US20020002262A1 - Uv-stabilizers for siloxane systems - Google Patents
Uv-stabilizers for siloxane systems Download PDFInfo
- Publication number
- US20020002262A1 US20020002262A1 US09/445,113 US44511399A US2002002262A1 US 20020002262 A1 US20020002262 A1 US 20020002262A1 US 44511399 A US44511399 A US 44511399A US 2002002262 A1 US2002002262 A1 US 2002002262A1
- Authority
- US
- United States
- Prior art keywords
- siloxane
- hydroxybenzotriazole
- coating
- general formula
- stabiliser mixture
- 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.)
- Granted
Links
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000012963 UV stabilizer Substances 0.000 title abstract 2
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 25
- 239000004417 polycarbonate Substances 0.000 claims abstract description 25
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims abstract description 15
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000077 silane Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- 150000004756 silanes Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000004922 lacquer Substances 0.000 description 14
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- FBMPWJWZZAAOHP-UHFFFAOYSA-N 4-[3-(benzotriazol-2-yl)-5-cyclohexyl-4-hydroxyphenyl]butanoic acid Chemical compound OC=1C(N2N=C3C=CC=CC3=N2)=CC(CCCC(=O)O)=CC=1C1CCCCC1 FBMPWJWZZAAOHP-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- QOBSKHIXSSCBTM-UHFFFAOYSA-N C.CC=O.CC=O Chemical compound C.CC=O.CC=O QOBSKHIXSSCBTM-UHFFFAOYSA-N 0.000 description 2
- WVFTUSFVHUZVQZ-UHFFFAOYSA-N C1=CC2=C(C=C1)N1OC3=C(C=CC=C3)N1N2.CC.CC.CCC(=O)OC Chemical compound C1=CC2=C(C=C1)N1OC3=C(C=CC=C3)N1N2.CC.CC.CCC(=O)OC WVFTUSFVHUZVQZ-UHFFFAOYSA-N 0.000 description 2
- ZHVUQBCJXOGFLB-UHFFFAOYSA-N CC(C)(C)C1=CC(C(=O)O)=CC(N2N=C3C=CC=CC3=N2)=C1O.CC(C)(C)C1=CC(CCC(=O)O)=CC(N2N=C3C=CC(Cl)=CC3=N2)=C1O.CC(C)(C)C1=CC(CCC(=O)O)=CC(N2N=C3C=CC=CC3=N2)=C1O.CC1=CC(N2N=C3C=CC=CC3=N2)=C(O)C(CCCC(=O)O)=C1.CCC(C)(C)C1=CC(CCC(=O)O)=CC(N2N=C3C=CC=CC3=N2)=C1O.O=C(O)CCC1=CC(N2N=C3C=CC=CC3=N2)=C(O)C(C2CCCCC2)=C1.O=C(O)CCCC1=CC(N2N=C3C=CC=CC3=N2)=C(O)C(C2CCCCC2)=C1 Chemical compound CC(C)(C)C1=CC(C(=O)O)=CC(N2N=C3C=CC=CC3=N2)=C1O.CC(C)(C)C1=CC(CCC(=O)O)=CC(N2N=C3C=CC(Cl)=CC3=N2)=C1O.CC(C)(C)C1=CC(CCC(=O)O)=CC(N2N=C3C=CC=CC3=N2)=C1O.CC1=CC(N2N=C3C=CC=CC3=N2)=C(O)C(CCCC(=O)O)=C1.CCC(C)(C)C1=CC(CCC(=O)O)=CC(N2N=C3C=CC=CC3=N2)=C1O.O=C(O)CCC1=CC(N2N=C3C=CC=CC3=N2)=C(O)C(C2CCCCC2)=C1.O=C(O)CCCC1=CC(N2N=C3C=CC=CC3=N2)=C(O)C(C2CCCCC2)=C1 ZHVUQBCJXOGFLB-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000006120 scratch resistant coating Substances 0.000 description 2
- 230000003678 scratch resistant effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NZUIPXSOGZSXQZ-UHFFFAOYSA-N CO[Si](CCC1CCC2OC2C1)(OC)OC.CO[Si](OC)(OC)C1CO1 Chemical compound CO[Si](CCC1CCC2OC2C1)(OC)OC.CO[Si](OC)(OC)C1CO1 NZUIPXSOGZSXQZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910020381 SiO1.5 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- DQAJDDUCDILVLR-UHFFFAOYSA-N aluminum 2,2,2-tributoxyethanolate Chemical compound [Al+3].CCCCOC(C[O-])(OCCCC)OCCCC.CCCCOC(C[O-])(OCCCC)OCCCC.CCCCOC(C[O-])(OCCCC)OCCCC DQAJDDUCDILVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- UTPQWRVOSYXUHO-UHFFFAOYSA-N trimethoxy-[1-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(C(C)[Si](OC)(OC)OC)CCC2OC21 UTPQWRVOSYXUHO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to non-volatile UV-stabilising mixtures for siloxane lacquer systems, which mixtures have certain hydroxybenzotriazoles as the UV-stabilising active structure and which are thus particularly suitable for the UV-stabilisation of thermoplastics, in particular of aromatic polycarbonates.
