CN1934139A - 包含表面改性粒子的可固化组合物 - Google Patents
包含表面改性粒子的可固化组合物 Download PDFInfo
- Publication number
- CN1934139A CN1934139A CN200580009620.0A CN200580009620A CN1934139A CN 1934139 A CN1934139 A CN 1934139A CN 200580009620 A CN200580009620 A CN 200580009620A CN 1934139 A CN1934139 A CN 1934139A
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- CN
- China
- Prior art keywords
- group
- alkyl
- particle
- sulphur
- ethylenically unsaturated
- 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.)
- Pending
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- 239000002245 particle Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005864 Sulphur Chemical group 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 150000001282 organosilanes Chemical class 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 6
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical group 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 229910008051 Si-OH Inorganic materials 0.000 claims description 2
- 229910006358 Si—OH Inorganic materials 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 abstract 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 3
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 125000000732 arylene group Chemical group 0.000 abstract 1
- 150000001925 cycloalkenes Chemical class 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
- -1 vinylformic acid dipentaerythritol ester Chemical class 0.000 description 21
- 229910004298 SiO 2 Inorganic materials 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 11
- 229910000077 silane Inorganic materials 0.000 description 11
- 125000005395 methacrylic acid group Chemical group 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- YYUPXWUUUZXFHG-UHFFFAOYSA-N ethoxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)OCC YYUPXWUUUZXFHG-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- NCHMPORHGFKNSI-UHFFFAOYSA-N methoxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)OC NCHMPORHGFKNSI-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- PCBMVQBBBGFXLZ-UHFFFAOYSA-N [dimethoxy(methyl)silyl]oxymethyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)OCOC(=O)C(C)=C PCBMVQBBBGFXLZ-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- YOQPJXKVVLAWRU-UHFFFAOYSA-N ethyl carbamate;methyl prop-2-enoate Chemical compound CCOC(N)=O.COC(=O)C=C YOQPJXKVVLAWRU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 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
- 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
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
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Abstract
本发明涉及可固化组合物Z,它包含带有至少一个烯属不饱和基团的粘结剂BM,此外还包含在它们的表面上具有至少一个烯属不饱和基团并含有通式(I)基团,SiR2 2-(CR3 2)n-A-D-C的粒子P。-SiR2 2-(CR3 2)n-A-D-C (I)在所述通式中,R2表示-(CR3 2)n-A-D-C或含有1-12个碳原子的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,R3表示氢或含有1-12个碳原子的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,R4表示氢或含有1-12个碳原子的烃基,A表示氧、硫、=NR4或=N-(D-C),D表示羰基、或含有1-12个碳原子的亚烷基、亚环烷基或亚芳基,碳链由不相邻的氧、硫或NR4基团间隔,C表示末端、不饱和基团,m表示大于或等于1的数值。
Description
技术领域
本发明涉及可固化组合物,该组合物包括带有至少一个烯属不饱和基团的粘结剂,也包括在它们的表面上具有至少一个烯属不饱和基团的粒子,还涉及这些组合物用于涂覆的用途。
背景技术
自由基可固化的涂料组合物是已知的,该组合物包括用有机基团表面改性的纳米级填料,且该组合物固化成高机械硬度和耐化学品性的涂层。采用此类涂料组合物适当改性的粒子表面能保证粒子与周围聚合物基质的相容性。另外,在粒子表面具有对于基质的合适反应性的情况下,使得其能够与粘结剂体系在涂层体系的特定固化条件下反应,从而可以在固化过程中将粒子化学性地引入到基质中,这对复合体系的性能方面通常具有积极的影响。
自由基可固化的、粒子增强的涂层组合物尤其描述于US 4455205A和US 4491508 A中,并通过例如:使胶体二氧化硅与3-甲基丙烯酰氧基丙基三甲氧基硅烷反应,并随后将含水和/或醇类溶剂替换为自由基可交联的有机粘结剂而获得。此类涂层组合物可用于,例如涂覆热塑性基材。
US 6306502 B公开了用于无划痕涂层的涂层组合物,该组合物可从胶体二氧化硅和自由基可聚合的硅烷制备。用于该情况的粘结剂是(甲基)丙烯酰氧基烷基官能异氰尿酸酯。DE102 00 928A1描述了包括表面改性纳米级粒子的可固化有机分散体,例如在五丙烯酸二季戊四醇酯中的分散步骤之后,通过混合亲水性热解二氧化硅与3-甲基丙烯酰氧基丙基三甲氧基硅烷、丁醇铝和水制备该纳米级粒子。此类分散体可以用作涂层材料、粘合剂和密封剂。
根据现有技术,通过使具有游离氢氧化硅(SiOH)或金属氢氧化物(MeOH)官能团的粒子与烷氧基硅烷反应来制备在涂层体系中包含的粒子,所述烷氧基硅烷包含作为其反应性官能团的烯属不饱和基团,如乙烯基、(甲基)丙烯酰基等。对现有技术中用粒子官能化的所有烷氧基硅烷来说,它们的共有特征在于它们具有二或三烷氧基甲硅烷基,如例如对于甲基丙烯酸根合丙基三甲氧基硅烷(methacrylatopropyltrimethoxysilane)的情况。
当二或三烷氧基硅烷用于表面官能化时,在水存在下、在获得的硅烷醇的水解和缩合之后会在粒子周围形成硅氧烷壳。Macromol.Chem.Phys.2003,204,375-383描述了在SiO2粒子周围形成的此类硅氧烷壳。此处的问题可以是如下事实:形成的硅氧烷壳仍然在其表面上具有大量SiOH官能团。此类SiOH官能粒子的稳定性在制备和贮存条件下被限制为是否合适,甚至在粘结剂存在下。可能会发生粒子的聚集和结块。分散体相关的受限制的稳定性使得更难以生产具有可再现性能的材料。而且,硅氧烷壳中的大多数反应性有机官能团以一定的方式被立体屏蔽,从而使得粒子不可能通过这些官能团连接到反应性粘结剂上。然而,理想的是连接到粒子表面的所有反应性有机官能团应当可用于共价引入到基体上。
