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;
C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;
- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;
- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy.
- Rcn1 is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:
- j is zero or an integer of 0 to 4;
- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:
- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;
C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;
- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;
- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy.
Among compounds (CN) which can be used in the context of the present invention, mention can be notably made of compounds complying with any of formulae below: 
and 
Compound (CN3) has been found particularly advantageous.
According to certain embodiments, absorber (UV) is at least one benzoxazin-4-one compound [compounds (BX)] of formula (VIII): 
wherein:
- RBX is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:
wherein E’ is a hydrocarbon group, preferably an aromatic group, more preferably a phenyl group;
- j is zero or an integer of 0 to 4;
- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:
- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;
C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;
- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;
- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy.
- RBX is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:
- j is zero or an integer of 0 to 4;
- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:
- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;
C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;
- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;
- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy.
Among compounds (BX) which can be used in the context of the present invention, mention can be notably made of compounds complying with any of formulae below: 
Compound (BX1) has been found particularly advantageous.
According to certain embodiments, absorber (UV) is at least one benzotriazole compound [compounds (BT)] of formula (IX):
wherein:
- RBT is independently H; C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:
wherein E” is a hydrocarbon group, preferably an aromatic group, more preferably a group of formula:
;
- j is zero or an integer of 0 to 4; j’ is zero or an integer of 0 to 3;
- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:
- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;
C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;
- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;
- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy.
- RBT is independently H; C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:
wherein E” is a hydrocarbon group, preferably an aromatic group, more preferably a group of formula:
- j is zero or an integer of 0 to 4; j’ is zero or an integer of 0 to 3;
- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:
- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;
C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;
- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;
- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy.
Among compounds (BT) which can be used in the context of the present invention, mention can be notably made of compounds complying with any of formulae below: 
Of above mentioned compounds (BT), compound of formula (BT1) has been found particularly advantageous. Compound (BT1) is notably commercially available under tradename TINUVIN® 360 benzotriazole UV absorber from BASF.
The amount of absorber (UV) used in the inventive composition is not particularly limited, provided that the same is used in an effective amount for delivering the expected UV resistance; one of ordinary skills in the art will be able to determine by routine experiments optimized amounts. Generally, nevertheless, the amount of absorber (UV) will be of at least 0.001, preferably at least 0.01, more preferably at least 0.1 weight parts per 100 weight parts of polymer (A).
It is also further understood that the amount of absorber (UV) will be generally of at most 10, preferably at least 8, more preferably at least 5 weight parts per 100 weight parts of polymer (A).
The heat of fusion of polymer (A) is determined by Differential Scanning Calorimetry (DSC) at a heating rate of 10°C/min, according to ASTM D 3418.
Polymer (A) possesses a heat of fusion of at most 35 J/g, preferably of at most 30 J/g, more preferably of at most 25 J/g.
Nevertheless, it is essential for polymer (A) of being a semi-crystalline polymer, i.e. a polymer having a detectable melting point when determined according to ASTM D 3418. Without lower limit for heat of fusion being critical, it is nevertheless understood that polymer (A) will generally possess a heat of fusion of at least 1 J/g, preferably of at least 2 J/g, more preferably of at least 5 J/g.
It is well known in the art that 50/50 mol/mol ECTFE or ETFE copolymers show a maximum of crystallinity, i.e. of both melting point and heat of fusion.
The requirement for a heat of fusion of at most 35 J/g can thus be achieved either by increasing or by decreasing in adequate/sufficient manner the amount of ethylene with respect to this 50/50 molar ratio.
It is nevertheless understood that polymers (A) which are preferred for the purpose of the invention are indeed those comprising an amount of recurring units derived from ethylene of less than 50 % moles, preferably of less than 48 % moles, more preferably of less than 45 % moles, with respect to the total number of moles of recurring units, as they enable achieving improved properties due to the fluoromonomer components.
Polymer (A) of the composition of the invention typically comprises:
(a) from 30 to 48%, preferably from 35 to 45 % by moles of recurring units derived from ethylene (E);
(b) from 52 to 70%, preferably from 55 to 65% by moles of recurring units derived from chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) or mixture thereof; and
(c) from 0 to 5%, preferably from 0 to 2.5 % by moles, based on the total amount of monomers (a) and (b), of recurring units derived from one or more fluorinated and/or hydrogenated comonomer(s),
with respect to the total number of moles of recurring units.