- These lacquers may contain so-called UV-stabilising substances in order to protect the lacquer itself and the underlying material, the so-called substrate, from harmful UV radiation.
- UV-stabilising substances Apart from providing long-term UV protection, one requirement placed upon these substances is, inter alia, that they are not volatile so that they remain homogeneously distributed within the lacquer layer and do not escape from the lacquer layer either during curing or during subsequent use of the laquer.
- the UV-stabilising substances must furthermore not decompose rapidly, must be durably homogeneously miscible with the lacquers and the lacquer containing the UV-stabilising substances should be transparent.
- U.S. Pat. No. 4,278,804 and U.S. Pat. No. 4,051,161 relate to UV-stabilising active substances and lacquers containing them.
- the substances disclosed therein exhibit the disadvantage that they provide inadequate UV protection, they decompose too rapidly and/or the siloxane system containing the stabilisers has a yellow tinge.
- U.S. Pat. No. 5,438,142 furthermore discloses the UV-stabilising active substance, 1-(3′-(benzotriazol-2′′-yl)-4′-hydroxyphenyl)-1,1-bis(4-hydroxyphenyl)ethane.
- This active substance exhibits the disadvantage that it is not durably miscible with siloxane-based lacquers.
- R 1 H, C 1 -C 18 alkyl, C 5 -C 6 cycloalkyl, C 6 -C 12 aryl,
- R 2 H, halogen, preferably Cl, or C 1 -C 12 alkyl,
- R 3 a single bond, C 1 -C 12 alkylene, C 5 -C 6 cycloalkylene or phenylene,
- R 4 H, alkali metal, ammonium, alkaline earth metal, C-C 12 alkyl,
- the present invention furthermore provides UV-stabilising mixtures having a molar ratio of epoxy groups of the silane to the hydroxybenzotriazole of the general formula (1) which is greater than 1.4, preferably greater than 2, particularly preferably greater than 8.
- the molar ratio of epoxy units of the silane to the hydroxybenzotriazole of the general formula (1) should not, however, exceed 1:100.
- mixtures according to the invention are suitable for the UV-stabilisation of siloxane systems, in particular of scratch- and abrasion-resistant siloxane coating
- the mixtures according to the invention are suitable for the UV-stabilisation of siloxane systems, in particular of scratch- and abrasion-resistant siloxane coating materials.
- Such UV-stabilised coating materials preferably lacquers, may be used for coating materials of all kinds, such as for example wood, textiles, paper, stone articles, but preferably for coating plastics, metals, glass and ceramics, particularly preferably for coating thermoplastics and very particularly preferably for coating polycarbonates.
- hydroxybenzotriazoles used for the non-volatile, UV-stabilising mixtures according to the invention are compounds of the general formula (1).
- Preferred compounds of the formula (1) are:
- Silanes containing epoxy groups are generally taken to mean compounds which, on the one hand, possess at least one epoxy ring and simultaneously have groups which form silanol structures under hydrolysing conditions.
- Epoxysilanes as are preferably used according to the invention are described, for example, in U.S. Pat. No. 2,946,701. They are compounds of the formulae (2) or (3):
- R 5 is a divalent hydrocarbon residue having at most 9 carbon atoms or a divalent residue having at most 9 carbon atoms consisting of C, H and O atoms, wherein the O atom is present as an ether bond residue.
- R 5 is preferably —CH 2 OCH 2 CH 2 CH 2 —.
- R 6 is an aliphatic hydrocarbon residue having at most 4 carbon atoms, an acyl residue having at most 4 carbon atoms or a residue of the formula (CH 2 CH 2 O) n Z, in which n is at least 1 and Z means an aliphatic hydrocarbon residue having at most 4 carbon atoms;
- m is 0 or 1.
- the UV-stabilising components are produced by homogeneously mixing compounds of the general formula (1) with the hydrolysable silanes containing epoxy groups and heating this mixture. Heating should be performed for at least 30 minutes at at least 90° C. The temperature should preferably be above 120° C. during heating. It has proved particularly favourable to use a mixing ratio at which stoichiometrically more epoxy groups are present than the —R 3 —CO—OR 4 — groups of the hydroxybenzotriazole of the general formula 1.
- the molar ratio of epoxy units of the silane to the hydroxy-benzotriazole of the general formula (1) should thus be greater than 1.4, preferably greater than 2, particularly preferably greater than 8.
