EP2087036A2 - Compositions containing phosphonate-functional particles - Google Patents
Compositions containing phosphonate-functional particlesInfo
- Publication number
- EP2087036A2 EP2087036A2 EP07821621A EP07821621A EP2087036A2 EP 2087036 A2 EP2087036 A2 EP 2087036A2 EP 07821621 A EP07821621 A EP 07821621A EP 07821621 A EP07821621 A EP 07821621A EP 2087036 A2 EP2087036 A2 EP 2087036A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- weight
- parts
- groups
- composition
- 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.)
- Withdrawn
Links
- 239000002245 particle Substances 0.000 title claims abstract description 159
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000011877 solvent mixture Substances 0.000 claims abstract description 12
- -1 (meth) acrylato Chemical group 0.000 claims description 85
- 239000003973 paint Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 29
- 239000004848 polyfunctional curative Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000004593 Epoxy Chemical group 0.000 claims description 8
- 125000006239 protecting group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000003573 thiols Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000000394 phosphonato group Chemical group [O-]P([O-])(*)=O 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000004438 BET method Methods 0.000 claims description 2
- 239000013466 adhesive and sealant Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 238000004382 potting Methods 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 150000004756 silanes Chemical class 0.000 description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 51
- 238000000034 method Methods 0.000 description 36
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 6
- 229920002050 silicone resin Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000002296 dynamic light scattering Methods 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 210000000056 organ Anatomy 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 150000008051 alkyl sulfates Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 3
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910020175 SiOH Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UWVNWQLRMZWFMC-UHFFFAOYSA-N [dimethyl(pentan-3-yloxy)silyl]methylphosphonic acid Chemical compound CCC(CC)O[Si](C)(C)CP(O)(O)=O UWVNWQLRMZWFMC-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229940043279 diisopropylamine Drugs 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical group CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C09D5/34—Filling pastes
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
-
- 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
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Definitions
- the invention relates to phosphonate functional particle-containing compositions, composite materials prepared therefrom and the use of the compositions.
- Particles - especially nanoparticles - containing composite materials are state of the art.
- Corresponding coatings of composite materials are described for example in EP 1 249 470, WO 03/16370, US 20030194550 or US 20030162015.
- the particles lead to an improvement in the properties of the corresponding coatings, in particular with regard to their scratch resistance and optionally also their chemical resistance.
- a common problem with the use of - usually inorganic - particles in organic matrix systems consists in a usually insufficient compatibility of particles and matrix. This can lead to the particles not being able to disperse sufficiently well in the matrix. In addition, even well-dispersed particles can settle at longer stand or storage times, possibly forming larger aggregates or agglomerates which can not or only poorly be separated into the original particles by an energy input. The processing of such inhomogeneous systems is in any case extremely difficult, often even impossible. Composite materials that have smooth surfaces after their application and curing can usually not be produced in this way, or can only be produced by cost-intensive processes.
- particles which have on their surface organic groups, which to a lead to better compatibility with the surrounding matrix and thus suppress unwanted agglomeration or aggregation of the particles.
- the inorganic particle is masked by an organic shell.
- particularly favorable composite properties can often be achieved if the organic functions on the particle surfaces are also reactive with respect to the matrix, so that they can react with the matrix under the respective curing conditions. It is thus possible to chemically incorporate the particles into the matrix during the curing of the composite, which often results in particularly good mechanical properties but also in an improved form
- a disadvantage is the inadequate stability despite masking of the nanoparticles used in the prior art.
- This insufficient stability of the particles occurs on the one hand in the processing of the particles, in particular when concentrating the particle dispersions or a solvent exchange, on the other during the storage of the uncured particle dispersions to light.
- Indications of a lack of stability of the particles are an increase in viscosity, or the sedimentation of the particles, which often progresses until gelation.
- the described nanoparticles can not be isolated as redispersible solids due to the high agglomeration or aggregation tendency.
- the particles which can be produced according to the prior art fall on isolation, for example by spray drying, as
- Particle agglomerates or aggregates which also under energy input, for example by means of a bead mill or by ultrasonic treatment, not to achieve redispersing the original primary particle size.
- the surface-modified particles contained in the composite materials are prepared by reacting particles having free silanol (SiOH) or metal hydroxide functions with alkoxysilanes or their hydrolysis and condensation products containing unreactive groups, e.g. Alkyl or aryl radicals, or reactive organic functions, e.g. Vinyl, (meth) acrylic, carbinol, etc. included.
- the silanes used in the art for particle functionalization are typically di- or trialkoxysilanes.
- siloxane shell is formed around the particle in the presence of water after hydrolysis and condensation of the resulting silanols.
- Macromol. Chem. Phys. 2003, 204, 375-383 the formation of such a siloxane shell around a SiO 2 -
- the problem here may be that the siloxane shell formed still has a large number of SiOH functions on the surface.
- the stability of such SiOH functional particles is among the
- particle-reinforced paints which are described, for example, in EP 0 768 351, EP 0 832 947, EP 0 872 500 or DE 10247359, represent a particularly important type of composite material.
- Surface-modified particles are used as reinforcing fillers have sufficient compatibility with the paint matrix. By introducing the surface-modified particles, in particular the scratch resistance of paints can be significantly increased.
- the handling of the particles is extremely difficult due to their described limited stability.
- it is not possible to isolate the particles since the agglomerates which form in the course of the drying do not revert back to the original particle size, i. the size of the primary particles, can be separated.
- the mechanical hardnesses - and in particular the scratch resistance - of the particle-reinforced coatings are not sufficient for many applications.
- a coating resin of hydroxy-functional prepolymers in particular of hydroxy-functional polyacrylates and / or polyesters, used in the paint curing with an isocyanate-functional hardener (polyurethane coatings) and / or a melamine (melamine) for reaction to be brought.
- the polyurethane coatings are characterized by particularly good properties. In particular, polyurethane coatings have superior chemical resistance, while melamine coatings generally have better scratch resistance.
- these types of paints are used in particularly high-quality and demanding fields of application, for example as clearcoats or topcoats for OEM coatings in the automotive and vehicle industry. Likewise, most automotive refinish topcoats are of such systems.
- the layer thicknesses of these coatings are typically in the range from 20 to 50 ⁇ m.
- the former consist of two components, one of which consists essentially of the Isocyanathärter, while the paint resin is contained with its isocyanate-reactive groups in the second component. Both components must be stored and transported separately and may only be mixed shortly before processing, since the finished mixture has only a very limited pot life. Often cheaper, therefore, are the so-called 1K systems, which consist of only one component in which there is a hardener with protected isocyanate groups in addition to the paint resin.
- 1K coatings are thermally cured, whereby the protecting groups of the isocyanate units are cleaved off and the deprotected isocyanates are then cleaved with the Resin can react.
- Typical baking temperatures of such 1- component paints are 120-160 ° C.
- Melamine paints are generally 1-component paints, and the baking temperatures are typically in a comparable temperature range.
- a particularly advantageous way of achieving this object is the use of particles which have on their surface organo-functions which are reactive with the paint resin or with respect to the hardener.
- Such particles with suitable organ functions are already known in principle. Like their use in coatings, they are described, for example, in EP 0 768 351, EP 0 832 947, EP 0 872 500 or DE 10247359.
- the scratch resistance of paints can be significantly increased by the incorporation of such particles.
- the corresponding coatings have such high particle contents that the use of such paints in large series finishes will be difficult to realize, for reasons of cost alone.
- paint-containing paint systems are described, which are characterized in that there are more particles in a surface segment of the paint than in a bulk segment.
- the advantage of this particle distribution is the comparatively low particle concentration, which is needed for a significant improvement in the scratch resistance.
- the desired high affinity of the particles to the paint surface is achieved by applying a silicone resin as a surface-active agent to the particle surfaces.
- a disadvantage of this method is the fact that not only the silicone resin modification of the particles, but also the preparation of the silicone resins required for this purpose is itself technically complex. The latter is particularly problematic because it is necessary to achieve a good scratch resistance, the silicone resins with
- Organo-functions e.g. Carbinol functions to provide, over which the appropriately modified particles can be chemically incorporated in the lacquer hardening in the paint.
- Such functionalized silicone resins are not available commercially or only to a very limited extent. Above all, though, is the
- the object of the invention was therefore the development of a composition for a composite material, which overcomes the disadvantages of the prior art.
- the invention provides a composition (Z) comprising (a) 0.02-200 parts by weight of particles (P) which contain at least one structural element of the general formula [1],
- L is a divalent optionally substituted by carbinol, amino, halogen, epoxy, phosphonato, thiol, (meth) acrylato, carbamato groups substituted aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, the carbon chain by non-adjacent oxygen atoms, Sulfur atoms, or NR ⁇ - groups may be interrupted,
- R ⁇ is a hydrocarbon radical having 1-8 carbon atoms mean.
- Composite materials (K) which can be produced from the composition (Z) are likewise provided by the invention.
- the particles (P) in addition to functions of the general formula [1] additionally also at least one organofunctional group (F), which is reactive with the binder (B) or the curing agent (H).
- the composite materials (K) are coating systems which can be prepared from a coating composition (Z) comprising (a) 0.02-60 parts by weight of particles (P) containing at least one structural element of the general formula [1] .
- the invention is based on the discovery that the
- Composite materials (K) prepared from the compositions (Z) have excellent mechanical properties.
- the preparation of the compositions (Z) is due to the high stability of the particles (P) contained in the compositions (Z) compared to the methods of the prior art significantly easier. Due to the presence of the structural elements of the general formula [1], the particles (P) have an extremely low agglomeration or
- L preferably represents a bivalent alkyl radical of 1-8
- R ⁇ - is preferably an alkyl radical having 1-6 carbon atoms, in particular methyl or ethyl radical.
- R 1 is preferably an alkyl radical, in particular methyl, ethyl or butyl radical.
- composition (Z) preferably contains at least 0.05 parts by weight, more preferably at least 0.1 parts by weight of particles (P). In very advantageous
- Embodiments of the invention contains the composition (Z) at least 0.3 parts by weight, in particular at least 0.5 parts by weight of particles (P).
- the composition (Z) preferably contains at most 50 parts by weight, more preferably at most 25 parts by weight of particles (P).
- the composition (Z) contains at most 10 parts by weight, in particular at most 5 parts by weight of particles (P).
- the particles (P) preferably have a specific surface area of from 0.1 to 1000 m 2 / g, more preferably from 10 to 500 m 2 / g (measured by the BET method according to DIN EN ISO 9277 / DIN 66132).
- the average size of the primary particles is preferably less than 10 microns, more preferably less than 1000 nm, wherein the primary particles as aggregates (definition according to DIN 53206) and agglomerates (definition according to DIN 53206) may be present, depending on the external shear stress (eg due to the measurement conditions) can have sizes from 1 to 1000 ⁇ m, and the average particle size is determined by means of transmission electron microscopy (TEM) or the hydrodynamic equivalent diameter by means of photon correlation spectroscopy.
- TEM transmission electron microscopy
- particles are used as described in WO 2004/089961 but additionally have structural elements of the general formula [1].
- the structural elements of the general formula [1] can be covalently bonded via ionic or van der Waals interactions.
- the structural elements of the general formula [1] are covalently attached.
- the particles (P) are formed by reaction of particles (P1) with functions selected from metal-OH, metal-O-metal, Si-OH,
- Si-O-Si Si-O metal
- Si-X Si-X
- metal-OR 3 Si-OR 3 with silanes (S) or their hydrolysis, alcoholysis and
- Reacted condensation products which have at least one structural element of the general formula [1] and at least one reactive silyl group
- R 1 represents an optionally substituted alkyl radical
- X represents a halogen atom
- Y represents a halogen, a hydroxy or alkoxy group, a carboxylate or an enolate.
- R 1 is preferably an alkyl radical having 1 to 10, in particular 1 to 6 carbon atoms.
- the radicals methyl, ethyl, n-propyl and i-propyl are particularly preferred.
- X is preferably fluorine or chlorine.
- the radicals Y are preferably a halogen, hydroxyl or alkoxy groups.
- the radicals Y are particularly preferably chlorine atoms, hydroxyl, ethoxy or methoxy radicals.
- P particles (Pl) particles (Pl) which have functions that are selected from metal-OH, Si-OH, Si-X, metal-X, metal-OR 3 , Si-OR 3 , so takes place the attachment of the silanes (S) by hydrolysis and / or condensation. If in the particle (Pl) exclusively metal O metal, metal O-Si or Si-O-Si functions, can the covalent attachment of silanes (S) by an equilibration reaction.
- the procedure and the catalysts required for the equilibration reaction are familiar to the person skilled in the art and have been described many times in the literature.
- the silanes (S) used for modifying the particles (P1) have a structure of the general formula [2],
- R5 is hydrogen, an optionally substituted aliphatic or aromatic hydrocarbon having 1-6
- R ⁇ and R ° have the meanings of R ⁇ .
- n preferably assumes the value 1 or 3, particularly preferably the value 1.
- a is preferably 0 or 2, more preferably a is 2.
- R 1 is preferably one
- R ⁇ is preferably hydrogen and R ° is preferably methyl or ethyl radical.
- the silanes (S) or their hydrolysis or condensation products used for modifying the particles (P1) are preferably present in an amount greater than 1% by weight (based on the particles (P)), preferably greater than 5% by weight, particularly preferred greater than 8 wt .-% used.
- silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L) are preferably reactive toward the functions of the surface of the particle (P).
- the silanes (S1) and siloxanes (S3) have either silanol groups or hydrolyzable silyl functions, the latter being preferred.
- silanes (S1), silazanes (S2) and siloxanes (S3) may have organic functions (F) which are reactive towards the binder (B) or the curing agent (H), but silanes (S1), Silazanes (S2) and siloxanes
- silanes and siloxanes (S) are used without organ functions.
- the silanes and siloxanes (S) can be used as a mixture with the silanes (S1), silazanes (S2) or siloxanes (S3).
- the particles can also be successively functionalized with the different silane types.
- Suitable compounds (L) are, for example, metal alcoholates, e.g. Titanium (IV) isopropoxide or aluminum (III) butanolate, protective colloids such as e.g. Polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing polymers and emulsifiers such. ethoxylated alcohols and phenols (alkyl radical C4-C18, EO grade 3-
- metal alcoholates e.g. Titanium (IV) isopropoxide or aluminum (III) butanolate
- protective colloids such as e.g. Polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing polymers and emulsifiers such. ethoxylated alcohols and phenols (alkyl radical C4-C18, EO grade 3-
- alkali metal and ammonium salts of alkyl sulfates (C ⁇ -CI Q)
- the proportion by weight of the silanes (S1), silazanes (S2), siloxanes (S3) and compounds (L) is based on the total amount consisting of the silanes (S) and (S1), silazanes (S2), siloxanes (S3) and compounds (L) is formed, at least 1 wt .-%, particularly preferably at least 5% by weight.
- the use of the compounds (S1), (S2), (S3) and (L) is completely dispensed with.
- Z is halogen atom, pseudohalogen radical, Si-N-bonded amine radical,
- R8 is an aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, whose carbon chain may be interrupted by non-adjacent oxygen atoms, sulfur atoms, or NR ⁇ groups and optionally also has an organofunctional group (F), compared to the binder (B) or the Hardener (H) is reactive, and a + b is less than or equal to 4.
- a is preferably 0, 1 or 2 while b is preferably 0 or 1.
- R ' is preferably a methyl or ethyl radical.
- Z is preferably a chlorine atom.
- R ⁇ is preferably a radical containing functional groups of the carbinol type, amine, (meth) acrylate, epoxy, thiol, isocyanato, ureido and / or carbamate.
- silazanes (S2) or siloxanes (S3) are particularly preferably hexamethyldisilazane or hexamethyldisiloxane or linear siloxanes which carry side or terminal organofunctional groups used.
- silanes (S1) which carry an organofunctional group (F) which are reactive with the binder (B) or hardener (H).
- organofunctional group (F) which are reactive with the binder (B) or hardener (H).
- silanes (S1) are amino-functional silanes, such as, for example, aminopropyltrimethoxysilane, cyclohexylaminomethyltrimethoxysilane,
- Phenylaminomethyltrimethoxysilane silanes having unsaturated functions such as vinyltrimethoxysilane, methacrylatopropyltrimethoxysilane, methacrylatomethyltrimethoxysilane, epoxyfunctional silanes such as glycidoxypropyltrimethoxysilane, mercapto functional silanes such as
- suitable oxides (c1) are oxides having a covalent bond fraction in the metal-oxygen bond, preferably oxides of the 3.
- Main group such as boron, aluminum, gallium or indium oxides
- the 4th main group such as silica, germanium dioxide, tin oxide, tin dioxide, lead oxide, lead dioxide, or oxides of 4.
- Subgroups such as titanium oxide, zirconium oxide and hafnium oxide. Further examples are nickel, cobalt, iron, manganese, chromium and vanadium oxides.
- zeolites a list of suitable zeolites can be found in: Atlas of Zeolite Framework Types, 5th edition, Ch. Baerlocher, W.M. Meier D. H. Olson, Amsterdam: Elsevier 2001
- silicates aluminates, aluminophosphates, titanates and
- Aluminum phyllosilicates eg bentonites, montmorillonites, smectites, hectorites
- the particles (P 1) preferably having a specific surface area of from 0.1 to 1000 m 2 / g, particularly preferably from 10 to 500 m 2 / g (measured by the BET standard) Method according to DIN 66131 and 66132).
- the particles (P1) which preferably have an average diameter of less than 10 .mu.m, more preferably less than 1000 nm, can be present as aggregates (definition according to DIN 53206) and agglomerates (definition according to DIN 53206), which depends on the external shear stress (eg due to the measurement conditions) sizes may have from 1 to 1000 microns.
- the mean particle size is determined by
- TEM Transmission electron microscopy
- colloidal silicon or metal oxides which are generally present as a dispersion of the corresponding submicron-sized oxide particles in an aqueous or organic solvent are used as particles (P1).
- the oxides of the metals aluminum, titanium, zirconium, tantalum,
- silica sols are 1-50% by weight Solutions, preferably 20-40 wt .-% solutions.
- typical solvents are, above all, alcohols, in particular alcohols having 1 to 6 carbon atoms, frequently also isopropanol but also other usually low molecular weight alcohols, for example methanol, ethanol, n-propanol, n-butanol, isobutanol and t-butanol.
- the average particle size of the silica particles (P1) is generally 1-100 nm, preferably 5-50 nm, more preferably 8-30 nm.
- silica sols which are suitable for the preparation of the particles (P) are silica sols of the product series LUDOX® (Grace Davison), Snowtex® (Nissan Chemical), Klebosol® (Clariant) and Levasil® (HC Starck), silica sols in organic solvents such as IPA-ST (Nissan Chemical) or those silica sols which can be prepared by the Stöber process.
- the preparation of the particles (P) can be carried out by various processes. However, it is preferably carried out by addition of the silanes (S) or their hydrolysis or condensation products - optionally in a solvent and / or in mixtures with other silanes (S1), silazanes (S2) or siloxanes (S3) - to the particle (P1). or its solution in an aqueous or organic solvent.
- the reaction is generally carried out at temperatures of 0-200 0 C, preferably at 20-80 0 C and particularly preferably at 20-60 0 C.
- the reaction times are typically from 5 min to 48 h, preferably from 1 to 24 h.
- acidic, basic or heavy metal-containing catalysts are preferably used in traces ( ⁇ 1000 ppm). Especially However, preference is given to dispense with the addition of separate catalysts.
- the addition of water is preferred for the reaction of the particles (P1) with the silanes (S).
- colloidal silicon or metal oxides are often present in aqueous or alcoholic dispersion, it may be advantageous to exchange the solvent or solvents during or after the preparation of the particles (P) for another solvent or for another solvent mixture. This can be done for example by distillative removal of the original solvent, wherein the new solvent or solvent mixture in one or in several steps before, during or even after the
- Suitable solvents may be, for example, water, aromatic or aliphatic alcohols, wherein aliphatic alcohols, in particular aliphatic alcohols having 1 to 6 carbon atoms (eg methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, the various regioisomers of Pentanols and hexanols), esters (eg ethyl acetate, propyl acetate, butyl acetate, butyl diglycol acetate, methoxypropyl acetate), ketones (eg acetone, methyl ethyl ketone), ethers (eg diethyl ether, t-butyl).
- aliphatic alcohols in particular aliphatic alcohols having 1 to 6 carbon atoms (eg methanol, ethanol, n-propanol, isopropanol
- modified particles (P) obtained from the particles (P1) can be prepared by common methods such as for example, by evaporation of the solvents used or by drying, for example in a spray dryer, thin-film evaporator or condenser, are isolated as a powder. Alternatively, it is possible to dispense with isolation of the particles (P).
- processes for deagglomerating the particles can be used, such as pin mills or devices for grinding sifting, such as
- Pin mills Pin mills, hammer mills, countercurrent mills, bead mills, ball mills, impact mills or devices for grinding sifting.
- particles (P1) are organopolysiloxanes of the general formula [4],
- R ⁇ is an OH function, an optionally halogen, hydroxyl, amino, epoxy, thiol, (meth) acrylic, carbamate, ureido or NCO-substituted hydrocarbon radical having 1-18 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent oxygen, sulfur, or NR 2 -O- groups;
- R ⁇ O the meanings of R ⁇ , i, j, k, 1 denote a value of greater than or equal to 0, with the proviso that i + j + k + 1 are greater than or equal to 3, in particular at least 10, and that at least 1 Rest R ⁇ represents an OH function.
- the preparation of the particles (P) from the organopolysiloxanes (P1) of the general formula [4] takes place as described above.
- Hydrocarbons or any volatilizable or sprayable mixtures of organosilicon compounds, as mentioned, and hydrocarbons, e.g. in a hydrogen-oxygen flame, or even a carbon monoxide oxygen flame is produced.
- hydrocarbons e.g. in a hydrogen-oxygen flame, or even a carbon monoxide oxygen flame is produced.
- Silica can be carried out optionally with and without the addition of water, for example in the step of purification; preferred is no addition of water.
- Pyrogenic silica or silica is known for example from Ullmann's Encyclopedia of Industrial Chemistry 4th Edition, Volume 21, page 464.
- the unmodified fumed silica has a BET specific surface area, measured according to DIN EN ISO 9277 / DIN 66132 of
- the preparation of the particles (P) from fumed silica can be carried out by various methods. In a preferred embodiment,
- Silazanes (S2), siloxanes (S3) or compounds (L) - implemented Silazanes (S2), siloxanes (S3) or compounds (L) - implemented.
- Processes which are suitable for the production of particles (P) from fumed silica are known and have been described many times. Thus, for example, all processes described in WO 2006/018144, in which preferably powdered silica is functionalized, can also be used for the preparation of the particles (P) according to the invention.