因此,所有包含粒子的已知粘结剂体系具有如下缺点:在固化形式中和在未固化形式中通常显示出难以重现的性能。然而,特别地,固化涂料的机械硬度-特别是耐擦划性-对于许多应用来说仍然是不够的。
发明内容
因此,本发明的目的是提供涂层体系,该涂层体系由光化辐射或热固化,并且不再具有已知体系的上述缺点。
本发明提供一种可固化组合物Z,该组合物Z包括带有至少一个烯属不饱和基团的粘结剂BM,还包括在它们的表面上具有至少一个烯属不饱和基团,并含有通式I基团的粒子P,
-SiR2 2-(CR3 2)n-A-D-C (I),
其中
R2是-(CR3 2)小n-A-D-C或含有1-12个碳原子的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,
R3是氢或含有1-12个碳原子的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,
R4是氢或含有1-12个碳原子的烃基,
A是氧、硫、=NR4或=N-(D-C),
D是羰基、在每种情况下含有1-12个碳原子的亚烷基、亚环烷基或亚芳基,这些基团的碳链可以由不相邻的氧、硫或NR4基团间隔,和
C是烯属不饱和基团和
n大于或等于1。
可固化的组合物Z包括经包含烯属不饱和基团的通式I的反应性基团表面改性的粒子P,所述反应性基团的突出之处为如下事实:甲硅烷基带有通过C-C键连接的三个有机基团,并通过另外的键连接到粒子表面。因此,相对于已知的包括粒子的组合物而言,所述可固化组合物Z的耐擦划性得到显著增加。
粒子优选P可通过使如下物质反应制备的:
(a)材料为选自金属氧化物、金属-硅混合氧化物、二氧化硅、胶体二氧化硅或有机聚硅氧烷树脂或它们的组合的粒子P1,并具有选自Me-OH、Si-OH、Me-O-Me、Me-O-Si-、Si-O-Si、Me-OR1或Si-OR1的官能团,
(b)与具有通式II的有机硅烷B,
(R1O)R2 2Si-(CR3 2)n-A-D-C (II),
和/或它们的水解和/或缩合产物,
(c)和任选地与水,
其中
R1是氢或含有1-6个碳原子的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,
Me是金属原子和
R2,R3,A,D,C和n如以上所定义。
通式II的单官能有机硅烷B的使用使粒子官能化,甚至在水的存在下。在这种情况下,事实上对于粒子表面上的所有MeOH和/或SiOH基团来说(在化学计量反应中)都可能由有机硅烷B饱和。剩余的MeOH和/或SiOH基团(它们可限制粒子的稳定性)因此在很大程度上是可避免的。也可以在化学计量反应中通过与有机硅烷B的反应来官能化可自由接近的Me-O-Me、Me-O-Si或Si-O-Si基团。
粒子P同样可优选地通过共水解通式II的有机硅烷B与通式III的烷氧基硅烷B*来制备,
(R5O)4-m(R6)mSi (III),
其中
R5与R1的定义相同,
R6是烃基,该烃基可以经取代,和
m表示数值0、1、2或3。
烃基R1优选是烷基、环烷基或芳基,特别是甲基、乙基或苯基,更优选是甲基或乙基。R2优选是烷基、环烷基、芳基或芳烷基,特别是甲基、乙基或苯基,更优选甲基。R3优选是氢或烷基、环烷基、芳基或芳烷基,特别是甲基,并且特别优选的是R3为氢。n优选表示数值1、2或3,特别优选的是n=1。基团C优选是含有2-12个碳原子,更优选是含有2-6个碳原子的不饱和烷基,特别是乙烯基、丙烯酰基或甲基丙烯酰基。基团(-A-D-C)优选是如下基团:OC(O)C(CH3)=CR3 2、OC(O)CH=CR3 2、NHC(O)C(CH3)=CR3 2或NHC(O)CH=CR3 2。特别优选的,它们是基团OC(O)C(CH3)=CR3 2或OC(O)CH=CR3 2。R5优选的基团为R1所列举的优选基团。R6优选经官能化或非官能化,如含有1-12个碳原子的芳族或脂族饱和或不饱和烃基。R6优选的基团为R2所列举的优选基团。R6也可采用CR3 2-A-D-C的定义;即在这种情况下,通式II的有机硅烷B与烷氧基硅烷B*相同。
烷氧基硅烷B*的优选例子是四乙氧基硅烷、四甲氧基硅烷、甲基三甲氧基硅烷、二甲基甲氧基硅烷、苯基甲基二甲氧基硅烷、苯基三甲氧基硅烷和乙烯基三甲氧基硅烷。
组合物Z优选用作涂层。在本发明中,它们特别优选用于改进涂覆表面的耐擦划性。与包含用常规的、三官能烷氧硅烷(如甲基丙烯酰氧基丙基三甲氧基硅烷)和/或它们的水解和/或缩合产物表面改性的粒子的涂层相比,从组合物Z通过固化获得的涂料具有更高的机械硬度和改进的耐擦划性。
考虑到在烷氧基甲硅烷基和杂原子之间含有亚甲基间隔物的烷氧基硅烷B的反应性(n=1),这些化合物特别适于官能化带有SiOH或MeOH的粒子P1。Me-O-Me、Me-O-Si-、Si-O-Si官能粒子与烷氧基硅烷B之间的平衡也可以进行以用于制备粒子P。粒子P1与烷氧基硅烷B的反应是快速和完全的。