- the UV-stabilising components need not necessarily be produced separately so that they may subsequently be added to the siloxane system to be stabilised, but may also be synthesised in situ as a sub-stage during synthesis of the siloxane systems/siloxane coating materials.
- the siloxane systems are substantially thermally curing systems which preferably crosslink by a condensation reaction to yield —Si—O—Si— linkages. Other crosslinking mechanisms may proceed in parallel. Such systems are described, for example, in U.S. Pat. Nos.
- the present invention accordingly also provides siloxane systems UV-stabilised according to the invention.
- Preferably used siloxane systems are those containing particulate material selected from among oxides, oxide hydrates, nitrides and carbides of Si, Al, Sb and B and of transition metals, preferably Ti, Ce, Fe and Zr, and having a particle size in the range from 1 to 100 nm, preferably from 2 to 50 nm.
- the UV-stabilising mixture according to the invention should be added to the siloxane system in such a quantity, relative to the solids content of the siloxane system, that the proportion of hydroxybenzotriazole, relative to the solids content of the siloxane system, is 0.3 to 20, preferably 3 to 15, particularly preferably 5 to 10 wt. %.
- the siloxane systems provided with the UV-stabilising mixture according to the invention may be used as bulk materials and as coating materials.
- substrate materials which may be selected for coating.
- These UV-stabilised coating materials are preferably suitable for coating wood, textiles, paper, stone articles, metals, glass, ceramics and plastics and in particular for coating thermoplastics, as are for example described in Becker/Braun Kunststoffhandbuch , Carl Hanser Verlag, Kunststoff, Vienna, 1972. They are very particularly suitable for coating transparent thermoplastics, preferably polycarbonates.
- the coating is applied to film thicknesses of, for example, 2 to 200 ⁇ m, preferably of 2 to 30 ⁇ m and particularly preferably of 5 to 15 ⁇ m.
- the substrate may optionally be primed with a coupling agent or primer coat before application of the coating.
- the lacquers are preferably cured at temperatures of >90° C.
- thermoplastic, aromatic polycarbonates include both homopolycarbonates and copolycarbonates; the polycarbonates may, in a known manner, be linear or branched.
- a proportion, up to 80 mol %, preferably of 20 mol % to 50 mol % of the carbonate groups in the suitable polycarbonates may be replaced by aromatic dicarboxylic acid ester groups.
- aromatic dicarboxylic acid ester groups Such polycarbonates, which contain both acid residues of carbonic acid and acid residues of aromatic dicarboxylic acids incorporated in the molecular chain, are more accurately termed aromatic polyester carbonates. They are to be subsumed within the superordinate term of thermoplastic, aromatic polycarbonates.
- thermoplastic polycarbonates have average molecular weights ⁇ overscore (M) ⁇ w (determined by measuring relative viscosity at 25° C. in CH 2 Cl 2 at a concentration of 0.5 g per 100 ml of CH 2 Cl 2 ) of 12000 to 400000, preferably of 18000 to 80000 and in particular of 22000 to 60000.
- the present invention accordingly also provides coated materials, preferably polycarbonate and particularly preferably polycarbonate provided with a scratch-resistant coating.
- UV-stabilising component prepared from a1 and 3-glycidyloxypropyltrimethoxysilane (Glymo)
- the two components ⁇ ) and ⁇ ) are mixed together in a 1:1 ratio and dissolved in a mixture prepared from 60 parts by weight of n-butanol, 40 parts by weight of acetic acid and 20 parts by weight of toluene.
- a boehmite sol was produced by combining 12.82 g of acetic acid-stabilised (6.4 wt. % acetic acid) boehmite powder with 104.62 g of 0.1 n HCl. Subsequent ultrasonication (20 minutes) produced a transparent, colourless solution, 24.3 g of which were combined with a mixture prepared from 118.17 g of GPTS (3-glycidyloxypropyltrimethoxysilane) and 62.50 g of TEOS (tetraethyl orthosilicate). The reaction mixture was stirred for 2 hours at room temperature and then, while being cooled with ice, combined with 18.93 g of aluminium tributoxyethanolate. The resultant clear sol was stirred for 2 hours at room temperature and then, while being cooled with ice, combined with 93.14 g of the above boehmite sol and 79.30 g of butoxyethanol.
- GPTS 3-glycidyloxypropyl
- a 60 g portion of the UV-stabilising mixture 2 according to the invention was added to a 1000 g portion of each of coating sols I and II.
- Silica glass was coated with these compositions and UV light transmission measured with a Beckmann DU 70 photometer in the wavelength range from 250 to 600 mn.
- the coating film was 5 ⁇ m thick and absorbed >98% of the radiation of a wavelength of ⁇ 350 nm critical for polycarbonate.
- the film thickness of the scratch-resistant lacquers was approx. 5 ⁇ m after drying. Once curing was complete, the coated sheets were stored for 2 days at room temperature and then exposed to a defined quantity of UV radiation.
