CA2004407A1 - Liquid, radiation-curable coating composition for coating glass surfaces - Google Patents
Liquid, radiation-curable coating composition for coating glass surfacesInfo
- Publication number
- CA2004407A1 CA2004407A1 CA002004407A CA2004407A CA2004407A1 CA 2004407 A1 CA2004407 A1 CA 2004407A1 CA 002004407 A CA002004407 A CA 002004407A CA 2004407 A CA2004407 A CA 2004407A CA 2004407 A1 CA2004407 A1 CA 2004407A1
- Authority
- CA
- Canada
- Prior art keywords
- coating
- weight
- coating composition
- radiation
- gamma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000008199 coating composition Substances 0.000 title claims abstract description 39
- 239000011521 glass Substances 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 title claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 239000005304 optical glass Substances 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical class CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000306 component Substances 0.000 claims 6
- DKMGLBSWNFXTJA-UHFFFAOYSA-N O(C1=CC=CC=C1)CCOC(C=C)=O.C(=C)N1C(CCC1)=O Chemical compound O(C1=CC=CC=C1)CCOC(C=C)=O.C(=C)N1C(CCC1)=O DKMGLBSWNFXTJA-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- -1 mercaptyl hydrogen Chemical compound 0.000 description 21
- 150000002009 diols Chemical class 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 4
- 241001024304 Mino Species 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 241001061036 Otho Species 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XJRIDJAGAYGJCK-UHFFFAOYSA-N (1-acetyl-5-bromoindol-3-yl) acetate Chemical compound C1=C(Br)C=C2C(OC(=O)C)=CN(C(C)=O)C2=C1 XJRIDJAGAYGJCK-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BVDQHCUOVIQIEJ-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol;propane-1,2,3-triol Chemical compound OCC(O)CO.OCC(C)(CO)CO BVDQHCUOVIQIEJ-UHFFFAOYSA-N 0.000 description 1
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- UVPJPMLNEZMEDT-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;hexane-1,2,6-triol Chemical compound CCC(CO)(CO)CO.OCCCCC(O)CO UVPJPMLNEZMEDT-UHFFFAOYSA-N 0.000 description 1
- CYVMBANVYOZFIG-UHFFFAOYSA-N 2-ethylbutane-1,4-diol Chemical compound CCC(CO)CCO CYVMBANVYOZFIG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AAAWJUMVTPNRDT-UHFFFAOYSA-N 2-methylpentane-1,5-diol Chemical compound OCC(C)CCCO AAAWJUMVTPNRDT-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 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
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-Threitol Natural products OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical group CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- 101100260565 Dictyostelium discoideum thyA gene Proteins 0.000 description 1
- 238000005773 Enders reaction Methods 0.000 description 1
- 241000854350 Enicospilus group Species 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000228957 Ferula foetida Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 238000005299 abrasion Methods 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 150000008064 anhydrides Chemical class 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 150000002513 isocyanates Chemical class 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229940061319 ovide Drugs 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001730 thiiranyl group Chemical group 0.000 description 1
- 101150068774 thyX gene Proteins 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/104—Coating to obtain optical fibres
- C03C25/106—Single coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
04 Nov. 1988 (0830z) Abstract of the disclosure Liquid, radiation-curable coating composition for coating glass surfaces The present invention relates to a liquid, radiation-curable coating composition which contains A) 56 to 89% by weight of at least one diethylenically unsaturated polyurethane optionally containing urea groups, B) 10 to 30% by weight of at least one ethylenically unsaturated monomer, C) 0.5 to 8% by weight of at least one photoinitiator, and D) 0.05 to 6% by weight of N-.beta.-aminoethyl-.gamma.-aminopro-pyltrimethoxysilane, .gamma.-aminopropyltrimethoxysilane, N-methyl-.gamma.-aminopropyltrimethoxysilane or triamino-modified propyltrimethoxysilane, the sum of components (A) to (D) in each case being 100%
by weight, and all % by weight data being based on the coating composition.
These coating agents are employed for coating glass surfaces, in particular optical glass fibers, and are distinguished by good adhesion, even on exposure to moisture.
by weight, and all % by weight data being based on the coating composition.
These coating agents are employed for coating glass surfaces, in particular optical glass fibers, and are distinguished by good adhesion, even on exposure to moisture.
Description
'7 4 Nov. 1988 (0830z) BASF Lacke und Farben AG
Liquid, radiation-curab~l~ coatinq om~positlon for coatinq qla~s surface~
The present invention relates to a liquid, radiation-curable coating compo~itioll for coating glas~
surfaces and containing A) 56 to 89% by weight, ba~ed on th~ coating compo-~ition, of at lea~t on~ diethylenically un~aturated polyurethane optionally containing urea group~, 0 B) 10 to 30~ by weight, ba~d on ~ha coating compo-sition, of at le3st one ethylenically un~ura~ed monomer, C) 0.5 to 8% by weight, base~ on tha coating compo ~ition, of at lea~t one photoinitiator, and 5 D~ 0O05 o 6~ by weight, ba~ed on the coating compo-sition, of an 21koxysilana, tha ~um of co~ponQnt~ (A) to ~D) in ea~h ca~e being 100%
by w~ight.
The present in~ention al~o relate~ to a proce~s for coating gla88 surface~, in particular op~ical gla~
iiber~,u~ingthes0radiation-curablecoatingcompo~ition~.
Optlcal gla~s fiher~ have achieved con~tantly increa~ing impor~ance in the Yec~,or of communications as optical waveguide ~i~er~. For thi~ application, it i~
absolutely nece~sary to protect the glass ~urface again3t mois~ure and abrasion. ~he glas~ ~iber3 are therefore provided, immsd~ately after production, with a pro~ecting paint coat.
3f~ )'7 Thu~, it i~ known~ for example, frcm EP-B-114,982 to p~ovide glas~ fibers fir~tly with ~ buffer coa ing (primer) which is ela~ic, but not very hard and not very tough~ and then to apply a radiation-curable top coat which ha~ high hardne~s and toughne3~. The two-laysred con~truction is intended to en~ure good protection of the optical fibers under mechanical load, even at low tem-peratures. A~ thQ top coat, radiation-curable coating compo~ition~ based on a polyurethane containing diethy-lenic end group~, a diethylenically un~aturated ester ofa diglycidyl ethes o~ a bi~phenol, and a monoethylenical-ly un~aturated monomer, the gla~ tran~itîon temperature of the homopolymer preparQd fro~ thi~ monomer beiny above 55C~ are employed in EP-~-114,9B2.
Howe~er~ gla~ fiber coatings of thi~ typs have the con~idQrable d~d~antage of only poor adhe~ion to the glas~ ~urface. In paxtlcular on exposure to moi~tuxa, th~3 adh~sion i8 further impaired, undex cextain circum~
~tance~ even ~o greatly that full lo~ of adhQsion on the gl~88 surfac~ occur~. The problem o~ poor adhe~ion of the coa~ing compo~ition~ to the gla~ ~urface i~ Xnown. In order to improve tho adhe~io~, organos~lane~; a~ adhesion promoters, are therefore freguen~ly added to the coating compo~itions. Thus, it i8 known, for e~ample, from 2S EP-~33,043 to add organosilanes, a~ sdhe3ion promoters, to radiation-curable coa~ing agen~ ba3ed on vinyl monomer~ and reactive polymers (not polyurethane~
being es~ential to the invention that eithex the vinyl monomer~ or the polymers hsva a thiirane ring. Example~
x~
_ 3 ~-mentioned of Ruitable compounds are ~-aminopropyltri-etho.~y~ilane, N,~-aminoethyl-~-aminopropyltrimetho~y-~ilane ~nd ~glycidylo ~ ropyltrime~ho~y~ilane. There is no mention in this application of the lo~ in adhe~ion of the glass fiber coating~ on exposura to moisture.
It is also known, from Japanese Patent 45,138/85 of 8 October 1985 (correspond-~ to Japane~e Praliminary Publishad Specification 42,244/80 of 25 ~arch 19803, to employ organosilane~ a~ adhasion promQters in radiation-curable gla~ fiber coating agents~ The film~forming component~ employed are polymer~ having azide group~.
~-methacryloxypropyltrimetho~y3ilane~ aminopropyltri-mQthoxysilane and ~-glycidyloxypropyltrimethoxy~ilane are me~tioned a~ ~uita~le ~ilane~. However, it i3 essential to Japane3e Patent 45,138 that the azide groups are incorporated into the polymar~ in order to inarease the curing rate. This publication too doe~ not therefore mention the problem of the effect of moisture on the adhe~ion og the glass fiber coating.
- ~inally, EP~A-149,741 disclose~ liq~id, radiation-curnble gla98 fiber coating agents which contain, be8Ldes a radiation-curable, polye~hylenically un~atura~ed polymoric compound, 0.5 to 5~, ~a~ed on tha coating compo~ition, o~ a polyalkoxysilane. Polyalkoxy-~ilanes which carr~ an organic ~ub~tituent which carrie~
a 3ingle acti~e amino or mercaptyl hydrogen a~om which is able to react with the ethylenically un~aturatad bond~ ln a Nichael addition are ~ui~able. An ~xample mentione~ of ~uitable ~ilanos i3 ~ mercaptopxopyltrimethoxysilane.
~C~ )'7 According to the teaching of EP-A-149,741, it is only po3sible to improve the adhesion even on exposure to moisture by u~ing silan~ of this type. By contra~t, compound~ usually employed a~ adhesion promoters, such a~, for example, y-aminopropyltriethoxy~ilane and N-~-(N-vinylbenzylaminopropyl~trimethoxysilane pro~e, according to EP-A-149,741, to be un~uitable for improving the adhe3ion on expo~ure to moistura~
The present invention therefore had the ob~ect o~
providing radiation~curable coating compo~i~ions for coa~ing glass surfaces, in particular optical glass fibers, in which the resultant coatingt after expo~ure to moisture, had only slight 1098 in adhe~ion, or none at all, compared with the corresponding fre~hly prepared coating examined Lmmediately aftar curing.
The ob~ect underlying the inYention i~ achieved by a liquid, radiation-curable coating composition for coating glas~ surface~ which contains A) 56 to 89% by weight, based on the coating compo-~ition, of at least one diethylenically unsaturated polyur~thane optionally containing urea group~, B) 10 to 30% by weight, basad on the coating compo-~ition, oP at least one ethylenically unsaturated monomer, C) 0.5 to 8% by weight, based on the coating compo-sition, of at lea~t one photoinihator tsic), D) 0.05 to 6% by weight, ba~ed on the coating compo-~ition, of an alkoxysilane, the sum o~ componsnts (A~ to ~D) in each case being 100%
by weight.
In the coating composition, component (D) i~
N-~-aminoethyl-~-aminopropyltxLmethoxy~ilane or ~-~mino-S propyltrimethoxy~ilane or N-methyl-7-aminopropyltri-methoxy~ilane or triamino-modified propyltrimethoxy-silane.
In view of the large number o~ organo~ilicon compound~ known a~ adhe~ion promoters, it was ~urprising and not for~eeable that the u~e of N-~-aminoethyl-~-aminopropyltr~methoxy~ilanQ, ~-aminopropyltr~methoxy-~ilane, N-methyl-~-aminopropyltrimethoxysilane a~d triamino-modified propyltrl~tho~ysilane tfor example DYNASYLAN~ adhesion promoter~, type "TRIAMO", co~mercial product fro~ Dyn~it-Nobel Che~ie) Lmpair~ the adhe~ion of radiation-curable coating agents ba~ed on unsatuxated polyurethanes on glass ~urace3 on expo~ure to moi~ure only insignificantly or not at all~ while con~iderable impairment in adhe~ion occur~ on exposure to moi~ture when other ~nown adheRion promoter~, such as, for exam-pl~ glyc~dyloxytrim2~he~ysilane and the monohydro-chloride o~ N~ N-~inylbenzylamino)ethyl~-aminopropyl-trLmethoxy~ilane, are u~ed.