组合物Z中包含的粘结剂BM必须带有一个或多个反应性基团,该基团优选由光化辐射或热处理引发,所述粘结剂能够与聚合物样结构(construction of a polymer)、与它们自身和与反应性粒子进行自由基、阳离子或阴离子聚合。反应性基团是包含烯属不饱和官能团的基团,特别是乙烯基、甲基丙烯酸酯基团、丙烯酸酯基团和丙烯酰胺基团。在本发明中,粘结剂BM可包括单体、低聚物或聚合物化合物。
合适的单体和低聚物化合物的例子是二丙烯酸己二醇酯、三丙烯酸季戊四醇酯、五丙烯酸二季戊四醇酯、二丙烯酸三甘醇酯等。合适的聚合物粘结剂BM的例子是带有烯属不饱和基团的(甲基)丙烯酸类共聚物、聚酯(甲基)丙烯酸酯、不饱和聚酯、尿烷(甲基)丙烯酸酯和硅氧烷(甲基)丙烯酸酯。
光化辐射是指在红外(MR)中、在可见光、在紫外光(UV)中,和在X辐射区域中的电磁辐射。
组合物Z的突出之处为如下事实:使用所有金属氧化物和金属混合的氧化物粒子(如,铝氧化物如刚玉、与其它金属和/或硅的铝混合氧化物、氧化钛、氧化锆、氧化铁等)、氧化硅粒子(如胶体二氧化硅、热解二氧化硅、沉淀二氧化硅、硅酸溶胶)或氧化硅化合物作为粒子P1,其中硅的一些化合价用有机基团(如硅树脂)来限定。此外,粒子P1的突出之处为如下事实:在它们的表面上它们具有金属氢氧化物(MeOH)、氢氧化硅(SiOH)、Me-O-Me、Me-O-Si和/或Si-O-Si官能团,通过它们可以与有机硅烷B进行反应。粒子P1的平均直径优选小于1000nm,更优选小于100nm,粒度由透射电镜测定。
在本发明的一个优选实施方案中,粒子P1由热解二氧化硅组成。在本发明进一步优选实施方案中,使用的粒子P1是胶体氧化硅或金属氧化物,它们优选采用的形式为亚微米尺寸的相应氧化物粒子在含水或有机溶剂中的分散体。在本发明中特别优选使用金属铝、钛、锆、钽、钨、铪和锡的氧化物。优选使用含水SiO2溶胶,它优选与通式II的有机硅烷B反应。
另外,同样优选采用由通式IV的硅树脂组成的粒子P1
(R7 3SiO1/2)e(R7 2SiO2/2)f(R7SiO3/2)g(SiO4/2)h (IV)
其中
R7是OR8官能团、OH官能团、任选地含有1-18个碳原子的经卤素-、羟基-、氨基-、环氧-、巯基-、(甲基)丙烯酰基-或NCO-取代的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,
R8是含有1-18个碳原子的任选经取代的单价烃基,
e表示大于或等于0的数值,
f表示大于或等于0的数值,
g表示大于或等于0的数值,和
h表示大于或等于0的数值,其条件是e+f+g+h的总和是至少为1,优选至少为5。
对于组合物Z,可以使用一种或多种不同的粒子类型P。因此其可用来例如制备涂层体系,该体系除包括纳米级SiO2以外,还包括纳米级刚玉。
以总重量计,涂层体系中包含的粒子P的量优选为至少5wt%,更优选为至少10wt%,非常优选为至少15wt%,并且优选为不大于90wt%。
组合物Z优选在两阶段工艺中制备。在第一阶段中制备粒子P。在第二步骤中将官能化粒子P引入粘结剂BM中。
在一个优选的方法中,将通过使反应粒子P1与有机硅烷B反应得到的粒子P在引入粘结剂BM之前进行精制。当在制备工艺中出现的杂质对(固化)涂层的性能具有不利影响时,此方案是特别适用的。粒子P可以通过例如使粒子沉淀,然后采用合适的溶剂洗涤而得到精制。
在替代的方法中,在粘结剂BM存在下通过采用硅烷B官能化粒子P1来制备组合物Z。在两种制备工艺中,粒子P1可以作为在含水或无水溶剂中的分散体存在,或可以以固态存在。
在使用粒子P1的含水或非水分散体的情况下,通常在将粒子P或P1引入到粘结剂BM之后除去相应的溶剂。溶剂的脱除优选由蒸馏完成,可以在粒子P1与硅烷B的反应之前或之后进行。
优选采用的硅烷B的例子是甲基丙烯酰氧基甲基二甲基甲氧基硅烷、甲基丙烯酸根合甲基二甲基乙氧基硅烷、甲基丙烯酸根合丙基二甲基甲氧基硅烷、甲基丙烯酸根合丙基二甲基乙氧基硅烷、丙烯酸根合甲基二甲基甲氧基硅烷、丙烯酸根合甲基二甲基乙氧基硅烷、丙烯酸根合丙基二甲基甲氧基硅烷和丙烯酸根合丙基二甲基乙氧基硅烷、
对于粒子的官能化,可以单独采用一种硅烷B或不同硅烷B的混合物,或硅烷B与其它烷氧基硅烷的混合物。
此外,组合物Z可包括常用的溶剂和在制剂中常见的添加剂和助剂。这样的例子包括流动控制助剂、表面活性物质、粘合促进剂、光稳定剂如UV吸收剂和/或自由基清除剂、触变剂,另外也包括固体物质和填料。为了得到既适合组合物,又适合固化材料的特别希望的性能,优选使用此类助剂。当组合物Z要用作涂料时尤其如此。这些涂料制剂也可另外包括染料和/或颜料。
组合物Z的固化优选是在烯属不饱和基团所必需的条件下,通过光化辐射或热引发的自由基聚合,采用熟练技术人员已知的方式完成。