- Yellowing as a function of exposure time was used as the evaluation criterion for the weathering resistance of the lacquer-coated sheets.
- the corresponding yellowness of the sheets was determined as the Yellowness Index (Y.I.) to ASTM D 1925-70.
Abstract
A UV-stabilizer comprising a mixture of hydroxybenzotriazole and a hydrolyzable silane containing at least one epoxy group is disclosed. The stabilizer is especially suitable as a component of a siloxane system for coating substrates, especially thermoplastic substrates and most especially polycarbonate substrates.
Description
- The present invention relates to non-volatile UV-stabilising mixtures for siloxane lacquer systems, which mixtures have certain hydroxybenzotriazoles as the UV-stabilising active structure and which are thus particularly suitable for the UV-stabilisation of thermoplastics, in particular of aromatic polycarbonates.
- Materials are frequently protected from the harmful influences of the environment by providing them with a protective surface. Siloxane-based lacquers have proved particularly suitable for this purpose, inter alia providing the materials with a scratch-resistant surface.
- These lacquers may contain so-called UV-stabilising substances in order to protect the lacquer itself and the underlying material, the so-called substrate, from harmful UV radiation. Apart from providing long-term UV protection, one requirement placed upon these substances is, inter alia, that they are not volatile so that they remain homogeneously distributed within the lacquer layer and do not escape from the lacquer layer either during curing or during subsequent use of the laquer. The UV-stabilising substances must furthermore not decompose rapidly, must be durably homogeneously miscible with the lacquers and the lacquer containing the UV-stabilising substances should be transparent.
- U.S. Pat. No. 4,278,804 and U.S. Pat. No. 4,051,161 relate to UV-stabilising active substances and lacquers containing them. The substances disclosed therein, however, exhibit the disadvantage that they provide inadequate UV protection, they decompose too rapidly and/or the siloxane system containing the stabilisers has a yellow tinge.
- U.S. Pat. No. 5,438,142 furthermore discloses the UV-stabilising active substance, 1-(3′-(benzotriazol-2″-yl)-4′-hydroxyphenyl)-1,1-bis(4-hydroxyphenyl)ethane. This active substance, however, exhibits the disadvantage that it is not durably miscible with siloxane-based lacquers.
- The object thus arises of providing a UV-stabiliser system which does not exhibit the above-stated disadvantages.
-
- R1: H, C1-C18 alkyl, C5-C6 cycloalkyl, C6-C12 aryl,
- R2: H, halogen, preferably Cl, or C1-C12 alkyl,
- R3: a single bond, C1-C12 alkylene, C5-C6 cycloalkylene or phenylene,
-
- The present invention furthermore provides UV-stabilising mixtures having a molar ratio of epoxy groups of the silane to the hydroxybenzotriazole of the general formula (1) which is greater than 1.4, preferably greater than 2, particularly preferably greater than 8. The molar ratio of epoxy units of the silane to the hydroxybenzotriazole of the general formula (1) should not, however, exceed 1:100.
- The mixtures according to the invention are suitable for the UV-stabilisation of siloxane systems, in particular of scratch- and abrasion-resistant siloxane coating
- The mixtures according to the invention are suitable for the UV-stabilisation of siloxane systems, in particular of scratch- and abrasion-resistant siloxane coating materials. Such UV-stabilised coating materials, preferably lacquers, may be used for coating materials of all kinds, such as for example wood, textiles, paper, stone articles, but preferably for coating plastics, metals, glass and ceramics, particularly preferably for coating thermoplastics and very particularly preferably for coating polycarbonates.
- The hydroxybenzotriazoles used for the non-volatile, UV-stabilising mixtures according to the invention are compounds of the general formula (1).
-
- The compounds of the formula (1) are either known from the literature or obtainable using processes known from the literature, for example in accordance with the reaction scheme disclosed on page 7 of EP-0 057 160. This patent application is introduced as a reference and is accordingly part of the disclosure of the present invention.
- Silanes containing epoxy groups are generally taken to mean compounds which, on the one hand, possess at least one epoxy ring and simultaneously have groups which form silanol structures under hydrolysing conditions.
-
- R5 is a divalent hydrocarbon residue having at most 9 carbon atoms or a divalent residue having at most 9 carbon atoms consisting of C, H and O atoms, wherein the O atom is present as an ether bond residue.
- R5 is preferably —CH2OCH2CH2CH2—.
- R6 is an aliphatic hydrocarbon residue having at most 4 carbon atoms, an acyl residue having at most 4 carbon atoms or a residue of the formula (CH2CH2O)nZ, in which n is at least 1 and Z means an aliphatic hydrocarbon residue having at most 4 carbon atoms;
- m is 0 or 1.