The coaking compo~i~ivn according to the inven-tion i~ described below in greater detail~
The d~ethylenlcally un~aturated polyurethane~ (A)employed a~ tho film orming component can be obtained by reactlng a diisocyanate or polyi~ocyante with a chain extender from the group comprl~ing diol~Jpolyols a~d/or 6 - 27293-~7 diaminQ0~poly~mlne~ andJor di~hiol~ps:~lythiolY and~or alkanol~nine~ and ~ubse~quently reacting the frae isocya-nate groups which remalrl ~arith st lea~t on~ hydroxyalkyl acrylate or hydroxyalltyl es~er of other ethylenically un~turated carboxyllc acids.
The amount~ of chain extender~, diisocyanate or polyisocyar~ate ~Ind hydroxyalkyl e~ter~ of an e~hyleni~ally un~aturated carboxylic acid are ~el~c~ted her~ 30 that 1~ ) the~ equivalent ratLo between the NC0 g:roups and the roac~ivo group~ of the~ chain sxtender (hydroxyl~
~nlno or mercaptyl group~ betwe~n 3 :1 ænd 1: 2, and i~ preferably 2 s 1, arld 2. ) the OH groups of th~ hydroxyalkyl es~ar~ of e~ hyl-enic~lly unsatur~ ed carboxyllc acid~ ar~ pr~ent in ~ stoichiomatric amount relative to the ~till-r~e i~ocyanate group~ of 'che prepolymer m~de f rom i~o~yanate and cha~n extend~r.
~n addition, it i~ pos~ible to prepare ~he polyurethan~ (A) by fir~tly re~ctln~ ~ome o~ the isocya-2 0 na~e . group~ o~ a dii~ocyanate or polyisooyan2te with at le~s~ one hydroxyalkyl e~cer of an etllylenically un-sA~u~at0d c~rboxylic acld, and ~ub~sequently re~ctlng the rem~inin~ i80Cyl!ln~ltl~ s~roups wi~h ~ chain ext~nder. In thi~ oa~e too, the amount~ o:E ch~in extender, i~oc~anate 2S and hydroxyalkyl e~t~x~ o~ un~aturated c~arbo~rllc acids are ~elected so th~t the equlvalent rfltio between the NC0 groupo And ~h~ r~3activel group~ of the~ ohain ex~ender i~
be~w~en 3 s 1 and 1 t 2, ~nd i9 pre~e~xably 2 2 1, and ~he e~uivalent r~tio between the remnininy ~aCo group~ and the o~ group~ of the hydroxyalkyl ester is 1:1~
~ of cour~e po~sible to use all interm~diate form~ of these two proces~es. FGr example~ some o~ the isocyanate group~ of a diisocyanate can firstly be S reactad with a diol, more 3f the isocyanate groups can subsequently be reacted with the hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid, and the remalning isocyanate groups can thsn be reacted with a diamine.
The~a various preparation processeR for polyure-thane~ are known (cf., for example, EP-A-204,161j and do not therefore require mor~ de ailed descriptionO
I~ocyanates which are ~uitable for preparation of the polyurethanes ~A3 are aromatic, aliphatic and cyclo-aliphatic dii~ocyanates and polyisocyanate~, such a3, for example, 2,4- and 2,6-toluylane diisocya~ate~ and mi~-ture3 ther~of, 4,4'-diphenyLmethane dii~ocyanate, m-phenylene diisocyanate, p~phenylene diisocyanate, 4,4~-diphenyl diisocyanate, 1,5-naphthalene dii~ocyanata, 1,4-naphthale~e di~ocyanate, 4,4'-toluidine diisocyanate, xylylene diiaocyanat~ and ~ub~ti~-uted aromatic ~y~tem~, ~uch 83, ~or example diani~idine diisocyanate~, 4,4'-diphenyl ether dii~ocyanateR or clorodiphenylene (~ic) dii~ocyanates~and hlgher-func~lonalaromatic isocyana~e~, such as, for example, 1,3,5-trii~ocyanatobenzene,4,4',4"-triisocyanattriphenylmethane (sic3, 2,4,6 trii~ocyanato toluene and 4,4~-diphenyldi~thylmsthane 2,2',5,5 tetxa-i.~ocyanate; cycloaliphatic l~ocyana~es, ~uch a~, for example, 1,3-cyclopontane dii~ocyanate, 1,4-cyclohexane ~ 0 0 ~
diisocyanate,1,2-cyclohexanediisocyandte,4,4'-methylene bis(cyclohexyl isocyanate) and i~ophorone dii~ocyanate;
aliphatic isocyanates, such a5, for example, tri-methy-lene diisocyanate, tetramethylene diisocyanate, penta-methylene d~isocyanate, hexamethylane diisocyanate,trimethylhexamethylene 1,6-dii~ocyanate and tris~hexa-methylene triisocyanate, and the diisocyanates derived from dimeric fatty acids described in EP-A-204,161, column 4, lines 42 to 49.
2,4- and 2,6-toluylene diisocyanate, 4,4'-diphenyl-methane dii~ocyanat0, hexamethylene diisocyanate, isopho-rone dii~ocyanate and 4,4'-methylene bis~(cyclohexyl iso-cyanate) are preferably employed.
Example~ o suitable diol~ and polyols are, for example, ethylene glycol, propylene 1,2-glycol and 1,3-glycol, butanediols, pentanediols, neopentyl glycol, hexanediol.~,2-methylpentane-1,5-diol,2-ethylbutane-1,4-diol, dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane and trimethylolbutane, e~ythritol, mesoerythritol, arabitol, adonitol, xylitol, mannitol, ~orbitol, dulcitol, hexanetriol, (poly)-pantaerythritol;
further monoethar~, ~uch a~ diethylene glycol and dipro-pylene glycol, and polyethex~, the adduc~ of the polyol~
mentioned and alkylene oxides. Exampl0~ of alkylene oxide~ ¦~héy-~ict¦are suitable for polyaddition to ~heYe polyols to form polyether~ are ethylene oxide, propylene oxide, butyl~ne oxide and styrene oxide. The~e polyaddi-tion products are generally called polyether~ having terminal hydroxyl group~. They may be linear or branched.
Example~ of polyethers of thi~ type are polyoxy~thylene glycol~ having a molecular weight of from 200 to 4,000, polyoxypropylene glycols having a molecular weight of from 200 to 4~000, polyoxytetramethylene glycol, poLyoxy-hexamethylene glycol, polyvxynonamethylene glycol,polyoxydecamethylene glycol, polyoxydodecamethylene glycol and mixture~ thexeof. Oth~r ~ype~ of polyo~yalky-lene glycol ethers may also be u~ed. Suitable polyether polyols are al~o those which are obtained by reacting polyol~ of this type, such a~ ethylens glycol, diethylene glycol, triethylene glycol, 1~4-butanediol, 1,3-butane~
diol, 1,6-hexanediol and mixtures thereof; glycerol trimethylolethane, trimethylolpropane 1,2,6-hexanetriol, dipsntaerythritol, tripentaerythritol, polypentaeryth-ritol, methyl glyco~ides and sucro~e, with alkyleneoxides, ~uch a3 ethylene oxide, propylene oxide or mixture~ thereof.
Examples of ~uitable polyether diols are al~o tha polymerization products of tetrahydrofuran or of butylene oxide. It i~ al50 po~ible to use polyestQr polyol~, preforably polyester diol~, which can be prepared, for example, ~y reacting the abovementioned glycol~ with dicarboxylic acids, ~uch a~, for example, phthallc acid~
i~ophthalic acid, hexahydroph~halic acid, adipic acid, azelalc acld, ~ebacic acid, maleic acid, glutaric acid, tetrachlorophthalic acid and hexachloroheptanedicar-boxylic acid. In~tead of these acids, it is al~o po~sible to use their anhydride~ if they exist.
It is also po3sible to use polycaprolactQne diol~
2 7 2 9 3~ ~ 7 ~nd trlols. ThesQ produot~ are obtain~d, for example, by reacting an ~-~aprolactonQ with a diol. Such product~ are d~ribed in US PatQnt 3 ,169, 945 .
The polylao~cone polyol~ ob~ain~sd by thi~ re~ction are di~tln~uish*d by the pr~en~e of a tsrmLnal hydroxyl group ~nd by recurring polye~t0r uni~ d~rlved from th~
l~c~one. ~rhe~s recurring molecular units may conform to the~ ~ormulfl o - C ~ (CHR)fl - CH20 ~
in wh~c:h n i~ pre~er~bly ~ to 6, and the Yubs~ tuent R is hyclrogen, an alkyl r~di~ll, a cycloalXyl radi~al or an alXoxy rad~l, no substltu~nt ~ont~ining more than 1~
oarbon a~com~ arld the total nwnber of carbon ai:om~ ~ n the ~ubs éituent in the la~ton~ ring nvt exceeding 12 .
~he l~oQe u~sed a~ atar~ing material CMn be any lactonQ or any combination of lactone~, but this l~ctene Jhould contaln at lela~t 6 carbon a~om~ in th6 ring, for exampl~ 6 to ~ carbon atom~, and at lea~t 2 hydrog~n sub~ cu~3nts ~hould be prQsen~ on ~h~ carbon atom bonded to the oxygon group ~ie the rirlg. The~ lac~one u~ed a4 ~tr,~rting m~lterl~l may b~3 repr~entecl by the genera.l ~ormul~ ~low.
f ,~ n O
o in which n and R axe es alr0ady de~ined abo~re. ~he 25 lac~one~ whlch ar~ pre~erred in the inven~ion ~or the preparatlon of th~3 polyester diol~ are caprolactone~ in whlch n h~ the v~luQ 4. ~he ~no~t-prePerr0d l~ctone i~
~ub~titued ~ ~caprolaotone ~ n whioh n ha~ the ~ralue 4 and all R ~ubstituent~ are hydrogen. Thi~ l~cton0 is particu-larly preferred ~ince it i~ a~r~ilabl~ in large amount~
and gives coating~ having excellent propertie~. In addition, various other la~tone~ c~n b~ us~d lndividually or in combinatlon.
Exampl~ss of ~1 f ph~tl~ diol3 which are ~ui tabl~
~0 for ~he re~csion wlth the lac~vn~ are th~ diol~ alre~dy men~lon~3d abov~ ~or the reac~lon with ~ha carbo~rll~
acid~ .