所述聚合例通过如加入合适的光敏引发剂例如,Darocur1178、Darocur1174、Irgacure184、Irgacure500后,由UV辐射进行。这些光敏引发剂典型地以0.1wt%-5wt%的量使用。聚合可以在加入有机过氧化物,如过氧二羧酸,或偶氮化合物如偶氮二异丁腈之后由热方式进行。
在本发明的一个特别优选实施方案中,组合物Z包括至少一种光敏引发剂,并且涂层由UV辐射固化。在本发明的进一步特别优选实施方案中,组合物由电子束固化。
在组合物Z固化之后获得的涂料具有突出的机械性能。与已知材料相比其在例如耐擦划性方面存在显著的改进。
本发明进一步提供组合物Z用于涂覆任何所需基材的用途。优选基材的例子包括氧化物材料,如玻璃,例如金属、木材或塑料如聚碳酸酯、聚对苯二甲酸丁二醇酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚氯乙烯和聚丙烯。
施加的涂层用于改进耐擦划性、耐磨性、化学稳定性,或用来影响粘合性能。
所述的组合物Z可以通过任何所需的技术如浸渍、喷涂、和流延施加。通过“湿上湿”方法的施加也是可以的。
以上通式中的所有符号具有在每种情况下各自彼此独立的意义。在所有的通式中硅原子是四价的。
在以下的实施例中,除非另外说明,则所有的量和百分比按重量计,所有压力是0.10MPa(abs.),所有的温度是20℃。
实施例1:
将20.00g SiO2有机溶胶(购自Nissan Chemicals的IPA-ST,30wt%SiO2,12nm)在1分钟内与2.00g甲基丙烯酸根合甲基二甲基甲氧基硅烷滴加混合,并将混合物在60℃下加热16小时。在将混合物冷却到室温之后,将15.00g二丙烯酸己二醇酯加入其中,然后在减压下蒸馏出异丙醇。透明分散体包含29wt%SiO2。
实施例2:
将20.00g含水SiO2溶胶(购自Grace Davison的LUDOXAS 40,40wt%SiO2,pH=9.1,22nm)在60分钟内与15ml乙醇滴加混合,并在5分钟内与2.00g甲基丙烯酸根合甲基二甲基甲氧基硅烷滴加混合,并将混合物在60℃下加热16小时。在将混合物冷却到室温之后,将15.00g二丙烯酸己二醇酯加入其中,然后在减压下将乙醇和水作为共沸物蒸馏出。透明分散体包含29wt%SiO2。
实施例3:
将20.00g SiO2有机溶胶(购自Nissan Chemicals的IPA-ST,30wt%SiO2,12nm)在1分钟内与2.00g甲基丙烯酸根合甲基二甲基甲氧基硅烷滴加混合,并将混合物在60℃下加热16小时。在蒸馏出溶剂之后,将残余物采用100ml(5×20ml)戊烷洗涤。将2.90g获得的固体在10ml乙醇中的分散体与7.10g HDDA混合,并蒸馏出溶剂。从而得到SiO2含量为29wt%的透明分散体。
对比实施例1:
将26.7g SiO2有机溶胶(购自Nissan Chemicals的IPA-ST,30wt%SiO2,12nm)在1分钟内与15.00g二丙烯酸己二醇酯混合,搅拌混合物30分钟,然后在减压下蒸馏出异丙醇。透明分散体包含35wt%SiO2。
对比实施例2:
将20.00g含水SiO2溶胶(购自Grace Davison的LUDOXAS 40,40wt%SiO2,pH=9.1,22nm)在60分钟内与20ml乙醇滴加混合,并在5分钟内与2.00g甲基丙烯酸根合甲基三甲氧基硅烷滴加混合,将混合物在60℃下加热16小时。在将混合物冷却到室温之后,将15.00g二丙烯酸己二醇酯加入其中,然后将乙醇和水作为共沸物蒸馏出。透明分散体包含35wt%SiO2。
对比实施例3:
将20.00g SiO2有机溶胶(购自Nissan Chemicals的IPA-ST,30wt%SiO2,12nm)和10g水的混合物在1分钟内与2.00g甲基丙烯酸根合丙基三甲氧基硅烷滴加混合。将混合物在60℃下加热16小时。在将混合物冷却到室温之后,将15g二丙烯酸己二醇酯加入其中,然后共沸蒸馏出异丙醇和水。透明分散体包含29wt%SiO2。
实施例4:
涂层膜的生产
使用来自Erichsen的Coatmaster509MC拉膜设备,采用槽高度为80μm的涂覆棒将来自实施例1,2,3,和来自对比实施例1,2和3的涂层材料,及由纯二丙烯酸1,6-己二醇酯组成的涂料各自分别施加到玻璃板上。其后,将获得的涂层在装在购自Dr.Honle的型号为UVA-Print 100CV1的UVA管中的氮气条件下固化,灯输出为约60mW/cm2,辐射时间为60秒。所有的涂层制剂都得到美观、平滑的涂层。对于所有6种涂层材料,所有五个涂层的光泽-采用购自Byk的Micro光泽20°光泽计测定-是大约155光泽单位。
实施例5:
涂层膜耐擦划性的评价
使用Peter-Dahn磨耗测试仪器测定根据实施例6生产的涂层膜的耐擦划性。为此目的,将面积为45×45mm的Scotch Brite07558磨料非织造物加载1kg重物,并使用500次行程擦划。使用购自Byk的Micro光泽20°光泽计分别测量擦划测试之前和测试之后涂层的光泽。作为各自涂层耐擦划性的量度,确定光泽的损失(每种情况为3个涂层样品的平均值):