(a) from 30 to 48%, preferably from 35 to 45 % by moles of recurring units derived from ethylene (E);
(b) from 52 to 70%, preferably from 55 to 65% by moles of recurring units derived from chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) or mixture thereof; and
(c) from 0 to 5%, preferably from 0 to 2.5 % by moles, based on the total amount of monomers (a) and (b), of recurring units derived from one or more fluorinated and/or hydrogenated comonomer(s),
with respect to the total number of moles of recurring units.
Preferably the said comonomer (c) is a hydrogenated comonomer selected from the group of the (meth)acrylic monomers. More preferably the hydrogenated comonomer is selected from the group of the hydroxyalkylacrylate comonomers, such as hydroxyethylacrylate, hydroxypropylacrylate and (hydroxy)ethylhexylacrylate, and alkyl acrylate comomnomers, such as n–butyl acrylate.
Among polymers (A), ECTFE copolymers, i.e. copolymers of ethylene and CTFE and optionally a third monomer (comonomer (c)), as above detailed, are preferred.
ECTFE polymers suitable in the composition of the invention typically possess a melting temperature not exceeding 210°C, preferably not exceeding 200°C, even not exceeding 198°C, preferably not exceeding 195°C, more preferably not exceeding 193°C, even more preferably not exceeding 190°C. The ECTFE polymer has a melting temperature of advantageously at least 120°C, preferably of at least 130°C, still preferably of at least 140°C, more preferably of at least 145°C, even more preferably of at least 150°C.
The melting temperature is determined by Differential Scanning Calorimetry (DSC) at a heating rate of 10°C/min, according to ASTM D 3418.
ECTFE polymers which have been found to give particularly good results are those consisting essentially of :
(a) from 35 to 47% by moles, with respect to the total number of moles of recurring units, of recurring units derived from ethylene (E);
(b) from 53 to 65% by moles, with respect to the total number of moles of recurring units, of recurring units derived from chlorotrifluoroethylene (CTFE).
(a) from 35 to 47% by moles, with respect to the total number of moles of recurring units, of recurring units derived from ethylene (E);
(b) from 53 to 65% by moles, with respect to the total number of moles of recurring units, of recurring units derived from chlorotrifluoroethylene (CTFE).
End chains, defects or minor amounts of monomer impurities leading to recurring units different from those above mentioned can be still comprised in the preferred ECTFE, without this affecting properties of the material.
The melt flow rate of the ECTFE polymer, measured following the procedure of ASTM 3275-81 at 230°C and 2.16 Kg, ranges generally from 0.01 to 75 g/10 min, preferably from 0.1 to 50 g/10 min, more preferably from 0.5 to 30 g/10 min.
Another aspect of the present invention is a method for manufacturing the composition, as above detailed.
The method of the invention advantageously comprises mixing at least the said polymer (A) and the organic UV absorber [absorber (UV)]. Other optional ingredients may be equally mixed in the method of the invention for finally providing for the composition as above detailed.
The polymer (A) is generally provided in the method of the invention under the form of a powder or under the form of pellets. The expression “powder” has to be understood as possessing the usual meaning, i.e. under the form of loose discrete particles of material.
The method generally comprises mixing the said ingredients by blending in the molten state (melt blending); conventional melt compounding devices, such as co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc-pack processors and various other types of extrusion equipment can be used. Preferably, extruders, more preferably twin screw extruders can be used.
If desired, the design of the compounding screw, e.g. flight pitch and width, clearance, length as well as operating conditions will be advantageously chosen so that sufficient heat and mechanical energy is provided to advantageously fully melt the polymer (A) and advantageously obtain a homogeneous distribution of the different ingredients. It is hence advantageously possible to obtain strand extrudates of the composition of the invention. Such strand extrudates can be chopped by means e.g. of a rotating cutting knife after some cooling time on a conveyer with water spray, so as to provide the composition under the form of pellets or beads, which can be further can processed for the manufacture of shaped articles.
The method may additionally comprise, prior to the melt blending, a preliminary step of dry blending a powder of polymer (A) in the solid state with the absorber (UV). Typically, the dry blending, as detailed above is carried out by using high intensity mixers, such as notably Henschel-type mixers and ribbon mixers.
Thus, the polymer composition (C) is notably very well suited for the manufacture of articles useful in a wide variety of end uses.
The composition of the invention is particularly suitable for being used for manufacturing films, sheets, coatings or other finished articles.
Still another object of the invention is the use of the polymer composition of the invention for manufacturing films.