Examples of ~ui~able amllle~ are! ethylenediamine, tri-, t~'cra , p~nta- hexa~, he pta -, nona-, d~ca- and dodecaMethylenedlamirle, 2,2,4- and 2,4,4-tr~methylhexa-m~thy1~n~diamine, propylenediamine and the eorrespondin~
poly~lkylenadiamlnes, ~u~h a8, for ex~ple, polypropy-len0dla~inQ, polyether dl~mine~ having a molecular weight of from 200 to 4,000, for exa~pl~ polyoxy1ethylsnediamine (~ic~, polyoxypropylenQdiamine, polyoxy~etramethylenedi-amln~, 1,3~ And 1,4-buty1enediamlne, Lsophoronediamine, 1,2- a~d 1,4-di~minocy~lohe~ne, 4,4'-~iaminadLcyclohe~
methane, bl~-(3-m~thyl-4-~mino~yclohexyl)meth~ne, 2,2-biY(4-omLnocy~lohe~yl~propane, 4,7-dloxadecane-1,10-di~mino, 4,9-dlox~dodeeane-1,12-dl~mine, 7-methy1-4,-10-dioxa~ridecanQ~1,13-di~mine, nitrilotri3(ethane~
æmine), ethflnolAmlne, propanol~mlnQ, N-~2-amino-ethyl)e~hanol, poly0ther poly~mine~, bi~(3-aminopropyl)-methy1~min0, 3 amino-l-(methyl~m~no)propane, 3-~mi.no-1-2~
- 12 _ 27293-47 (cyclohe~yl~mino)propane, N~2-hydroxyethyl)ethylenedl-~mlne, ~rl~-~2-~mlnoQthyl)~mine, and polyamines of ~he formula H2N-(R2-NH~nRl~NH2. n i9 an integer between 1 ~nd 6, proferably 1-3. Rl ~nd R2 are iden~i~al or different ~lkylene groups or cycloalkylene gr~up~ or alXylene group3 containing ether groups, in each case having 2-~, pref~rably 2~4, C atom~. Ex~mple~ of polyalXylenepoly~
nmln~ of thl~ t~pe ~re d1ethylenetri~mln~, ~riethylene-tetr~mine, totra~thylenep~nt~min~, dipropylanetri~minel txipropyl~nete~ramine, t~trapropylenepentamin~ and dlbutylene~riamine.
Chain extender~ which ~an also be employed are dlthiol~ ~nd poly~hiol~, ~uoh as, for exampls, dith~o~
ethylene glycol, 1,2- and 1,3 propanedlthiol 9 butane-dlth~als, pent~n~dl~hiol~, hexanedithiol~ ~nd th~ otherS~ analogou~ compound~ of ~he diol~ and polyol~
m~ntloned.
Suitahle for introducing ~he ethyl~nically unJaturated group~ in~o the polyure~h~ne ar~ hydxoxy-~lkyl e~ter~ of ethyleni~ally unsa~ura~d ~arbo~ylicac~d~, ~uch as, or example, hydroxyethyl acrylate, hydroxypropylacrylate,hydroxybutylacryl~te,hydroxy~myl ~crylat~, hydroxyhexyl ~ryl~te, hydroxyoc~yl ~cryla~e ~nd tho correspondLng hy~roxyal~yl ester~ o~ m~th~cxylLc ~cid, fum~rlc ~cid~ m~le~c ~cid, it~conic nGi~ crotonic ncid, and l~ocrokonic ~cld.
~ h~ un~atur~ted polyur~th~n~ l~ employed in the coa~lng compo~ition~ in ~n ~mount o~ ~rom 56 to 89~ by welght, b~ed on ~he ~oatlng compo~ition.
~ e~ides the polyurethane (A~ ju~t de cribed, the coating agent accordi~g to ~he invention also contains 10 to 30~ by weight, based on the coating composition, of at least one ethylenically unsatuxated monomer (B). Examples of suitable monomer~ are ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dim~thylamino-ethyl acrylate, hydroxyethyl acrylate; butoxyethyl acrylate, isobornyl acrylate, dLmethylacxylamide and dicyclopentyl acrylate. Also suitable are diacrylate~ and polyacrylat~s, such as, for example, butanediol diacry-late, trimethylo~propane diacrylate and triacrylate, pentaerythritol diacrylate and ~he long-chain linear diacrylate~ having a molecular weight of from 400 to 4,000, preferably 600 to 2,500, which are described in EP-A-250,631. For example, the two acrylate groups may be separated by a polyoxybutylene structure. It i~ al~o po~sible to employ 1,12-dodecyl diacrylats and the product of the reactlon of 2 mole~ of acrylic acid with one mole of a dimeric fatty alcohol, which genexally has 36 C atom~.
Mixtures o~ the monomer3 ~u~t de~cribed are al~o ~uit~ble.
Preferably employed are N-vinylpyrroliclone, phenoxyethyl acrylate, isobornyl acrylate ancl mixtures of thzse monomer~.
The photoinitiator employed in the coating compositions according to the invention in an amount of from 0,5 to ~% by weight, preferably 2 to 5% by weight, based on the coating compositionr varie~ with the X ~ 7 r~dl~tion amp10yed to ~ure thQ coatln~ agent~ t W radia-tion, e1ec~ron r~diati.on, vi~lble 1ight~. The coating composition~ according to the ~nvention ~re preferably cured by maanq of W radiation. In thi~ ca~e, k~ton~-S ba~d pho~olnltator~ ~re u~uall~ emp10yed, for examp1eacetophenon~, benzophenone, diethoxyacQtoph~none, m-chloroa~etopheQone, prop~ophenone, benzoin, b~nzil, ben211 dLm~thyl ket~19 anthraquinone, thixanthone ~1c) and thlox~n~hono dar1v~ti~s, ~nd mixtur~s of differens photolnitiator~.
Togeth~r with the photoinit1~or~ mentionedt var10u~ amines, for examp1e dlethylamin~ and triethanol-am1ne, can b~ emp10yed, if approprl~to, in ~mount~ of up to 4~ by weight, b~sQd on th~ ~o~ting ~ompo~itionJ and 8C~ a~ ~yn~rgis~.
A# the component Q~sentl~1 to the invention, the co~ting composition~ cont~in 0.05 to 6~ by weight, b~sed on the ~oating composi~ion~ of N-~-~mlnoethyl-7~am:ino-propyltrlm~tho~ysil~ne,~-~minopropyltr~me~hoxysilanQ,N-m~hyl~y-~mlnopropyltrLmethoxy~ilan~ortrl~mino~modified propyltrlmo~hoxy~llan~ (for ex~mple DYN~SYI~NP adhe~ion promot~r~, Ntyp~*R~AMO~, comM~rcial product ~rom Dyn~it Nob~l Ch~mLe). ~h~ lk~xy~ilan~s ~re commercially availabl~ product~ and therefore nsed not be d~crlbod in great~r detail. Preerre~ coating agents ar~ obtained by employing oither 0.5 to 2~ by weigh~, ~a~ed on the coating compo~ition, of N~-aminoethyl-~-aminopropyltrL-methoxysilane or 2 ~o 4~ by weight, bAsed on ~he co~ting compooltLon, of ~-aminoprepyl~rLm~ho~y~ilan~ or 3 ~o 5~
2~3~
- 15 ~
by weight, based on the coating composition, of N-methyl-~-~minopropyltrimethoxysilane or 4 to 6% by weight, basad on the coating composition, of triamino-modified propyl-trimethoxy~ilane ~for example DYNASYLAN~ adhe~ion promo-ters, "type TRIAMO"~ commercial product from Dynamit Nobel Chemie) a~ component (D).
The coating composition~ according to the inven-tion mayt if appropriate, additionally contain customary auxiliaries and addikives in cu~tomary amount~, prefe~-ably 0.05 to 10% by weight, based o~ the coating compo~i-tion. Examples of subskance~ of this type are flow agent~
and plasticizer~. The coating compo~ition~ may be applied to the glass ~ur~ace by means of known methods of appli cation, æuch a~, for e~amplel sprayingj rollingl flow-coating, dipping, knife coating or bru~hing.
- ~he paint films are cured by mean~ of radiation, pra~erably by means of W radiation. The equipment and condition~ for the~e method~ of curing are known fro~ the literature tcf., for example, R. Holmes, U.V. and E.B.
Curing Formulatiorl~ for Printing Ink~, Coatings and Paints, ~ITA Technology, Academic Pre~, London, United Kingdo~ 198~) and require no further de~cription.
The pre~ent invention al~o relate~ to a proce~
for coating a gla~ ~urface, in which I.~ a radiation curable coating composition is applied which contain~
~) 56 to 89~ by weight, ba~ed on the coatiny composi-tion, o~ at least one diethylenically un~aturated polyurethane optionally containing urea groups~
'7 B) 10 to 30% by weight, based on th coating compo~ition, of at least one ethylsnically un~aturated monomer, C) 0.5 to 8% by weight, based on the coatLng compo-sition, of at least one photoinitia~or, and D) 0.05 to 6~ by weight, based on the coating compo-sition, of an alkoxysilane, the qt~ of components (A~ to (D) in each ca~e being 100% by weight, and II.) the coating composition is cured by means of W or electron radia~ion.
In th~ proces~, the coating compo~ition contain3, a~ component (D), N-~ aminoethyl-~-aminopropyltrimathoxy-silane or y-aminopropyltrime~hoxysilane or N-methyl-~-lS aminopropyltrimethoxysilane or tri~mino-modified propyl-trLme~hoxysilane.
For a more detailed de~cription of the coating agent employed Ln the proces~ according to the invention and of the way in which thi~ proce~-q i~ carried out, reference is made to pages 5 to 13 of this de~cription.
The proce8 according to the invention i~ par-ticularly sultable for coating optical glaas fiber3. In particular when optical glas~ fibers ara used a~ optical waveguide8, it i~ important ~hat the coa~ing compositiQn~
applied to protect the ~urface have good adheslon to the gla~fl surfac0 even on expo~tlre to moisture. Lo~e~ in adhe~ion of ~he coating after exposure to moi~ture -which cannot be avoided when glas~ fiber8 ars u~ed a~
op~ical waveguides - (for example gla~ ~iber~ ars ~3~ '7 expo~ed to the air at coupling station~, result in paint damage on the glass fiber surface. This surface, which is then unprotected, can very easily be damaged, for example by grains of dust, which result3 in a loss in op~ical propertie~. The process according to the invention and the coating compositions according to the invention, in particular, make it possible, howevler, to ~void the~e disadvantages and to provide coating~ having very good adhesion, even after expo~ure to moisture.
The coating compositions according to the inven-tion can be applied to the glas3 fib~r either in the form of a 3ingle coat or as the prLmer of a two-coat sy~tem. Suitable top coat in the ca~e of the two-coat system are described, for exampla, in EP-B-114,982~
The invention i~ describ~d in greate-c detail in the example~ below. All part3 and percentage~ are by weight, unle~s expre~sly stated otherwise.
Example 1_15EEYb!E___nl A radiation-curable coating compo ition compris-ing ~5.8 part~ of unsaturated polyurethane, 9.2 parts of trimethylolpropane triacrylate, 12 part~ of phenoxyethyl acrylate, 0.5 part o~ benzll dimethyl ketal and 2.5 parts of benzophenone i~ prepared by known mathods (cf., for example, EP-B-114,982~, by firstly reacting 4 mole~ of 4,4'-methylene bis-(cyclohexyl i~ocyanate) with 2 moles of polyoxypropylene glycol (moleculAr weight 1,000) in the pre~ence o~ trimethylolpropane triacrylate and phenoxyethyl acrylate. Thi~ intermediate obtained i~
reacted with 2 mole~ o~ 2-hydroxyethyl acrylate and then ~ L~
with 1 mole of polyoxypropylenediamine (molecular weight 230~. The photoinitiatorA are then added to the mixture.
Thoxoughly purified lin parti.cular grea~e~free~
glass plates (width x length = 98 x 151 mm) are ma~ked a~
the edge with Te~akrepp adhesive tape No. 4432 (width 19 mm~, and tha coating composition is applied by knife coa~ing (dry film thickne~s 180 ~m).
The curing is carried out using a W irradiation apparatu~ equipped with two Hg medium-pressure lamps each with a lamp power of 80 W/cm, at a belt spesd of 40 m/minu~e, in 2 passes at half power (= 40 W~cm).