涂料样品 | 光泽损失 |
实施例1 | 15+4% |
实施例2 | 10+5% |
实施例3 | <5% |
对比例1 | 78+7% |
对比例2 | 25±5% |
对比例3 | 43±5% |
二丙烯酸1,6-己二醇酯 | 75±10% |
表1:在Peter-Dahn擦划测试中的光泽损失
Claims (10)
1.一种可固化组合物Z,该组合物包括带有至少一个烯属不饱和基团的粘结剂BM,还包括在它们的表面上具有至少一个烯属不饱和基团,并包含通式I基团的粒子P,
-SiR2 2-(CR3 2)n-A-D-C (I),
其中
R2是-(CR3 2)n-A-D-C或含有1-12个碳原子的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,
R3是氢或含有1-12个碳原子的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,
R4是氢或含有1-12个碳原子的烃基,
A是氧、硫、=NR4或=N-(D-C),
D是羰基、在每种情况下含有1-12个碳原子的亚烷基、亚环烷基或亚芳基,这些基团的碳链可以由不相邻的氧、硫或NR4基团间隔,和
C是烯属不饱和基团和
n大于或等于1。
2.根据权利要求1所述的组合物Z,其中粒子P通过使如下物质反应来制备:
(a)材料为选自金属氧化物、金属-硅混合氧化物、二氧化硅、胶体二氧化硅或有机聚硅氧烷树脂或及它们的组合的粒子P1,并具有选自Me-OH、Si-OH、Me-O-Me、Me-O-Si-、Si-O-Si、Me-OR1或Si-OR1的官能团,
(b)与具有通式II的有机硅烷B,
(R1O)R2 2Si-(CR3 2)n-A-D-C (II),
和/或它们的水解和/或缩合产物,
(c)和任选地与水,
其中
R1是氢或含有1-6个碳原子的烃基,该烃基的碳链可以由不相邻的氧、硫或NR4基团间隔,
Me是金属原子和
R2,R3,A,D,C和n如权利要求1所定义。
3.根据权利要求1所述的组合物Z,其中,所述粒子P可以共水解通式II的有机硅烷B与通式III的烷氧基硅烷B*来制备,
(R5O)4-m(R6)mSi (III),
其中
R5与R1的定义相同,
R6是可以经取代的烃基,和
m表示数值0、1、2或3。
4.根据权利要求2或3所述的组合物Z,其中烃基R1是甲基、乙基或苯基。
5.根据权利要求1-4所述的组合物Z,其中基团(-A-D-C)是基团OC(O)C(CH3)=CR3 2、OC(O)CH=CR3 2、NHC(O)C(CH3)=CR3 2或NHC(O)CH=CR3 2。
6.根据权利要求1-5所述的组合物Z,其中所述的在粘结剂BM中的烯属不饱和基团能够进行自由基、阳离子或阴离子聚合。
7.根据权利要求1-6所述的组合物Z,其中在粘结剂BM中的烯属不饱和基团可以由光化辐射或热处理聚合。
8.根据权利要求1-7所述的组合物Z,其中在粘结剂BM中的烯属不饱和基团选自乙烯基、甲基丙烯酸酯基团、丙烯酸酯基团或丙烯酰胺基团。
9.根据权利要求1-8所述的组合物Z,其中所述粒子P1的平均直径小于1000nm,粒度由透射电镜测定。
10.根据权利要求1-9所述的组合物Z用于涂覆基材中的用途。
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CN101945954A (zh) * | 2007-12-12 | 2011-01-12 | 克罗诺特克股份公司 | 用于官能化硬质材料颗粒的方法 |
CN102575024A (zh) * | 2009-10-20 | 2012-07-11 | 瓦克化学股份公司 | 具有两段式固化动力学的稳定的可湿度固化聚合物 |
CN104395260A (zh) * | 2012-04-30 | 2015-03-04 | H.B.富勒公司 | 可固化的水性组合物 |
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DE102004022400A1 (de) * | 2004-05-06 | 2005-12-15 | Consortium für elektrochemische Industrie GmbH | Feuchtigkeitsvernetzbare alkoxysilyfunktionelle Partikel enthaltende Zusammensetzung |
DE102006001771A1 (de) * | 2006-01-12 | 2007-07-19 | Röhm Gmbh | Verfahren zur Aufreinigung von (Meth)acrylaten |