- Production of these epoxysilanes is also described in U.S. Pat. No. 2,946,701. This patent is accordingly introduced as a reference. Particularly preferred epoxysilanes are those compounds in which R6 is methyl. They are commercially available, inter alia from the companies Union Carbide and Hüls AG as:
- A-187 or Dynasilan Glymo 3-glycidyloxypropyltrimethoxysilane
- A-186 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
- Production of the UV-stabilising mixtures
- The UV-stabilising components are produced by homogeneously mixing compounds of the general formula (1) with the hydrolysable silanes containing epoxy groups and heating this mixture. Heating should be performed for at least 30 minutes at at least 90° C. The temperature should preferably be above 120° C. during heating. It has proved particularly favourable to use a mixing ratio at which stoichiometrically more epoxy groups are present than the —R3—CO—OR4— groups of the hydroxybenzotriazole of the general formula 1. The molar ratio of epoxy units of the silane to the hydroxy-benzotriazole of the general formula (1) should thus be greater than 1.4, preferably greater than 2, particularly preferably greater than 8.
- The UV-stabilising components need not necessarily be produced separately so that they may subsequently be added to the siloxane system to be stabilised, but may also be synthesised in situ as a sub-stage during synthesis of the siloxane systems/siloxane coating materials.
- Siloxane systems/siloxane coating materials
- The siloxane systems are substantially thermally curing systems which preferably crosslink by a condensation reaction to yield —Si—O—Si— linkages. Other crosslinking mechanisms may proceed in parallel. Such systems are described, for example, in U.S. Pat. Nos. 3,790,527, 3,865,755, 3,887,514, 4,243,720, 4,278,804, 4,680,232, 4,006,271, 4,476,281, in DE-A 4,011,045, 4,122,743, 4,020,316, 3,917,535, 3,706,714, 3,407,087, 3,836,815, 2,914,427, 3,135,241, 3,134,777, 3,100,532, 3,151,350, in DE-A 3,005,541, 3,014,411, 2,834,606, 2,947,879, 3,016,021, 2,914,427 and 4,338,361 and should be considered part of the present disclosure.
- The present invention accordingly also provides siloxane systems UV-stabilised according to the invention.
- Preferably used siloxane systems are those containing particulate material selected from among oxides, oxide hydrates, nitrides and carbides of Si, Al, Sb and B and of transition metals, preferably Ti, Ce, Fe and Zr, and having a particle size in the range from 1 to 100 nm, preferably from 2 to 50 nm.
- The UV-stabilising mixture according to the invention should be added to the siloxane system in such a quantity, relative to the solids content of the siloxane system, that the proportion of hydroxybenzotriazole, relative to the solids content of the siloxane system, is 0.3 to 20, preferably 3 to 15, particularly preferably 5 to 10 wt. %.
- Reference is made to DE-A 2 914 427 and DE-A 4 338 361 with regard to the production of siloxane-based scratch-resistant coating systems and components thereof and these documents are thus part of the present description.
- Substrates, materials
- The siloxane systems provided with the UV-stabilising mixture according to the invention may be used as bulk materials and as coating materials. There are no restrictions as to the substrate materials which may be selected for coating. These UV-stabilised coating materials are preferably suitable for coating wood, textiles, paper, stone articles, metals, glass, ceramics and plastics and in particular for coating thermoplastics, as are for example described in Becker/BraunKunststoffhandbuch, Carl Hanser Verlag, Munich, Vienna, 1972. They are very particularly suitable for coating transparent thermoplastics, preferably polycarbonates.
- Conventional coating processes are used for coating purposes, for example dipping, flooding, pouring, spinning, spraying or brushing.
- The coating is applied to film thicknesses of, for example, 2 to 200 μm, preferably of 2 to 30 μm and particularly preferably of 5 to 15 μm. The substrate may optionally be primed with a coupling agent or primer coat before application of the coating.
- The lacquers are preferably cured at temperatures of >90° C.
- For the purposes of the present invention, thermoplastic, aromatic polycarbonates include both homopolycarbonates and copolycarbonates; the polycarbonates may, in a known manner, be linear or branched.
- A proportion, up to 80 mol %, preferably of 20 mol % to 50 mol % of the carbonate groups in the suitable polycarbonates may be replaced by aromatic dicarboxylic acid ester groups. Such polycarbonates, which contain both acid residues of carbonic acid and acid residues of aromatic dicarboxylic acids incorporated in the molecular chain, are more accurately termed aromatic polyester carbonates. They are to be subsumed within the superordinate term of thermoplastic, aromatic polycarbonates.