- the fumed silica is preferably reacted with silanes (S), which preferably correspond to the formula [2], and optionally additional other silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L).
- the fumed silica is not powdered but in dispersions in water or typical industrially used solvents such as alcohols such as methanol, ethanol, i-propanol, such as ketones, such as acetone, methyl ethyl ketone, such as ethers, such as diethyl ether, THF, Hydrocarbons such as pentane, hexanes, aromatics such as toluene or other volatile solvents such as hexamethyldisiloxane or mixtures thereof with silanes (S) and optionally the silanes (Sl), silazanes (S2), siloxanes (S3) or compounds (L) implemented.
- solvents such as alcohols such as methanol, ethanol, i-propanol, such as ketones, such as acetone, methyl ethyl ketone, such as ethers, such as diethyl ether, THF, Hydrocarbons such as pentane, hexanes,
- the process can be carried out continuously or batchwise and be composed of one or more steps. Preferred is a continuous process.
- the modified fumed silica is prepared by a process in which the silica (1) is mixed in one of the abovementioned solvents, (2) with the silanes (S) and optionally the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) is reacted, and (3) freed of solvents, excess silanes and by-products.
- the dispersion (1), reaction (2) and drying (3) are preferably carried out in an atmosphere with less than 10% by volume of oxygen, more preferably less than 2.5% by volume, best results are achieved with less than 1% by volume of oxygen.
- the mixing (1) can by means of conventional mixing units such
- Anchor stirrer or bar stirrer optionally, the mixing under high shear by means of dissolvers, rotor-stator assemblies, optionally with direct metered addition into the shear gap, by means of ultrasonic generators or by means of grinding units such as ball mills.
- various of the above aggregates can be used in parallel or sequentially.
- silanes (S) and optionally of the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) with the silica are added in pure form or as a solution in suitable solvents of the silica dispersion and homogeneously mixed.
- the addition of the silanes (S) and optionally of the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) can be carried out in the container used to prepare the dispersion or in a separate reaction vessel. If the silanes are added in the dispersing container, this can take place parallel to or after completion of the dispersion.
- the silanes (S) and optionally the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) dissolved in the dispersing medium can be added directly in the dispersing step.
- water is added to the reaction mixture.
- the reaction mixture acidic catalysts such as Bronsted acids such as liquid or gaseous HCl, sulfuric acid, phosphoric acid or acetic acid, or basic
- Catalysts such as Brönsted bases such as liquid or gaseous ammonia, amines such as NEt3 or NaOH added.
- the reaction step is at a temperature of 0 0 C to 200 ° C, preferably 10 0 C to 180 0 C and more preferably carried out from 20 0 C to 150 0 C.
- the removal of solvents, excess silanes (S) and optionally silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) and by-products (3) can be carried out by means of dryers or by spray drying.
- an annealing step to complete the reaction may be connected to the drying step.
- drying processes for mechanical densification of the silica can be used, such as press rolls, grinding units, such as edge mills and ball mills, continuously or discontinuously, compaction by screws or screw mixer,
- Screw compressors Screw compressors, briquetting, or compacting by suction of the air or gas content by suitable vacuum methods.
- processes for the mechanical densification of the silica are used following the drying, such as compression by suction of the air or gas contents by suitable vacuum methods or pressure rollers or combination of both methods.
- processes for deagglomerating the silica can be used, such as pin mills, hammer mills, countercurrent mills, impact mills or devices for grinding sifting.
- the particles (P) are the particles (P) via a cohydrolysis of organosilanes (S) with other silanes (S4) or compounds (L).
- silanes (S4) it is possible to use all hydrolyzable silanes and silanes containing hydroxysilyl groups.
- silanes (S4) are tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane.
- S4 different mixtures of different silanes (S4) can be used. Mixtures can be used which, in addition to the silanes (S), contain only silanes (S4) without additional organ functions, as well
- silanes (S) and silanes (S4) without additional organo-function and silanes (S4) with additional organo function.
- the various silanes can be added together or successively.
- compositions (Z) may contain one or more different types of particles (P), for example modified silica and modified alumina.
- binder (B) both inorganic and organic polymers are used.
- polymer matrices (B) are polyethylenes, polypropylenes, polyamides, polyimides, polycarbonates, polyesters, polyetherimides, polyethersulfones, polyphenylene oxides, polyphenylene sulfides, polysulfones (PSU), polyphenylsulfones (PPSU), polyurethanes, polyvinyl chlorides, polytetrafluoroethylenes (PTFE), polystyrenes (PS ), Polyvinyl alcohols (PVA), polyether glycols (PEG), Polyphenylene oxides (PPO), polyaryletherketones, epoxy resins, polyacrylates, polymethacrylates and silicone resins.
- Polymers which are likewise suitable as binders (B) are oxidic materials which are accessible by customary sol-gel processes known to the person skilled in the art. According to the sol-gel process, hydrolyzable and condensable silanes and / or organometallic reagents are hydrolyzed by means of water and if appropriate in the presence of a catalyst and hardened by suitable methods to give the silicatic or oxidic materials.
- sol-gel materials can additionally be cured via their organic moiety.
- the curing of the organic fraction may - optionally after addition of further reactive organic components - u.a. thermally or by UV irradiation.
- sol-gel materials are suitable as matrix (B), which are accessible by reaction of an epoxy-functional alkoxysilane with an epoxy resin and optionally in the presence of an amine curing agent.
- sol-gel materials can be prepared from amino-functional alkoxysilanes and epoxy resins.
- Reactive resins are included Understood compounds having one or more reactive groups. Examples which may be mentioned here as reactive groups are hydroxy, amino, isocyanate, epoxide, mercapto groups, ethylenically unsaturated groups and moisture-crosslinking alkoxysilyl groups.
- the reactive resins can be polymerized by thermal treatment, actinic radiation and / or (air) moisture.
- the reactive resins may be present in monomeric, oligomeric and polymeric form. Examples of common reactive resins are: hydroxy-functional resins, e.g.
- H isocyanate-functional hardeners
- acrylic and methacrylic functional resins which can be cured thermally, by actinic radiation or by an amino-functional hardener (H) after addition of an initiator
- vinyl-functional siloxanes which can be crosslinked by reaction with a SiH-functional hardener (H)
- SiOH-functional siloxanes which can be cured by
- the binders (B) are preferably carbinol, (meth) acrylate, epoxy and isocyanate functional resins.
- the coating resins used are preferably hydroxyl-containing prepolymers, particularly preferably hydroxyl-containing polyacrylates or polyesters.
- hydroxyl-containing polyacrylates and polyesters are well known to those skilled in and widely described in the relevant literature. They are manufactured by many manufacturers and distributed commercially.
- Other suitable binders (B) are mixtures of various matrix polymers, corresponding copolymers, and monomeric, oligomeric and polymeric reactive resins.
- hardener (H) the compounds typically used for the abovementioned binders (B) are used.
- suitable hardeners are amino-, epoxy-, isocyanato-functional monomers, oligomers or polymers.
- compositions (Z), which are used in particular as a coating system may be 1-component (1K) or 2-component (2K) systems.
- hardeners (H) are preferably compounds which have protected isocyanate groups.
- preferred hardeners (H) are compounds with free ones
- Isocyanate groups used Both in IK and in 2K paints are used as isocyanates diisocyanates and / or polyisocyanates, which may have been previously provided with the respective protective groups. In principle, all customary isocyanates are used, as described in the
- diisocyanates are, for example, diisocyanatodiphenylmethane (MDI), both in the form of crude or industrial MDI and in the form of pure 4,4'- or 2, 4 'isomers or mixtures thereof, tolylene diisocyanate (TDI) in the form of its various regioisomers,
- MDI diisocyanatodiphenylmethane
- TDI tolylene diisocyanate
- Diisocyanatonaphthalene NDI
- isophorone diisocyanate IPDI
- perhydrogenated MDI H-MDI
- tetramethylene diisocyanate 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1,3-diisocyanato-4- methylcyclohexane or hexamethylene diisocyanate (HDI).
- HDI hexamethylene diisocyanate
- polyisocyanates examples include polymeric MDI (P-MDI), triphenylmethane triisocyanate and also all isocyanurate or biuret trimers of the diisocyanates listed above.
- P-MDI polymeric MDI
- triphenylmethane triisocyanate examples include triphenylmethane triisocyanate and also all isocyanurate or biuret trimers of the diisocyanates listed above.
- further oligomers of the abovementioned isocyanates with blocked NCO groups All di- and / or polyisocyanates can be used individually or in mixtures. Preference is given here to the isocyanurate and biuret trimerates of the comparatively UV-stable aliphatic isocyanates, particularly preferably the trimers of HDI and IPDI.
- protecting groups are preferred which are cleaved at temperatures of 80 to 200 0 C, more preferably at 100 to 170 0 C.
- Suitable protecting groups are secondary or tertiary alcohols, such as isopropanol or t-butanol, CH-acidic compounds such as diethyl malonate, acetylacetone, ethyl acetoacetate, oximes such as formaldoxime, acetaldoxime, butanoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime or diethylene glycol, lactams such as caprolactam, Valerolactam, butyrolactam, phenols such as phenol, o-methylphenol, W-alkylamides such as N-methylacetamide, imides such as phthalimide, secondary amines such as diisopropylamine, imidazole, 2-isopropylimidazole, pyrazo
- Isocyanate groups to the isocyanate-reactive groups of paint resin (B) in the composition (Z) is usually 0.5 to 2, preferably 0.8 to 1.5 and particularly preferably 1.0 to 1.2.
- hardeners (H) are mixtures of different hardeners (H).
- compositions (Z) may also contain common solvents and the additives and additives customary in formulations. To call here would be u.a. Leveling agents, surface-active substances, adhesion promoters, light stabilizers such as UV absorbers and / or radical scavengers, thixotropic agents and other solids and fillers. To produce the respective desired property profiles of both the compositions (Z) and the composites (K), such additives are preferred.
- compositions (Z) are prepared by mixing the particles (P), the binder (B) and optionally the hardener (H) and other additives and additives.
- the compositions (Z) are prepared by mixing the particles (P), the binder (B) and optionally the hardener (H) and other additives and additives.
- the compositions (Z) are prepared by mixing the particles (P), the binder (B) and optionally the hardener (H) and other additives and additives.
- the compositions (Z) are prepared by mixing the particles (P), the binder (B) and optionally the hardener (H) and other additives and additives.
- Compositions (Z) by curing, i. by drying, by reaction between the binder (B) and hardener (H), by (air) moisture and / or by treatment with thermal or actinic radiation in the composite materials (K).
- the binder (B), the particles (P) and optionally the hardener (H) and, if appropriate, further additives dissolved or dispersed in a solvent or a solvent mixture are preferred.
- Solvent or solvent mixtures having a boiling point or boiling range of up to 120 ° C at 0.1 MPa are preferred.
- Suitable solvents are ethers such as THF, alcohols such as methanol, ethanol, isopropanol, esters such as butyl acetate, aromatic hydrocarbons such as toluene and xylenes, linear and branched aliphatic solvents such as pentane, hexane, dodecane and dimethylformamide, dimethylacetamide, methoxyproyl acetate, dimethyl sulfoxide , N-methyl-2-pyrrolidone and water.
- ethers such as THF
- alcohols such as methanol, ethanol, isopropanol
- esters such as butyl acetate
- aromatic hydrocarbons such as toluene and xylenes
- linear and branched aliphatic solvents such as pentane, hexane, dodecane and dimethylformamide, dimethylacetamide, methoxyproyl acetate, dimethyl sulfoxide , N-
- Brönsted acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, trifluoroacetic acid, acetic acid, methylsulfonic acid, Bronsted bases, such as triethylamine and ethyldiisopropylamine.
- emulsifiers and / or protective colloids can be used as further additives.
- protective colloids are polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing polymers.
- emulsifiers are, for example, ethoxylated alcohols and phenols (alkyl radical C4-C18, EO grade 3-100), alkali metal and ammonium salts of alkyl sulfates (C3-C18), sulfuric acid and phosphoric acid esters and alkyl sulfonates. Particularly preferred are succinic acid esters as well as alkali alkyl sulfates and polyvinyl alcohols. It is also possible to use a plurality of protective colloids and / or emulsifiers as a mixture. Preference is given to the dispersion of the
- Particle (P) requires no additives.
- the particles (P) in the composition (Z) it may be helpful to carry out the incorporation of the particles by means of a bead mill, ultrasonic treatment or other common agitators.
- compositions (Z) as well as the composites (K) can be prepared in a melt or extrusion process from particles (P), binder (B) and optionally a hardener (H) and other additives.
- the composition (Z) can be prepared by modifying particles (P1) in the binder (B) or in a mixture of binder (B), hardener (H) and optionally further additives.
- the particles (P1) are dispersed in the binder (B) and subsequently reacted with the silanes (S) to form the particles (P).
- the compositions (Z) are prepared by adding the particles (P) during a mixing process as a powder or as a dispersion in a suitable solvent.
- a further method is preferred in which first of all a masterbatch is produced from the particles (P) and one or more components of the composition (Z), with particle concentrations> 15% by weight, preferably> 25% by weight and particularly preferably> 30% by weight. In preparing the compositions (Z), this masterbatch is then mixed with the remaining components.
- a particle dispersion is used in the preparation of the masterbatch, it may be advantageous if the solvent of the particle dispersion is removed in the course of the preparation of the masterbatch, for example via a distillation step, or exchanged for another solvent or solvent mixture.
- the compositions contain (Z) aqueous or organic solvents, the corresponding solvents are optionally removed after preparation of the composition (Z). The removal of the solvent is preferably carried out by distillation. Alternatively, the solvent may remain in the composition (Z) and be removed by drying in the course of the preparation of the composite material (K).
- compositions (Z) are preferably wound on a substrate. Further processes are immersion, spraying, casting and extrusion processes.
- Suitable substrates include i.a. Glass, metal, wood, silicon wafers and plastics such as e.g. Polycarbonate, polyethylene, polypropylene, polystyrene and PTFE.
- compositions (Z) contain reactive resins (B)
- the curing preferably takes place after addition of a curing agent (H) or initiator by actinic radiation or thermal energy.
- the curing conditions correspond to those of the particle-free compositions.
- the particles (P) carry organofunctional groups which are reactive towards the binder (B) or the curing agent (H), then the particles (P) can be covalently bonded to the binder (B) or the hardener.
- the particles (P) may have a distribution gradient in the composite material (K) or be homogeneously distributed.
- the concentration of particles (P) at the coating / air interface is higher than in the bulk segment and at the coating / substrate interface.
- an interface Coating / air is understood to mean the near-surface layer which has a thickness of at most 150 nm.
- the concentration of particles (P) at the coating / substrate interface may be higher than in the bulk segment and at the coating / air interface.
- the coating / substrate interface is understood to be the near-surface layer which has a maximum thickness of 150 nm.
- the concentration of particles (P) is higher both at the coating / air interface and at the coating / substrate interface than in the bulk segment.
- the particles increase mechanical stability, chemical resistance, corrosion stability and adhesion.
- compositions (Z) can be used in particular as adhesives and sealants and as sealants, potting compounds and dental compounds.
- the composite materials (K) produced from the compositions (Z) serve as scratch-resistant clearcoats or topcoats, especially in the automotive industry as OEM and refinish paints.
- the application of the compositions (Z) can be carried out by any methods such as dipping, spraying, and casting. Also an application of the compositions (Z) to a basecoat for a "wet on wet” method is possible. Curing is generally carried out by heating under the particular conditions required (2K coatings typically at 0-100 0 C, preferably at 20 -80 0 C, IK Paints at 100-200 0 C preferably at 120-160 0 C).
- suitable catalysts are acidic, basic and also heavy metal-containing compounds.
- Example 1 Synthesis of phosphonate-functional particles from an aqueous silica sol.
- Example 2 Synthesis of phosphonate-functional particles from an organic silica sol.
- the mean particle size of the modified silica sol determined by means of dynamic light scattering (Zetasizer Nano from MALVERN), was 13 nm. After distilling off the solvent, 191 g of a colorless solid were obtained which could be redispersed by stirring in both acetone and isopropanol.
- the mean particle size of the silica sol in isopropanol was 14.5 nm.
- IPA-ST isopropanol
- the mean particle size of the modified silica sol determined by means of dynamic light scattering (Zetasizer Nano from MALVERN), was 12 nm. After distilling off the solvent, 184 g of a colorless solid were obtained which could be redispersed by stirring in both acetone and isopropanol. The average particle size of the silica sol in isopropanol was 23 nm.
- Example 4 Preparation of a particle-reinforced epoxy resin.
- Example 5 Preparation of a particle-containing IK-PU coating formulation
- an acrylate-based coating polyol having a solids content of 52% by weight and an OH value of 156 (Parocryl® 54.4 from BASF AG) with Desmodur® BL 3175 SN from Bayer AG (butanoxime-blocked polyisocyanate, having a FG of 75 Wt .-% and a blocked NCO content of 11.1%).
- Blend 2 10.00 g 6, 03 g 0.3 g 1.5
- Blend 4 10.00 g 6, 03 g 0.6 g 3.0
- Example 6 Preparation of a particle-containing 2K PU coating formulation
- an acrylate-based coating polyol having a solids content of 65% by weight and an OH value of 180 (Parocryl® 49.5 from BASF AG) is diluted with 20% by weight of butyl acetate, mixed with the modified silica sol of Examples 2 or 3, and Stirred for 24 hours at room temperature.
- Powder-isolated particles of Examples 1-3 were predispersed in acetone.
- the coating compositions from Examples 5 and 6 are in each case by means of a film applicator Coatmaster® 509 MC Fa. Erichsen with a doctor blade of gap height 120 microns on a glass plate geräkelt. Subsequently, the resulting coating films are dried in a circulating air dryer for 30 minutes at 70 ° C and then for 30 min at 150 0 C. From blends 1-10 of Examples 5 and 6 optically flawless, smooth coatings are obtained. The gloss of the coatings is determined with a gloss meter Micro gloss 20 ° from Byk and is in all paints between 160 and 170 gloss units.
- the scratch resistance of the cured coating films produced in this way is determined using a scouring tester according to Peter-Dahn. For this, a scouring fleece Scotch Brite® 2297 with an area of 45 x 45 mm and a weight of 500 g is weighted. With this, the paint samples are scratched with a total of 50 strokes. Both before and after completion of the scratching tests, the gloss of the respective coating is measured with a gloss meter Micro gloss 20 ° from Byk. As a measure of the scratch resistance of the respective coating, the loss in gloss was determined in comparison with the starting value:
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Abstract
The invention relates to a composition (Z) which contains (a) 0.02-200 parts by weight of particles (P) having at least one structural element of general formula =Si-L-P(O)(OR<SUP>1</SUP>)<SUB>2</SUB>, (b) 100 parts by weight of a binder (B), (c) 0-100 parts by weight of a curing agent (H) which is reactive to the binder (B), and (d) 0-1000 parts by weigh of a solvent or a solvent mixture, L being a bivalent aliphatic or aromatic hydrocarbon group with 1 to 12 hydrocarbon atoms as defined in claim 1 and R<SUP>1 </SUP>and R<SUP>2 </SUP> being defined as in claim 1. The invention also relates to composite materials (K) that can be produced from the composition and to the use thereof.
Description
Zusammensetzungen enthaltend Phosphonat-funktionelle Partikel Compositions containing phosphonate-functional particles
Die Erfindung betrifft Phosphonat-funktionelle Partikel enthaltende Zusammensetzungen, daraus hergestellte Kompositmaterialien und die Verwendung der Zusammensetzungen.The invention relates to phosphonate functional particle-containing compositions, composite materials prepared therefrom and the use of the compositions.
Partikel - insbesondere Nanopartikel - enthaltende Kompositmaterialien sind Stand der Technik. Entsprechende Beschichtungen aus Kompositmaterialien sind beispielsweise in EP 1 249 470, WO 03/16370, US 20030194550 oder US 20030162015 beschrieben. Die Partikel führen dabei zu einer Verbesserung der Eigenschaften der entsprechenden Beschichtungen, insbesondere hinsichtlich ihrer Kratzfestigkeit sowie gegebenenfalls auch ihrer Chemikalienbeständigkeit.Particles - especially nanoparticles - containing composite materials are state of the art. Corresponding coatings of composite materials are described for example in EP 1 249 470, WO 03/16370, US 20030194550 or US 20030162015. The particles lead to an improvement in the properties of the corresponding coatings, in particular with regard to their scratch resistance and optionally also their chemical resistance.
Ein häufig auftretendes Problem beim Einsatz der - in der Regel anorganischen - Partikel in organischen Matrixsystemen besteht in einer meist unzureichenden Verträglichkeit von Partikel und Matrix. Dies kann dazu führen, dass sich die Teilchen nicht hinreichend gut in der Matrix dispergieren lassen. Zudem können sich selbst gut dispergierte Partikel bei längeren Stand- oder Lagerzeiten absetzen, wobei sich gegebenenfalls größere Aggregate bzw. Agglomerate ausbilden, die sich auch durch einen Energieeintrag nicht bzw. nur schlecht in die ursprünglichen Teilchen auftrennen lassen. Die Verarbeitung von solchen inhomogenen Systemen ist in jedem Falle äußerst schwierig, oftmals sogar unmöglich. Kompositmaterialien, die nach ihrer Auftragung und Härtung über glatte Oberflächen verfügen, lassen sich auf diesem Weg in der Regel nicht oder nur nach kostenintensiven Verfahren herstellen.A common problem with the use of - usually inorganic - particles in organic matrix systems consists in a usually insufficient compatibility of particles and matrix. This can lead to the particles not being able to disperse sufficiently well in the matrix. In addition, even well-dispersed particles can settle at longer stand or storage times, possibly forming larger aggregates or agglomerates which can not or only poorly be separated into the original particles by an energy input. The processing of such inhomogeneous systems is in any case extremely difficult, often even impossible. Composite materials that have smooth surfaces after their application and curing can usually not be produced in this way, or can only be produced by cost-intensive processes.