The incident dose here is 0.08 J/cm2 (mea,~ured using the do~imeter, WICURE, ~y~tem EIT from ~ltosch).
The adhesion is tested immediately thereafter a~
~ollow~:
~arefully datach the beginning of the foil from the gla~ using a razor blade.
- Attach a wire hook to the detached part of the foil u~ing adhesi~e tape .
0 - .Hook in a spring balance and xemove at right angle~
at the mo~t con~tan~ rate po~ibl0.
- Read ~ff the xemoval force requirad in g from the mea~urement scale.
The adhesion te~t i~ evaluated by averaging the value~ obtained from a double determination and checki~g the repreducibility of good (~ high~ adhesion values by ~everal repetition~.
The re ul~ of the adhe~ion te8t is ~hown in Table 1.
4~t7 27293-~7 ~ eside~ thiR adhe~ion te~t, which waR carried out, a roll peeling test in accordanc3 with DIN 55 289 i~
also possible/ but wa~ not carried out~
In order to test the adhe~ion after exposure ~o moi~ture, the glass plate~ wera a~ditionally ~tored for 12 hour~ after curing in ~uitable clLmatic chambar~
having a defined atmoqpheric humidity o~ 90~ relative atmospheric humidity (r.h.~ ~corrsspond.Lng to DIN 50005) at room temperature ~25C).
Immadiately aft~r compl~tion of exposure, the removal te-qt using the spring balance wa~ carried out analogouRly to the adhe~ion test Lmm~diately aft~r irradiation.
In this case too, the adhe~ion te~t wa~ evaluated by taking the average of a double determination. In the ca~e of good adhesion values, at le~st -two rep~at measurements were carr$ed out in order to check t~e reproducibility.
The result of thi~ test i~ likewise ~hown in Table 1.
The te~t carried out for adhesion to window gla~s gives good, meaningful xesults as a laborato~y method.
This method i8 also carried out at gla88 fiber manufac-~urer~ ~ince it giv~s ValUQ8 c108~ to those Ln pract,ice 2S which agree very well with the adhe3ion valu~s on optical gla8~ ~iber~ (typical ~iber thicknes~ 125 ~m).
~L
A radiation-curable coating agent based on the un~aturated polyurethane i8 prapared analogou~ly to 272~3-47 Comp4rlson Example 1, lrl contr~t to Comp~rl~s~n Exomple 1, tha co~ting agent ~dditlon~lly oont~ln~ 2~ by waight, b~sed on the tot~l compo~itlon, of ~-glycidyloxypropyl-trimetho~ysilane.
Analogou~ly to CornparL~on Ex,Ample 1, this coating ~gent i~ ~ppl ~ ed to gl~8~ plate~ by me~n~ of ~ knife co~ter (dry film thlckne~ 0 ~m) ~rld cured u~ng a mercury medlwn-pre~ure vapor lamp (do~e l~kewlse 0.08 J/cm2). rh~ ~dh~lon of the co~ting i~ me~su~-0 etit ~IZI dq~ncrlbed in Comp~rl~o~ Ex~mpl~ 1, ~nm~diately a~t~r curlng o~ the co~ting ~gent ~nd a~ter ~orage for 12 hours ~t 90~ rol~tlve atmo~pherlc humldley ~t room ~cemp~rature~. ~he reoult~ ~o ~hown in Ta~Dle 1.
Exam~le~ 3 an~d 4_~compAr~on~
lS Gla~s co~tlngs ~e prep~rad analogouæly to ~xnmpl~ 2r bu~ with the dlffer~nce th~t ~he 2~ by we~ght, based on the total composition, o~ t-glycidyloxypropyl-trLmethoxysll~n~ ~ro now repl~ced by 2~ by we~ght of 3-but~nyltrie~hoxy~ilan~ (Ex~mple 3~ or 2~ by wai~ht o~ ~he monohydrochloride of ~ 5N-viny~-N-benzylamino)ethyl~-~
amlnopropyltrlmothoxy~ilnne ~formula ~CH~O)JSi tC~2)3 NR ~CH2)2 NH~C~2~ ~ ~ CH ~ CH2 HCl tEx~mplo 4)/ ~ ch c~o ba~Qd on the totAl composit:lon.
Tha re~ult~ o~ the ~dhe~lon te~t aro shown in 2S ~ble 1.
Gl~ coa~clng~ ~re prep~red an~logou~ly to Exnmpl~ 2, bu~ with the dlfference th~t ~he 2% by weight of ~-glycLdylox~propyltxime~hoxy~ilane ~ra now replaced ~7 by 1 IExample S) or 2 ~Example 6) or 3 (Example 7) % by woight of N-~-aminoethyl-~-~minopropyltrimethoxysilane, in each case ba~ed on the total compo~ition.
Tha rasults of the adhe~ion tes~ are shown in Table 1.
Exam~le (sic) 8-9 Gla~s coating~ are prepared analogously to~
Example 2, but with the difference that the 2% by weight of ~-glycidyloxypropyltrimethoxysilane are now replaced by ~ (Example 8) or 4 (Example 9~ % by weight of N-methyl-~-aminopropyltrLmethoxysilane, in sach case based on the toal compo3ition.
Tho result~ of the adhe~ion test are shown in Table 1.
~i~DEihaL_L~:lL
Gla~ coating~ are prepared analo~ously to Example 2, but with the difference that the 2~ by weight of y-glycidylo~ypropyltrLmethoxy~Llane are now replaced by 2% byw eight of t-aminopropyltr~methoxy~ilane (E~ample 10) ~r 2% by weight of triamino-modlfied propyltri-methoxsilane ( 8iC ) ( DYN~5YLA~ adhe~ion promoters, type "TRIAMO", commercial product from Dyn~mit-Nobel Chemie), in each ca8a ba~ed on the ~otal composition.
The results of the adhesion ta3t are shown in ~S Table 1.
~ ~2 - 27293-~7 Table 1 ~r~lo ~-olon pro~ottr ~D~ ~unt o~ Adb~ n Adh~ COr ~D~ urlnll 12 ho~lr~ ~Ib ~ht 3 90~ r h.
- -1, 000- 1, 100 Z o-Clycl~Yloryprovylcr~ hoxy-no 2~,000-~, 100 ~0- ~00 0 9 3-~ut~nyLCrlotho~ 2900-1,000 2S-30 Monoh~drorblorld~ ot ~ n-vln~ n~yl~lno~-ChyL~7-~lno-propylcr~thu~ ne 2 7S0-1,000 1~0 l~-O-Aolno~hYl-7~lnopro~yLt~l-~-Choqrlhno 11,000~1,100 D00-1,000 O 11 J-h~lr,04Chyl~-~lnop~o~lerl-hor~ o 2~,000-1,100 900-1,000 7 1~ no-Ch~ 7~ no~rop~ rl-~otho~rll-n- 3800-1,900 800- 000 2 0 ~ N-Hoch~ ~Lno5tro~LCrl~otho~-n~ 211~0- 9~0 a~o- s~o I~ tb~L-7~ ,noproprltrl~hox~-1, 200~ 00~, 000- 1, 100 10 7-A~inop~o~lCrl0~tbo~eil-n- Z 1,000~1,150 7~0~ ~0 l~ Trl~lno~l~ ~d proprlcrl~
n~tbo~r-112no ~rRI~o~) 2 S,000-1, 100 S00 Example~ 1-11 show th~t only very low 1O9~ in ~dhs~ion, i~ any, oct:ur~ ~tor ~xpo~ure to mol~'cure of compo-sitions containing N-~,~ noe'chyl-t-~ninC)propyltr:lme*Ch-oxy~ ne, N-methy~ m1nopropylerim~tho;ty~l;an0, ~-aminop~opyltxlmethoxy~ n~ and trl~m~no-modi~10d p2-opy1-trimathoxy~ n~ (DYNASYI~ dhosion promoter~, type ~T~I~MO~, fxo~ ~yn~it ~obol Chemie)~ while con3iderable 10B~ in a~he~lon i~ ob~erve~ on expo~ur0 to mois~ure when o~her, known sil~ne ~dhesion promo~.ers, such ~, for ex~mple~ ~-glycidyloxypropyltrimethoxy~ ne, 3-butenyl-triethoxy~ ne and the monohydr w hlorids o~ N-~- ( N-vinylbenzylamino)~Ayl-y-~mlnopropyltrime~hoxy~ilane, ~re u.sed.
Liquid, radiation-curab~l~ coatinq om~positlon for coatinq qla~s surface~
The present invention relates to a liquid, radiation-curable coating compo~itioll for coating glas~
surfaces and containing A) 56 to 89% by weight, ba~ed on th~ coating compo-~ition, of at lea~t on~ diethylenically un~aturated polyurethane optionally containing urea group~, 0 B) 10 to 30~ by weight, ba~d on ~ha coating compo-sition, of at le3st one ethylenically un~ura~ed monomer, C) 0.5 to 8% by weight, base~ on tha coating compo ~ition, of at lea~t one photoinitiator, and 5 D~ 0O05 o 6~ by weight, ba~ed on the coating compo-sition, of an 21koxysilana, tha ~um of co~ponQnt~ (A) to ~D) in ea~h ca~e being 100%
by w~ight.
The present in~ention al~o relate~ to a proce~s for coating gla88 surface~, in particular op~ical gla~
iiber~,u~ingthes0radiation-curablecoatingcompo~ition~.
Optlcal gla~s fiher~ have achieved con~tantly increa~ing impor~ance in the Yec~,or of communications as optical waveguide ~i~er~. For thi~ application, it i~
absolutely nece~sary to protect the glass ~urface again3t mois~ure and abrasion. ~he glas~ ~iber3 are therefore provided, immsd~ately after production, with a pro~ecting paint coat.
3f~ )'7 Thu~, it i~ known~ for example, frcm EP-B-114,982 to p~ovide glas~ fibers fir~tly with ~ buffer coa ing (primer) which is ela~ic, but not very hard and not very tough~ and then to apply a radiation-curable top coat which ha~ high hardne~s and toughne3~. The two-laysred con~truction is intended to en~ure good protection of the optical fibers under mechanical load, even at low tem-peratures. A~ thQ top coat, radiation-curable coating compo~ition~ based on a polyurethane containing diethy-lenic end group~, a diethylenically un~aturated ester ofa diglycidyl ethes o~ a bi~phenol, and a monoethylenical-ly un~aturated monomer, the gla~ tran~itîon temperature of the homopolymer preparQd fro~ thi~ monomer beiny above 55C~ are employed in EP-~-114,9B2.
Howe~er~ gla~ fiber coatings of thi~ typs have the con~idQrable d~d~antage of only poor adhe~ion to the glas~ ~urface. In paxtlcular on exposure to moi~tuxa, th~3 adh~sion i8 further impaired, undex cextain circum~
~tance~ even ~o greatly that full lo~ of adhQsion on the gl~88 surfac~ occur~. The problem o~ poor adhe~ion of the coa~ing compo~ition~ to the gla~ ~urface i~ Xnown. In order to improve tho adhe~io~, organos~lane~; a~ adhesion promoters, are therefore freguen~ly added to the coating compo~itions. Thus, it i8 known, for e~ample, from 2S EP-~33,043 to add organosilanes, a~ sdhe3ion promoters, to radiation-curable coa~ing agen~ ba3ed on vinyl monomer~ and reactive polymers (not polyurethane~
being es~ential to the invention that eithex the vinyl monomer~ or the polymers hsva a thiirane ring. Example~
x~
_ 3 ~-mentioned of Ruitable compounds are ~-aminopropyltri-etho.~y~ilane, N,~-aminoethyl-~-aminopropyltrimetho~y-~ilane ~nd ~glycidylo ~ ropyltrime~ho~y~ilane. There is no mention in this application of the lo~ in adhe~ion of the glass fiber coating~ on exposura to moisture.