DE102006029429A1 (de) * | 2006-06-27 | 2008-01-03 | Wacker Chemie Ag | Alkoxysilylfunktionelle Oligomere und damit oberflächenmodifizierte Partikel |
DE102006033236A1 (de) * | 2006-07-18 | 2008-01-24 | Wacker Chemie Ag | Zusammensetzung auf der Basis von Organosiliciumverbindungen |
DE102006053160A1 (de) * | 2006-11-10 | 2008-05-15 | Wacker Chemie Ag | Dispergierbare Nanopartikel |
DE102006055734A1 (de) * | 2006-11-25 | 2008-05-29 | Nanogate Ag | Permanenter Griffschutz durch UV-Härtung |
US7754787B2 (en) * | 2007-08-30 | 2010-07-13 | Ppg Industries Ohio, Inc. | Curable film-forming compositions containing colloidal particle sols having improved appearance and mar and scratch resistance |
NO328788B1 (no) * | 2008-03-14 | 2010-05-18 | Jotun As | Bindemiddel til lufttørkende maling |
DE102008058318B3 (de) * | 2008-11-21 | 2010-06-17 | Schott Ag | Kratzfeste Silikonbeschichtung für Kochflächen aus Glas oder Glaskeramik |
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US4491508A (en) * | 1981-06-01 | 1985-01-01 | General Electric Company | Method of preparing curable coating composition from alcohol, colloidal silica, silylacrylate and multiacrylate monomer |
US4455205A (en) * | 1981-06-01 | 1984-06-19 | General Electric Company | UV Curable polysiloxane from colloidal silica, methacryloyl silane, diacrylate, resorcinol monobenzoate and photoinitiator |
WO1997011129A1 (fr) * | 1995-09-20 | 1997-03-27 | Mitsubishi Rayon Co., Ltd. | Composition de revetement resistant a l'usure et article ainsi revetu de cette composition |
JP2006526668A (ja) * | 2003-04-07 | 2006-11-24 | コンゾルテイウム フユール エレクトロケミツシエ インヅストリー ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | オルガノシリル官能化された粒子およびその製造 |
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CN101945954A (zh) * | 2007-12-12 | 2011-01-12 | 克罗诺特克股份公司 | 用于官能化硬质材料颗粒的方法 |
CN102575024A (zh) * | 2009-10-20 | 2012-07-11 | 瓦克化学股份公司 | 具有两段式固化动力学的稳定的可湿度固化聚合物 |
CN104395260A (zh) * | 2012-04-30 | 2015-03-04 | H.B.富勒公司 | 可固化的水性组合物 |
CN104395260B (zh) * | 2012-04-30 | 2017-07-28 | H.B.富勒公司 | 可固化的水性组合物 |
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