Günstig ist daher der Einsatz von Partikeln, die auf ihrer Oberfläche über organische Gruppen verfügen, welche zu einer
besseren Verträglichkeit mit der umgebenden Matrix führen und somit eine unerwünschte Agglomeration bzw. Aggregation der Partikel unterdrücken. Auf diese Weise wird das anorganische Partikel durch eine organische Hülle maskiert. Besonders günstige Kompositeigenschaften können zudem häufig erreicht werden, wenn die organischen Funktionen auf den Partikeloberflächen auch noch gegenüber der Matrix reaktiv sind, so dass sie unter den jeweiligen Härtungsbedingungen mit der Matrix reagieren können. So gelingt es, die Partikel während der Härtung des Komposits chemisch in die Matrix einzubauen, was oftmals besonders gute mechanische Eigenschaften aber auch eine verbesserteTherefore, it is advantageous to use particles which have on their surface organic groups, which to a lead to better compatibility with the surrounding matrix and thus suppress unwanted agglomeration or aggregation of the particles. In this way, the inorganic particle is masked by an organic shell. In addition, particularly favorable composite properties can often be achieved if the organic functions on the particle surfaces are also reactive with respect to the matrix, so that they can react with the matrix under the respective curing conditions. It is thus possible to chemically incorporate the particles into the matrix during the curing of the composite, which often results in particularly good mechanical properties but also in an improved form
Chemikalienbeständigkeit zur Folge hat. Derartige Systeme sind beispielsweise in DE 102 47 359 Al, EP 0 832 947 Al oder EP 0 872 500 Al beschrieben.Chemical resistance results. Such systems are described, for example, in DE 102 47 359 A1, EP 0 832 947 A1 or EP 0 872 500 A1.
Nachteilig ist die trotz Maskierung unzureichende Stabilität der im Stand der Technik eingesetzten Nanopartikel . Diese unzureichende Stabilität der Partikel tritt zum einen bei der Verarbeitung der Partikel, insbesondere beim Aufkonzentrieren der Partikeldispersionen bzw. einem Lösungsmittelaustausch, zum anderen bei der Lagerung der ungehärteten Partikeldispersionen zu Tage. Anzeichen für eine mangelnde Stabilität der Partikel sind ein - häufig bis zur Vergelung fortschreitender - Viskositätsanstieg oder die Sedimentation der Partikel. Zudem lassen sich die beschriebenen Nanopartikel aufgrund der hohen Agglomerations- bzw. Aggregationsneigung nicht als redispergierbare Feststoffe isolieren. Die nach dem Stand der Technik herstellbaren Partikel fallen bei Isolierung, beispielsweise durch Sprühtrocknung, alsA disadvantage is the inadequate stability despite masking of the nanoparticles used in the prior art. This insufficient stability of the particles occurs on the one hand in the processing of the particles, in particular when concentrating the particle dispersions or a solvent exchange, on the other during the storage of the uncured particle dispersions to light. Indications of a lack of stability of the particles are an increase in viscosity, or the sedimentation of the particles, which often progresses until gelation. In addition, the described nanoparticles can not be isolated as redispersible solids due to the high agglomeration or aggregation tendency. The particles which can be produced according to the prior art fall on isolation, for example by spray drying, as
Partikelagglomerate bzw. -aggregate an, die sich auch unter Energieeintrag, beispielsweise mittels einer Perlmühle oder durch Ultraschallbehandlung, nicht unter Erreichung der
ursprünglichen Primärpartikelgröße redispergieren lassen. Dies wäre aber im Hinblick auf die Lagerung, den Transport und insbesondere für eine mögliche Verarbeitung der Pulver in Extrusionsprozessen besonders wünschenswert.Particle agglomerates or aggregates, which also under energy input, for example by means of a bead mill or by ultrasonic treatment, not to achieve redispersing the original primary particle size. However, this would be particularly desirable in terms of storage, transport and in particular for possible processing of the powders in extrusion processes.
Nach dem Stand der Technik werden die in den Kompositmaterialien enthaltenen oberflächenmodifizierten Partikel hergestellt, indem man Partikel, die über freie Silanol- (SiOH) oder Metallhydroxidfunktionen verfügen, mit Alkoxysilanen oder deren Hydrolyse- und Kondensationsprodukten umsetzt, die unreaktive Gruppen, wie z.B. Alkyl- oder Arylreste, oder reaktive organische Funktionen, wie z.B. Vinyl, (Meth)acryl, Carbinol etc., enthalten. Bei den im Stand der Technik zur Partikelfunktionalisierung eingesetzten Silanen handelt es sich typischerweise um Di- oder Trialkoxysilane .In the prior art, the surface-modified particles contained in the composite materials are prepared by reacting particles having free silanol (SiOH) or metal hydroxide functions with alkoxysilanes or their hydrolysis and condensation products containing unreactive groups, e.g. Alkyl or aryl radicals, or reactive organic functions, e.g. Vinyl, (meth) acrylic, carbinol, etc. included. The silanes used in the art for particle functionalization are typically di- or trialkoxysilanes.
Werden diese Silane zur Oberflächenfunktionalisierung eingesetzt, wird in Gegenwart von Wasser nach Hydrolyse und Kondensation der erhaltenen Silanole eine Siloxan-Hülle um das Partikel gebildet. In Macromol. Chem. Phys . 2003, 204, 375-383 wird die Ausbildung einer solchen Siloxan-Hülle um ein SiO2-If these silanes are used for surface functionalization, a siloxane shell is formed around the particle in the presence of water after hydrolysis and condensation of the resulting silanols. In Macromol. Chem. Phys. 2003, 204, 375-383, the formation of such a siloxane shell around a SiO 2 -
Partikel beschrieben. Problematisch kann hierbei sein, dass die gebildete Siloxan-Hülle noch über eine große Anzahl von SiOH- Funktionen auf der Oberfläche verfügt. Die Stabilität derartiger SiOH-funktioneller Partikel ist unter denParticles described. The problem here may be that the siloxane shell formed still has a large number of SiOH functions on the surface. The stability of such SiOH functional particles is among the
Bedingungen der Herstellung und Lagerung, auch in Gegenwart des Bindemittels, häufig nur eingeschränkt gegeben.Conditions of manufacture and storage, even in the presence of the binder, often given only limited.
Die Herstellung von Kern-Hülle-Partikeln, die an ihrer Oberfläche frei von Alkoxysilyl- und Silanolgruppen sind und folglich eine geringere Agglomerationsneigung aufweisen, lehren die Schriften EP 0 492 376 A und DE 10 2004 022 406 A. Hierzu wird in einem ersten Schritt durch Cokondensation verschiedener
Silane und Siloxane, wobei mindestens ein Silan oder Siloxan Methacrylgruppen trägt, ein Siloxanpartikel erzeugt, auf das im Folgeschritt durch Umsetzung mit Methylmethacrylat eine Polymethylmethacrylat-Hülle aufgepfropft wird. Die erhaltenen Partikel zeigen hervorragende Verträglichkeiten in organischen Polymeren wie z.B. Polymethylmethacrylat und PVC. Diese Siloxan-Pfropfpolymerisate haben zudem den Vorteil, dass sie bei geeigneter Zusammensetzung und Dicke der gepfropften Hülle redispergierbar sind. Sie besitzen jedoch den Nachteil, in ihrer Herstellung relativ aufwendig zu sein, was zu hohen Herstellungskosten führt.The production of core-shell particles which are free of alkoxysilyl and silanol groups on their surface and consequently have a lower tendency to agglomerate is taught by the documents EP 0 492 376 A and DE 10 2004 022 406 A. For this purpose, in a first step Cocondensation of various Silanes and siloxanes, wherein at least one silane or siloxane carries methacrylic groups, generates a siloxane particle, to which a polymethyl methacrylate shell is grafted in the subsequent step by reaction with methyl methacrylate. The resulting particles show excellent compatibility in organic polymers such as polymethylmethacrylate and PVC. These siloxane graft polymers also have the advantage that they are redispersible with a suitable composition and thickness of the grafted shell. However, they have the disadvantage of being relatively expensive to produce, which leads to high production costs.
Aufgrund ihrer breiten Einsetzbarkeit stellen partikelverstärkte Lacke, die beispielsweise in EP 0 768 351, EP 0 832 947, EP 0 872 500 oder DE 10247359 beschrieben sind, einen besonders wichtigen Typ von Kompositmaterialien dar. Dabei werden als verstärkende Füllstoffe oberflächenmodifizierte Partikel eingesetzt, die eine ausreichende Kompatibilität mit der Lackmatrix aufweisen. Durch das Einbringen der oberflächenmodifizierten Partikel lässt sich insbesondere die Kratzfestigkeit von Lacken merklich steigern.Because of their broad applicability, particle-reinforced paints, which are described, for example, in EP 0 768 351, EP 0 832 947, EP 0 872 500 or DE 10247359, represent a particularly important type of composite material. Surface-modified particles are used as reinforcing fillers have sufficient compatibility with the paint matrix. By introducing the surface-modified particles, in particular the scratch resistance of paints can be significantly increased.
Allerdings ist die Handhabung der Partikel, insbesondere wenn diese in Form einer hochkonzentrierten Dispersion vorliegen, aufgrund ihrer beschriebenen eingeschränkten Stabilität äußerst schwierig. Zudem ist eine Isolierung der Partikel nicht möglich, da sich die sich im Verlauf der Trocknung bildenden Agglomerate nicht wieder in die ursprüngliche Partikelgröße, d.h. die Größe der Primärpartikel, auftrennen lassen. Zudem sind die mechanischen Härten - und insbesondere die Kratzfestigkeiten - der partikelverstärkten Lacke für viele Anwendungen noch nicht ausreichend.However, the handling of the particles, especially when in the form of a highly concentrated dispersion, is extremely difficult due to their described limited stability. In addition, it is not possible to isolate the particles, since the agglomerates which form in the course of the drying do not revert back to the original particle size, i. the size of the primary particles, can be separated. In addition, the mechanical hardnesses - and in particular the scratch resistance - of the particle-reinforced coatings are not sufficient for many applications.
Bei einem besonders wichtigen Lacktyp, für den eine weitere
Verbesserung der Kratzfestigkeit durch einen Zusatz an Partikeln angestrebt wird, wird ein Lackharz aus hydroxyfunktionellen Prepolymeren, insbesondere aus hydroxyfunktionellen Polyacrylaten und/oder Polyestern, eingesetzt, die bei der Lackhärtung mit einem isocyanatfunktionellen Härter (Polyurethanlacke) und/oder einem Melaminhärter (Melaminlacke) zur Reaktion gebracht werden. Die Polyurethanlacke zeichnen sich durch besonders gute Eigenschaften aus. So besitzen Polyurethanlacke vor allem eine überlegene Chemikalienbeständigkeit, während die Melaminlacke in der Regel über bessere Kratzfestigkeiten verfügen. Typischerweise werden diese Lacktypen in besonders hochwertigen und anspruchsvollen Anwendungsgebieten verwendet, beispielsweise als Klar- bzw. Decklacke für OEM-Lackierungen in der Automobil- und Fahrzeugindustrie. Ebenso bestehen auch die meisten Decklacke für Automobilreparaturen aus derartigen Systemen. Die Schichtdicken dieser Lacke liegen typischerweise in Bereichen von 20 bis 50 μm.For a particularly important type of paint, for another To improve the scratch resistance is sought by an addition of particles, a coating resin of hydroxy-functional prepolymers, in particular of hydroxy-functional polyacrylates and / or polyesters, used in the paint curing with an isocyanate-functional hardener (polyurethane coatings) and / or a melamine (melamine) for reaction to be brought. The polyurethane coatings are characterized by particularly good properties. In particular, polyurethane coatings have superior chemical resistance, while melamine coatings generally have better scratch resistance. Typically, these types of paints are used in particularly high-quality and demanding fields of application, for example as clearcoats or topcoats for OEM coatings in the automotive and vehicle industry. Likewise, most automotive refinish topcoats are of such systems. The layer thicknesses of these coatings are typically in the range from 20 to 50 μm.
Bei den Polyurethan-Lacksystemen unterscheidet man generell zwischen den sogenannten 2K- und 1K-Systemen. Erstere bestehen aus zwei Komponenten, von denen eine im wesentlichen aus dem Isocyanathärter besteht, während das Lackharz mit seinen isocyanatreaktiven Gruppen in der zweiten Komponente enthalten ist. Beide Komponenten müssen dabei getrennt gelagert und transportiert werden und dürfen erst kurz vor der Verarbeitung vermischt werden, da die fertige Mischung nur eine stark eingeschränkte Topfzeit besitzt. Oftmals günstiger sind daher die sogenannten 1K-Systeme, die nur aus einer Komponente bestehen, in der neben dem Lackharz ein Härter mit geschützten Isocyanatgruppen vorliegt. 1K-Lacke werden thermisch gehärtet, wobei die Schutzgruppen der Isocyanateinheiten abgespalten werden und die entschützten Isocyanate anschließend mit dem
Lackharz reagieren können. Typische Einbrenntemperaturen von derartigen 1K-Lacken liegen bei 120-160 0C. Bei Melaminlacken handelt es sich in der Regel um 1K-Lacke, die Einbrenntemperaturen liegen typischerweise in einem vergleichbaren Temperaturbereich.In polyurethane paint systems, a distinction is generally made between the so-called 2K and 1K systems. The former consist of two components, one of which consists essentially of the Isocyanathärter, while the paint resin is contained with its isocyanate-reactive groups in the second component. Both components must be stored and transported separately and may only be mixed shortly before processing, since the finished mixture has only a very limited pot life. Often cheaper, therefore, are the so-called 1K systems, which consist of only one component in which there is a hardener with protected isocyanate groups in addition to the paint resin. 1K coatings are thermally cured, whereby the protecting groups of the isocyanate units are cleaved off and the deprotected isocyanates are then cleaved with the Resin can react. Typical baking temperatures of such 1- component paints are 120-160 ° C. Melamine paints are generally 1-component paints, and the baking temperatures are typically in a comparable temperature range.
Insbesondere bei diesen hochwertigen Lacken wäre eine weitere Eigenschaftsverbesserung wünschenswert. Dies gilt insbesondere für Fahrzeug-Decklackierungen . So ist vor allem die erreichbare Kratzfestigkeit von herkömmlichen Autolacken noch nicht hinreichend, so dass es z.B. in der Waschstraße durch Partikel im Waschwasser zu einer merklichen Verkratzung des Lackes kommt. Auf Dauer wird dadurch der Glanz des Lackes nachhaltig geschädigt. Hier wären Formulierungen wünschenswert, mit denen sich bessere Kratzfestigkeiten erreichen lassen.Especially with these high-quality paints, a further property improvement would be desirable. This applies in particular to vehicle topcoats. Above all, the achievable scratch resistance of conventional car paints is not yet sufficient, so that it can be used e.g. In the washing line by particles in the washing water to a noticeable scratching of the paint comes. In the long term, the gloss of the paint is sustainably damaged. Here would be desirable formulations that can achieve better scratch resistance.
Ein besonders vorteilhafter Weg zur Lösung dieser Aufgabe ist die Verwendung von Partikeln, die auf ihrer Oberfläche Organofunktionen aufweisen, die gegenüber dem Lackharz oder aber gegenüber dem Härter reaktiv sind. Zudem führen dieseA particularly advantageous way of achieving this object is the use of particles which have on their surface organo-functions which are reactive with the paint resin or with respect to the hardener. In addition, these lead
Organofunktionen auf der Partikeloberfläche zu einer Maskierung der Partikel und verbessern so die Verträglichkeit von Partikel und Lackmatrix.Organ functions on the particle surface to mask the particles and thus improve the compatibility of particles and paint matrix.
Derartige Partikel mit geeigneten Organofunktionen sind prinzipiell bereits bekannt. Sie sind, ebenso wie ihr Einsatz in Beschichtungen, beispielsweise in EP 0 768 351, EP 0 832 947, EP 0 872 500 oder DE 10247359 beschrieben.Such particles with suitable organ functions are already known in principle. Like their use in coatings, they are described, for example, in EP 0 768 351, EP 0 832 947, EP 0 872 500 or DE 10247359.
Tatsächlich lässt sich die Kratzfestigkeit von Lacken durch den Einbau von derartigen Partikeln merklich steigern. Allerdings werden bei sämtlichen im Stand der Technik beschriebenen Verfahren beim Einsatz dieser Partikel noch keine optimalen
Ergebnisse erzielt. Insbesondere weisen die entsprechenden Beschichtungen dermaßen hohe Partikelgehalte auf, dass eine Verwendung derartiger Lacke in großen Serienlackierungen schon allein aus Kostengründen nur schwer realisierbar sein wird.In fact, the scratch resistance of paints can be significantly increased by the incorporation of such particles. However, in all of the methods described in the prior art when using these particles are still not optimal Results achieved. In particular, the corresponding coatings have such high particle contents that the use of such paints in large series finishes will be difficult to realize, for reasons of cost alone.
In WO 01/09231 werden partikelhaltige Lacksysteme beschrieben, die dadurch gekennzeichnet sind, dass sich in einem Oberflächensegment des Lackes mehr Partikel befinden als in einem Bulksegment. Vorteil dieser Partikelverteilung ist die vergleichsweise geringe Partikelkonzentration, die für eine deutliche Verbesserung der Kratzfestigkeit benötigt wird. Die gewünschte hohe Affinität der Partikel zur Lackoberfläche wird dabei erreicht, indem man auf die Partikeloberflächen ein Siliconharz als oberflächenaktives Agens aufbringt. Nachteilig an diesem Verfahren ist allerdings die Tatsache, dass nicht nur die Siliconharzmodifizierung der Partikel, sondern auch die Herstellung der dafür benötigten Siliconharze selbst technisch aufwändig ist. Letzteres ist insbesondere deshalb problematisch, weil es für das Erreichen einer guten Kratzfestigkeit notwendig ist, die Siliconharze mitIn WO 01/09231, paint-containing paint systems are described, which are characterized in that there are more particles in a surface segment of the paint than in a bulk segment. The advantage of this particle distribution is the comparatively low particle concentration, which is needed for a significant improvement in the scratch resistance. The desired high affinity of the particles to the paint surface is achieved by applying a silicone resin as a surface-active agent to the particle surfaces. A disadvantage of this method, however, is the fact that not only the silicone resin modification of the particles, but also the preparation of the silicone resins required for this purpose is itself technically complex. The latter is particularly problematic because it is necessary to achieve a good scratch resistance, the silicone resins with
Organofunktionen, z.B. Carbinolfunktionen, zu versehen, über die die entsprechend modifizierten Partikel bei der Lackhärtung chemisch in den Lack eingebaut werden können. Derartig funktionalisierte Siliconharze sind kommerziell nicht bzw. nur sehr eingeschränkt verfügbar. Vor allem aber ist auch dieOrgano-functions, e.g. Carbinol functions to provide, over which the appropriately modified particles can be chemically incorporated in the lacquer hardening in the paint. Such functionalized silicone resins are not available commercially or only to a very limited extent. Above all, though, is the
Auswahl der überhaupt möglichen Organofunktionen bei diesem System relativ begrenzt. Daher werden bei diesem System, wie auch bei sämtlichen weiteren Systemen entsprechend des Standes der Technik, noch keine optimalen Ergebnisse erzielt.Selection of the possible organ functions with this system relatively limited. Therefore, in this system, as well as in all other systems according to the prior art, no optimal results are achieved.
Aufgabe der Erfindung war daher die Entwicklung einer Zusammensetzung für ein Kompositmaterial, das die Nachteile des Standes der Technik überwindet.
Gegenstand der Erfindung ist eine Zusammensetzung (Z) enthaltend (a) 0,02-200 Gewichtsteile an Partikeln (P), die mindestens ein Strukturelement der allgemeinen Formel [1],The object of the invention was therefore the development of a composition for a composite material, which overcomes the disadvantages of the prior art. The invention provides a composition (Z) comprising (a) 0.02-200 parts by weight of particles (P) which contain at least one structural element of the general formula [1],
≡Si-L-P (O) (OR1) 2 [1] '≡Si-LP (O) (OR 1 ) 2 [1] '
aufweisen,exhibit,
(b) 100 Gewichtsteile eines Bindemittels (B) ,(b) 100 parts by weight of a binder (B),
(c) 0-100 Gewichtsteile eines Härters (H) , der gegenüber dem Bindemittel (B) reaktiv ist, sowie(c) 0-100 parts by weight of a curing agent (H) which is reactive with the binder (B), as well as
(d) 0-1000 Gewichtsteile eines Lösungsmittels oder eines Lösungsmittelgemisches, wobei(D) 0-1000 parts by weight of a solvent or a solvent mixture, wherein
L einen zweiwertigen gegebenenfalls mit Carbinol-, Amino-, Halogen-, Epoxy-, Phosphonato-, Thiol-, (Meth) acrylato-, Carbamato-Gruppen substituierten aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen, dessen Kohlenstoffkette durch nicht benachbarte Sauerstoffatome, Schwefelatome, oder NR^- Gruppen unterbrochen sein kann,L is a divalent optionally substituted by carbinol, amino, halogen, epoxy, phosphonato, thiol, (meth) acrylato, carbamato groups substituted aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, the carbon chain by non-adjacent oxygen atoms, Sulfur atoms, or NR ^ - groups may be interrupted,
R! Wasserstoff, ein Metallkation, ein Ammoniumkation derR! Hydrogen, a metal cation, an ammonium cation of
Formel -N (R^) ^+, Phosphoniumkation der Formel -P (R^) 4+ oder einen gegebenenfalls mit Carbinol-, Amino-, Halogen-,Formula -N (R ^) ^ + , phosphonium cation of the formula -P (R ^) 4+ or an optionally with carbinol, amino, halogen,
Epoxy-, Phosphonato-, Thiol-, (Meth) acrylato-, Carbamato-, Ureido-Gruppen substituierten aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen, dessen Kohlenstoffkette durch nicht benachbarte Sauerstoffatome, Schwefelatome, oder NR^- Gruppen unterbrochen sein kann, undEpoxy, phosphonato, thiol, (meth) acrylato, carbamato, ureido groups substituted aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, whose carbon chain may be interrupted by non-adjacent oxygen atoms, sulfur atoms, or NR ^ groups, and
R^ einen Kohlenwasserstoffrest mit 1-8 Kohlenstoffatomen
bedeuten .R ^ is a hydrocarbon radical having 1-8 carbon atoms mean.
Kompositmaterialien (K) , die herstellbar sind aus der Zusammensetzung (Z) sind ebenfalls Gegenstand der Erfindung.Composite materials (K) which can be produced from the composition (Z) are likewise provided by the invention.
In einer Ausführungsform der Erfindung weisen die Partikel (P) neben Funktionen der allgemeinen Formel [1] zusätzlich auch noch mindestens eine organofunktionelle Gruppe (F) auf, die gegenüber dem Bindemittel (B) oder dem Härter (H) reaktiv ist.In one embodiment of the invention, the particles (P) in addition to functions of the general formula [1] additionally also at least one organofunctional group (F), which is reactive with the binder (B) or the curing agent (H).