It is also known, from Japanese Patent 45,138/85 of 8 October 1985 (correspond-~ to Japane~e Praliminary Publishad Specification 42,244/80 of 25 ~arch 19803, to employ organosilane~ a~ adhasion promQters in radiation-curable gla~ fiber coating agents~ The film~forming component~ employed are polymer~ having azide group~.
~-methacryloxypropyltrimetho~y3ilane~ aminopropyltri-mQthoxysilane and ~-glycidyloxypropyltrimethoxy~ilane are me~tioned a~ ~uita~le ~ilane~. However, it i3 essential to Japane3e Patent 45,138 that the azide groups are incorporated into the polymar~ in order to inarease the curing rate. This publication too doe~ not therefore mention the problem of the effect of moisture on the adhe~ion og the glass fiber coating.
- ~inally, EP~A-149,741 disclose~ liq~id, radiation-curnble gla98 fiber coating agents which contain, be8Ldes a radiation-curable, polye~hylenically un~atura~ed polymoric compound, 0.5 to 5~, ~a~ed on tha coating compo~ition, o~ a polyalkoxysilane. Polyalkoxy-~ilanes which carr~ an organic ~ub~tituent which carrie~
a 3ingle acti~e amino or mercaptyl hydrogen a~om which is able to react with the ethylenically un~aturatad bond~ ln a Nichael addition are ~ui~able. An ~xample mentione~ of ~uitable ~ilanos i3 ~ mercaptopxopyltrimethoxysilane.
~C~ )'7 According to the teaching of EP-A-149,741, it is only po3sible to improve the adhesion even on exposure to moisture by u~ing silan~ of this type. By contra~t, compound~ usually employed a~ adhesion promoters, such a~, for example, y-aminopropyltriethoxy~ilane and N-~-(N-vinylbenzylaminopropyl~trimethoxysilane pro~e, according to EP-A-149,741, to be un~uitable for improving the adhe3ion on expo~ure to moistura~
The present invention therefore had the ob~ect o~
providing radiation~curable coating compo~i~ions for coa~ing glass surfaces, in particular optical glass fibers, in which the resultant coatingt after expo~ure to moisture, had only slight 1098 in adhe~ion, or none at all, compared with the corresponding fre~hly prepared coating examined Lmmediately aftar curing.
The ob~ect underlying the inYention i~ achieved by a liquid, radiation-curable coating composition for coating glas~ surface~ which contains A) 56 to 89% by weight, based on the coating compo-~ition, of at least one diethylenically unsaturated polyur~thane optionally containing urea group~, B) 10 to 30% by weight, basad on the coating compo-~ition, oP at least one ethylenically unsaturated monomer, C) 0.5 to 8% by weight, based on the coating compo-sition, of at lea~t one photoinihator tsic), D) 0.05 to 6% by weight, ba~ed on the coating compo-~ition, of an alkoxysilane, the sum o~ componsnts (A~ to ~D) in each case being 100%
by weight.
In the coating composition, component (D) i~
N-~-aminoethyl-~-aminopropyltxLmethoxy~ilane or ~-~mino-S propyltrimethoxy~ilane or N-methyl-7-aminopropyltri-methoxy~ilane or triamino-modified propyltrimethoxy-silane.
In view of the large number o~ organo~ilicon compound~ known a~ adhe~ion promoters, it was ~urprising and not for~eeable that the u~e of N-~-aminoethyl-~-aminopropyltr~methoxy~ilanQ, ~-aminopropyltr~methoxy-~ilane, N-methyl-~-aminopropyltrimethoxysilane a~d triamino-modified propyltrl~tho~ysilane tfor example DYNASYLAN~ adhesion promoter~, type "TRIAMO", co~mercial product fro~ Dyn~it-Nobel Che~ie) Lmpair~ the adhe~ion of radiation-curable coating agents ba~ed on unsatuxated polyurethanes on glass ~urace3 on expo~ure to moi~ure only insignificantly or not at all~ while con~iderable impairment in adhe~ion occur~ on exposure to moi~ture when other ~nown adheRion promoter~, such as, for exam-pl~ glyc~dyloxytrim2~he~ysilane and the monohydro-chloride o~ N~ N-~inylbenzylamino)ethyl~-aminopropyl-trLmethoxy~ilane, are u~ed.
The coaking compo~i~ivn according to the inven-tion i~ described below in greater detail~
The d~ethylenlcally un~aturated polyurethane~ (A)employed a~ tho film orming component can be obtained by reactlng a diisocyanate or polyi~ocyante with a chain extender from the group comprl~ing diol~Jpolyols a~d/or 6 - 27293-~7 diaminQ0~poly~mlne~ andJor di~hiol~ps:~lythiolY and~or alkanol~nine~ and ~ubse~quently reacting the frae isocya-nate groups which remalrl ~arith st lea~t on~ hydroxyalkyl acrylate or hydroxyalltyl es~er of other ethylenically un~turated carboxyllc acids.
The amount~ of chain extender~, diisocyanate or polyisocyar~ate ~Ind hydroxyalkyl e~ter~ of an e~hyleni~ally un~aturated carboxylic acid are ~el~c~ted her~ 30 that 1~ ) the~ equivalent ratLo between the NC0 g:roups and the roac~ivo group~ of the~ chain sxtender (hydroxyl~
~nlno or mercaptyl group~ betwe~n 3 :1 ænd 1: 2, and i~ preferably 2 s 1, arld 2. ) the OH groups of th~ hydroxyalkyl es~ar~ of e~ hyl-enic~lly unsatur~ ed carboxyllc acid~ ar~ pr~ent in ~ stoichiomatric amount relative to the ~till-r~e i~ocyanate group~ of 'che prepolymer m~de f rom i~o~yanate and cha~n extend~r.
~n addition, it i~ pos~ible to prepare ~he polyurethan~ (A) by fir~tly re~ctln~ ~ome o~ the isocya-2 0 na~e . group~ o~ a dii~ocyanate or polyisooyan2te with at le~s~ one hydroxyalkyl e~cer of an etllylenically un-sA~u~at0d c~rboxylic acld, and ~ub~sequently re~ctlng the rem~inin~ i80Cyl!ln~ltl~ s~roups wi~h ~ chain ext~nder. In thi~ oa~e too, the amount~ o:E ch~in extender, i~oc~anate 2S and hydroxyalkyl e~t~x~ o~ un~aturated c~arbo~rllc acids are ~elected so th~t the equlvalent rfltio between the NC0 groupo And ~h~ r~3activel group~ of the~ ohain ex~ender i~
be~w~en 3 s 1 and 1 t 2, ~nd i9 pre~e~xably 2 2 1, and ~he e~uivalent r~tio between the remnininy ~aCo group~ and the o~ group~ of the hydroxyalkyl ester is 1:1~
~ of cour~e po~sible to use all interm~diate form~ of these two proces~es. FGr example~ some o~ the isocyanate group~ of a diisocyanate can firstly be S reactad with a diol, more 3f the isocyanate groups can subsequently be reacted with the hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid, and the remalning isocyanate groups can thsn be reacted with a diamine.
The~a various preparation processeR for polyure-thane~ are known (cf., for example, EP-A-204,161j and do not therefore require mor~ de ailed descriptionO
I~ocyanates which are ~uitable for preparation of the polyurethanes ~A3 are aromatic, aliphatic and cyclo-aliphatic dii~ocyanates and polyisocyanate~, such a3, for example, 2,4- and 2,6-toluylane diisocya~ate~ and mi~-ture3 ther~of, 4,4'-diphenyLmethane dii~ocyanate, m-phenylene diisocyanate, p~phenylene diisocyanate, 4,4~-diphenyl diisocyanate, 1,5-naphthalene dii~ocyanata, 1,4-naphthale~e di~ocyanate, 4,4'-toluidine diisocyanate, xylylene diiaocyanat~ and ~ub~ti~-uted aromatic ~y~tem~, ~uch 83, ~or example diani~idine diisocyanate~, 4,4'-diphenyl ether dii~ocyanateR or clorodiphenylene (~ic) dii~ocyanates~and hlgher-func~lonalaromatic isocyana~e~, such as, for example, 1,3,5-trii~ocyanatobenzene,4,4',4"-triisocyanattriphenylmethane (sic3, 2,4,6 trii~ocyanato toluene and 4,4~-diphenyldi~thylmsthane 2,2',5,5 tetxa-i.~ocyanate; cycloaliphatic l~ocyana~es, ~uch a~, for example, 1,3-cyclopontane dii~ocyanate, 1,4-cyclohexane ~ 0 0 ~
diisocyanate,1,2-cyclohexanediisocyandte,4,4'-methylene bis(cyclohexyl isocyanate) and i~ophorone dii~ocyanate;
aliphatic isocyanates, such a5, for example, tri-methy-lene diisocyanate, tetramethylene diisocyanate, penta-methylene d~isocyanate, hexamethylane diisocyanate,trimethylhexamethylene 1,6-dii~ocyanate and tris~hexa-methylene triisocyanate, and the diisocyanates derived from dimeric fatty acids described in EP-A-204,161, column 4, lines 42 to 49.
2,4- and 2,6-toluylene diisocyanate, 4,4'-diphenyl-methane dii~ocyanat0, hexamethylene diisocyanate, isopho-rone dii~ocyanate and 4,4'-methylene bis~(cyclohexyl iso-cyanate) are preferably employed.
Example~ o suitable diol~ and polyols are, for example, ethylene glycol, propylene 1,2-glycol and 1,3-glycol, butanediols, pentanediols, neopentyl glycol, hexanediol.~,2-methylpentane-1,5-diol,2-ethylbutane-1,4-diol, dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane and trimethylolbutane, e~ythritol, mesoerythritol, arabitol, adonitol, xylitol, mannitol, ~orbitol, dulcitol, hexanetriol, (poly)-pantaerythritol;
further monoethar~, ~uch a~ diethylene glycol and dipro-pylene glycol, and polyethex~, the adduc~ of the polyol~
mentioned and alkylene oxides. Exampl0~ of alkylene oxide~ ¦~héy-~ict¦are suitable for polyaddition to ~heYe polyols to form polyether~ are ethylene oxide, propylene oxide, butyl~ne oxide and styrene oxide. The~e polyaddi-tion products are generally called polyether~ having terminal hydroxyl group~. They may be linear or branched.
Example~ of polyethers of thi~ type are polyoxy~thylene glycol~ having a molecular weight of from 200 to 4,000, polyoxypropylene glycols having a molecular weight of from 200 to 4~000, polyoxytetramethylene glycol, poLyoxy-hexamethylene glycol, polyvxynonamethylene glycol,polyoxydecamethylene glycol, polyoxydodecamethylene glycol and mixture~ thexeof. Oth~r ~ype~ of polyo~yalky-lene glycol ethers may also be u~ed. Suitable polyether polyols are al~o those which are obtained by reacting polyol~ of this type, such a~ ethylens glycol, diethylene glycol, triethylene glycol, 1~4-butanediol, 1,3-butane~
diol, 1,6-hexanediol and mixtures thereof; glycerol trimethylolethane, trimethylolpropane 1,2,6-hexanetriol, dipsntaerythritol, tripentaerythritol, polypentaeryth-ritol, methyl glyco~ides and sucro~e, with alkyleneoxides, ~uch a3 ethylene oxide, propylene oxide or mixture~ thereof.