Techniques for manufacturing films are well known in the art. The composition of the invention will be preferably processed under the form of a film by cast extrusion or hot blown extrusion techniques, optionally with mono- or bi-axial orientation.
A technique particularly adapted to the manufacture of films of the composition of the invention involve extruding the composition, as above detailed, in the molten state through a die having elongated shape so as to obtain an extruded tape and casting/calendering said extruded tape so as to obtain a film.
Tape can be calendered into a film by passing through appropriate rolls, which can be maintained at appropriate temperatures, and whose speed can be adjusted so as to achieve the required thickness.
Films made from the composition of the invention are preferably transparent films, i.e. films having a total transmittance of more than 80 %, preferably more than 85 %, even more preferably more than 92 % when determined on films having a thickness of about 50 µm, when measured according to ASTM D 1003 standard in air.
Total transmittance and haze can also be determined according to ASTM D1003 standard in water, e.g; by placing the film in a quartz cuvette filled with deionized water.
When measured in water, as above detailed, total transmittance of films obtained from the inventive composition if generally of more than 85 %, more preferably of more than 90%, even more preferably of more than 94 %.
Further, in addition, films made from the composition of the invention are preferably such that in transmission, the scattering of light responsible for the reduction of contrast of images viewed through it is limited. In other words, films obtained from the composition of the invention have values of Haze of less than 15, preferably of less than 10 %, even more preferably of less than 7 %, when determined on films having a thickness of about 50 µm, when measured according to ASTM D 1003 standard in air.
Similarly, when haze is measured in water, as above detailed for total transmittance, it is generally preferred for the films obtained from the inventive compositions to possess a haze of less than 12 %, more preferably of less than 8 %, even more preferably of less than 5 %.
Films so obtained are another object of the present invention.
The film of the invention can be advantageously assembled in a multilayer structure. Multilayer structures comprising the film of the invention, as above detailed, and at least one additional layer adhered thereto, are still objects of the present invention.
Similarly to the films of the invention, the multilayer assemblies as above detailed are particularly suitable for being used as protective films for photovoltaic modules, as films for transportation, for industrial and food packaging, for pharmaceutical storage and packaging, as architectural membranes or capstocks.
Still within the frame of the present invention is thus the use of the film obtained from the composition of the invention as above detailed, and/or of the multilayer assembly comprising the same, as above specified, as protective films for photovoltaic modules, as films for transportation, for industrial and food packaging, for pharmaceutical storage and packaging, as architectural membranes or capstocks.
Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
The invention will be now described in more detail with reference to the following examples, whose purpose is merely illustrative.
Raw materials
Polymers
ECTFE-c is a 50/50 mole% ethylene/chlorotrifluoroethylene (E/CTFE) copolymer commercially available under trade name HALAR® 500 having a melting point (Tm2 ) of 242°C and a heat of fusion (ΔH2f ) of 42 J/g and a MFI of 18 g/10min (275°C/2.16 kg).
ECTFE 1: is a 41/59 mole% E/CTFE copolymer having a melting point (Tm2 ) of 180°C, a heat of fusion (ΔH2f ) of about 18 J/g and a MFI of 1.4 g/10min (230°C/2.16 kg).
ECTFE-c is a 50/50 mole% ethylene/chlorotrifluoroethylene (E/CTFE) copolymer commercially available under trade name HALAR® 500 having a melting point (Tm2 ) of 242°C and a heat of fusion (ΔH2f ) of 42 J/g and a MFI of 18 g/10min (275°C/2.16 kg).
ECTFE 1: is a 41/59 mole% E/CTFE copolymer having a melting point (Tm2 ) of 180°C, a heat of fusion (ΔH2f ) of about 18 J/g and a MFI of 1.4 g/10min (230°C/2.16 kg).
UV-1: Tinuvin ® 1600 is a hydroxyphenyl triazine UV absorber of formula (T1), as above detailed, from BASF.
UV-2: Tinuvin ® 1577 is a hydroxyphenyl triazine UV absorber of formula (T11) from BASF.
UV-3: Tinuvin ® 360 is a benzotriazole UV absorber of formula (BT1), as above detailed, from BASF.
General manufacturing procedure of the compositions of the invention
The polymer, under the form of powder, and the organic UV absorber particles were pre-mixed in a rapid mixer equipped with a three stages paddles mixer so as to obtain a homogeneous powder mixture having required weight ratio between mentioned ingredients.