In einer bevorzugten Ausführungsformsform der Erfindung sind die Kompositmaterialien (K) Lacksysteme, die herstellbar sind aus einer Beschichtungszusammensetzung (Z) enthaltend, (a) 0,02-60 Gewichtsteile an Partikeln (P), die mindestens ein Strukturelement der allgemeinen Formel [1],In a preferred embodiment of the invention, the composite materials (K) are coating systems which can be prepared from a coating composition (Z) comprising (a) 0.02-60 parts by weight of particles (P) containing at least one structural element of the general formula [1] .
≡Si-L-P(O) (OR1J2 [1] '≡Si-LP (O) (OR 1 J 2 [1] '
aufweisen, b) 100 Gewichtsteile eines hydroxylgruppen-funktionellen Lackharzes (B) , c) 1-100 Gewichtsteile eines Lackhärters (H) , der Isocyanatgruppen enthält, die ausgewählt werden aus freien Isocyanatgruppen und geschützten Isocyanatgruppen, die bei thermischer Behandlung unter Abspaltung einer Schutzgruppe eine Isocyanatfunktion freisetzen, d) 0-1000 Gewichtsteile eines Lösungsmittels oder eines Lösungsmittelgemisches .c) 100 parts by weight of a hydroxyl-functional paint resin (B), c) 1-100 parts by weight of a paint curing agent (H) containing isocyanate groups selected from free isocyanate groups and protected isocyanate groups which upon thermal treatment with elimination of a protective group Releasing isocyanate function, d) 0-1000 parts by weight of a solvent or a solvent mixture.
Der Erfindung liegt die Entdeckung zugrunde, dass dieThe invention is based on the discovery that the
Kompositmaterialien (K) , hergestellt aus den Zusammensetzungen (Z), hervorragende mechanische Eigenschaften aufweisen. Zudem ist die Herstellung der Zusammensetzungen (Z) aufgrund der
hohen Stabilität der in den Zusammensetzungen (Z) enthaltenen Partikeln (P) gegenüber den Verfahren des Standes der Technik deutlich erleichtert. Aufgrund der Anwesenheit der Strukturelemente der allgemeinen Formel [1] weisen die Partikel (P) eine äußerst geringe Agglomerations- bzw.Composite materials (K) prepared from the compositions (Z) have excellent mechanical properties. In addition, the preparation of the compositions (Z) is due to the high stability of the particles (P) contained in the compositions (Z) compared to the methods of the prior art significantly easier. Due to the presence of the structural elements of the general formula [1], the particles (P) have an extremely low agglomeration or
Aggregationsneigung auf, die es ermöglicht, die Partikel (P) in Dispersionen mit hohem Festgehalt zu handhaben. In Abhängigkeit von der Art der Partikelmodifizierung ist es teilweise möglich, die Partikel (P) als Feststoff zu isolieren und in der Zusammensetzung (Z) zu redispergieren .Aggregation tendency, which makes it possible to handle the particles (P) in dispersions with high solids content. Depending on the type of particle modification, it is sometimes possible to isolate the particles (P) as a solid and to redisperse them in the composition (Z).
Das Bindemittel (B), der Härter (H) und die Partikel (P) - sofern sie über organofunktionelle Gruppen (F) verfügen, die gegenüber dem Bindemittel oder dem Härter reaktiv sind - besitzen bevorzugt hinreichend viele reaktive Gruppen, dass sich bei der Härtung der Zusammensetzungen (Z) zu den Kompositmaterialien (K) ein dreidimensional vernetztes Polymernetzwerk ausbilden kann.The binder (B), the hardener (H) and the particles (P) - if they have organofunctional groups (F) which are reactive with the binder or the curing agent - preferably have sufficiently many reactive groups that in curing the compositions (Z) to the composite materials (K) can form a three-dimensionally crosslinked polymer network.
L stellt vorzugsweise einen zweiwertigen Alkylrest mit 1-8L preferably represents a bivalent alkyl radical of 1-8
Kohlenstoffatomen oder einen Aryl- oder Heteroarylrest mit 1-10 Kohlenstoffatomen dar; besonders bevorzugt ist L ein Methylenoder Propylenrest . Bei R^- handelt es sich bevorzugt um einen Alkylrest mit 1-6 Kohlenstoffatomen, insbesondere Methyl- oder Ethylrest. R^ stellt bevorzugt einen Alkylrest, insbesondere Methyl-, Ethyl- oder Butylrest dar.Carbon atoms or an aryl or heteroaryl radical having 1-10 carbon atoms; L is particularly preferably a methylene or propylene radical. When R ^ - is preferably an alkyl radical having 1-6 carbon atoms, in particular methyl or ethyl radical. R 1 is preferably an alkyl radical, in particular methyl, ethyl or butyl radical.
Die Zusammensetzung (Z) enthält bevorzugt mindestens 0,05 Gewichtsteile, besonders bevorzugt mindestens 0,1 Gewichtsteile an Partikeln (P) . In ganz besonders vorteilhaftenThe composition (Z) preferably contains at least 0.05 parts by weight, more preferably at least 0.1 parts by weight of particles (P). In very advantageous
Ausführungsformen der Erfindung enthält die Zusammensetzung (Z) mindestens 0,3 Gewichtsteile, insbesondere mindestens 0,5 Gewichtsteile an Partikeln (P) .
Die Zusammensetzung (Z) enthält bevorzugt höchstens 50 Gewichtsteile, besonders bevorzugt höchstens 25 Gewichtsteile an Partikeln (P) . In ganz besonders vorteilhaften Ausführungsformen der Erfindung enthält die Zusammensetzung (Z) höchstens 10 Gewichtsteile, insbesondere höchstens 5 Gewichtsteile an Partikeln (P) .Embodiments of the invention contains the composition (Z) at least 0.3 parts by weight, in particular at least 0.5 parts by weight of particles (P). The composition (Z) preferably contains at most 50 parts by weight, more preferably at most 25 parts by weight of particles (P). In very particularly advantageous embodiments of the invention, the composition (Z) contains at most 10 parts by weight, in particular at most 5 parts by weight of particles (P).
Die Partikel (P) besitzen bevorzugt eine spezifische Oberfläche von 0,1 bis 1000 m^/g, besonders bevorzugt von 10 bis 500 m^/g (gemessen nach der BET-Methode nach DIN EN ISO 9277/DIN 66132) . Die mittlere Größe der Primärteilchen beträgt bevorzugt kleiner 10 μm, besonders bevorzugt kleiner 1000 nm, wobei die Primärteilchen als Aggregate (Definition nach DIN 53206) und Agglomerate (Definition nach DIN 53206) vorliegen können, die in Abhängigkeit von der äußeren Scherbelastung (z.B. bedingt durch die Messbedingungen) Größen von 1 bis 1000 μm aufweisen können, und die mittlere Partikelgröße mittels Transmissionselektronenmikroskopie (TEM) oder der hydrodynamische Äquivalenzdurchmesser mittels Photonenkorrelationsspektroskopie bestimmt wird.The particles (P) preferably have a specific surface area of from 0.1 to 1000 m 2 / g, more preferably from 10 to 500 m 2 / g (measured by the BET method according to DIN EN ISO 9277 / DIN 66132). The average size of the primary particles is preferably less than 10 microns, more preferably less than 1000 nm, wherein the primary particles as aggregates (definition according to DIN 53206) and agglomerates (definition according to DIN 53206) may be present, depending on the external shear stress (eg due to the measurement conditions) can have sizes from 1 to 1000 μm, and the average particle size is determined by means of transmission electron microscopy (TEM) or the hydrodynamic equivalent diameter by means of photon correlation spectroscopy.
In einer besonderen Ausführungsform der Erfindung kommen Partikel zum Einsatz, wie sie in der WO 2004/089961 beschrieben sind aber zusätzlich über Strukturelemente der allgemeinen Formel [1] verfügen.In a particular embodiment of the invention, particles are used as described in WO 2004/089961 but additionally have structural elements of the general formula [1].
In den Partikeln (P) können die Strukturelemente der allgemeinen Formel [1] kovalent, über ionische oder van-der- Waals-Wechselwirkungen angebunden sein. Bevorzugt sind die Strukturelemente der allgemeinen Formel [1] kovalent angebunden .
In einer bevorzugten Ausführungsform der Erfindung werden die Partikel (P) durch Reaktion von Partikeln (Pl) mit Funktionen, die ausgewählt werden aus Metall-OH, Metall-O-Metall, Si-OH,In the particles (P), the structural elements of the general formula [1] can be covalently bonded via ionic or van der Waals interactions. Preferably, the structural elements of the general formula [1] are covalently attached. In a preferred embodiment of the invention, the particles (P) are formed by reaction of particles (P1) with functions selected from metal-OH, metal-O-metal, Si-OH,
Si-O-Si, Si-O-Metall, Si-X, Metall-X, Metall-OR3, Si-OR3 mit Silanen (S) oder deren Hydrolyse-, Alkoholyse- undSi-O-Si, Si-O metal, Si-X, metal-X, metal-OR 3 , Si-OR 3 with silanes (S) or their hydrolysis, alcoholysis and
Kondensationsprodukten umgesetzt, die über mindestens ein Strukturelement der allgemeinen Formel [1] sowie über mindestens eine reaktive SilylgruppeReacted condensation products which have at least one structural element of the general formula [1] and at least one reactive silyl group
≡Si-Y≡Si-Y
verfügen, die gegenüber den Oberflächenfunktionen des Partikels (Pl) reaktiv sind, wobei R^ einen gegebenenfalls substituierten Alkylrest, X ein Halogenatom undwhich are reactive with the surface functions of the particle (P1), wherein R 1 represents an optionally substituted alkyl radical, X represents a halogen atom and
Y ein Halogen, eine Hydroxy- oder Alkoxygruppe, ein Carboxylat oder ein Enolat darstellt.Y represents a halogen, a hydroxy or alkoxy group, a carboxylate or an enolate.
R^ ist vorzugsweise ein Alkylrest mit 1 bis 10, insbesondere 1 bis 6 Kohlenstoffatomen . Besonders bevorzugt sind die Reste Methyl, Ethyl, n-Propyl und i-Propyl. X ist vorzugsweise Fluor oder Chlor. Bei den Resten Y handelt es sich bevorzugt um ein Halogen, Hydroxy- oder Alkoxygruppen . Besonders bevorzugt stellen die Reste Y Chloratome, Hydroxy-, Ethoxy- oder Methoxyreste dar.R 1 is preferably an alkyl radical having 1 to 10, in particular 1 to 6 carbon atoms. The radicals methyl, ethyl, n-propyl and i-propyl are particularly preferred. X is preferably fluorine or chlorine. The radicals Y are preferably a halogen, hydroxyl or alkoxy groups. The radicals Y are particularly preferably chlorine atoms, hydroxyl, ethoxy or methoxy radicals.
Werden zur Herstellung der Partikel (P) Partikel (Pl) eingesetzt, welche Funktionen aufweisen, die ausgewählt werden aus Metall-OH, Si-OH, Si-X, Metall-X, Metall-OR3, Si-OR3, so erfolgt die Anbindung der Silane (S) durch Hydrolyse und/oder Kondensation. Liegen in dem Partikel (Pl) ausschließlich Metall-O-Metall-, Metall-O-Si oder Si-O-Si-Funktionen vor, kann
die kovalente Anbindung der Silane (S) durch eine Äquilibrierungsreaktion erfolgen. Die Vorgehensweise sowie die für die Äquilibrierungsreaktion benötigten Katalysatoren sind dem Fachmann geläufig und in der Literatur vielfach beschrieben.Are used for the preparation of the particles (P) particles (Pl), which have functions that are selected from metal-OH, Si-OH, Si-X, metal-X, metal-OR 3 , Si-OR 3 , so takes place the attachment of the silanes (S) by hydrolysis and / or condensation. If in the particle (Pl) exclusively metal O metal, metal O-Si or Si-O-Si functions, can the covalent attachment of silanes (S) by an equilibration reaction. The procedure and the catalysts required for the equilibration reaction are familiar to the person skilled in the art and have been described many times in the literature.
Alternativ kann die Anbindung der Strukturelemente der allgemeinen Formel [1] während der Partikelsynthese erfolgen.Alternatively, the attachment of the structural elements of the general formula [1] can take place during the particle synthesis.
In einer bevorzugten Ausführungsform der Erfindung weisen die zur Modifizierung der Partikel (Pl) eingesetzten Silane (S) eine Struktur der allgemeinen Formel [2],In a preferred embodiment of the invention, the silanes (S) used for modifying the particles (P1) have a structure of the general formula [2],
(R4O)3_aR4 aSi-(CR5)n-P(O) (OR6)2 [2](R 4 O) 3 _ a R 4 a Si (CR 5) n -P (O) (OR 6) 2 [2]
auf, wobei a die Werte 0, 1 oder 2 und n die Werte 1, 2 oder 3 bedeuten,where a is 0, 1 or 2 and n is 1, 2 or 3,
R5 Wasserstoff, einen gegebenenfalls substituierten aliphatischen oder aromatischen Kohlenwasserstoff mit 1-6R5 is hydrogen, an optionally substituted aliphatic or aromatic hydrocarbon having 1-6
Kohlenstoffatomen darstellt und R^ und R° die Bedeutungen von R^ aufweisen.Represents carbon atoms and R ^ and R ° have the meanings of R ^.
Dabei nimmt n bevorzugt den Wert 1 oder 3, besonders bevorzugt den Wert 1 an. a bedeutet vorzugsweise den Wert 0 oder 2, besonders bevorzugt ist a gleich 2. R^ stellt bevorzugt einenIn this case, n preferably assumes the value 1 or 3, particularly preferably the value 1. a is preferably 0 or 2, more preferably a is 2. R 1 is preferably one
Methyl oder Ethylrest, R^ bevorzugt Wasserstoff und R° bevorzugt Methyl- oder Ethylrest dar.Methyl or ethyl radical, R ^ is preferably hydrogen and R ° is preferably methyl or ethyl radical.
Die zur Modifizierung der Partikel (Pl) eingesetzten Silane (S) bzw. deren Hydrolyse- oder Kondensationsprodukte werden dabei vorzugsweise in einer Menge größer 1 Gew.-% (bezogen auf die Partikel (P)), bevorzugt größer 5 Gew.-%, besonders bevorzugt
größer 8 Gew.-% eingesetzt.The silanes (S) or their hydrolysis or condensation products used for modifying the particles (P1) are preferably present in an amount greater than 1% by weight (based on the particles (P)), preferably greater than 5% by weight, particularly preferred greater than 8 wt .-% used.
Bei der Herstellung der Partikel (P) aus Partikeln (Pl) können neben den Silanen (S) bzw. deren Hydrolyse- und Kondensationsprodukten zusätzlich andere Silane (Sl), Silazane (S2), Siloxane (S3) oder andere Verbindungen (L) eingesetzt werden. Bevorzugt sind die Silane (Sl), Silazane (S2), Siloxane (S3) oder anderen Verbindungen (L) gegenüber den Funktionen der Oberfläche des Partikels (P) reaktiv. Die Silane (Sl) und Siloxane (S3) verfügen dabei entweder über Silanolgruppen oder über hydrolysierbare Silylfunktionen, wobei letztere bevorzugt werden. Dabei können die Silane (Sl), Silazane (S2) und Siloxane (S3) über organische Funktionen (F) verfügen, die gegenüber dem Bindemittel (B) oder dem Härter (H) reaktiv sind, es können aber auch Silane (Sl), Silazane (S2) und SiloxaneIn the production of the particles (P) from particles (P1), in addition to the silanes (S) or their hydrolysis and condensation products, it is additionally possible to use other silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L) become. The silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L) are preferably reactive toward the functions of the surface of the particle (P). The silanes (S1) and siloxanes (S3) have either silanol groups or hydrolyzable silyl functions, the latter being preferred. The silanes (S1), silazanes (S2) and siloxanes (S3) may have organic functions (F) which are reactive towards the binder (B) or the curing agent (H), but silanes (S1), Silazanes (S2) and siloxanes
(S3) ohne Organofunktionen verwendet werden. Dabei können die Silane und Siloxane (S) als Mischung mit den Silanen (Sl), Silazanen (S2) oder Siloxanen (S3) eingesetzt werden. Daneben können die Partikel auch sukzessive mit den unterschiedlichen Silantypen funktionalisiert werden.(S3) are used without organ functions. The silanes and siloxanes (S) can be used as a mixture with the silanes (S1), silazanes (S2) or siloxanes (S3). In addition, the particles can also be successively functionalized with the different silane types.
Als Verbindungen (L) eignen sich beispielsweise Metallalkoholate, wie z.B. Titan (IV) isopropanolat oder Aluminium ( III ) butanolat, Schutzkolloide wie z.B. Polyvinylalkohole, Cellulosederivate oder Vinylpyrrolidon enthaltende Polymerisate sowie Emulgatoren wie z.B. ethoxylierte Alkohole und Phenole (Alkylrest C4-C18, EO-Grad 3-Suitable compounds (L) are, for example, metal alcoholates, e.g. Titanium (IV) isopropoxide or aluminum (III) butanolate, protective colloids such as e.g. Polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing polymers and emulsifiers such. ethoxylated alcohols and phenols (alkyl radical C4-C18, EO grade 3-
100), Alkali- und Ammoniumsalze von Alkylsulfaten (C^-CIQ) ,100), alkali metal and ammonium salts of alkyl sulfates (C ^ -CI Q),
Schwefelsäure- sowie Phosphorsäureester und Alkylsulfonate . Besonders bevorzugt sind SuIfobernsteinsäureester sowie Alkalialkylsulfate sowie Polyvinylalkohole. Es können auch mehrere Schutzkolloide und/oder Emulgatoren als Gemisch eingesetzt werden.
Bevorzugt liegt der gewichtsmäßige Anteil der Silane (Sl), Silazane (S2), Siloxane (S3) und Verbindungen (L) an der Gesamtmenge, die aus den Silanen (S) und (Sl), Silazanen (S2), Siloxanen (S3) und Verbindungen (L) gebildet wird, bei mindestens 1 Gew.-%, besonders bevorzugt bei mindestens 5 Gew.- %. In einer weiteren besonders bevorzugten Ausführungsform der Erfindung wird auf den Einsatz der Verbindungen (Sl), (S2), (S3) und (L) vollständig verzichtet.Sulfuric acid and phosphoric acid esters and alkyl sulfonates. Particularly preferred are succinic acid esters and alkali alkyl sulfates and polyvinyl alcohols. It is also possible to use a plurality of protective colloids and / or emulsifiers as a mixture. Preferably, the proportion by weight of the silanes (S1), silazanes (S2), siloxanes (S3) and compounds (L) is based on the total amount consisting of the silanes (S) and (S1), silazanes (S2), siloxanes (S3) and compounds (L) is formed, at least 1 wt .-%, particularly preferably at least 5% by weight. In a further particularly preferred embodiment of the invention, the use of the compounds (S1), (S2), (S3) and (L) is completely dispensed with.
Besonders bevorzugt sind dabei Mischungen aus Silanen (S) mit Silanen (Sl) der allgemeinen Formel [3],Particular preference is given to mixtures of silanes (S) with silanes (S1) of the general formula [3],
(R7O)4_a_b(Z)aSi(R8)b [3],(R 7 O) 4 _ a _ b (Z) a Si (R 8 ) b [3],
bzw. deren Hydrolyse- oder Kondensationsprodukte, wobeior their hydrolysis or condensation products, wherein
Z Halogenatom, Pseudohalogenrest, Si-N-gebundenen Aminrest,Z is halogen atom, pseudohalogen radical, Si-N-bonded amine radical,
Amidrest, Oximrest, Aminoxyrest oder Acyloxyrest bedeutet, a 0, 1, 2 oder 3, b 0, 1, 2 oder 3, R' die Bedeutungen von R^ aufweisenAmide radical, oxime radical, aminoxy radical or acyloxy radical, a 0, 1, 2 or 3, b 0, 1, 2 or 3, R 'have the meanings of R ^
R8 einen aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen, dessen Kohlenstoffkette durch nicht benachbarte Sauerstoffatome, Schwefelatome, oder NR^-Gruppen unterbrochen sein kann und gegebenenfalls auch noch eine organofunktionelle Gruppe (F) aufweist, die gegenüber dem Bindemittel (B) oder dem Härter (H) reaktiv ist, bedeutet und a+b kleiner oder gleich 4 ist.R8 is an aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, whose carbon chain may be interrupted by non-adjacent oxygen atoms, sulfur atoms, or NR ^ groups and optionally also has an organofunctional group (F), compared to the binder (B) or the Hardener (H) is reactive, and a + b is less than or equal to 4.
Dabei steht a bevorzugt für 0, 1 oder 2, während b bevorzugt 0 oder 1 bedeutet. R' ist vorzugsweise ein Methyl- oder Ethylrest. Z ist vorzugsweise ein Chloratom. Bei R^ handelt es
sich vorzugsweise um einen Rest, der funktionelle Gruppen des Typs Carbinol, Amin, (Meth) acrylat, Epoxy, Thiol, Isocyanato, Ureido und/oder Carbamat enthält.In this case, a is preferably 0, 1 or 2, while b is preferably 0 or 1. R 'is preferably a methyl or ethyl radical. Z is preferably a chlorine atom. R ^ is preferably a radical containing functional groups of the carbinol type, amine, (meth) acrylate, epoxy, thiol, isocyanato, ureido and / or carbamate.
Als Silazane (S2) bzw. Siloxane (S3) werden besonders bevorzugt Hexamethyldisilazan bzw. Hexamethyldisiloxan oder lineare Siloxane, die Seiten- oder endständig organofunktionelle Gruppen tragen, eingesetzt.As silazanes (S2) or siloxanes (S3) are particularly preferably hexamethyldisilazane or hexamethyldisiloxane or linear siloxanes which carry side or terminal organofunctional groups used.
Besonders bevorzugt sind die Silane (Sl), die eine organofunktionelle Gruppe (F) tragen, welche gegenüber dem Bindemittel (B) oder Härter (H) reaktiv sind. Beispiele für solche Silane (Sl) sind aminofunktionelle Silane, wie beispielsweise Aminopropyltrimethoxysilan, Cyclohexylaminomethyltrimethoxysilan,Particularly preferred are the silanes (S1) which carry an organofunctional group (F) which are reactive with the binder (B) or hardener (H). Examples of such silanes (S1) are amino-functional silanes, such as, for example, aminopropyltrimethoxysilane, cyclohexylaminomethyltrimethoxysilane,
Phenylaminomethyltrimethoxysilan, Silane mit ungesättigten Funktionen, wie beispielsweise Vinyltrimethoxysilan, Methacrylatopropyltrimethoxysilan, Methacrylatomethyltrimethoxysilan, epoxyfunktionelle Silane, wie beispielsweise Glycidoxypropyltrimethoxysilan, mercaptofunktionelle Silane, wie beispielsweisePhenylaminomethyltrimethoxysilane, silanes having unsaturated functions such as vinyltrimethoxysilane, methacrylatopropyltrimethoxysilane, methacrylatomethyltrimethoxysilane, epoxyfunctional silanes such as glycidoxypropyltrimethoxysilane, mercapto functional silanes such as
Mercaptopropyltrimethoxysilan, Silane, die über eine maskierte NCO-Gruppe verfügen und bei thermischer Behandlung unter Abspaltung der Schutzgruppe eine NCO-Funktion freisetzen, und Silane, die bei der Reaktion mit einem Partikel (Pl) Carbinol- oder Aminfunktionen freisetzen.Mercaptopropyltrimethoxysilane, silanes that have a masked NCO group and release an NCO function upon deprotection upon thermal treatment, and silanes that release carbinol or amine functions upon reaction with a particle (P1).