Examples of ~uitable polyether diols are al~o tha polymerization products of tetrahydrofuran or of butylene oxide. It i~ al50 po~ible to use polyestQr polyol~, preforably polyester diol~, which can be prepared, for example, ~y reacting the abovementioned glycol~ with dicarboxylic acids, ~uch a~, for example, phthallc acid~
i~ophthalic acid, hexahydroph~halic acid, adipic acid, azelalc acld, ~ebacic acid, maleic acid, glutaric acid, tetrachlorophthalic acid and hexachloroheptanedicar-boxylic acid. In~tead of these acids, it is al~o po~sible to use their anhydride~ if they exist.
It is also po3sible to use polycaprolactQne diol~
2 7 2 9 3~ ~ 7 ~nd trlols. ThesQ produot~ are obtain~d, for example, by reacting an ~-~aprolactonQ with a diol. Such product~ are d~ribed in US PatQnt 3 ,169, 945 .
The polylao~cone polyol~ ob~ain~sd by thi~ re~ction are di~tln~uish*d by the pr~en~e of a tsrmLnal hydroxyl group ~nd by recurring polye~t0r uni~ d~rlved from th~
l~c~one. ~rhe~s recurring molecular units may conform to the~ ~ormulfl o - C ~ (CHR)fl - CH20 ~
in wh~c:h n i~ pre~er~bly ~ to 6, and the Yubs~ tuent R is hyclrogen, an alkyl r~di~ll, a cycloalXyl radi~al or an alXoxy rad~l, no substltu~nt ~ont~ining more than 1~
oarbon a~com~ arld the total nwnber of carbon ai:om~ ~ n the ~ubs éituent in the la~ton~ ring nvt exceeding 12 .
~he l~oQe u~sed a~ atar~ing material CMn be any lactonQ or any combination of lactone~, but this l~ctene Jhould contaln at lela~t 6 carbon a~om~ in th6 ring, for exampl~ 6 to ~ carbon atom~, and at lea~t 2 hydrog~n sub~ cu~3nts ~hould be prQsen~ on ~h~ carbon atom bonded to the oxygon group ~ie the rirlg. The~ lac~one u~ed a4 ~tr,~rting m~lterl~l may b~3 repr~entecl by the genera.l ~ormul~ ~low.
f ,~ n O
o in which n and R axe es alr0ady de~ined abo~re. ~he 25 lac~one~ whlch ar~ pre~erred in the inven~ion ~or the preparatlon of th~3 polyester diol~ are caprolactone~ in whlch n h~ the v~luQ 4. ~he ~no~t-prePerr0d l~ctone i~
~ub~titued ~ ~caprolaotone ~ n whioh n ha~ the ~ralue 4 and all R ~ubstituent~ are hydrogen. Thi~ l~cton0 is particu-larly preferred ~ince it i~ a~r~ilabl~ in large amount~
and gives coating~ having excellent propertie~. In addition, various other la~tone~ c~n b~ us~d lndividually or in combinatlon.
Exampl~ss of ~1 f ph~tl~ diol3 which are ~ui tabl~
~0 for ~he re~csion wlth the lac~vn~ are th~ diol~ alre~dy men~lon~3d abov~ ~or the reac~lon with ~ha carbo~rll~
acid~ .
Examples of ~ui~able amllle~ are! ethylenediamine, tri-, t~'cra , p~nta- hexa~, he pta -, nona-, d~ca- and dodecaMethylenedlamirle, 2,2,4- and 2,4,4-tr~methylhexa-m~thy1~n~diamine, propylenediamine and the eorrespondin~
poly~lkylenadiamlnes, ~u~h a8, for ex~ple, polypropy-len0dla~inQ, polyether dl~mine~ having a molecular weight of from 200 to 4,000, for exa~pl~ polyoxy1ethylsnediamine (~ic~, polyoxypropylenQdiamine, polyoxy~etramethylenedi-amln~, 1,3~ And 1,4-buty1enediamlne, Lsophoronediamine, 1,2- a~d 1,4-di~minocy~lohe~ne, 4,4'-~iaminadLcyclohe~
methane, bl~-(3-m~thyl-4-~mino~yclohexyl)meth~ne, 2,2-biY(4-omLnocy~lohe~yl~propane, 4,7-dloxadecane-1,10-di~mino, 4,9-dlox~dodeeane-1,12-dl~mine, 7-methy1-4,-10-dioxa~ridecanQ~1,13-di~mine, nitrilotri3(ethane~
æmine), ethflnolAmlne, propanol~mlnQ, N-~2-amino-ethyl)e~hanol, poly0ther poly~mine~, bi~(3-aminopropyl)-methy1~min0, 3 amino-l-(methyl~m~no)propane, 3-~mi.no-1-2~
- 12 _ 27293-47 (cyclohe~yl~mino)propane, N~2-hydroxyethyl)ethylenedl-~mlne, ~rl~-~2-~mlnoQthyl)~mine, and polyamines of ~he formula H2N-(R2-NH~nRl~NH2. n i9 an integer between 1 ~nd 6, proferably 1-3. Rl ~nd R2 are iden~i~al or different ~lkylene groups or cycloalkylene gr~up~ or alXylene group3 containing ether groups, in each case having 2-~, pref~rably 2~4, C atom~. Ex~mple~ of polyalXylenepoly~
nmln~ of thl~ t~pe ~re d1ethylenetri~mln~, ~riethylene-tetr~mine, totra~thylenep~nt~min~, dipropylanetri~minel txipropyl~nete~ramine, t~trapropylenepentamin~ and dlbutylene~riamine.
Chain extender~ which ~an also be employed are dlthiol~ ~nd poly~hiol~, ~uoh as, for exampls, dith~o~
ethylene glycol, 1,2- and 1,3 propanedlthiol 9 butane-dlth~als, pent~n~dl~hiol~, hexanedithiol~ ~nd th~ otherS~ analogou~ compound~ of ~he diol~ and polyol~
m~ntloned.
Suitahle for introducing ~he ethyl~nically unJaturated group~ in~o the polyure~h~ne ar~ hydxoxy-~lkyl e~ter~ of ethyleni~ally unsa~ura~d ~arbo~ylicac~d~, ~uch as, or example, hydroxyethyl acrylate, hydroxypropylacrylate,hydroxybutylacryl~te,hydroxy~myl ~crylat~, hydroxyhexyl ~ryl~te, hydroxyoc~yl ~cryla~e ~nd tho correspondLng hy~roxyal~yl ester~ o~ m~th~cxylLc ~cid, fum~rlc ~cid~ m~le~c ~cid, it~conic nGi~ crotonic ncid, and l~ocrokonic ~cld.
~ h~ un~atur~ted polyur~th~n~ l~ employed in the coa~lng compo~ition~ in ~n ~mount o~ ~rom 56 to 89~ by welght, b~ed on ~he ~oatlng compo~ition.
~ e~ides the polyurethane (A~ ju~t de cribed, the coating agent accordi~g to ~he invention also contains 10 to 30~ by weight, based on the coating composition, of at least one ethylenically unsatuxated monomer (B). Examples of suitable monomer~ are ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dim~thylamino-ethyl acrylate, hydroxyethyl acrylate; butoxyethyl acrylate, isobornyl acrylate, dLmethylacxylamide and dicyclopentyl acrylate. Also suitable are diacrylate~ and polyacrylat~s, such as, for example, butanediol diacry-late, trimethylo~propane diacrylate and triacrylate, pentaerythritol diacrylate and ~he long-chain linear diacrylate~ having a molecular weight of from 400 to 4,000, preferably 600 to 2,500, which are described in EP-A-250,631. For example, the two acrylate groups may be separated by a polyoxybutylene structure. It i~ al~o po~sible to employ 1,12-dodecyl diacrylats and the product of the reactlon of 2 mole~ of acrylic acid with one mole of a dimeric fatty alcohol, which genexally has 36 C atom~.
Mixtures o~ the monomer3 ~u~t de~cribed are al~o ~uit~ble.
Preferably employed are N-vinylpyrroliclone, phenoxyethyl acrylate, isobornyl acrylate ancl mixtures of thzse monomer~.
The photoinitiator employed in the coating compositions according to the invention in an amount of from 0,5 to ~% by weight, preferably 2 to 5% by weight, based on the coating compositionr varie~ with the X ~ 7 r~dl~tion amp10yed to ~ure thQ coatln~ agent~ t W radia-tion, e1ec~ron r~diati.on, vi~lble 1ight~. The coating composition~ according to the ~nvention ~re preferably cured by maanq of W radiation. In thi~ ca~e, k~ton~-S ba~d pho~olnltator~ ~re u~uall~ emp10yed, for examp1eacetophenon~, benzophenone, diethoxyacQtoph~none, m-chloroa~etopheQone, prop~ophenone, benzoin, b~nzil, ben211 dLm~thyl ket~19 anthraquinone, thixanthone ~1c) and thlox~n~hono dar1v~ti~s, ~nd mixtur~s of differens photolnitiator~.
Togeth~r with the photoinit1~or~ mentionedt var10u~ amines, for examp1e dlethylamin~ and triethanol-am1ne, can b~ emp10yed, if approprl~to, in ~mount~ of up to 4~ by weight, b~sQd on th~ ~o~ting ~ompo~itionJ and 8C~ a~ ~yn~rgis~.
A# the component Q~sentl~1 to the invention, the co~ting composition~ cont~in 0.05 to 6~ by weight, b~sed on the ~oating composi~ion~ of N-~-~mlnoethyl-7~am:ino-propyltrlm~tho~ysil~ne,~-~minopropyltr~me~hoxysilanQ,N-m~hyl~y-~mlnopropyltrLmethoxy~ilan~ortrl~mino~modified propyltrlmo~hoxy~llan~ (for ex~mple DYN~SYI~NP adhe~ion promot~r~, Ntyp~*R~AMO~, comM~rcial product ~rom Dyn~it Nob~l Ch~mLe). ~h~ lk~xy~ilan~s ~re commercially availabl~ product~ and therefore nsed not be d~crlbod in great~r detail. Preerre~ coating agents ar~ obtained by employing oither 0.5 to 2~ by weigh~, ~a~ed on the coating compo~ition, of N~-aminoethyl-~-aminopropyltrL-methoxysilane or 2 ~o 4~ by weight, bAsed on ~he co~ting compooltLon, of ~-aminoprepyl~rLm~ho~y~ilan~ or 3 ~o 5~
2~3~
- 15 ~
by weight, based on the coating composition, of N-methyl-~-~minopropyltrimethoxysilane or 4 to 6% by weight, basad on the coating composition, of triamino-modified propyl-trimethoxy~ilane ~for example DYNASYLAN~ adhe~ion promo-ters, "type TRIAMO"~ commercial product from Dynamit Nobel Chemie) a~ component (D).
The coating composition~ according to the inven-tion mayt if appropriate, additionally contain customary auxiliaries and addikives in cu~tomary amount~, prefe~-ably 0.05 to 10% by weight, based o~ the coating compo~i-tion. Examples of subskance~ of this type are flow agent~
and plasticizer~. The coating compo~ition~ may be applied to the glass ~ur~ace by means of known methods of appli cation, æuch a~, for e~amplel sprayingj rollingl flow-coating, dipping, knife coating or bru~hing.
- ~he paint films are cured by mean~ of radiation, pra~erably by means of W radiation. The equipment and condition~ for the~e method~ of curing are known fro~ the literature tcf., for example, R. Holmes, U.V. and E.B.
Curing Formulatiorl~ for Printing Ink~, Coatings and Paints, ~ITA Technology, Academic Pre~, London, United Kingdo~ 198~) and require no further de~cription.