- Details of the production of polycarbonates have been described in hundreds of patents over the past approx. 40 years. Reference is made, merely by way of example, to “Schnell, Chemistry & Physics of Polycarbonates”,Polymer Reviews, volume 9, Interscience Publishers, New York, London, Sydney 1964, to D.C. Prevorsek, B. T. Debona & Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Morristown, N.J. 07960, “Synthesis of poly(ester carbonate) copolymers” in Journal of Polymer Science, Polymer Chemistry edition, volume 19, 75-90 (1980), to D. Freitag, U. Grigo, P. R. Müller, N. Nouvertne', Bayer A G, “Polycarbonates” in Encyclopedia of Polymer Science & Engineering, volume 11, second edition, 1988, pages 648-718 and finally to Dr. U. Grigo, Dr. K. Kircher & Dr. P. R. Müller “Polycarbonate” in Becker/Braun, Kunststoff-Handbuch, volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag, Munich, Vienna, 1992, pages 117-299.
- The thermoplastic polycarbonates have average molecular weights {overscore (M)}w (determined by measuring relative viscosity at 25° C. in CH2Cl2 at a concentration of 0.5 g per 100 ml of CH2Cl2) of 12000 to 400000, preferably of 18000 to 80000 and in particular of 22000 to 60000.
- The present invention accordingly also provides coated materials, preferably polycarbonate and particularly preferably polycarbonate provided with a scratch-resistant coating.
- a) UV-absorbing starting materials
- a1) 2-(2-hydroxy-3 -tert.-butyl-5-(2-carboxyethyl)phenyl)benzotriazole, m.p. 195° C. (produced as in EP 0 057 160, Example 1)
- a2) 2-(2-hydroxy-3-cyclohexyl-5(3-carboxypropyl)phenyl)benzotriazole
- α) 132 g (0.75 mol) of 2-cyclohexylphenol are dissolved in 800 ml of dry chlorobenzene. 200 g (1.5 mol) of AlCl3 are then added at 5 to 10° C. followed at 0 to 10° C. by a solution of 73.5 g (0.75 mol) of maleic anhydride in 400 ml of chlorobenzene. After 12 hours at room temperature, the mixture is poured into iced water and acidified with concentrated HCl. 85 g of a powder having an m.p. of 187 to 190° C. are obtained.
- β) 34.5 g (0.25 mol) of o-nitroaniline are stirred in 300 ml of water and 69 ml of concentrated HCl. A solution of 17.3 g (0.25 mol) of sodium nitrite in 155 ml of water is then added dropwise at 5° C. This solution is then added dropwise at 5° C. to a solution of 68.5 g (0.25 mol) of compound α and 79.5 g (0.75 mol) of sodium carbonate in 1 liter of water. 117 g of a solid having an m.p. of 155° C. are obtained.
- γ) 42.5 g (0.1 mol) of the azo dye β are combined with 200 ml of 2 n NaOH. 50 g of zinc powder are then added and 80 ml of 10 n NaOH are run in within 1 hour such that the temperature remains below 45° C. The mixture is then heated to 90° C. for 4 hours, filtered and the filtrate acidified with HCl.
- After recrystallisation from cyclohexane, 31 g of 2-(2-hydroxy-3-cyclohexyl-5-(3-carboxypropyl)phenyl)benzotriazole are obtained as colourless crystals of an m.p. of 165° C.
- b) UV-stabilising component prepared from a1 and 3-glycidyloxypropyltrimethoxysilane (Glymo)
- 50 g of a1 and 450 g of 3-glycidyloxypropyltrimethoxysilane are introduced into a vessel and heated to 140 to 150° C. under a nitrogen atmosphere while being stirred and are maintained at this temperature for one hour.
This mixture (mixture 1) was varied as follows: Mixture: 2 100 g a1 400 g Glymo 3 150 g a1 350 g Glymo 4 200 g a1 300 g Glymo 5 100 g a1 400 g α-(3,4-epoxycyclohexyl)ethyltri- methoxysilane - c) Production of the siloxane coating material according to DE-A 2 914 427 (coating sol I)
- α) 19.8 g of glacial acetic acid, 210 g of distilled water and 227 g of isopropanol are added to 300 g of colloidal silicic acid having an SiO2 content of 30 wt. %. After thorough mixing, 900 g of methyltriethoxy-silane are added and the mixture heated to 60° C. while being stirred. The mixture is left at this temperature for 4 hours and then a further 1200 g of isopropanol are added to the mixture. Once the product has cooled to room temperature, the slightly opaque solution is filtered.
- β) 340 g of isopropanol, 190 g of tetraethoxysilane and 360 g of methyltriethoxysilane are introduced into a vessel fitted with a stirrer and reflux condenser. This mixture is combined with 180 g of 0.05 n hydrochloric acid and co-hydrolysed by refluxing for five hours. The mixture is cooled to room temperature after the reaction. A solution is obtained which is a partial hydrolysate of tetraethoxysilane (5.1%, calculated as SiO2) and a partial hydrolysate of methyltriethoxysilane (12.6%, calculated as CH3SiO1.5).