Als Partikel (Pl) eignen sich aus Gründen der technischen Handhabbarkeit Oxide mit kovalentem Bindungsanteil in der Metall-Sauerstoff-Bindung, vorzugsweise Oxide der 3.For reasons of technical handling, suitable oxides (c1) are oxides having a covalent bond fraction in the metal-oxygen bond, preferably oxides of the 3.
Hauptgruppe, wie Bor-, Aluminium-, Gallium- oder Indiumoxide, der 4. Hauptgruppe, wie Siliciumdioxid, Germaniumdioxid, Zinnoxid, Zinndioxid, Bleioxid, Bleidioxid, oder Oxide der 4.
Nebengruppe, wie Titanoxid, Zirkoniumoxid und Hafniumoxid. Weitere Beispiele sind Nickel-, Cobalt-, Eisen-, Mangan-, Chrom- und Vanadiumoxide.Main group, such as boron, aluminum, gallium or indium oxides, the 4th main group, such as silica, germanium dioxide, tin oxide, tin dioxide, lead oxide, lead dioxide, or oxides of 4. Subgroups such as titanium oxide, zirconium oxide and hafnium oxide. Further examples are nickel, cobalt, iron, manganese, chromium and vanadium oxides.
Zudem eignen sich Metalle mit oxidierter Oberfläche, Zeolithe (eine Auflistung geeigneter Zeolithe findet sich in: Atlas of Zeolite Framework Types, 5th edition, Ch. Baerlocher, W. M. Meier D.H. Olson, Amsterdam: Elsevier 2001), Silikate, Aluminate, Aluminophosphate, Titanate undIn addition, metals with oxidized surface, zeolites (a list of suitable zeolites can be found in: Atlas of Zeolite Framework Types, 5th edition, Ch. Baerlocher, W.M. Meier D. H. Olson, Amsterdam: Elsevier 2001), silicates, aluminates, aluminophosphates, titanates and
Aluminiumschichtsilikate (z.B. Bentonite, Montmorillonite, Smektite, Hektorite) , wobei die Partikel (Pl) bevorzugt eine spezifische Oberfläche von 0,1 bis 1000 m^/g, besonders bevorzugt von 10 bis 500 m^/g aufweisen (gemessen nach der BET- Methode nach DIN 66131 und 66132). Die Partikel (Pl), die bevorzugt einen mittleren Durchmesser von kleiner 10 μm, besonders bevorzugt kleiner 1000 nm, aufweisen, können als Aggregate (Definition nach DIN 53206) und Agglomerate (Definition nach DIN 53206) vorliegen, die in Abhängigkeit von der äußeren Scherbelastung (z.B. bedingt durch die Messbedingungen) Größen von 1 bis 1000 μm aufweisen können. Dabei wird die mittlere Partikelgröße mittelsAluminum phyllosilicates (eg bentonites, montmorillonites, smectites, hectorites), the particles (P 1) preferably having a specific surface area of from 0.1 to 1000 m 2 / g, particularly preferably from 10 to 500 m 2 / g (measured by the BET standard) Method according to DIN 66131 and 66132). The particles (P1), which preferably have an average diameter of less than 10 .mu.m, more preferably less than 1000 nm, can be present as aggregates (definition according to DIN 53206) and agglomerates (definition according to DIN 53206), which depends on the external shear stress (eg due to the measurement conditions) sizes may have from 1 to 1000 microns. The mean particle size is determined by
Transmissionselektronenmikroskopie (TEM) oder der hydrodynamische Äquivalenzdurchmesser mittels Photonenkorrelationsspektroskopie bestimmt .Transmission electron microscopy (TEM) or the hydrodynamic equivalent diameter determined by means of photon correlation spectroscopy.
In einer bevorzugten Ausführungsform der Erfindung werden als Partikel (Pl) kolloidale Silicium- oder Metalloxide eingesetzt, die im Allgemeinen als Dispersion der entsprechenden Oxidteilchen von Submikrongröße in einem wässrigen oder organischen Lösungsmittel vorliegen. Dabei können unter anderem die Oxide der Metalle Aluminium, Titan, Zirkonium, Tantal,In a preferred embodiment of the invention, colloidal silicon or metal oxides which are generally present as a dispersion of the corresponding submicron-sized oxide particles in an aqueous or organic solvent are used as particles (P1). Among other things, the oxides of the metals aluminum, titanium, zirconium, tantalum,
Wolfram, Hafnium und Zinn oder die entsprechenden Mischoxide verwendet werden. Besonders bevorzugt sind Kieselsole. In der Regel handelt es sich bei den Kieselsolen um 1-50 Gew.-%ige
Lösungen, bevorzugt um 20-40 Gew.-%ige Lösungen. Typische Lösungsmittel sind dabei neben Wasser vor allem Alkohole, insbesondere Alkohole mit 1 bis 6 Kohlenstoffatomen, - häufig Isopropanol aber auch andere meist niedermolekulare Alkohole wie z.B. Methanol, Ethanol, n-Propanol, n-Butanol, Isobutanol und t-Butanol. Ebenso sind auch Organosole in polaren aprotischen Lösungsmitteln wie z.B. Methylethylketon oder aromatische Lösungsmittel wie z.B. Toluol verfügbar. Die mittlere Teilchengröße der Siliciumdioxidpartikel (Pl) liegt im Allgemeinen bei 1-100 nm, bevorzugt bei 5-50 nm, besonders bevorzugt bei 8-30 nm.Tungsten, hafnium and tin or the corresponding mixed oxides are used. Particularly preferred are silica sols. As a rule, the silica sols are 1-50% by weight Solutions, preferably 20-40 wt .-% solutions. In addition to water, typical solvents are, above all, alcohols, in particular alcohols having 1 to 6 carbon atoms, frequently also isopropanol but also other usually low molecular weight alcohols, for example methanol, ethanol, n-propanol, n-butanol, isobutanol and t-butanol. Likewise, organosols in polar aprotic solvents such as methyl ethyl ketone or aromatic solvents such as toluene are available. The average particle size of the silica particles (P1) is generally 1-100 nm, preferably 5-50 nm, more preferably 8-30 nm.
Beispiele für kommerziell erhältliche Kieselsole, die sich zur Herstellung der Partikel (P) eignen, sind Kieselsole der Produktserien LUDOX® (Grace Davison) , Snowtex® (Nissan Chemical), Klebosol® (Clariant) und Levasil® (H. C. Starck) , Kieselsole in organischen Lösungsmitteln wie z.B. IPA-ST (Nissan Chemical) oder solche Kieselsole, die sich nach dem Stöber-Verfahren herstellen lassen.Examples of commercially available silica sols which are suitable for the preparation of the particles (P) are silica sols of the product series LUDOX® (Grace Davison), Snowtex® (Nissan Chemical), Klebosol® (Clariant) and Levasil® (HC Starck), silica sols in organic solvents such as IPA-ST (Nissan Chemical) or those silica sols which can be prepared by the Stöber process.
Ausgehend von den kolloidalen Silicium- oder Metalloxiden (Pl) kann die Herstellung der Partikel (P) nach verschiedenen Verfahren erfolgen. Bevorzugt erfolgt sie jedoch durch Zugabe der Silane (S) bzw. deren Hydrolyse- oder Kondensationsprodukte - gegebenenfalls in einem Lösungsmittel und/oder in Mischungen mit anderen Silanen (Sl), Silazanen (S2) oder Siloxanen (S3) - zum Partikel (Pl) bzw. dessen Lösung in einem wässrigen oder organischen Lösungsmittel. Die Reaktion erfolgt in der Regel bei Temperaturen von 0-200 0C, bevorzugt bei 20-80 0C und besonders bevorzugt bei 20-60 0C. Die Reaktionszeiten liegen typischerweise bei 5 Min bis 48 h, bevorzugt bei 1 bis 24 h. Wahlweise können auch noch saure, basische oder schwermetallhaltige Katalysatoren zugesetzt werden. Bevorzugt werden diese in Spuren (< 1000 ppm) einsetzt. Besonders
bevorzugt wird jedoch auf den Zusatz von gesonderten Katalysatoren verzichtet.Starting from the colloidal silicon or metal oxides (P1), the preparation of the particles (P) can be carried out by various processes. However, it is preferably carried out by addition of the silanes (S) or their hydrolysis or condensation products - optionally in a solvent and / or in mixtures with other silanes (S1), silazanes (S2) or siloxanes (S3) - to the particle (P1). or its solution in an aqueous or organic solvent. The reaction is generally carried out at temperatures of 0-200 0 C, preferably at 20-80 0 C and particularly preferably at 20-60 0 C. The reaction times are typically from 5 min to 48 h, preferably from 1 to 24 h. Alternatively, it is also possible to add acidic, basic or heavy metal-containing catalysts. These are preferably used in traces (<1000 ppm). Especially However, preference is given to dispense with the addition of separate catalysts.
Gegebenenfalls ist für die Umsetzung der Partikel (Pl) mit den Silanen (S) die Zugabe von Wasser bevorzugt.Optionally, the addition of water is preferred for the reaction of the particles (P1) with the silanes (S).
Da kolloidale Silicium- oder Metalloxide oftmals in wässriger oder alkoholischer Dispersion vorliegen, kann es vorteilhaft sein, das bzw. die Lösungsmittel während oder nach der Herstellung der Partikel (P) gegen ein anderes Lösungsmittel bzw. gegen ein anderes Lösungsmittelgemisch auszutauschen. Dies kann beispielsweise durch destillatives Entfernen des ursprünglichen Lösungsmittels geschehen, wobei das neue Lösungsmittel bzw. Lösungsmittelgemisch in einem oder auch in mehreren Schritten vor, während oder auch erst nach derSince colloidal silicon or metal oxides are often present in aqueous or alcoholic dispersion, it may be advantageous to exchange the solvent or solvents during or after the preparation of the particles (P) for another solvent or for another solvent mixture. This can be done for example by distillative removal of the original solvent, wherein the new solvent or solvent mixture in one or in several steps before, during or even after the
Destillation zugegeben werden kann. Geeignete Lösungsmittel können dabei beispielsweise Wasser, aromatische oder aliphatische Alkohole, wobei aliphatische Alkohole, insbesondere aliphatische Alkohole mit 1 bis 6 Kohlenstoffatomen (z.B. Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, t-Butanol, die verschiedenen Regioisomere des Pentanols und Hexanols) bevorzugt werden, Ester (z.B. Ethylacetat, Propylacetat, Butylacetat, Butyldiglycolacetat, Methoxypropylacetat) , Ketone (z.B. Aceton, Metylethylketon) , Ether (z.B. Diethylether, t-Distillation can be added. Suitable solvents may be, for example, water, aromatic or aliphatic alcohols, wherein aliphatic alcohols, in particular aliphatic alcohols having 1 to 6 carbon atoms (eg methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, the various regioisomers of Pentanols and hexanols), esters (eg ethyl acetate, propyl acetate, butyl acetate, butyl diglycol acetate, methoxypropyl acetate), ketones (eg acetone, methyl ethyl ketone), ethers (eg diethyl ether, t-butyl).
Butylmethylether, THF) , aromatische Lösungsmittel (Toluol, die verschiedenen Regioisomere des Xylols aber auch Mischungen wieButylmethylether, THF), aromatic solvents (toluene, the various regioisomers of xylene but also mixtures such
Solvent Naphta) , Lactone (z.B. Butyrolacton etc.) oder LactameSolvent naphtha), lactones (e.g., butyrolactone, etc.) or lactams
(z.B. N-Methylpyrrolidon) darstellen. Dabei werden aprotische Lösungsmittel bzw. Lösungsmittelgemische, die ausschließlich oder aber zumindest teilweise aus aprotischen Lösungsmitteln bestehen, bevorzugt. Die aus den Partikeln (Pl) erhaltenen modifizierten Partikel (P) können durch gängige Verfahren wie
beispielsweise durch Abdampfen der verwendeten Lösungsmittel oder durch Trocknung, beispielsweise im Sprühtrockner, Dünnschichtverdampfer oder Konustrockner, als Pulver isoliert werden . Alternativ kann auf eine Isolierung der Partikel (P) verzichtet werden .(eg N-methylpyrrolidone). In this case, aprotic solvents or solvent mixtures which consist exclusively or at least partly of aprotic solvents are preferred. The modified particles (P) obtained from the particles (P1) can be prepared by common methods such as for example, by evaporation of the solvents used or by drying, for example in a spray dryer, thin-film evaporator or condenser, are isolated as a powder. Alternatively, it is possible to dispense with isolation of the particles (P).
Zusätzlich können in einer bevorzugten Verfahrensweise im Anschluss an die Herstellung der Partikel (P) Verfahren zur Desagglomerierung der Partikel eingesetzt werden, wie Stiftmühlen oder Vorrichtungen zur Mahlsichtung, wieIn addition, in a preferred procedure, following the production of the particles (P), processes for deagglomerating the particles can be used, such as pin mills or devices for grinding sifting, such as
Stiftmühlen, Hammermühlen, Gegenstrommühlen, Perlmühlen, Kugelmühlen, Prallmühlen oder Vorrichtungen zur Mahlsichtung.Pin mills, hammer mills, countercurrent mills, bead mills, ball mills, impact mills or devices for grinding sifting.
In einer weiteren bevorzugten Ausführungsform der Erfindung werden als Partikel (Pl) Organopolysiloxane der allgemeinen Formel [4],In a further preferred embodiment of the invention, as particles (P1) are organopolysiloxanes of the general formula [4],
[R93SiO1/2]i[R92Siθ2/2] j [R9SiO3Z2Ik[SiO4Z2Ii [4][R 9 3SiO 1/2 ] i [R 9 2SiO 2/2] j [R 9 SiO 3 Z 2 Ik [SiO 4 Z 2 Ii [4]
eingesetzt, wobeiused, where
R^ eine OH-Funktion, einen gegebenenfalls halogen-, hydroxyl-, amino-, epoxy-, thiol-, (meth) acryl-, carbamat-, ureido- oder auch NCO-substituierten Kohlenwasserstoffrest mit 1-18 Kohlenstoffatomen, wobei die Kohlenstoffkette durch nicht benachbarte Sauerstoff-, Schwefel-, oder NR^-O-Qruppen unterbrochen sein kann,R ^ is an OH function, an optionally halogen, hydroxyl, amino, epoxy, thiol, (meth) acrylic, carbamate, ureido or NCO-substituted hydrocarbon radical having 1-18 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent oxygen, sulfur, or NR 2 -O- groups;
R^O die Bedeutungen von R^, i, j, k, 1 einen Wert von größer oder gleich 0 bedeuten, mit der Maßgabe, dass i + j + k + 1 größer oder gleich 3, insbesondere mindestens 10 sind und dass mindestens 1 Rest R^ eine OH-Funktion bedeutet.
Die Herstellung der Partikel (P) aus den Organopolysiloxanen (Pl) der allgemeinen Formel [4] erfolgt wie vorstehend beschrieben .R ^ O the meanings of R ^, i, j, k, 1 denote a value of greater than or equal to 0, with the proviso that i + j + k + 1 are greater than or equal to 3, in particular at least 10, and that at least 1 Rest R ^ represents an OH function. The preparation of the particles (P) from the organopolysiloxanes (P1) of the general formula [4] takes place as described above.
Besonders bevorzugt als Partikel (Pl) ist pyrogene Kieselsäure, die in einer Flammenreaktion aus Organosiliciumverbindungen hergestellt wird, z.B. aus Siliciumtetrachlorid oder Methyldichlorsilan, oder Hydrogentrichlorsilan oder Hydrogenmethyldichlorsilan, oder anderen Methylchlorsilanen oder Alkylchlorsilanen, auch im Gemisch mitParticularly preferred as particles (P1) is fumed silica prepared in a flame reaction from organosilicon compounds, e.g. of silicon tetrachloride or methyldichlorosilane, or hydrogentrichlorosilane or hydrogenmethyldichlorosilane, or other methylchlorosilanes or alkylchlorosilanes, also in admixture with
Kohlenwasserstoffen, oder beliebigen verflüchtigbaren oder versprühbaren Gemischen aus Organosiliciumverbindungen, wie genannt, und Kohlenwasserstoffen, z.B. in einer Wasserstoff- Sauerstoff-Flamme, oder auch einer Kohlenmonoxid- Sauerstoffflamme, hergestellt wird. Die Herstellung derHydrocarbons, or any volatilizable or sprayable mixtures of organosilicon compounds, as mentioned, and hydrocarbons, e.g. in a hydrogen-oxygen flame, or even a carbon monoxide oxygen flame is produced. The production of
Kieselsäure kann dabei wahlweise mit und ohne Zusatz von Wasser erfolgen, zum Beispiel im Schritt der Reinigung; bevorzugt ist kein Zusatz von Wasser. Pyrogen hergestellte Kieselsäure oder Siliciumdioxid ist beispielsweise bekannt aus Ullmann's Enzyklopädie der Technischen Chemie 4. Auflage, Band 21, Seite 464. Die unmodifizierte pyrogene Kieselsäure hat eine spezifische BET-Oberfläche, gemessen gemäß DIN EN ISO 9277 / DIN 66132 vonSilica can be carried out optionally with and without the addition of water, for example in the step of purification; preferred is no addition of water. Pyrogenic silica or silica is known for example from Ullmann's Encyclopedia of Industrial Chemistry 4th Edition, Volume 21, page 464. The unmodified fumed silica has a BET specific surface area, measured according to DIN EN ISO 9277 / DIN 66132 of
10 m^/g bis 600 m^/g, bevorzugt von 50 m^/g bis 400 m^/g.10 m ^ / g to 600 m ^ / g, preferably from 50 m ^ / g to 400 m ^ / g.
Die Herstellung der Partikel (P) aus pyrogener Kieselsäure kann nach verschiedenen Verfahren erfolgen. In einem bevorzugtenThe preparation of the particles (P) from fumed silica can be carried out by various methods. In a preferred
Verfahren wird die trockene pulverförmige pyrogene Kieselsäure direkt mit den feinstverteilten Silanen (S) - gegebenenfalls in Mischungen mit anderen Silanen (Sl),Method, the dry powdery fumed silica directly with the finely divided silanes (S) - optionally in admixture with other silanes (Sl),
Silazanen (S2), Siloxanen (S3) oder Verbindungen (L) - umgesetzt .
Verfahren, die zur Herstellung von Partikeln (P) aus pyrogener Kieselsäure geeignet sind, sind bekannt und vielfach beschrieben. So können z.B. sämtliche in WO 2006/018144 beschriebenen Verfahren, bei denen bevorzugt pulverförmige Kieselsäure funktionalisiert wird, auch zur Herstellung der erfindungsgemäßen Partikel (P) eingesetzt werden. Bevorzugt wird die pyrogene Kieselsäure dabei mit Silanen (S) , die bevorzugt der Formel [2] entsprechen, und gegebenenfalls zusätzlichen anderen Silanen (Sl), Silazanen (S2), Siloxanen (S3) oder anderen Verbindungen (L) umgesetzt.Silazanes (S2), siloxanes (S3) or compounds (L) - implemented. Processes which are suitable for the production of particles (P) from fumed silica are known and have been described many times. Thus, for example, all processes described in WO 2006/018144, in which preferably powdered silica is functionalized, can also be used for the preparation of the particles (P) according to the invention. The fumed silica is preferably reacted with silanes (S), which preferably correspond to the formula [2], and optionally additional other silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L).
In einem weiteren bevorzugten Verfahren wird die pyrogene Kieselsäure nicht pulverförmig sondern in Dispersionen in Wasser oder typischen industriell eingesetzten Lösungsmitteln wie Alkoholen wie Methanol, Ethanol, i-Propanol, wie Ketonen wie Aceton, Methyl-Ethyl-Keton, wie Ethern wie Diethylether, THF, Kohlenwasserstoffen wie Pentan, Hexanen, Aromaten wie Toluol oder anderen flüchtigen Lösungsmitteln wie Hexamethyldisiloxan oder deren Mischungen mit Silanen (S) und gegebenenfalls den Silanen (Sl), Silazanen (S2), Siloxanen (S3) oder Verbindungen (L) umgesetzt.In another preferred method, the fumed silica is not powdered but in dispersions in water or typical industrially used solvents such as alcohols such as methanol, ethanol, i-propanol, such as ketones, such as acetone, methyl ethyl ketone, such as ethers, such as diethyl ether, THF, Hydrocarbons such as pentane, hexanes, aromatics such as toluene or other volatile solvents such as hexamethyldisiloxane or mixtures thereof with silanes (S) and optionally the silanes (Sl), silazanes (S2), siloxanes (S3) or compounds (L) implemented.
Das Verfahren kann kontinuierlich oder diskontinuierlich durchgeführt werden und aus einem oder mehreren Schritten aufgebaut sein. Bevorzugt ist ein kontinuierliches Verfahren. Bevorzugt wird die modifizierte pyrogene Kieselsäure mittels eines Verfahren hergestellt, bei dem die Kieselsäure (1) in einem der oben genannten Lösungsmittel eingemischt wird, (2) mit den Silanen (S) und gegebenenfalls den Silanen (Sl), Silazanen (S2), Siloxanen (S3) oder Verbindungen (L) zur Reaktion gebracht wird, und (3) von Lösungsmitteln, überschüssigen Silanen und Nebenprodukten befreit wird.The process can be carried out continuously or batchwise and be composed of one or more steps. Preferred is a continuous process. Preferably, the modified fumed silica is prepared by a process in which the silica (1) is mixed in one of the abovementioned solvents, (2) with the silanes (S) and optionally the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) is reacted, and (3) freed of solvents, excess silanes and by-products.