Powder mixture was then processed by extrusion in a double screw conical extruder (Brabender), equipped with 4 temperature zones and a 3 mm2 holes die. Processing set points were set as follows, for ECTFE-c (Table 1) and ECTFE-1 (Table 2), respectively:
The polymer, under the form of powder, and the organic UV absorber particles were pre-mixed in a rapid mixer equipped with a three stages paddles mixer so as to obtain a homogeneous powder mixture having required weight ratio between mentioned ingredients.
Powder mixture was then processed by extrusion in a double screw conical extruder (Brabender), equipped with 4 temperature zones and a 3 mm2 holes die. Processing set points were set as follows, for ECTFE-c (Table 1) and ECTFE-1 (Table 2), respectively:
| T1 (head) | T2 | T3 | T4 |
| 230°C | 240°C | 260°C | 270°C |
Screws speed was set at 20 rpm, with a torque of 15%, so as to yield a throughput rate of about 4.6 kg/h, and a melt extrudate temperature of 274°C.
| T1(head) | T2 | T3 | T4 |
| 210°C | 220°C | 230°C | 240°C |
Screws speed was set at 20 rpm, with a torque of 40%, so as to yield a throughput rate of about 4.7 kg/h, and a melt extrudate temperature of 244°C.
Extruded strands were cooled in a water bath, dried, calibrated and cut in a pelletizer.
General procedure for the manufacture of films
For manufacturing thin films, pellets were processed in a 19mm single screw extruder equipped with conventional three zones screw (L/D= 25) without mixing elements. The die used was a flat-die 100 mm wide having a die gap of 500 µm. Upon exit from the die, molten tape was casted on a three subsequent chill rolls, whose speed was adapted so as to obtain a film thickness of about 50 µm. Conditions are summarized in Table 3.
| Material | ECTFE-1 | ECTFE-c | |
| T1 | ° |
200 | 235 |
| T2 | °C | 210 | 250 |
| T3 | °C | 220 | 260 |
| T4 (head) | °C | 230 | 270 |
| T MELT (@ clamp) | °C | 235 | 276 |
| Head pressure | bar | 150 | 31 |
| Screw speed | rpm | 15 | 15 |
In Table 4, details of weight ratios between ingredients of the compositions are provided.
| Run | ECTFE polymer | UV blocker | |||
| type | | %wt | |||
| 1C | ECTFE- | none | |||
| 2C | ECTFE-c | UV-1 | 1% | ||
| 3C | ECTFE-1 | |
|||
| 4 | ECTFE-1 | UV-1 | 1% | ||
| 5 | ECTFE-1 | UV-2 | 1% | ||
| 6 | ECTFE-1 | UV-3 | 4% | ||
Characterization of films
Films obtained as above detailed were submitted to optical testing.
Total luminous transmittance and Haze were measured according to ASTM D1003, Procedure A, using a Gardner Haze-Gard Plus instrument. For evaluating spurious contributions possibly related to surface roughness or defects, specimens were analysed both in air and in water, i.e. by immersing film samples in a quartz cell filled with water. Graph of UV-Visible transmittance (in %) as a function of wavelength (in nm) from 190 nm to 1100 nm, measured with a Perkin-Elmer lambda 6 spectrophotometer, are reported in figures 2 to 7, for films from examples 1C (= figure 2), 2C (= figure 3), 3C (= figure 4), 4 (= figure 5) and 5 (= figure 6), and 6 (= figure 7 ). Those spectra show substantial opacity against UV rays for ex. 2C, 4, 5 and 6 (i.e. by addition of different types of organic UV absorbers) both in a “normal” ECTFE matrix (Ex. 2C) and in a matric of low crystallinity (Ex. 4 to 6). Nevertheless, substantial transparency in the visible region is only achieved in films made from compositions of example 4, 5 and 6 (transmittance percentages approaching or exceeding 90 % for wavelengths of 400 nm or more), while in film of Ex. 2C, transmittance percentages of about 30 to 70 % is observed in spectral region of 400 to 700 nm. Haze properties obtained for films having thicknesses from 40 to 50 µm are summarized in table 5, as averaged values of three specimens.