- Before use as a coating material, the two components α) and β) are mixed together in a 1:1 ratio and dissolved in a mixture prepared from 60 parts by weight of n-butanol, 40 parts by weight of acetic acid and 20 parts by weight of toluene.
- d) Production of a siloxane coating material according to DE-A 4 338 361 (coating sol II)
- A boehmite sol was produced by combining 12.82 g of acetic acid-stabilised (6.4 wt. % acetic acid) boehmite powder with 104.62 g of 0.1 n HCl. Subsequent ultrasonication (20 minutes) produced a transparent, colourless solution, 24.3 g of which were combined with a mixture prepared from 118.17 g of GPTS (3-glycidyloxypropyltrimethoxysilane) and 62.50 g of TEOS (tetraethyl orthosilicate). The reaction mixture was stirred for 2 hours at room temperature and then, while being cooled with ice, combined with 18.93 g of aluminium tributoxyethanolate. The resultant clear sol was stirred for 2 hours at room temperature and then, while being cooled with ice, combined with 93.14 g of the above boehmite sol and 79.30 g of butoxyethanol.
- e) UV-stabilised coating sols I and II
- A 60 g portion of the UV-stabilising mixture 2 according to the invention was added to a 1000 g portion of each of coating sols I and II. Silica glass was coated with these compositions and UV light transmission measured with a Beckmann DU 70 photometer in the wavelength range from 250 to 600 mn. The coating film was 5 μm thick and absorbed >98% of the radiation of a wavelength of <350 nm critical for polycarbonate.
- Coating of substrates and testing of coating properties
- Bisphenol A polycarbonate sheets (Tg=147° C., Mw 27500) of dimensions 105×150×4 mm were cleaned with isopropanol and primed by dipping in a mixture prepared from 3 wt. % of aminopropyltrimethoxysilane and 97 wt. % of ethylene glycol monobutyl ether followed by 30 minutes' heat treatment at 130° C. The sheets were then provided with a 20 μm film of one of coating sols I or II at a dipping speed V=100 cm/min. After flashing off for 10 minutes at room temperature, the coated sheets were dried for 1 hour at 130° C. The film thickness of the scratch-resistant lacquers was approx. 5 μm after drying. Once curing was complete, the coated sheets were stored for 2 days at room temperature and then exposed to a defined quantity of UV radiation.
- UV exposure testing
- The polycarbonate sheets were exposed to filtered xenon arc radiation with a water spray cycle to DIN 53387-1-A-X under the following test conditions:
Weathering apparatus: Xenon-WOM Radiation intensity at 340 nm: 0.35 W/m2 (preferably) Filter combination: inner: Pyrex, outer: Pyrex Blackboard temperature: 60° C. ± 5° C. Black standard temperature: 65° C. ± 3° C. Mode of operation: constant Water spray cycle: 102:18 Relative atmospheric humidity: 60-80% - Yellowing as a function of exposure time was used as the evaluation criterion for the weathering resistance of the lacquer-coated sheets. The corresponding yellowness of the sheets was determined as the Yellowness Index (Y.I.) to ASTM D 1925-70.
- Y.I. values after Xenon-WOM 102:18 weathering
1000 2000 3000 5000 Specimens 0 h h h h h Polycarbonate with UV-stabilised 2.1 2.2 2.7 2.8 4.3 coating sol I according to mixture 2 Polycarbonate with UV-stabilised 2.5 2.7 3.2 3.3 4.8 coating sol II according to mixture 2 Comparison Polycarbonate with coating sol I 1.8 2.2 6.4a) 7.6a) —b) without UV stabilisation Polycarbonate with coating sol II 1.9 2.6 6.3a) 7.9a) —b) without UV stabilisation
Claims (10)
1. UV-stabiliser mixture containing
A) hydroxybenzotriazole according to the general formula (1):
R1: H, C1-C18 alkyl, C5-C6 cycloalkyl, C6-C12 aryl,
R2: H, halogen, preferably Cl, or C1-C12 alkyl,
R3: a single bond, C1-C12 alkylene, C5-C6 cycloalkylene or phenylene,
R4: H, alkali metal, ammonium, alkaline earth metal, C1-C12 alkyl,
and
B) hydrolysable silanes containing epoxy groups.
2. UV-stabiliser mixture according to claim 1 , characterised in that the molar ratio of epoxy groups of the silane to the hydroxybenzotriazole of the general formula (1) is greater than 1.4.
4. Process for the production of a UV-stabiliser mixture according to anyone of claims 1-3, characterised in that the hydroxybenzotriazole of the general formula (1) and the hydrolysable silanes containing epoxy groups are mixed and heated to at least 90° C. for at least 30 minutes.