Die Dispergierung (1), Reaktion (2) und Trocknung (3) werden
bevorzugt durchgeführt in einer Atmosphäre mit weniger als 10 Vol.% Sauerstoff, besonders bevorzugt weniger als 2,5 Vol.%, beste Ergebnisse werden erzielt bei weniger als 1 Vol.% Sauerstoff . Das Einmischen (1) kann mittels üblicher Mischaggregate wieThe dispersion (1), reaction (2) and drying (3) are preferably carried out in an atmosphere with less than 10% by volume of oxygen, more preferably less than 2.5% by volume, best results are achieved with less than 1% by volume of oxygen. The mixing (1) can by means of conventional mixing units such
Ankerrührer oder Balkenrührer erfolgen. Gegebenenfalls kann das Einmischen unter hoher Scherung mittels Dissolvern, Rotor- Stator-Aggregaten, gegebenenfalls unter direkter Zudosierung in den Scherspalt, mittels Ultraschallgebern oder mittels Mahlaggregaten wie Kugelmühlen erfolgen. Gegebenenfalls können verschiedene der oben genannten Aggregate parallel oder nacheinander eingesetzt werden.Anchor stirrer or bar stirrer. Optionally, the mixing under high shear by means of dissolvers, rotor-stator assemblies, optionally with direct metered addition into the shear gap, by means of ultrasonic generators or by means of grinding units such as ball mills. Optionally, various of the above aggregates can be used in parallel or sequentially.
Zur Reaktion (2) der Silane (S) und gegebenenfalls der Silane (Sl), Silazane (S2), Siloxane (S3) oder Verbindungen (L) mit der Kieselsäure werden diese in reiner Form oder als Lösung in geeigneten Lösungsmitteln der Kieselsäuredispersion zugegeben und homogen vermischt. Die Zugabe der Silane (S) und gegebenenfalls der Silane (Sl), Silazane (S2), Siloxane (S3) oder Verbindungen (L) kann dabei in dem Behälter, der zur Herstellung der Dispersion eingesetzt wird oder in einem separaten Reaktionsbehälter erfolgen. Werden die Silane im Dispergierbehälter zugefügt, kann dies parallel zur oder nach Abschluss der Dispergierung erfolgen. Gegebenenfalls können die Silane (S) und gegebenenfalls die Silane (Sl), Silazane (S2), Siloxane (S3) oder Verbindungen (L) gelöst im Dispergiermedium direkt im Dispergierschritt zugefügt werden. Gegebenenfalls wird der Reaktionsmischung Wasser zugefügt. Gegebenenfalls werden der Reaktionsmischung saure Katalysatoren wie Brönsted-Säuren wie flüssige oder gasförmige HCl, Schwefelsäure, Phosphorsäure oder Essigsäure, oder basischeFor the reaction (2) of the silanes (S) and optionally of the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) with the silica, these are added in pure form or as a solution in suitable solvents of the silica dispersion and homogeneously mixed. The addition of the silanes (S) and optionally of the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) can be carried out in the container used to prepare the dispersion or in a separate reaction vessel. If the silanes are added in the dispersing container, this can take place parallel to or after completion of the dispersion. If appropriate, the silanes (S) and optionally the silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) dissolved in the dispersing medium can be added directly in the dispersing step. Optionally, water is added to the reaction mixture. Optionally, the reaction mixture acidic catalysts such as Bronsted acids such as liquid or gaseous HCl, sulfuric acid, phosphoric acid or acetic acid, or basic
Katalysatoren wie Brönsted-Basen wie flüssiger oder gasförmiger Ammoniak, Amine wie NEt3 oder NaOH zugefügt.Catalysts such as Brönsted bases such as liquid or gaseous ammonia, amines such as NEt3 or NaOH added.
Der Reaktionsschritt wird bei einer Temperatur von 0 0C bis 200
°C, bevorzugt 10 0C bis 180 0C und besonders bevorzugt von 20 0C bis 150 0C durchgeführt.The reaction step is at a temperature of 0 0 C to 200 ° C, preferably 10 0 C to 180 0 C and more preferably carried out from 20 0 C to 150 0 C.
Das Entfernen von Lösungsmitteln, überschüssigen Silanen (S) und gegebenenfalls Silanen (Sl), Silazanen (S2), Siloxanen (S3) oder Verbindungen (L) und Nebenprodukten (3) kann mittels Trocknern oder durch Sprühtrocknen erfolgen. Gegebenenfalls kann an den Trocknungsschritt noch ein Temperschritt zur Vervollständigung der Reaktion angeschlossen sein.The removal of solvents, excess silanes (S) and optionally silanes (S1), silazanes (S2), siloxanes (S3) or compounds (L) and by-products (3) can be carried out by means of dryers or by spray drying. Optionally, an annealing step to complete the reaction may be connected to the drying step.
Zusätzlich können im Anschluss an die Trocknung Verfahren zur mechanischen Verdichtung der Kieselsäure eingesetzt werden, wie zum Beispiel Presswalzen, Mahlaggregate, wie Kollergänge und wie Kugelmühlen, kontinuierlich oder diskontinuierlich, Verdichtung durch Schnecken oder Schraubenmischer,In addition, after the drying processes for mechanical densification of the silica can be used, such as press rolls, grinding units, such as edge mills and ball mills, continuously or discontinuously, compaction by screws or screw mixer,
Schraubenverdichter, Brikettierer, oder Verdichten durch Absaugen des Luft- oder Gasinhaltes durch geeignete Vakuummethoden .Screw compressors, briquetting, or compacting by suction of the air or gas content by suitable vacuum methods.
In einer weiteren besonders bevorzugten Verfahrensweise werden im Anschluss an die Trocknung Verfahren zur mechanischen Verdichtung der Kieselsäure eingesetzt, wie Verdichten durch Absaugen des Luft- oder Gasinhaltes durch geeignete Vakuummethoden oder Presswalzen oder Kombination von beiden Verfahren.In a further particularly preferred procedure, processes for the mechanical densification of the silica are used following the drying, such as compression by suction of the air or gas contents by suitable vacuum methods or pressure rollers or combination of both methods.
Zusätzlich können in einer besonders bevorzugten Verfahrensweise im Anschluss an die Trocknung Verfahren zur Desagglomerierung der Kieselsäure eingesetzt werden, wie Stiftmühlen, Hammermühlen, Gegenstrommühlen, Prallmühlen oder Vorrichtungen zur Mahlsichtung.In addition, in a particularly preferred procedure, following the drying, processes for deagglomerating the silica can be used, such as pin mills, hammer mills, countercurrent mills, impact mills or devices for grinding sifting.
Bei einem weiteren bevorzugten Verfahren zur Herstellung der
Partikel (P) werden die Partikel (P) über eine Cohydrolyse der Organosilane (S) mit anderen Silanen (S4) oder Verbindungen (L) hergestellt. Als Silane (S4) können dabei sämtliche hydrolysierbaren Silane sowie hydroxysilylgruppenhaltigen Silane eingesetzt werden. Ebenso können auch Siloxane oderIn a further preferred method for producing the Particles (P) are the particles (P) via a cohydrolysis of organosilanes (S) with other silanes (S4) or compounds (L). As silanes (S4) it is possible to use all hydrolyzable silanes and silanes containing hydroxysilyl groups. Likewise, siloxanes or
Silazane zum Einsatz kommen. Typische Beispiele für geeignete Silane (S4) sind Tetraethoxysilan, Tetramethoxysilan, Methyltrimethoxysilan, Phenyltrimethoxysilan, Methyltriethoxysilan, Phenyltriethoxysilan, Dimethyldimethoxysilan, Dimethyldiethoxysilan, Trimethyl- methoxysilan oder Trimethylethoxysilan . Selbstverständlich können auch verschiedene Mischungen aus verschiedenen Silanen (S4) eingesetzt werden. Dabei können sowohl Mischungen verwendet werden, die neben den Silanen (S) nur Silane (S4) ohne zusätzliche Organofunktionen enthalten, als auchSilazane are used. Typical examples of suitable silanes (S4) are tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane. Of course, different mixtures of different silanes (S4) can be used. Mixtures can be used which, in addition to the silanes (S), contain only silanes (S4) without additional organ functions, as well
Mischungen, die neben den Silanen (S) auch Silane (S4) ohne zusätzliche Organofunktion und Silane (S4) mit zusätzlicher Organofunktion enthalten. Bei der Herstellung der Partikel (P) über eine Cohydrolyse können die verschiedenen Silane gemeinsam als auch sukzessive zugegeben werden.Mixtures containing in addition to the silanes (S) and silanes (S4) without additional organo-function and silanes (S4) with additional organo function. In the preparation of the particles (P) via cohydrolysis, the various silanes can be added together or successively.
Die Zusammensetzungen (Z) können einen oder mehrere verschiedene Partikeltypen (P) enthalten, beispielsweise modifiziertes Siliciumdioxid sowie modifiziertes Aluminiumoxid.The compositions (Z) may contain one or more different types of particles (P), for example modified silica and modified alumina.
Als Bindemittel (B) kommen sowohl anorganische als auch organische Polymere zum Einsatz. Beispiele für derartige Polymermatrices (B) sind Polyethylene, Polypropylene, Polyamide, Polyimide, Polycarbonate, Polyester, Polyetherimide, Polyethersulfone, Polyphenylenoxide, Polyphenylensulfide, Polysulfone (PSU) , Polyphenylsulfone (PPSU), Polyurethane, Polyvinylchloride, Polytetrafluorethylene (PTFE), Polystyrole (PS), Polyvinylalkohole (PVA), Polyetherglykole (PEG),
Polyphenylenoxide (PPO) , Polyaryletherketone, Epoxidharze, Polyacrylate, Polymethacrylate und Siliconharze.As binder (B) both inorganic and organic polymers are used. Examples of such polymer matrices (B) are polyethylenes, polypropylenes, polyamides, polyimides, polycarbonates, polyesters, polyetherimides, polyethersulfones, polyphenylene oxides, polyphenylene sulfides, polysulfones (PSU), polyphenylsulfones (PPSU), polyurethanes, polyvinyl chlorides, polytetrafluoroethylenes (PTFE), polystyrenes (PS ), Polyvinyl alcohols (PVA), polyether glycols (PEG), Polyphenylene oxides (PPO), polyaryletherketones, epoxy resins, polyacrylates, polymethacrylates and silicone resins.
Polymere, die sich ebenfalls als Bindemittel (B) eignen, sind oxidische Materialien, die nach gängigen, dem Fachmann bekannten Sol-Gel-Verfahren zugänglich sind. Nach dem Sol-Gel- Verfahren werden hydrolysierbare und kondensierbare Silane und/oder metallorganische Reagenzien mittels Wasser und gegebenenfalls in Gegenwart eines Katalysators hydrolysiert und durch geeignete Methoden zu den silikatischen bzw. oxidischen Materialien gehärtet.Polymers which are likewise suitable as binders (B) are oxidic materials which are accessible by customary sol-gel processes known to the person skilled in the art. According to the sol-gel process, hydrolyzable and condensable silanes and / or organometallic reagents are hydrolyzed by means of water and if appropriate in the presence of a catalyst and hardened by suitable methods to give the silicatic or oxidic materials.
Tragen die Silane oder metallorganischen Reagenzien organofunktionelle Gruppen (wie z.B. Epoxy-, Methacryl-, Amingruppen) , die zu einer Vernetzung herangezogen werden können, so können diese modifizierten Sol-Gel-Materialien zusätzlich über ihren organischen Anteil gehärtet werden. Die Härtung des organischen Anteils kann dabei - gegebenenfalls nach Zugabe weiterer reaktiver organischer Komponenten - u.a. thermisch oder durch UV-Bestrahlung erfolgen. Beispielsweise sind so Sol-Gel-Materialien als Matrix (B) geeignet, die durch Reaktion eines epoxyfunktionellen Alkoxysilans mit einem Epoxidharz und gegebenenfalls in Gegenwart eines Aminhärters zugänglich sind. Ein weitere Beispiel für derartige anorganische-organische Polymere sind Sol-Gel-Materialien (B) , die sich aus aminofunktionellen Alkoxysilanen und Epoxidharzen herstellen lassen. Durch das Einbringen des organischen Anteils kann beispielsweise die Elastizität eines Sol-Gel-Films verbessert werden. Derartige anorganisch-organische Polymere sind beispielsweise in Thin Solid Films 1999, 351, 198-203 beschrieben.When the silanes or organometallic reagents carry organofunctional groups (such as epoxy, methacrylic, amine groups) that can be used for crosslinking, these modified sol-gel materials can additionally be cured via their organic moiety. The curing of the organic fraction may - optionally after addition of further reactive organic components - u.a. thermally or by UV irradiation. For example, as sol-gel materials are suitable as matrix (B), which are accessible by reaction of an epoxy-functional alkoxysilane with an epoxy resin and optionally in the presence of an amine curing agent. Another example of such inorganic-organic polymers are sol-gel materials (B), which can be prepared from amino-functional alkoxysilanes and epoxy resins. By introducing the organic fraction, for example, the elasticity of a sol-gel film can be improved. Such inorganic-organic polymers are described, for example, in Thin Solid Films 1999, 351, 198-203.
Es können zudem auch Reaktivharze als Bindemittel (B) eingesetzt werden. Unter Reaktivharzen werden dabei
Verbindungen verstanden, die über eine oder mehrere reaktionsfähige Gruppen verfügen. Beispielhaft seien hier als reaktionsfähige Gruppen Hydroxy-, Amino-, Isocyanat-, Epoxid-, Mercaptogruppen, ethylenisch ungesättigte Gruppen sowie feuchtigkeitsvernetzende Alkoxysilylgruppen genannt. InIt is also possible to use reactive resins as binders (B). Reactive resins are included Understood compounds having one or more reactive groups. Examples which may be mentioned here as reactive groups are hydroxy, amino, isocyanate, epoxide, mercapto groups, ethylenically unsaturated groups and moisture-crosslinking alkoxysilyl groups. In
Gegenwart eines geeigneten Härters (H) bzw. eines Initiators können die Reaktivharze durch thermische Behandlung, aktinische Strahlung und/oder (Luft-) feuchtigkeit polymerisiert werden. Die Reaktivharze können dabei in monomerer, oligomerer und polymerer Form vorliegen. Beispiele für gängige Reaktivharze sind: hydroxyfunktionelle Harze wie z.B. hydroxylgruppen- haltige Polyacrylate oder Polyester, die mit isocyanatfunktionellen Härtern (H) vernetzt werden können; acryl- sowie methacrylfunktionelle Harze, die nach Zugabe eines Initiators thermisch, durch aktinische Strahlung oder durch einen aminofunktionellen Härter (H) gehärtet werden können; Epoxidharze, die mit Aminhärtern (H) vernetzt werden können; vinylfunktionelle Siloxane, die durch Reaktion mit einem SiH- funktionellen Härter (H) vernetzt werden können; SiOH- funktionelle Siloxane, die durch eine Polykondensation gehärtet werden können.In the presence of a suitable hardener (H) or an initiator, the reactive resins can be polymerized by thermal treatment, actinic radiation and / or (air) moisture. The reactive resins may be present in monomeric, oligomeric and polymeric form. Examples of common reactive resins are: hydroxy-functional resins, e.g. hydroxyl-containing polyacrylates or polyesters which can be crosslinked with isocyanate-functional hardeners (H); acrylic and methacrylic functional resins which can be cured thermally, by actinic radiation or by an amino-functional hardener (H) after addition of an initiator; Epoxy resins that can be crosslinked with amine hardeners (H); vinyl-functional siloxanes which can be crosslinked by reaction with a SiH-functional hardener (H); SiOH-functional siloxanes which can be cured by a polycondensation.
Bevorzugt handelt es sich bei den Bindemitteln (B) um carbinol- , (meth) acrylat-, epoxy- und isocyanatfuktionelle Harze. Für die Herstellung von Lacksystemen werden als Lackharze bevorzugt hydroxylgruppen-haltige Prepolymere, besonders bevorzugt hydroxylgruppen-haltige Polyacrylate oder Polyester eingesetzt. Derartige für die Lackherstellung geeignete hydroxylgruppen-haltige Polyacrylate und Polyester sind dem Fachmann hinlänglich bekannt und in der einschlägigen Literatur vielfach beschrieben. Sie werden von zahlreichen Herstellern hergestellt und kommerziell vertrieben.
Als Bindemittel (B) eignen sich zudem auch Mischungen verschiedener Matrixpolymere, entsprechender Copolymere, sowie monomerer, oligomerer und polymerer Reaktivharze.The binders (B) are preferably carbinol, (meth) acrylate, epoxy and isocyanate functional resins. For the preparation of coating systems, the coating resins used are preferably hydroxyl-containing prepolymers, particularly preferably hydroxyl-containing polyacrylates or polyesters. Such suitable for the paint preparation hydroxyl-containing polyacrylates and polyesters are well known to those skilled in and widely described in the relevant literature. They are manufactured by many manufacturers and distributed commercially. Other suitable binders (B) are mixtures of various matrix polymers, corresponding copolymers, and monomeric, oligomeric and polymeric reactive resins.
Als Härter (H) werden die für die oben genannten Bindemittel (B) typischerweise eingesetzten Verbindungen eingesetzt. Beispiele für geeignete Härter sind amino-, epoxy-, isocyanato- funktionelle Monomere, Oligomere oder Polymere.As hardener (H), the compounds typically used for the abovementioned binders (B) are used. Examples of suitable hardeners are amino-, epoxy-, isocyanato-functional monomers, oligomers or polymers.
Bei den Zusammensetzungen (Z) , die insbesondere als Lacksystem Verwendung finden, kann es sich dabei um 1-komponentige (IK) oder auch um 2-komponentige (2K) Systeme handeln. Im ersten Fall werden als Härter (H) bevorzugt Verbindungen eingesetzt, die über geschützte Isocyanatgruppen verfügen. Im zweiten Fall werden als Härter (H) bevorzugt Verbindungen mit freienThe compositions (Z), which are used in particular as a coating system, may be 1-component (1K) or 2-component (2K) systems. In the first case, hardeners (H) are preferably compounds which have protected isocyanate groups. In the second case, preferred hardeners (H) are compounds with free ones
Isocyanatgruppen verwendet. Sowohl in IK- als auch in 2K-Lacken werden als Isocyanate gängige Di- und/oder Polyisocyanate eingesetzt, die gegebenenfalls zuvor mit den jeweiligen Schutzgruppen versehen worden sind. Dabei prinzipiell sämtliche gebräuchliche Isocyanate eingesetzt werden, wie sie in derIsocyanate groups used. Both in IK and in 2K paints are used as isocyanates diisocyanates and / or polyisocyanates, which may have been previously provided with the respective protective groups. In principle, all customary isocyanates are used, as described in the
Literatur vielfach beschrieben sind. Gängige Diisocyanate sind beispielsweise Diisocyanatodiphenylmethan (MDI), sowohl in Form von rohem oder technischem MDI als auch in Form reiner 4,4'- bzw. 2, 4 ' -Isomeren oder deren Mischungen, Tolylendiisocyanat (TDI) in Form seiner verschiedenen Regioisomere,Literature are often described. Common diisocyanates are, for example, diisocyanatodiphenylmethane (MDI), both in the form of crude or industrial MDI and in the form of pure 4,4'- or 2, 4 'isomers or mixtures thereof, tolylene diisocyanate (TDI) in the form of its various regioisomers,
Diisocyanatonaphthalin (NDI), Isophorondiisocyanat (IPDI), perhydriertes MDI (H-MDI), Tetramethylendiisocyanat, 2-Methyl- pentamethylendiisocyanat, 2,2,4- Trimethylhexamethylendiisocyanat, Dodecamethylendiisocyanat, 1, 4-Diisocyanatocyclohexan, 1, 3-Diisocyanato-4-methylcyclohexan oder auch Hexamethylendiisocyanat (HDI). Beispiele für Polyisocyanate sind polymeres MDI (P-MDI), Triphenylmethantriisocyanat sowie auch sämtliche Isocyanurat-
oder Biuret-Trimerisate der oben aufgeführten Diisocyanate . Daneben können auch weitere Oligomere der oben genannten Isocyanate mit blockierten NCO-Gruppen eingesetzt werden. Sämtliche Di- und/oder Polyisocyanate können einzeln oder auch in Mischungen eingesetzt werden. Bevorzugt werden dabei die Isocyanurat- und Biuret-Trimerisate der - vergleichsweise UV- stabilen - aliphatischen Isocyanate, besonders bevorzugt die Trimerisate von HDI und IPDI, verwendet.Diisocyanatonaphthalene (NDI), isophorone diisocyanate (IPDI), perhydrogenated MDI (H-MDI), tetramethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1,3-diisocyanato-4- methylcyclohexane or hexamethylene diisocyanate (HDI). Examples of polyisocyanates are polymeric MDI (P-MDI), triphenylmethane triisocyanate and also all isocyanurate or biuret trimers of the diisocyanates listed above. In addition, it is also possible to use further oligomers of the abovementioned isocyanates with blocked NCO groups. All di- and / or polyisocyanates can be used individually or in mixtures. Preference is given here to the isocyanurate and biuret trimerates of the comparatively UV-stable aliphatic isocyanates, particularly preferably the trimers of HDI and IPDI.
Werden als Härter (H) Isocyanate mit geschütztenAre hardened as (H) isocyanates with protected
Isocyanatgruppen eingesetzt, so werden Schutzgruppen bevorzugt, die bei Temperaturen von 80 bis 200 0C, besonders bevorzugt bei 100 bis 170 0C abgespalten werden. Als Schutzgruppen können sekundäre oder tertiäre Alkohole, wie Isopropanol oder t- Butanol, CH-acide Verbindungen wie z.B. Malonsäurediethylester, Acetylaceton, Acetessigsäureethylester, Oxime wie z.B. Formaldoxim, Acetaldoxim, Butanoxim, Cyclohexanonoxim, Acetophenonoxim, Benzophenonoxim oder Diethylenglyoxim, Lactame, wie z.B. Caprolactam, Valerolactam, Butyrolactam, Phenole wie Phenol, o-Methylphenol, W-Alkylamide wie z.B. N- Methylacetamid, Imide wie Phthalimid, sekundäre Amine wie z.B. Diisopropylamin, Imidazol, 2-Isopropylimidazol, Pyrazol, 3,5- Dimethylpryazol, 1, 2, 4-Triazol und 2,5 Dimethyl-1, 2, 4-triazol eingesetzt werden. Vorzugsweise werden dabei Schutzgruppen wie Butanoxim, 3, 5-Dimethylpyrazol, Caprolactam,Isocyanate groups are used, protecting groups are preferred which are cleaved at temperatures of 80 to 200 0 C, more preferably at 100 to 170 0 C. Suitable protecting groups are secondary or tertiary alcohols, such as isopropanol or t-butanol, CH-acidic compounds such as diethyl malonate, acetylacetone, ethyl acetoacetate, oximes such as formaldoxime, acetaldoxime, butanoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime or diethylene glycol, lactams such as caprolactam, Valerolactam, butyrolactam, phenols such as phenol, o-methylphenol, W-alkylamides such as N-methylacetamide, imides such as phthalimide, secondary amines such as diisopropylamine, imidazole, 2-isopropylimidazole, pyrazole, 3,5-dimethylpryazole, 1, 2, 4 Triazole and 2,5-dimethyl-1,2,4-triazole. Preferably, protecting groups such as butane oxime, 3, 5-dimethylpyrazole, caprolactam,
Malonsäurediethylester, Malonsäuredemethylester, Acetessigester, Diisopropylamin, Pyrrolidon, 1, 2, 4-Triazol, Imidazol und 2-Isopropylimidazol verwendet. Besonders bevorzugt werden Schutzgruppen eingesetzt, die eine niedrige Einbrenntemperatur ermöglichen wie z.B. Malonsäurediethylester, Malonsäuredimethylester, Butanoxim, Diisopropylamin, 3,5- Dimethylpyrazol und 2-Isopropylimidazol.