The pre~ent invention al~o relate~ to a proce~
for coating a gla~ ~urface, in which I.~ a radiation curable coating composition is applied which contain~
~) 56 to 89~ by weight, ba~ed on the coatiny composi-tion, o~ at least one diethylenically un~aturated polyurethane optionally containing urea groups~
'7 B) 10 to 30% by weight, based on th coating compo~ition, of at least one ethylsnically un~aturated monomer, C) 0.5 to 8% by weight, based on the coatLng compo-sition, of at least one photoinitia~or, and D) 0.05 to 6~ by weight, based on the coating compo-sition, of an alkoxysilane, the qt~ of components (A~ to (D) in each ca~e being 100% by weight, and II.) the coating composition is cured by means of W or electron radia~ion.
In th~ proces~, the coating compo~ition contain3, a~ component (D), N-~ aminoethyl-~-aminopropyltrimathoxy-silane or y-aminopropyltrime~hoxysilane or N-methyl-~-lS aminopropyltrimethoxysilane or tri~mino-modified propyl-trLme~hoxysilane.
For a more detailed de~cription of the coating agent employed Ln the proces~ according to the invention and of the way in which thi~ proce~-q i~ carried out, reference is made to pages 5 to 13 of this de~cription.
The proce8 according to the invention i~ par-ticularly sultable for coating optical glaas fiber3. In particular when optical glas~ fibers ara used a~ optical waveguide8, it i~ important ~hat the coa~ing compositiQn~
applied to protect the ~urface have good adheslon to the gla~fl surfac0 even on expo~tlre to moisture. Lo~e~ in adhe~ion of ~he coating after exposure to moi~ture -which cannot be avoided when glas~ fiber8 ars u~ed a~
op~ical waveguides - (for example gla~ ~iber~ ars ~3~ '7 expo~ed to the air at coupling station~, result in paint damage on the glass fiber surface. This surface, which is then unprotected, can very easily be damaged, for example by grains of dust, which result3 in a loss in op~ical propertie~. The process according to the invention and the coating compositions according to the invention, in particular, make it possible, howevler, to ~void the~e disadvantages and to provide coating~ having very good adhesion, even after expo~ure to moisture.
The coating compositions according to the inven-tion can be applied to the glas3 fib~r either in the form of a 3ingle coat or as the prLmer of a two-coat sy~tem. Suitable top coat in the ca~e of the two-coat system are described, for exampla, in EP-B-114,982~
The invention i~ describ~d in greate-c detail in the example~ below. All part3 and percentage~ are by weight, unle~s expre~sly stated otherwise.
Example 1_15EEYb!E___nl A radiation-curable coating compo ition compris-ing ~5.8 part~ of unsaturated polyurethane, 9.2 parts of trimethylolpropane triacrylate, 12 part~ of phenoxyethyl acrylate, 0.5 part o~ benzll dimethyl ketal and 2.5 parts of benzophenone i~ prepared by known mathods (cf., for example, EP-B-114,982~, by firstly reacting 4 mole~ of 4,4'-methylene bis-(cyclohexyl i~ocyanate) with 2 moles of polyoxypropylene glycol (moleculAr weight 1,000) in the pre~ence o~ trimethylolpropane triacrylate and phenoxyethyl acrylate. Thi~ intermediate obtained i~
reacted with 2 mole~ o~ 2-hydroxyethyl acrylate and then ~ L~
with 1 mole of polyoxypropylenediamine (molecular weight 230~. The photoinitiatorA are then added to the mixture.
Thoxoughly purified lin parti.cular grea~e~free~
glass plates (width x length = 98 x 151 mm) are ma~ked a~
the edge with Te~akrepp adhesive tape No. 4432 (width 19 mm~, and tha coating composition is applied by knife coa~ing (dry film thickne~s 180 ~m).
The curing is carried out using a W irradiation apparatu~ equipped with two Hg medium-pressure lamps each with a lamp power of 80 W/cm, at a belt spesd of 40 m/minu~e, in 2 passes at half power (= 40 W~cm).
The incident dose here is 0.08 J/cm2 (mea,~ured using the do~imeter, WICURE, ~y~tem EIT from ~ltosch).
The adhesion is tested immediately thereafter a~
~ollow~:
~arefully datach the beginning of the foil from the gla~ using a razor blade.
- Attach a wire hook to the detached part of the foil u~ing adhesi~e tape .
0 - .Hook in a spring balance and xemove at right angle~
at the mo~t con~tan~ rate po~ibl0.
- Read ~ff the xemoval force requirad in g from the mea~urement scale.
The adhesion te~t i~ evaluated by averaging the value~ obtained from a double determination and checki~g the repreducibility of good (~ high~ adhesion values by ~everal repetition~.
The re ul~ of the adhe~ion te8t is ~hown in Table 1.
4~t7 27293-~7 ~ eside~ thiR adhe~ion te~t, which waR carried out, a roll peeling test in accordanc3 with DIN 55 289 i~
also possible/ but wa~ not carried out~
In order to test the adhe~ion after exposure ~o moi~ture, the glass plate~ wera a~ditionally ~tored for 12 hour~ after curing in ~uitable clLmatic chambar~
having a defined atmoqpheric humidity o~ 90~ relative atmospheric humidity (r.h.~ ~corrsspond.Lng to DIN 50005) at room temperature ~25C).
Immadiately aft~r compl~tion of exposure, the removal te-qt using the spring balance wa~ carried out analogouRly to the adhe~ion test Lmm~diately aft~r irradiation.
In this case too, the adhe~ion te~t wa~ evaluated by taking the average of a double determination. In the ca~e of good adhesion values, at le~st -two rep~at measurements were carr$ed out in order to check t~e reproducibility.
The result of thi~ test i~ likewise ~hown in Table 1.
The te~t carried out for adhesion to window gla~s gives good, meaningful xesults as a laborato~y method.
This method i8 also carried out at gla88 fiber manufac-~urer~ ~ince it giv~s ValUQ8 c108~ to those Ln pract,ice 2S which agree very well with the adhe3ion valu~s on optical gla8~ ~iber~ (typical ~iber thicknes~ 125 ~m).
~L
A radiation-curable coating agent based on the un~aturated polyurethane i8 prapared analogou~ly to 272~3-47 Comp4rlson Example 1, lrl contr~t to Comp~rl~s~n Exomple 1, tha co~ting agent ~dditlon~lly oont~ln~ 2~ by waight, b~sed on the tot~l compo~itlon, of ~-glycidyloxypropyl-trimetho~ysilane.
Analogou~ly to CornparL~on Ex,Ample 1, this coating ~gent i~ ~ppl ~ ed to gl~8~ plate~ by me~n~ of ~ knife co~ter (dry film thlckne~ 0 ~m) ~rld cured u~ng a mercury medlwn-pre~ure vapor lamp (do~e l~kewlse 0.08 J/cm2). rh~ ~dh~lon of the co~ting i~ me~su~-0 etit ~IZI dq~ncrlbed in Comp~rl~o~ Ex~mpl~ 1, ~nm~diately a~t~r curlng o~ the co~ting ~gent ~nd a~ter ~orage for 12 hours ~t 90~ rol~tlve atmo~pherlc humldley ~t room ~cemp~rature~. ~he reoult~ ~o ~hown in Ta~Dle 1.
Exam~le~ 3 an~d 4_~compAr~on~
lS Gla~s co~tlngs ~e prep~rad analogouæly to ~xnmpl~ 2r bu~ with the dlffer~nce th~t ~he 2~ by we~ght, based on the total composition, o~ t-glycidyloxypropyl-trLmethoxysll~n~ ~ro now repl~ced by 2~ by we~ght of 3-but~nyltrie~hoxy~ilan~ (Ex~mple 3~ or 2~ by wai~ht o~ ~he monohydrochloride of ~ 5N-viny~-N-benzylamino)ethyl~-~
amlnopropyltrlmothoxy~ilnne ~formula ~CH~O)JSi tC~2)3 NR ~CH2)2 NH~C~2~ ~ ~ CH ~ CH2 HCl tEx~mplo 4)/ ~ ch c~o ba~Qd on the totAl composit:lon.
Tha re~ult~ o~ the ~dhe~lon te~t aro shown in 2S ~ble 1.
Gl~ coa~clng~ ~re prep~red an~logou~ly to Exnmpl~ 2, bu~ with the dlfference th~t ~he 2% by weight of ~-glycLdylox~propyltxime~hoxy~ilane ~ra now replaced ~7 by 1 IExample S) or 2 ~Example 6) or 3 (Example 7) % by woight of N-~-aminoethyl-~-~minopropyltrimethoxysilane, in each case ba~ed on the total compo~ition.
Tha rasults of the adhe~ion tes~ are shown in Table 1.
Exam~le (sic) 8-9 Gla~s coating~ are prepared analogously to~
Example 2, but with the difference that the 2% by weight of ~-glycidyloxypropyltrimethoxysilane are now replaced by ~ (Example 8) or 4 (Example 9~ % by weight of N-methyl-~-aminopropyltrLmethoxysilane, in sach case based on the toal compo3ition.
Tho result~ of the adhe~ion test are shown in Table 1.
~i~DEihaL_L~:lL
Gla~ coating~ are prepared analo~ously to Example 2, but with the difference that the 2~ by weight of y-glycidylo~ypropyltrLmethoxy~Llane are now replaced by 2% byw eight of t-aminopropyltr~methoxy~ilane (E~ample 10) ~r 2% by weight of triamino-modlfied propyltri-methoxsilane ( 8iC ) ( DYN~5YLA~ adhe~ion promoters, type "TRIAMO", commercial product from Dyn~mit-Nobel Chemie), in each ca8a ba~ed on the ~otal composition.
The results of the adhesion ta3t are shown in ~S Table 1.
~ ~2 - 27293-~7 Table 1 ~r~lo ~-olon pro~ottr ~D~ ~unt o~ Adb~ n Adh~ COr ~D~ urlnll 12 ho~lr~ ~Ib ~ht 3 90~ r h.
- -1, 000- 1, 100 Z o-Clycl~Yloryprovylcr~ hoxy-no 2~,000-~, 100 ~0- ~00 0 9 3-~ut~nyLCrlotho~ 2900-1,000 2S-30 Monoh~drorblorld~ ot ~ n-vln~ n~yl~lno~-ChyL~7-~lno-propylcr~thu~ ne 2 7S0-1,000 1~0 l~-O-Aolno~hYl-7~lnopro~yLt~l-~-Choqrlhno 11,000~1,100 D00-1,000 O 11 J-h~lr,04Chyl~-~lnop~o~lerl-hor~ o 2~,000-1,100 900-1,000 7 1~ no-Ch~ 7~ no~rop~ rl-~otho~rll-n- 3800-1,900 800- 000 2 0 ~ N-Hoch~ ~Lno5tro~LCrl~otho~-n~ 211~0- 9~0 a~o- s~o I~ tb~L-7~ ,noproprltrl~hox~-1, 200~ 00~, 000- 1, 100 10 7-A~inop~o~lCrl0~tbo~eil-n- Z 1,000~1,150 7~0~ ~0 l~ Trl~lno~l~ ~d proprlcrl~
n~tbo~r-112no ~rRI~o~) 2 S,000-1, 100 S00 Example~ 1-11 show th~t only very low 1O9~ in ~dhs~ion, i~ any, oct:ur~ ~tor ~xpo~ure to mol~'cure of compo-sitions containing N-~,~ noe'chyl-t-~ninC)propyltr:lme*Ch-oxy~ ne, N-methy~ m1nopropylerim~tho;ty~l;an0, ~-aminop~opyltxlmethoxy~ n~ and trl~m~no-modi~10d p2-opy1-trimathoxy~ n~ (DYNASYI~ dhosion promoter~, type ~T~I~MO~, fxo~ ~yn~it ~obol Chemie)~ while con3iderable 10B~ in a~he~lon i~ ob~erve~ on expo~ur0 to mois~ure when o~her, known sil~ne ~dhesion promo~.ers, such ~, for ex~mple~ ~-glycidyloxypropyltrimethoxy~ ne, 3-butenyl-triethoxy~ ne and the monohydr w hlorids o~ N-~- ( N-vinylbenzylamino)~Ayl-y-~mlnopropyltrime~hoxy~ilane, ~re u.sed.