Total luminous transmittance and Haze were measured according to ASTM D1003, Procedure A, using a Gardner Haze-Gard Plus instrument. For evaluating spurious contributions possibly related to surface roughness or defects, specimens were analysed both in air and in water, i.e. by immersing film samples in a quartz cell filled with water. Graph of UV-Visible transmittance (in %) as a function of wavelength (in nm) from 190 nm to 1100 nm, measured with a Perkin-
| Run | Film thickness (µm) |
Haze in air |
Haze in | |
| 1C | ||||
| 40 | 7.2 | 3.4 | ||
| |
50 | 22.4 | 11.6 | |
| |
50 | 1.8 | 0.35 | |
| 4 | 50 | 0.6 | 0.6 | |
| 5 | 50 | 1.1 | 0.4 | |
| 6 | 50 | 1.1 | 3.0 | |
Haze data further corroborate the findings evidences in transmittance spectra; when the organic UV blocker is used in a standard ECTFE matrix (see Ex. 2C), a substantial loss in haze is detected, hence corresponding to a film which promote light scattering. On the other side, when the organic UV blocker is mixed with a polymer (A), as above described, possessing a heat of fusion of at most 35 J/g, haze is maintained at values similar to haze of films of "neat" polymer, hence demonstrating that the UV blocker is not detrimentally affecting transparency and/or causing scattering phenomena.
Claims (15)
- A composition comprising:- at least one semi-crystalline polymer comprising recurring units derived from ethylene and at least one of chlorotrifluoroethylene (CTFE) and tetrafluoroethylene (TFE), said polymer having a heat of fusion of at most 35 J/g [polymer (A)]; and- at least one organic UV absorber [absorber (UV)].
- The composition of claim 1, wherein the said organic UV absorber is at least one hydroxylphenyl-triazine compound [compound (T)] of formula (I): wherein:
- Ara and Arb, equal to or different from each other, are independently aromatic groups, said aromatic groups possibly comprising one or more than one heteroatom;- Rj is a halogen or a hydrocarbon group possibly comprising one or more than one heteroatom;- j is zero or is an integer of 1 to 4, in particular 1 to 2. - The composition of Claim 2, wherein the compound (T) is selected from the group consisting of compounds complying with any of formulae below:
with m being an integer of 1 to 20, preferably a mixture of 11 and 12;
- The composition of claim 1, wherein said absorber (UV) is at least one cyanoacrylate compound [compound (CN)] of formula (VI):wherein:
- Ara and Arb, equal to or different from each other, are independently aromatic groups, said aromatic groups possibly comprising one or more than one heteroatom;- Rcn is a hydrocarbon group possibly comprising one or more than one heteroatom, and preferably compound (CN) complies with formula (VII):wherein:
- Rcn1 is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:wherein n is an integer of 1 to 4, and E is a hydrocarbon group, preferably an aliphatic group;
- j is zero or an integer of 0 to 4;- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy. - The composition of claim 1, wherein said absorber (UV) is at least one benzoxazin-4-one compounds [compounds (BX)] of formula (VIII):wherein:
- RBX is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:wherein E’ is a hydrocarbon group, preferably an aromatic group, more preferably a phenyl group;
- j is zero or an integer of 0 to 4;- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy. - The composition of claim 1, wherein said absorber (UV) is at least one benzotriazole compound [compounds (BT)] of formula (IX):wherein:
- RBT is independently H; C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; or is a group of formula:
wherein E” is a hydrocarbon group, preferably an aromatic group, more preferably a group of formula:;
- j is zero or an integer of 0 to 4; j’ is zero or an integer of 0 to 3;- each of Rj, equal to or different from each other, is independently C1-C18 alkyl; C3-C6 alkenyl; C5-C12 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-C11 phenylalkyl; C7-C14 alkylphenyl; halogen; C1-C18 haloalkyl; or C1-C18 alkoxy; or is NH2, NHRcn2, -N(Rcn2)(Rcn3), NH-CO-Rcn4; -S-Rcn5, or -ORcn5; wherein:- Rcn2 and Rcn3, equal to or different from each other, are independently C1-C12 alkyl; C3-C12 alkoxyalkyl;C4-C16dialkylaminoalkyl; or C5-C12cycloalkyl; or, when simultaneously present, may together form C3-C9-alkylene, -oxaalkylene or -azaalkylene;- Rcn4 is independently H; C1-C18 alkyl; C1-C18 alkyl substituted by COOH or by COORcn2; C2-C18 alkenyl; C2-C18 alkenyl substituted by COOH or by COORcn2; C5-C12 cycloalkyl; phenyl; C7-C11 phenylalkyl; C6-C15 bicycloalkyl; C6-C15 