Das Verhältnis an - gegebenenfalls blockierten -Diethyl malonate, methyl malonate, acetoacetic ester, diisopropylamine, pyrrolidone, 1, 2, 4-triazole, imidazole and 2-isopropylimidazole used. Particular preference is given to using protective groups which allow a low stoving temperature, for example diethyl malonate, dimethyl malonate, butane oxime, diisopropylamine, 3,5-dimethylpyrazole and 2-isopropylimidazole. The ratio of - possibly blocked -
Isocyanatgruppen zu den isocyanatreaktiven Gruppen von Lackharz (B) liegt in der Zusammensetzung (Z) üblicherweise bei 0,5 bis 2, bevorzugt bei 0,8 bis 1,5 und besonders bevorzugt bei 1,0 bis 1,2.Isocyanate groups to the isocyanate-reactive groups of paint resin (B) in the composition (Z) is usually 0.5 to 2, preferably 0.8 to 1.5 and particularly preferably 1.0 to 1.2.
Als Härter (H) eignen sich zudem auch Mischungen verschiedener Härter (H) .Other suitable hardeners (H) are mixtures of different hardeners (H).
Die Zusammensetzungen (Z) können zudem gängige Lösungsmittel sowie die in Formulierungen üblichen Additive und Zusätze erhalten. Zu nennen wären hier u.a. Verlaufshilfsmittel, oberflächenaktive Substanzen, Haftvermittler, Lichtschutzmittel wie UV-Absorber und/oder Radikalfänger, Thixotropiermittel sowie weitere Fest- und Füllstoffe. Zur Erzeugung der jeweils gewünschten Eigenschaftsprofile sowohl der Zusammensetzungen (Z) als auch der Komposite (K) sind derartige Zusätze bevorzugt .The compositions (Z) may also contain common solvents and the additives and additives customary in formulations. To call here would be u.a. Leveling agents, surface-active substances, adhesion promoters, light stabilizers such as UV absorbers and / or radical scavengers, thixotropic agents and other solids and fillers. To produce the respective desired property profiles of both the compositions (Z) and the composites (K), such additives are preferred.
Die Herstellung der Kompositmaterialien (K) erfolgt vorzugsweise in einem zweistufigen Verfahren. In einer ersten Stufe werden durch Vermischen der Partikel (P) , des Bindemittels (B) und gegebenenfalls des Härters (H) und weiterer Additive und Zusätze die Zusammensetzungen (Z) hergestellt. In einem zweiten Schritt werden dieThe preparation of the composite materials (K) is preferably carried out in a two-stage process. In a first stage, the compositions (Z) are prepared by mixing the particles (P), the binder (B) and optionally the hardener (H) and other additives and additives. In a second step, the
Zusammensetzungen (Z) durch Härtung, d.h. durch Auftrocknen, durch Reaktion zwischen Bindemittel (B) und Härter (H) , durch (Luft-) Feuchtigkeit und/oder durch Behandeln mit thermischer oder aktinischer Strahlung in die Kompositmaterialien (K) überführt.Compositions (Z) by curing, i. by drying, by reaction between the binder (B) and hardener (H), by (air) moisture and / or by treatment with thermal or actinic radiation in the composite materials (K).
In einer bevorzugten Ausführungsform zur Herstellung der Zusammensetzungen (Z) werden das Bindemittel (B) , die Partikel
(P) sowie gegebenenfalls der Härter (H) und gegebenenfalls weitere Zusätze in einem Lösungsmittel oder einem Lösungsmittelgemisch gelöst bzw. dispergiert. Lösungsmittel oder Lösungsmittelgemische mit einem Siedepunkt bzw. Siedebereich von bis zu 120° C bei 0,1 MPa sind bevorzugt. Geeignete Lösungsmittel sind Ether wie beispielsweise THF, Alkohole wie beispielsweise Methanol, Ethanol, Isopropanol, Ester wie beispielsweise Butylacetat, aromatische Kohlenwasserstoffe wie beispielsweise Toluol und Xylole, lineare und verzweigte aliphatische Lösungsmittel wie beispielsweise Pentan, Hexan, Dodecan sowie Dimethylformamid, Dimethylacetamid, Methoxyproylacetat, Dimethylsulfoxid, N- Methyl-2-pyrrolidon und Wasser. Zur Dispergierung der Partikel (P) in der Zusammensetzung (Z) können weitere zur Dispergierung üblicherweise eingesetzte Additive und Zusätze verwendet werden. Zu nennen sind hier Brönstedt-Säuren, wie z.B. Salzsäure, Phosphorsäure, Schwefelsäure, Salpetersäure, Trifluoressigsäure, Essigsäure, Methylsulfonsäure, Brönstedt- Basen, wie z.B. Triethylamin und Ethyldiisopropylamin . Zudem können als weitere Zusätze alle üblicherweise verwendeten Emulgatoren und/oder Schutzkolloide eingesetzt werden. Beispiele für Schutzkolloide sind Polyvinylalkohole, Cellulosederivate oder Vinylpyrrolidon enthaltende Polymerisate. Gebräuchliche Emulgatoren sind z.B. ethoxylierte Alkohole und Phenole (Alkylrest C4-C18, EO-Grad 3-100), Alkali- und Ammoniumsalze von Alkylsulfaten (C3-C18), Schwefelsäure- sowie Phosphorsäureester und Alkylsulfonate . Besonders bevorzugt werden SuIfobernsteinsäureester sowie Alkalialkylsulfate sowie Polyvinylalkohole. Es können auch mehrere Schutzkolloide und/oder Emulgatoren als Gemisch eingesetzt werden. Bevorzugt werden zur Dispergierung derIn a preferred embodiment for the preparation of the compositions (Z), the binder (B), the particles (P) and optionally the hardener (H) and, if appropriate, further additives dissolved or dispersed in a solvent or a solvent mixture. Solvent or solvent mixtures having a boiling point or boiling range of up to 120 ° C at 0.1 MPa are preferred. Suitable solvents are ethers such as THF, alcohols such as methanol, ethanol, isopropanol, esters such as butyl acetate, aromatic hydrocarbons such as toluene and xylenes, linear and branched aliphatic solvents such as pentane, hexane, dodecane and dimethylformamide, dimethylacetamide, methoxyproyl acetate, dimethyl sulfoxide , N-methyl-2-pyrrolidone and water. In order to disperse the particles (P) in the composition (Z) it is possible to use further additives and additives usually used for dispersion. These include Brönsted acids, such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, trifluoroacetic acid, acetic acid, methylsulfonic acid, Bronsted bases, such as triethylamine and ethyldiisopropylamine. In addition, all commonly used emulsifiers and / or protective colloids can be used as further additives. Examples of protective colloids are polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing polymers. Common emulsifiers are, for example, ethoxylated alcohols and phenols (alkyl radical C4-C18, EO grade 3-100), alkali metal and ammonium salts of alkyl sulfates (C3-C18), sulfuric acid and phosphoric acid esters and alkyl sulfonates. Particularly preferred are succinic acid esters as well as alkali alkyl sulfates and polyvinyl alcohols. It is also possible to use a plurality of protective colloids and / or emulsifiers as a mixture. Preference is given to the dispersion of the
Partikel (P) keine Zusätze benötigt.Particle (P) requires no additives.
Zur Dispergierung der Partikel (P) in der Zusammensetzung (Z)
kann es hilfreich sein, die Einarbeitung der Partikel mittels Perlmühle, Ultraschallbehandlung oder anderen gängigen Rührwerken durchzuführen.For dispersing the particles (P) in the composition (Z) it may be helpful to carry out the incorporation of the particles by means of a bead mill, ultrasonic treatment or other common agitators.
Alternativ können die Zusammensetzungen (Z) wie auch die Komposite (K) in einem Schmelz- oder Extrusionsprozess ausgehend von Partikeln (P), Bindemittel (B) und gegebenenfalls einem Härter (H) und weiteren Zusätzen hergestellt werden.Alternatively, the compositions (Z) as well as the composites (K) can be prepared in a melt or extrusion process from particles (P), binder (B) and optionally a hardener (H) and other additives.
Alternativ kann die Zusammensetzung (Z) hergestellt werden, indem Partikel (Pl) im Bindemittel (B) bzw. im Gemisch von Bindemittel (B) , Härter (H) und gegebenenfalls weiteren Zusätzen modifiziert werden. Dazu werden die Partikel (Pl) im Bindemittel (B) dispergiert und anschließend mit den Silanen (S) zu den Partikeln (P) umgesetzt.Alternatively, the composition (Z) can be prepared by modifying particles (P1) in the binder (B) or in a mixture of binder (B), hardener (H) and optionally further additives. For this purpose, the particles (P1) are dispersed in the binder (B) and subsequently reacted with the silanes (S) to form the particles (P).
Bei einem bevorzugten Verfahren werden die Zusammensetzungen (Z) hergestellt, indem die Partikel (P) während eines Mischprozesses als Pulver oder als Dispersion in einem geeigneten Lösungsmittel zugesetzt werden. Daneben wird aber noch ein weiteres Verfahren bevorzugt, bei dem aus den Partikeln (P) und einer oder mehreren Komponenten der Zusammensetzung (Z) zunächst ein Masterbatch hergestellt wird, mit Partikelkonzentrationen >15 Gew.-%, bevorzugt >25 Gew.-% und besonders bevorzugt >30 Gew.-%. Bei der Herstellung der Zusammensetzungen (Z) wird dieses Masterbatch dann mit den übrigen Komponenten vermischt. Wird bei der Herstellung des Masterbatches von einer Partikeldispersion ausgegangen, so kann es vorteilhaft sein, wenn das Lösungsmittel der Partikeldispersion im Verlauf der Herstellung des Masterbatches entfernt wird, z.B. über einen Destillationsschritt, oder aber gegen ein anderes Lösungsmittel bzw. Lösungsmittelgemisch ausgetauscht wird.
Enthalten die Zusammensetzungen (Z) wässrige oder organische Lösungsmittel, so werden die entsprechenden Lösungsmittel nach Herstellen der Zusammensetzung (Z) gegebenenfalls entfernt. Die Entfernung des Lösungsmittels erfolgt dabei bevorzugt destillativ. Alternativ kann das Lösungsmittel in der Zusammensetzung (Z) verbleiben und im Zuge der Herstellung des Kompositmaterials (K) durch Auftrocknen entfernt werden.In a preferred method, the compositions (Z) are prepared by adding the particles (P) during a mixing process as a powder or as a dispersion in a suitable solvent. In addition, however, a further method is preferred in which first of all a masterbatch is produced from the particles (P) and one or more components of the composition (Z), with particle concentrations> 15% by weight, preferably> 25% by weight and particularly preferably> 30% by weight. In preparing the compositions (Z), this masterbatch is then mixed with the remaining components. If a particle dispersion is used in the preparation of the masterbatch, it may be advantageous if the solvent of the particle dispersion is removed in the course of the preparation of the masterbatch, for example via a distillation step, or exchanged for another solvent or solvent mixture. If the compositions contain (Z) aqueous or organic solvents, the corresponding solvents are optionally removed after preparation of the composition (Z). The removal of the solvent is preferably carried out by distillation. Alternatively, the solvent may remain in the composition (Z) and be removed by drying in the course of the preparation of the composite material (K).
Zur Herstellung der Kompositmaterialien (K) werden die Zusammensetzungen (Z) vorzugsweise auf ein Substrat aufgeräkelt. Weitere Verfahren sind Eintauch-, Sprüh-, Giess- und Extrusionsprozesse . Geeignete Substrate sind u.a. Glas, Metall, Holz, Silicium-Wafer und Kunststoffe wie z.B. Polycarbonat, Polyethylen, Polypropylen, Polystyrol und PTFE.For the preparation of the composite materials (K), the compositions (Z) are preferably wound on a substrate. Further processes are immersion, spraying, casting and extrusion processes. Suitable substrates include i.a. Glass, metal, wood, silicon wafers and plastics such as e.g. Polycarbonate, polyethylene, polypropylene, polystyrene and PTFE.
Enthalten die Zusammensetzungen (Z) Reaktivharze (B), erfolgt die Aushärtung bevorzugt nach Zugabe eines Härters (H) oder Initiators durch aktinische Strahlung oder thermische Energie. Die Härtungsbedingungen entsprechen dabei denen der partikelfreien Zusammensetzungen .If the compositions (Z) contain reactive resins (B), the curing preferably takes place after addition of a curing agent (H) or initiator by actinic radiation or thermal energy. The curing conditions correspond to those of the particle-free compositions.
Tragen die Partikel (P) organofunktionelle Gruppen, die gegenüber dem Bindemittel (B) oder dem Härter (H) reaktiv sind, so können die Partikel (P) kovalent an das Bindemittel (B) bzw. den Härter angebunden werden.If the particles (P) carry organofunctional groups which are reactive towards the binder (B) or the curing agent (H), then the particles (P) can be covalently bonded to the binder (B) or the hardener.
Die Partikel (P) können im Kompositmaterial (K) einen Verteilungsgradienten aufweisen oder homogen verteilt sein. In einer besonderen Ausführungsform der Erfindung ist die Konzentration an Partikeln (P) an der Grenzfläche Beschichtung/Luft höher als im Bulksegment und an der Grenzfläche Beschichtung/Substrat . Als Grenzfläche
Beschichtung/Luft wird hierbei die grenzflächennahe Schicht, die eine Dicke von maximal 150 nm aufweist, verstanden. Alternativ kann die Konzentration an Partikeln (P) an der Grenzfläche Beschichtung/Substrat höher als im Bulksegment und an der Grenzfläche Beschichtung/Luft sein. Als Grenzfläche Beschichtung/Substrat wird hierbei die grenzflächennahe Schicht, die eine Dicke von maximal 150 nm aufweist, verstanden. In einer weiteren bevorzugten Ausführungsform der Erfindung ist die Konzentration an Partikeln (P) sowohl an der Grenzfläche Beschichtung/Luft als auch an der Grenzfläche Beschichtung/Substrat höher als im Bulksegment In Abhängigkeit vom gewählten Matrixsystem kann sich sowohl eine homogene Verteilung als auch eine ungleichmäßige Verteilung der Partikel beispielsweise die mechanische Stabilität, die Chemikalienbeständigkeit, die Korrosionsstabilität und die Haftung steigern.The particles (P) may have a distribution gradient in the composite material (K) or be homogeneously distributed. In a particular embodiment of the invention, the concentration of particles (P) at the coating / air interface is higher than in the bulk segment and at the coating / substrate interface. As an interface Coating / air is understood to mean the near-surface layer which has a thickness of at most 150 nm. Alternatively, the concentration of particles (P) at the coating / substrate interface may be higher than in the bulk segment and at the coating / air interface. The coating / substrate interface is understood to be the near-surface layer which has a maximum thickness of 150 nm. In a further preferred embodiment of the invention, the concentration of particles (P) is higher both at the coating / air interface and at the coating / substrate interface than in the bulk segment. Depending on the matrix system selected, both a homogeneous distribution and an uneven distribution can occur For example, the particles increase mechanical stability, chemical resistance, corrosion stability and adhesion.
Die Zusammensetzungen (Z) können aufgrund der hervorragenden chemischen, thermischen und mechanischen Eigenschaften der daraus hergestellten Kompositmaterialien (K) insbesondere als Kleb- und Dichtstoffe sowie als Versiegelungs-, Verguss- und Dentalmassen eingesetzt werden.Due to the outstanding chemical, thermal and mechanical properties of the composite materials (K) produced therefrom, the compositions (Z) can be used in particular as adhesives and sealants and as sealants, potting compounds and dental compounds.
Besonders bevorzugt dienen die aus den Zusammensetzungen (Z) hergestellten Kompositmaterialien (K) als kratzfeste Klar- oder Decklacke, insbesondere in der Fahrzeugindustrie als OEM- und Reparaturlacke. Das Aufbringen der Zusammensetzungen (Z) kann durch beliebige Verfahren wie Eintauch-, Sprüh-, und Gießverfahren erfolgen. Auch ein Aufbringen der Zusammensetzungen (Z) auf einem Basecoat nach einem „wet in wet"-Verfahren ist möglich. Die Aushärtung erfolgt in der Regel durch Erwärmen unter den jeweils erforderlichen Bedingungen (2K Lacke typischerweise bei 0-100 0C, bevorzugt bei 20-80 0C, IK-
Lacke bei 100-200 0C bevorzugt bei 120-160 0C) . Selbstverständlich kann die Härtung der Zusammensetzung (Z) durch den Zusatz von geeigneten Katalysatoren beschleunigt werden. Als Katalysatoren eignen sich dabei insbesondere saure, basische sowie auch schwermetallhaltige Verbindungen.Particularly preferably, the composite materials (K) produced from the compositions (Z) serve as scratch-resistant clearcoats or topcoats, especially in the automotive industry as OEM and refinish paints. The application of the compositions (Z) can be carried out by any methods such as dipping, spraying, and casting. Also an application of the compositions (Z) to a basecoat for a "wet on wet" method is possible. Curing is generally carried out by heating under the particular conditions required (2K coatings typically at 0-100 0 C, preferably at 20 -80 0 C, IK Paints at 100-200 0 C preferably at 120-160 0 C). Of course, the curing of the composition (Z) can be accelerated by the addition of suitable catalysts. Particularly suitable catalysts are acidic, basic and also heavy metal-containing compounds.
Alle vorstehenden Symbole der vorstehenden Formeln weisen ihre Bedeutungen jeweils unabhängig voneinander auf. In allen Formeln ist das Siliziumatom vierwertig.All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent.
Soweit nicht anders angegeben sind alle Mengen- und Prozentangaben auf das Gewicht bezogen, alle Drücke 0,10 MPa (abs.) und alle Temperaturen 20 0C.Unless otherwise indicated, all amounts and percentages are by weight, all pressures are 0.10 MPa (abs.) And all temperatures are 20 ° C.
Beispiel 1: Synthese Phosphonat-funktioneller Partikel aus einem wässrigen Kieselsol.Example 1: Synthesis of phosphonate-functional particles from an aqueous silica sol.
Eine Lösung von 1,96 g Diethylphosphonatomethyl- dimethylmethoxysilan in 40 ml Methoxypropylacetat wurde innerhalb von 10 min unter starkem Rühren zu 14,0 g eines wässrigen Kieselsols (LUDOX® AS 40 der Firma GRACE DAVISON, 24 nm, 40 Gew.-%) getropft und das Gemisch für 4 h auf 60 0C erwärmt. Anschließend wurde die resultierende milchige Emulsion so lange im Vakuum eingeengt, bis ein transparentes Kieselsol erhalten wurde. Die mittlere Partikelgröße des modifizierten Kieselsols, bestimmt mittels dynamischer Lichtstreuung (Zetasizer Nano der Firma Malvern) , betrug 32 nm. Nach Abdestillieren des Lösungsmittels wurden 7,16 g eines farblosen Feststoffs erhalten, der sich durch Einrühren in Isopropanol redispergieren liess. Die mittlere Partikelgröße des Kieselsols in Isopropanol betrug 44 nm.A solution of 1.96 g Diethylphosphonatomethyl- dimethylmethoxysilane in 40 ml of methoxypropyl acetate was added dropwise within 10 min with vigorous stirring to 14.0 g of an aqueous silica sol (LUDOX® AS 40 from Grace DAVISON, 24 nm, 40 wt .-%) and the mixture heated at 60 0 C for 4 h. Subsequently, the resulting milky emulsion was concentrated in vacuo until a transparent silica sol was obtained. The mean particle size of the modified silica sol, determined by means of dynamic light scattering (Zetasizer Nano from Malvern), was 32 nm. After distilling off the solvent, 7.16 g of a colorless solid were obtained, which could be redispersed by stirring in isopropanol. The average particle size of the silica sol in isopropanol was 44 nm.
Beispiel 2: Synthese Phosphonat-funktioneller Partikel aus einem organischen Kieselsol .
Ein Gemisch bestehend aus 480 g eines Kieselsols in Isopropanol (IPA-ST der Firma NISSAN CHEMICAL, 12 nm, 30 Gew.-%) und 48,0 g Diethylphosphonatomethyl-dimethylmethoxysilan wurde für 6 h auf 60 0C erwärmt. Die mittlere Partikelgröße des modifizierten Kieselsols, bestimmt mittels dynamischer Lichtstreuung (Zetasizer Nano der Firma MALVERN) , betrug 13 nm. Nach Abdestillieren des Lösungsmittels wurden 191 g eines farblosen Feststoffs erhalten, der sich durch Einrühren sowohl in Aceton als auch in Isopropanol redispergieren liess. Die mittlere Partikelgröße des Kieselsols in Isopropanol betrug 14,5 nm.Example 2: Synthesis of phosphonate-functional particles from an organic silica sol. A mixture consisting of 480 g of a silica sol in isopropanol (IPA-ST from NISSAN CHEMICAL, 12 nm, 30 wt .-%) and 48.0 g Diethylphosphonatomethyl-dimethylmethoxysilane was heated to 60 0 C for 6 h. The mean particle size of the modified silica sol, determined by means of dynamic light scattering (Zetasizer Nano from MALVERN), was 13 nm. After distilling off the solvent, 191 g of a colorless solid were obtained which could be redispersed by stirring in both acetone and isopropanol. The mean particle size of the silica sol in isopropanol was 14.5 nm.
Beispiel 3: Synthese Phosphonat-funktioneller Partikel, die über geschützte Isocyanatfunktionen verfügen.Example 3: Synthesis of Phosphonate-Functional Particles Having Protected Isocyanate Functions.