Claims (12)
1. A liquid, radiation-curable coating composition for coating glass surfaces and containing A) 56 to 89% by weight, based on the coating compo-sition, of at least one diethylenically unsaturated polyurethane optionally containing urea groups, B) 10 to 30% by weight, based on the coating compo-sition, of at least one ethylenically unsaturated monomer, C) 0.5 to 8% by weight, based on the coating compo-sition, of at least one photoinitiator, and D) 0.05 to 6% by weight, based on the coating compo-sition, of an alkoxysilane, the sum of components (A) to (D) in each case being 100%
by weight, wherein component (D) is N-.beta.-aminoethyl-.gamma.-aminopropyltri-methoxysilane or .gamma.-aminopropyltrimethoxysilane or N-methyl-.gamma.-aminopropyltrimethoxysilane or triamino-modified propyltrimethoxysilane.
by weight, wherein component (D) is N-.beta.-aminoethyl-.gamma.-aminopropyltri-methoxysilane or .gamma.-aminopropyltrimethoxysilane or N-methyl-.gamma.-aminopropyltrimethoxysilane or triamino-modified propyltrimethoxysilane.
2. A coating composition as claimed in claim 1, which contains 0.5 to 2% by weight, based on the coating composition, of N-.beta.-aminoethyl-.gamma.-aminopropyltrimethoxy-silane as component (D).
3. A coating composition as claimed in claim 1, which contains 2 to 4% by weight, based on the coating composition, of .gamma.-aminopropyltrimethoxysilane as com-ponent (D).
4. A coating composition as claimed in claim 1, which contains 3 to 5% by weight of N-methyl-.gamma.-amino-propyltrimethoxysilane as component (D).
5. A coating composition as claimed in claim 1, which contains 4 to 6% by weight of triamino-modified propyltrim-ethoxysilane as component (D).
6. A coating composition as claimed in one of claims 1 to 5, wherein monomer (B) is selected from N-vinylpyrrolidone phenoxyethyl acrylate, isobornyl acrylate and mixtures thereof.
7. A coating composition as claimed in one of claims 1 to 5, which additionally contains at least one synergist, customary auxiliary or additive.
8. A process for coating a glass surface, in which I) a radiation-curable coating composition is applied, and II) the coating composition is cured by means of UV or electron radiation, wherein the radiation-curable coating composition is a coating composition as claimed in one of claims 1 to 5.
9. The process as claimed in claim 8, wherein the glass surface is the surface of an optical glass fiber.
10. An optical glass fiber which is coated with a cured coating of a composition as claimed in one of claims 1 to 5.
11. The use of an optical glass fiber as claimed in claim 10 as an optical waveguide.
12. The use of a radiation-curable coating composition as claimed in one of claims 1 to 5 for coating optical glass fibers.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3840644.6 | 1988-12-02 | ||
DE3840644A DE3840644A1 (en) | 1988-12-02 | 1988-12-02 | LIQUID, RADIANT-COVERABLE COATING MEASUREMENT FOR THE COATING OF GLASS SURFACES |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2004407A1 true CA2004407A1 (en) | 1990-06-02 |
Family
ID=6368328
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002004407A Abandoned CA2004407A1 (en) | 1988-12-02 | 1989-12-01 | Liquid, radiation-curable coating composition for coating glass surfaces |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0446222B1 (en) |
JP (1) | JPH0776120B2 (en) |
KR (1) | KR930006328B1 (en) |
AU (1) | AU624196B2 (en) |
BR (1) | BR8907803A (en) |
CA (1) | CA2004407A1 (en) |
DE (2) | DE3840644A1 (en) |
DK (1) | DK166079C (en) |
ES (1) | ES2039097T3 (en) |
FI (1) | FI96432C (en) |
LT (1) | LT3310B (en) |
LV (1) | LV10766A (en) |
MD (1) | MD940077A (en) |
WO (1) | WO1990006289A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5527835A (en) * | 1992-04-24 | 1996-06-18 | Borden, Inc. | Organic solvent and water resistant hydrolytically stable ultraviolet radiation curable coatings for optical fibers |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3914411A1 (en) | 1989-04-29 | 1990-11-15 | Basf Lacke & Farben | LIQUID, RADIANT-COVERABLE COATING MEASUREMENT FOR THE COATING OF GLASS SURFACES |
US5149592A (en) * | 1990-05-09 | 1992-09-22 | Avery Dennison Corporation | Ultraviolet radiation curable clearcoat |
DE4139127A1 (en) * | 1991-11-28 | 1993-06-03 | Basf Lacke & Farben | LIQUID, RADIANT-COVERABLE COATING FOR THE COATING OF GLASS SURFACES |
CA2107448A1 (en) * | 1992-11-13 | 1994-05-14 | Lee Landis Blyler, Jr. | Optical transmission media having enhanced strength retention capabilities |
DE19535936A1 (en) * | 1995-09-27 | 1997-04-03 | Basf Lacke & Farben | Acrylated polyether polyol and its use for radiation-curable formulations |
DE19535935A1 (en) * | 1995-09-27 | 1997-04-03 | Basf Lacke & Farben | Radiation-curable coating |
US6023547A (en) * | 1997-06-09 | 2000-02-08 | Dsm N.V. | Radiation curable composition comprising a urethane oligomer having a polyester backbone |
US6391936B1 (en) | 1997-12-22 | 2002-05-21 | Dsm N.V. | Radiation-curable oligomers radiation-curable compositions, coated optical glass fibers, and ribbon assemblies |
US6797746B2 (en) * | 1998-12-22 | 2004-09-28 | Vidriera Monterrey, S.A. De C.V. | Ultraviolet radiation curable ink composition and a process for its application on glass substrates |
US6171698B1 (en) * | 1999-08-19 | 2001-01-09 | Alcatel | Radiation curable coating composition for optical fibers and optical fibers coated thereby |
DE10049153A1 (en) * | 2000-09-27 | 2002-04-11 | Degussa | Paint, varnish, pollutants, bioorganisms, oil, water, and / or dirt-repellent coating |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57209855A (en) * | 1981-06-17 | 1982-12-23 | Unitika Ltd | Water-based sizing agent for glass fiber |
US4932750A (en) * | 1982-12-09 | 1990-06-12 | Desoto, Inc. | Single-coated optical fiber |
US4472019A (en) | 1982-12-28 | 1984-09-18 | Desoto, Inc. | Topcoats for buffer-coated optical fiber using urethane acrylate and epoxy acrylate and vinyl monomer |
JPS6083907A (en) * | 1983-10-14 | 1985-05-13 | Nitto Electric Ind Co Ltd | Coating material for optical glass fiber |
CA1236623A (en) | 1983-11-10 | 1988-05-10 | Timothy E. Bishop | Ultraviolet-curable coatings for optical glass fibers having improved adhesion |
EP0250631A1 (en) | 1986-07-02 | 1988-01-07 | DeSOTO, INC. | Ultraviolet curable buffer coatings for optical fiber |
JPH0781488B2 (en) | 1988-07-13 | 1995-08-30 | 株式会社東電通 | Shield machine propulsion device |
DE3914411A1 (en) * | 1989-04-29 | 1990-11-15 | Basf Lacke & Farben | LIQUID, RADIANT-COVERABLE COATING MEASUREMENT FOR THE COATING OF GLASS SURFACES |
JPH0513885A (en) | 1991-07-04 | 1993-01-22 | Mitsubishi Electric Corp | Manufacture of visible light semiconductor laser |
-
1988
- 1988-12-02 DE DE3840644A patent/DE3840644A1/en not_active Ceased
-
1989
- 1989-11-17 EP EP89912446A patent/EP0446222B1/en not_active Revoked
- 1989-11-17 DE DE8989912446T patent/DE58903477D1/en not_active Revoked
- 1989-11-17 ES ES198989912446T patent/ES2039097T3/en not_active Expired - Lifetime
- 1989-11-17 WO PCT/EP1989/001382 patent/WO1990006289A1/en active IP Right Grant
- 1989-11-17 BR BR898907803A patent/BR8907803A/en not_active Application Discontinuation
- 1989-11-17 JP JP1511562A patent/JPH0776120B2/en not_active Expired - Lifetime
- 1989-11-17 KR KR1019900701680A patent/KR930006328B1/en not_active IP Right Cessation
- 1989-11-17 AU AU45121/89A patent/AU624196B2/en not_active Ceased
- 1989-12-01 CA CA002004407A patent/CA2004407A1/en not_active Abandoned
-
1991
- 1991-05-31 FI FI912625A patent/FI96432C/en not_active IP Right Cessation
- 1991-05-31 DK DK103991A patent/DK166079C/en active
-
1993
- 1993-05-06 LT LTIP529A patent/LT3310B/en not_active IP Right Cessation
- 1993-05-27 LV LV930429A patent/LV10766A/en unknown
-
1994
- 1994-04-05 MD MD94-0077A patent/MD940077A/en unknown
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5527835A (en) * | 1992-04-24 | 1996-06-18 | Borden, Inc. | Organic solvent and water resistant hydrolytically stable ultraviolet radiation curable coatings for optical fibers |
US5538791A (en) * | 1992-04-24 | 1996-07-23 | Borden, Inc. | Organic solvent and water resistant, thermally, oxidatively and hydrolytically stable radiation-curable coatings for optical fibers, optical fibers coated therewith and processes for making same |
US5587403A (en) * | 1992-04-24 | 1996-12-24 | Borden, Inc. | Organic solvent & water resistant hydrolytically stable ultraviolet radiation curable coatings for optical fibers |
Also Published As
Publication number | Publication date |
---|---|
FI912625A0 (en) | 1991-05-31 |
WO1990006289A1 (en) | 1990-06-14 |
AU624196B2 (en) | 1992-06-04 |
ES2039097T3 (en) | 1993-08-16 |
EP0446222A1 (en) | 1991-09-18 |
DK166079C (en) | 1993-08-02 |
BR8907803A (en) | 1991-08-27 |
LT3310B (en) | 1995-06-26 |
DE58903477D1 (en) | 1993-03-18 |
MD940077A (en) | 1996-01-31 |
DK103991D0 (en) | 1991-05-31 |
JPH0776120B2 (en) | 1995-08-16 |
FI96432C (en) | 1996-06-25 |
FI96432B (en) | 1996-03-15 |
DE3840644A1 (en) | 1990-06-07 |
KR910700207A (en) | 1991-03-14 |
DK166079B (en) | 1993-03-08 |
LTIP529A (en) | 1994-11-25 |
JPH03505197A (en) | 1991-11-14 |
DK103991A (en) | 1991-07-18 |
KR930006328B1 (en) | 1993-07-14 |
LV10766A (en) | 1995-08-20 |
AU4512189A (en) | 1990-06-26 |
EP0446222B1 (en) | 1993-02-03 |
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