5. Siloxane system containing a UV-stabiliser mixture according to anyone of claims 1 to 3 .
6. Siloxane system containing a UV-stabiliser mixture obtained according to claim 4 .
7. Siloxane system according to claim 5 or 6, characterised in that the proportion of hydroxybenzotriazole relative to the solids content of the siloxane system is 0.3 to 20.
8. Siloxane coating material containing a siloxane system according to anyone of claims 5 to 7 and optionally particulate material consisting of a compound selected from the group consisting of oxides, oxide hydrates, nitrides and carbides of Si, Al, Sb and B and of transition metals, preferably Ti, Ce, Fe and Zr, wherein the material has a particle size in the range from 1 to 100 nm.
9. Use of the siloxane coating material according to claim 8 for coating substrate materials of any kind, preferably thermoplastics, particularly preferably polycarbonates.
10. Coated material, preferably polycarbonate, characterised in that at least the surfaces of the material exposed to radiation are coated with a siloxane coating material according to claim 8.
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PCT/EP1998/003157 WO1998056853A1 (en) | 1997-06-10 | 1998-05-28 | Uv-stabilizers for siloxane systems |
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- 1998-05-15 TW TW087107508A patent/TW459011B/en active
- 1998-05-28 IL IL13279598A patent/IL132795A0/en unknown
- 1998-05-28 BR BR9810434-9A patent/BR9810434A/en not_active IP Right Cessation
- 1998-05-28 AU AU79163/98A patent/AU7916398A/en not_active Abandoned
- 1998-05-28 DK DK98929392T patent/DK0988340T3/en active
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- 1998-05-28 WO PCT/EP1998/003157 patent/WO1998056853A1/en active IP Right Grant
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- 1998-05-28 JP JP50143499A patent/JP4228124B2/en not_active Expired - Fee Related
- 1998-05-28 ID IDW991375A patent/ID23428A/en unknown
- 1998-05-28 CN CN98806105A patent/CN1124309C/en not_active Expired - Fee Related
- 1998-05-28 EP EP98929392A patent/EP0988340B1/en not_active Expired - Lifetime
- 1998-05-28 KR KR1019997011582A patent/KR100541298B1/en not_active IP Right Cessation
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US8044046B2 (en) | 2002-11-15 | 2011-10-25 | Boehringer Ingelheim Pharma Gmbh & Co Kg | Medicaments for the treatment of chronic obstructive pulmonary disease |
US8034809B2 (en) | 2004-05-14 | 2011-10-11 | Boehringer Ingelheim International Gmbh | Enantiomerically pure beta agonists, process for the manufacture thereof and use thereof as medicaments |
US20110124859A1 (en) * | 2005-08-15 | 2011-05-26 | Boehringer Ingelheim International Gmbh | Process for the manufacturing of betamimetics |
US8420809B2 (en) | 2005-08-15 | 2013-04-16 | Boehringer Ingelheim International Gmbh | Process for the manufacturing of betamimetics |
US20070195613A1 (en) * | 2006-02-09 | 2007-08-23 | Rajan Suresh N | Memory module with memory stack and interface with enhanced capabilities |
EP1988138A1 (en) * | 2006-02-24 | 2008-11-05 | Idemitsu Kosan Co., Ltd. | Coating composition, hardened film and resin laminate |
US20090011256A1 (en) * | 2006-02-24 | 2009-01-08 | Idemitsu Kosan Co., Ltd. | Coating composition, hardened film and resin laminate |
EP1988138A4 (en) * | 2006-02-24 | 2010-04-21 | Idemitsu Kosan Co | Coating composition, hardened film and resin laminate |
US11814408B2 (en) | 2012-05-08 | 2023-11-14 | Nicox Ophthalmics, Inc. | Preparations of hydrophobic therapeutic agents, methods of manufacture and use thereof |
Also Published As
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KR20010013575A (en) | 2001-02-26 |
DK0988340T3 (en) | 2002-05-21 |
DE19724397A1 (en) | 1999-01-14 |
WO1998056853A1 (en) | 1998-12-17 |
AU7916398A (en) | 1998-12-30 |
DE59802740D1 (en) | 2002-02-21 |
US6306512B1 (en) | 2001-10-23 |
IL132795A0 (en) | 2001-03-19 |
JP4228124B2 (en) | 2009-02-25 |
TW459011B (en) | 2001-10-11 |
CN1259973A (en) | 2000-07-12 |
EP0988340A1 (en) | 2000-03-29 |
JP2002511894A (en) | 2002-04-16 |
CA2293603C (en) | 2007-07-31 |
ID23428A (en) | 2000-04-20 |
KR100541298B1 (en) | 2006-01-12 |
ES2167903T3 (en) | 2002-05-16 |
CA2293603A1 (en) | 1998-12-17 |
EP0988340B1 (en) | 2001-11-21 |
CN1124309C (en) | 2003-10-15 |
BR9810434A (en) | 2000-09-19 |
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