bicycloalkenyl; or C6-C15 tricycloalkyl;- Rcn5 is independently H, C1-C18 alkyl; C5-C12 cycloalkyl; C3-C18 alkenyl; phenyl; C1-C18 alkyl that is substituted by phenyl, OH, C1-C18 alkoxy, C5-C12cycloalkoxy, C3-C18alkenyloxy, halogen, -COOH, -COORcn2, -O-CO-Rcn2, -O-CO-O-Rcn2, -CO-NH2, -CO-NHRcn2, -CO-N(Rcn2)(Rcn3), CN, NH2, NHRcn2, -N(Rcn2)(Rcn3), -NH-CO-Rcn2, phenoxy, C1-C18 alkyl-substituted phenoxy, phenyl-C1-C4-alkoxy, C6-C15 bicycloalkoxy, C6-C15 bicycloalkyl-alkoxy, C6-C15 bicycloalkenyl-alkoxy and/or by C6-C15-tricycloalkoxy; C5-C12 cycloalkyl that is substituted by OH, C1-C4 alkyl, C2-C6 alkenyl and/or by -O-CO-Rcn2; -CO-Rcn2 or -SO2-Rcn2; or C3-C50 alkyl that is interrupted by one or more oxygen atoms and is unsubstituted or substituted by OH, phenoxy and/or by C7-C18 alkylphenoxy. - The composition according to anyone of the preceding claims, wherein the amount of absorber (UV) is of at least 0.001, preferably at least 0.01, more preferably at least 0.1 weight parts per 100 weight parts of polymer (A), and/or wherein the amount of absorber (UV) is of at most 10, preferably at least 8, more preferably at least 5 weight parts per 100 weight parts of polymer (A).
- The composition according to anyone of the preceding claims, wherein polymer (A) comprises:(a) from 30 to 48%, preferably from 35 to 45 % by moles of recurring units derived from ethylene (E);(b) from 52 to 70%, preferably from 55 to 65% by moles of recurring units derived from chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) or mixture thereof; and(c) from 0 to 5%, preferably from 0 to 2.5 % by moles, based on the total amount of monomers (a) and (b), of recurring units derived from one or more fluorinated and/or hydrogenated comonomer(s), different from E, CTFE and TFE,with respect to the total number of moles of recurring units.
- The composition of claim 8, wherein polymer (A) is selected from the group consisting of ECTFE copolymers, said ECTFE copolymers being copolymers of ethylene and CTFE and optionally said third monomer.
- The composition of claim 9, wherein said ECTFE copolymers possess a melting temperature not exceeding 210°C, preferably not exceeding 200°C, even not exceeding 198°C, preferably not exceeding 195°C, more preferably not exceeding 193°C, even more preferably not exceeding 190°C, and/or possessing a melting temperature of advantageously at least 120°C, preferably of at least 130°C, still preferably of at least 140°C, more preferably of at least 145°C, even more preferably of at least 150°C, wherein the melting temperature is determined by Differential Scanning Calorimetry (DSC) at a heating rate of 10°C/min, according to ASTM D 3418.
- The composition of claim 10, wherein said ECTFE copolymers consist essentially of:(a) from 35 to 47% by moles, with respect to the total number of moles of recurring units, of recurring units derived from ethylene (E);(b) from 53 to 65% by moles, with respect to the total number of moles of recurring units, of recurring units derived from chlorotrifluoroethylene (CTFE).
- A method for manufacturing the composition according to anyone of the preceding claims, said method comprising mixing at least the said polymer (A); and the said organic UV absorber [absorber (UV)], said method comprising mixing the said polymer (A), absorber (UV) by blending in the molten state, preferably by using conventional melt compounding devices, such as co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc-pack processors and various other types of extrusion.
- A method of manufacturing a film comprising using the composition according to anyone of 1 to 11, said method comprising preferably extruding the composition in the molten state through a die having elongated shape so as to obtain an extruded tape, and casting/calendering said extruded tape so as to obtain a film.
- Film made from the composition according to anyone of 1 to 11, or obtained through the method of claim 13.
- Multilayer structures comprising the film of claim 14, and at least one additional layer adhered thereto.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| EP14186119.5 | 2014-09-24 | ||
| EP14186119 | 2014-09-24 |
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| KR102740680B1 (en) | 2018-10-03 | 2024-12-11 | 아크로마 (스위처랜드) 게엠베하 | Novel pyridine and pyrimidine substituted triazine UV absorbers |
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| US11981110B2 (en) | 2021-12-21 | 2024-05-14 | Saint-Gobain Performance Plastics Corporation | Multilayer film and method of forming the same |
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