Ein Gemisch bestehend aus 48,0 g eines Kieselsols in Isopropanol (IPA-ST der Firma NISSAN CHEMICAL, 12 nm, 30 Gew.- %) , 4,32 g Diethylphosphonatomethyl-dimethylmethoxysilan sowie 0,48 g des geschützten Isocyanatosilans [5] wurde für 6 h auf 60 0C erwärmt.A mixture consisting of 48.0 g of a silica sol in isopropanol (IPA-ST from NISSAN CHEMICAL, 12 nm, 30% by weight), 4.32 g Diethylphosphonatomethyl-dimethylmethoxysilane and 0.48 g of the protected isocyanatosilane heated to 60 0 C for 6 h.
Die mittlere Partikelgröße des modifizierten Kieselsols, bestimmt mittels dynamischer Lichtstreuung (Zetasizer Nano der Firma MALVERN) , betrug 12 nm. Nach Abdestillieren des Lösungsmittels wurden 184 g eines farblosen Feststoffs erhalten, der sich durch Einrühren sowohl in Aceton als auch in Isopropanol redispergieren liess. Die mittlere Partikelgröße des Kieselsols in Isopropanol betrug 23 nm.
Beispiel 4: Herstellung eines partikelverstärkten Epoxidharzes.The mean particle size of the modified silica sol, determined by means of dynamic light scattering (Zetasizer Nano from MALVERN), was 12 nm. After distilling off the solvent, 184 g of a colorless solid were obtained which could be redispersed by stirring in both acetone and isopropanol. The average particle size of the silica sol in isopropanol was 23 nm. Example 4: Preparation of a particle-reinforced epoxy resin.
7,48 g des in Beispiel 2 beschriebenen pulverförmigen Partikels wurden in 30 ml Aceton dispergiert. Das transparente Kieselsol wurde anschließend zu einer Lösung von 30,0 g Epoxidharz D. E. R. 332 (Firma DOW CHEMICAL) und 8,00 g 4-Aminophenylsulfon in 100 ml Aceton getropft. Nach Abdestillieren des Lösungsmittels unter vermindertem Druck wurde die niedrigviskose Mischung in eine Aluminiumschale gegossen und 30 min bei 190 0C sowie 3 h bei 240 0C gehärtet. Man erhielt einen transparenten Feststoff mit einer Dicke von 6 mm. Elektronenmikroskopische Aufnahmen zeigten, dass die eingesetzten Partikel im Komposit isoliert vorliegen .7.48 g of the powdery particle described in Example 2 were dispersed in 30 ml of acetone. The transparent silica sol was then added dropwise to a solution of 30.0 g of DER 332 epoxy resin (DOW CHEMICAL) and 8.00 g of 4-aminophenylsulfone in 100 ml of acetone. After distilling off the solvent under reduced pressure, the low-viscosity mixture was poured into an aluminum pan and cured at 190 ° C. for 30 minutes and at 240 ° C. for 3 hours. A transparent solid having a thickness of 6 mm was obtained. Electron micrographs showed that the particles used are isolated in the composite.
Beispiel 5: Herstellung einer Partikel-haltigen IK-PU- BeschichtungsformulierungExample 5: Preparation of a particle-containing IK-PU coating formulation
Zur Herstellung einer Beschichtungsformulierung wird ein acrylatbasierendes Lackpolyol mit einem Festgehalt von 52 Gew.- % und einer OHZ von 156 (Parocryl® 54.4 der BASF AG) mit Desmodur® BL 3175 SN der Bayer AG (butanoxim-blockiertes Polyisocyanat, mit einem FG von 75 Gew.-% und einem blockierten NCO-Gehalt von 11,1%) vermischt. Des weiteren werden 1 Gew.-% Dibutylzinndilaurat (l%ig in Butylacetat) und 1 Gew.-% TEGO ADDID® 100 der TEGO AG (Verlaufshilfsmittel auf Basis Polydimethylsiloxan; 10%ige Lösung in Butylacetat) zugemischt, sowie die modifizierten Kieselsole der Beispiele 1-3, wodurch Beschichtungsformulierungen mit ca. 60 Gew.-% Festgehalt erhalten wurden. Die dabei eingesetzten Mengen der jeweiligen Komponenten sind in Tabelle 1 aufgeführt. Die anfänglich noch leicht trüben Mischungen werden für 24 h bei Raumtemperatur gerührt, wobei klare Beschichtungsformulierungen (Abmischungen 2-5) erhalten werden.To prepare a coating formulation, an acrylate-based coating polyol having a solids content of 52% by weight and an OH value of 156 (Parocryl® 54.4 from BASF AG) with Desmodur® BL 3175 SN from Bayer AG (butanoxime-blocked polyisocyanate, having a FG of 75 Wt .-% and a blocked NCO content of 11.1%). Furthermore, 1% by weight of dibutyltin dilaurate (1% in butyl acetate) and 1% by weight of TEGO ADDID® 100 from TEGO AG (flow control agent based on polydimethylsiloxane, 10% strength solution in butyl acetate) are mixed in, and the modified silica sols of the examples 1-3, whereby coating formulations were obtained with about 60 wt .-% solids content. The amounts of the respective components used are listed in Table 1. The initially slightly cloudy mixtures are stirred for 24 h at room temperature to give clear coating formulations (blends 2-5).
Tabelle 1.
Parocryl® Desmodur® Modifiziertes Partikel¬Table 1. Parocryl® Desmodur® Modified Particle
54.4 BL 317ϊ Kieselsol gehalt (in54.4 BL 317ϊ Silica sol content (in
SN (50 Gew. -s 3 in Gew.-%)SN (50 wt -. S 3 in wt .-%)
Aceton) **Acetone) **
Abmischung 1 10, 00 g 6,03 g 0,0 g 0, 0Mixture 1 10, 00 g 6.03 g 0.0 g 0, 0
(Vergleich* )(Comparison* )
Abmischung 2 10,00 g 6, 03 g 0,3 g 1,5Blend 2 10.00 g 6, 03 g 0.3 g 1.5
(Partikel aus(Particles out
Beispiel 2)Example 2)
Abmischung 3 10, 00 g 6,03 g 0,3 g 1,5Mixture 3 10, 00 g 6.03 g 0.3 g 1.5
(Partikel aus(Particles out
Beispiel DExample D
Abmischung 4 10,00 g 6, 03 g 0,6 g 3,0Blend 4 10.00 g 6, 03 g 0.6 g 3.0
(Partikel aus(Particles out
Beispiel 2)Example 2)
Abmischung 5 10, 00 g 6,03 g 0,6 g 3,0Mixture 5 10, 00 g 6.03 g 0.6 g 3.0
(Partikel aus(Particles out
Beispiel 3)Example 3)
* nicht erfindungsgemäß* not according to the invention
** als Pulver isolierte Partikel der Beispiele 1-3 wurden in** particles of Examples 1-3 which were isolated as powder were used in
Aceton vordispergiert .Acetone predispersed.
Beispiel 6: Herstellung einer Partikel-haltigen 2K-PU- BeschichtungsformulierungExample 6: Preparation of a particle-containing 2K PU coating formulation
Zur Herstellung einer Beschichtungsformulierung wird ein acrylatbasierendes Lackpolyol mit einem Festgehalt von 65 Gew, % und einer OHZ von 180 (Parocryl® 49.5 der BASF AG) mit 20 Gew.-% Butylacetat verdünnt, mit dem modifizierten Kieselsol der Beispiele 2 bzw. 3 vermischt und 24 Stunden bei Raumtemperatur gerührt. Nach Zugabe der Härterkomponente
Basonat 100 der Fa. BASF Coatings (aliphatisches Polyisocyanat auf Basis isocyanuratisierten Hexamethylendiisocyanats, NCO- Gehalt 22 Gew.-%)und 1 Gew.-% ADDID® 100 der TEGO AG (Verlaufshilfsmittel auf Basis Polydimethylsiloxan; 10%ige Lösung in Butylacetat) wird die Mischung weitere 5 Stunden gerührt, wobei klare Beschichtungsformulierungen (Abmischungen 7-10) mit ca. 50 Gew.-% Festgehalt erhalten werden. Die dabei eingesetzten Mengen der jeweiligen Komponenten sind in Tabelle 2 aufgeführt.To prepare a coating formulation, an acrylate-based coating polyol having a solids content of 65% by weight and an OH value of 180 (Parocryl® 49.5 from BASF AG) is diluted with 20% by weight of butyl acetate, mixed with the modified silica sol of Examples 2 or 3, and Stirred for 24 hours at room temperature. After addition of the hardener component Basonat 100 from BASF Coatings (aliphatic polyisocyanate based on isocyanurated hexamethylene diisocyanate, NCO content 22% by weight) and 1% by weight of ADDID® 100 from TEGO AG (leveling agent based on polydimethylsiloxane, 10% strength solution in butyl acetate) the mixture is stirred for a further 5 hours to give clear coating formulations (blends 7-10) with about 50% by weight solids. The quantities of the respective components used are listed in Table 2.
Tabelle 2.Table 2.
* nicht erfindungsgemäß
** als Pulver isolierte Partikel der Beispiele 1-3 wurden in Aceton vordispergiert .* not according to the invention ** Powder-isolated particles of Examples 1-3 were predispersed in acetone.
Beispiel 7. Herstellung und Bewertung der Lackfilme aus den Abmischungen der Beispiele 5 und 6Example 7. Preparation and Evaluation of Paint Films from the Blends of Examples 5 and 6
Die Beschichtungsmassen aus den Beispielen 5 und 6 werden jeweils mittels eines Filmziehgerätes Coatmaster® 509 MC der Fa. Erichsen mit einem Rakel der Spalthöhe 120 μm auf eine Glasplatte geräkelt. Anschließend werden die erhaltenen Beschichtungsfilme in einem Umlufttrockenschrank für 30 Minuten bei 70 °C und anschließend für 30 min bei 150 0C getrocknet. Aus den Abmischungen 1-10 der Beispiele 5 und 6 werden optisch einwandfreie, glatte Beschichtungen erhalten. Der Glanz der Beschichtungen wird mit einem Glanzmeßgerät Micro gloss 20° der Fa. Byk bestimmt und liegt bei sämtlichen Lacken zwischen 160 und 170 Glanz-Einheiten.The coating compositions from Examples 5 and 6 are in each case by means of a film applicator Coatmaster® 509 MC Fa. Erichsen with a doctor blade of gap height 120 microns on a glass plate geräkelt. Subsequently, the resulting coating films are dried in a circulating air dryer for 30 minutes at 70 ° C and then for 30 min at 150 0 C. From blends 1-10 of Examples 5 and 6 optically flawless, smooth coatings are obtained. The gloss of the coatings is determined with a gloss meter Micro gloss 20 ° from Byk and is in all paints between 160 and 170 gloss units.
Die Kratzfestigkeit der so erzeugten ausgehärteten Lackfilme wird mit einem Scheuerprüfgerät nach Peter-Dahn ermittelt. Hierzu wird ein Scheuervlies Scotch Brite® 2297 mit einer Fläche von 45 x 45 mm mit einem Gewicht von 500 g beschwert. Mit diesem werden die Lackproben mit insgesamt 50 Hüben verkratzt. Sowohl vor Beginn als auch nach Beendigung der Kratzversuche wird der Glanz der jeweiligen Beschichtung mit einem Glanzmeßgerät Micro gloss 20° der Fa. Byk gemessen. Als Maß für die Kratzfestigkeit der jeweiligen Beschichtung wurde der Glanzverlust im Vergleich zum Ausgangswert bestimmt:The scratch resistance of the cured coating films produced in this way is determined using a scouring tester according to Peter-Dahn. For this, a scouring fleece Scotch Brite® 2297 with an area of 45 x 45 mm and a weight of 500 g is weighted. With this, the paint samples are scratched with a total of 50 strokes. Both before and after completion of the scratching tests, the gloss of the respective coating is measured with a gloss meter Micro gloss 20 ° from Byk. As a measure of the scratch resistance of the respective coating, the loss in gloss was determined in comparison with the starting value:
nicht erfindungsgemäßnot according to the invention
Die Ergebnisse zeigen, dass bereits kleine Gehalte der Partikel (P) zu einer deutlichen Steigerung der Kratzfestigkeit der entsprechenden Beschichtung führen. Zudem wird eine Steigerung der Kratzfestigkeit für Lacke beobachtet, die Partikel (P) enthalten, welche über Funktionen (F) verfügen, die gegenüber dem Bindemittel (B) reaktiv sind (Lackproben aus Abmischung 5 und 10) .
The results show that even small contents of the particles (P) lead to a significant increase in the scratch resistance of the corresponding coating. In addition, an increase in scratch resistance is observed for paints containing particles (P) which have functions (F) which are reactive with the binder (B) (paint samples from blends 5 and 10).
Claims
1. Zusammensetzung (Z) enthaltend1. containing composition (Z)
(a) 0,02-200 Gewichtsteile an Partikeln (P), die mindestens ein Strukturelement der allgemeinen Formel [1],(a) 0.02-200 parts by weight of particles (P) containing at least one structural element of the general formula [1],
≡Si-L-P(O) (OR1J2 [1] '≡Si-LP (O) (OR 1 J 2 [1] '
aufweisen, (b) 100 Gewichtsteile eines Bindemittels (B) ,(b) 100 parts by weight of a binder (B),
(c) 0-100 Gewichtsteile eines Härters (H) , der gegenüber dem Bindemittel (B) reaktiv ist, sowie(c) 0-100 parts by weight of a curing agent (H) which is reactive with the binder (B), as well as
(d) 0-1000 Gewichtsteile eines Lösungsmittels oder eines Lösungsmittelgemisches, wobei L einen zweiwertigen gegebenenfalls mit Carbinol-, Amino-, Halogen-, Epoxy-, Phosphonato-, Thiol-, (Meth) acrylato-, Ureido-, Carbamato-Gruppen substituierten aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen, dessen Kohlenstoffkette durch nicht benachbarte Sauerstoffatome, Schwefelatome, oder NR^- Gruppen unterbrochen sein kann,(d) 0-1000 parts by weight of a solvent or solvent mixture, wherein L is a divalent optionally substituted with carbinol, amino, halogen, epoxy, phosphonato, thiol, (meth) acrylato, ureido, carbamato groups aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, the carbon chain of which may be interrupted by nonadjacent oxygen atoms, sulfur atoms, or NR 1 - groups,
R! Wasserstoff, ein Metallkation, ein Ammoniumkation derR! Hydrogen, a metal cation, an ammonium cation of
Formel -N (R^) 4+, Phosphoniumkation der Formel -P (R^) 4"1" oder einen gegebenenfalls mit Carbinol-, Amino-, Halogen-, Epoxy-, Phosphonato-, Thiol-, (Meth) acrylato-, Carbamato-, Ureido-Gruppen substituierten aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen, dessen Kohlenstoffkette durch nicht benachbarte Sauerstoffatome, Schwefelatome, oder NR^- Gruppen unterbrochen sein kann, undFormula -N (R 1) 4+, phosphonium cation of the formula -P (R 1) 4 "1" or an optionally with carbinol, amino, halogen, epoxy, phosphonato, thiol, (meth) acrylato , Carbamato, ureido groups substituted aliphatic or aromatic hydrocarbon radical having 1 to 12 carbon atoms, whose carbon chain may be interrupted by non-adjacent oxygen atoms, sulfur atoms, or NR ^ - groups, and
R^ einen Kohlenwasserstoffrest mit 1-8 Kohlenstoffatomen bedeuten . R ^ is a hydrocarbon radical having 1-8 carbon atoms.
2. Zusammensetzung (Z) nach Anspruch 1, bei der die Partikel (P) neben Funktionen der allgemeinen Formel [1] zusätzlich auch noch mindestens eine organofunktionelle Gruppe (F) aufweisen, die gegenüber dem Bindemittel (B) oder dem Härter (H) reaktiv ist.2. Composition (Z) according to claim 1, in which the particles (P) in addition to functions of the general formula [1] additionally also have at least one organofunctional group (F) which is resistant to the binder (B) or the hardener (H) is reactive.
3. Zusammensetzung (Z) nach Anspruch 1 oder 2, bei der L ein Methylen- oder Propylenrest ist.3. Composition (Z) according to claim 1 or 2, wherein L is a methylene or propylene radical.
4. Zusammensetzung (Z) nach Anspruch 1 bis 3, bei der R^ ein Alkylrest mit 1-6 Kohlenstoffatomen ist.4. The composition (Z) of claims 1 to 3 wherein R 1 is an alkyl radical of 1-6 carbon atoms.
5. Zusammensetzung (Z) nach Anspruch 1 bis 3, bei der die Partikel (P) eine spezifische Oberfläche von 10 bis 500 m^/g besitzen, gemessen nach der BET-Methode nach DIN EN ISO 9277/DIN 66132.5. Composition (Z) according to claim 1 to 3, wherein the particles (P) have a specific surface of 10 to 500 m ^ / g, measured by the BET method according to DIN EN ISO 9277 / DIN 66132.
6. Kompositmaterialien (K), die herstellbar sind aus der Zusammensetzung (Z) gemäss Anspruch 1 bis 5.6. Composite materials (K) which can be produced from the composition (Z) according to claims 1 to 5.
7. Kompositmaterialien (K) nach Anspruch 6, welche Lacksysteme sind, die herstellbar sind aus einer Beschichtungszusammensetzung (Z) enthaltend, (a) 0,02-60 Gewichtsteile an Partikeln (P), die mindestens ein Strukturelement der allgemeinen Formel [1],7. Composite materials (K) according to claim 6, which are coating systems which can be prepared from a coating composition (Z) comprising, (a) 0.02-60 parts by weight of particles (P) containing at least one structural element of the general formula [1] .
≡Si-L-P (O) (OR1) 2 [1] '≡Si-LP (O) (OR 1 ) 2 [1] '
aufweisen, b) 100 Gewichtsteile eines hydroxylgruppen-funktionellen Lackharzes (B) , c) 1-100 Gewichtsteile eines Lackhärters (H) , der Isocyanatgruppen enthält, die ausgewählt werden aus freien Isocyanatgruppen und geschützten Isocyanatgruppen, die bei thermischer Behandlung unter Abspaltung einer Schutzgruppe eine Isocyanatfunktion freisetzen, d) 0-1000 Gewichtsteile eines Lösungsmittels oder eines Lösungsmittelgemisches .b) 100 parts by weight of a hydroxyl-functional paint resin (B), c) 1-100 parts by weight of a paint curing agent (H), the Contains isocyanate groups which are selected from free isocyanate groups and protected isocyanate groups which release an isocyanate function upon thermal treatment with elimination of a protective group, d) 0-1000 parts by weight of a solvent or a solvent mixture.
8. Verwendung der Zusammensetzungen (Z) gemäss Anspruch 1 bis8. Use of the compositions (Z) according to claim 1 to
5 als Kleb- und Dichtstoffe sowie als Versiegelungs-, Verguss- und Dentalmassen und Lacke. 5 as adhesives and sealants as well as sealing, potting and dental compounds and paints.
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DE102006053156A DE102006053156A1 (en) | 2006-11-10 | 2006-11-10 | Compositions containing phosphonate-functional particles |
PCT/EP2007/061257 WO2008055768A2 (en) | 2006-11-10 | 2007-10-22 | Compositions containing phosphonate-functional particles |
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US (1) | US20100063187A1 (en) |
EP (1) | EP2087036A2 (en) |
JP (1) | JP2010509416A (en) |
KR (1) | KR20090073155A (en) |
CN (1) | CN101522777A (en) |
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US20140072815A1 (en) * | 2012-09-12 | 2014-03-13 | Ppg Industries Ohio, Inc. | Curable film-forming compositions demonstrating burnish resistance and low gloss |
US9969900B2 (en) | 2012-09-12 | 2018-05-15 | Ppg Industries Ohio, Inc. | Methods of improving burnish resistance using curable film-forming compositions demonstrating burnish resistance and low gloss |
US8961671B2 (en) | 2013-01-30 | 2015-02-24 | Illinois Tool Works, Inc. | Super hydrophobic and antistatic composition |
FR3061184A1 (en) * | 2016-12-22 | 2018-06-29 | Compagnie Generale Des Etablissements Michelin | RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN |
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DE4040986A1 (en) * | 1990-12-20 | 1992-06-25 | Wacker Chemie Gmbh | ELASTOMERIC Graft Copolymers With Core-Shell Structure |
US5981652A (en) * | 1996-09-30 | 1999-11-09 | Toyota Jidosha Kabushiki Kaisha | One-liquid low temperature hardenable type colored enamel paint and clear paint |
DE19715426A1 (en) * | 1997-04-14 | 1998-10-15 | Bayer Ag | Colloidal metal oxides containing blocked isocyanate groups |
WO2002088222A1 (en) * | 2001-03-13 | 2002-11-07 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Phosphorous-containing, organic polymerisable silanes and silicic acid polycondensates produced therewith |
DE10132654A1 (en) * | 2001-03-13 | 2002-10-31 | Fraunhofer Ges Forschung | Phosphorus-containing, organically polymerizable silanes and silica polycondensates produced with them |
EP1249470A3 (en) * | 2001-03-30 | 2005-12-28 | Degussa AG | Highly filled pasty siliconorganic nano and/or microhybridcapsules containing composition for scratch and/or abrasion resistant coatings |
US6916368B2 (en) * | 2002-02-20 | 2005-07-12 | Ppg Industries Ohio, Inc. | Curable film-forming composition exhibiting improved scratch resistance |
US6833186B2 (en) * | 2002-04-10 | 2004-12-21 | Ppg Industries Ohio, Inc. | Mineral-filled coatings having enhanced abrasion resistance and wear clarity and methods for using the same |
DE10247359A1 (en) * | 2002-10-10 | 2004-04-29 | Basf Coatings Ag | Nanoparticles, processes for modifying their surface, dispersion of the nanoparticles, processes for their production and their use |
WO2004089961A1 (en) * | 2003-04-07 | 2004-10-21 | Consortium für elektrochemische Industrie GmbH | Organosilyl functionalized particles and the production thereof |
DE10331289A1 (en) * | 2003-07-10 | 2005-02-17 | Consortium für elektrochemische Industrie GmbH | New organosilicon compounds and a process for their preparation |
US7183370B2 (en) * | 2003-09-11 | 2007-02-27 | Toyota Technical Center Usa, Inc | Phosphonic-acid grafted hybrid inorganic-organic proton electrolyte membranes (PEMs) |
DE102004022406A1 (en) * | 2004-05-06 | 2005-12-15 | Wacker-Chemie Gmbh | Polysiloxane graft polymer |
DE102004040264A1 (en) * | 2004-08-19 | 2006-02-23 | Consortium für elektrochemische Industrie GmbH | Particles with protected isocyanate groups |
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