CN101115812A - Varnish containing particles with protected isocyanate groups - Google Patents
Varnish containing particles with protected isocyanate groups Download PDFInfo
- Publication number
- CN101115812A CN101115812A CNA2006800045311A CN200680004531A CN101115812A CN 101115812 A CN101115812 A CN 101115812A CN A2006800045311 A CNA2006800045311 A CN A2006800045311A CN 200680004531 A CN200680004531 A CN 200680004531A CN 101115812 A CN101115812 A CN 101115812A
- Authority
- CN
- China
- Prior art keywords
- group
- coating
- particle
- weight
- functional
- 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
Links
- 239000002245 particle Substances 0.000 title claims abstract description 122
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002966 varnish Substances 0.000 title abstract 7
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 125000000524 functional group Chemical group 0.000 claims abstract description 19
- 125000004429 atom Chemical group 0.000 claims abstract description 18
- 239000008199 coating composition Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000011877 solvent mixture Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 171
- 239000011248 coating agent Substances 0.000 claims description 163
- 238000002360 preparation method Methods 0.000 claims description 129
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 84
- -1 butane oxime Chemical class 0.000 claims description 68
- 239000003795 chemical substances by application Substances 0.000 claims description 59
- 239000007787 solid Substances 0.000 claims description 50
- 239000001273 butane Substances 0.000 claims description 33
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 239000003973 paint Substances 0.000 claims description 24
- 230000008030 elimination Effects 0.000 claims description 23
- 238000003379 elimination reaction Methods 0.000 claims description 23
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 150000001282 organosilanes Chemical class 0.000 claims description 11
- 229920002050 silicone resin Polymers 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 11
- 238000007669 thermal treatment Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 238000013021 overheating Methods 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 229940009098 aspartate Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 abstract description 6
- 150000002513 isocyanates Chemical class 0.000 abstract description 5
- 239000011343 solid material Substances 0.000 abstract 3
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 71
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 64
- 229910000077 silane Inorganic materials 0.000 description 60
- 239000000377 silicon dioxide Substances 0.000 description 39
- 239000000203 mixture Substances 0.000 description 33
- 229960001866 silicon dioxide Drugs 0.000 description 27
- 235000012239 silicon dioxide Nutrition 0.000 description 27
- 239000006185 dispersion Substances 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 229940043279 diisopropylamine Drugs 0.000 description 21
- 238000012986 modification Methods 0.000 description 18
- 230000004048 modification Effects 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 7
- 238000005243 fluidization Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000005580 one pot reaction Methods 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000007790 scraping Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-N 2,2-diethylpropanedioic acid Chemical compound CCC(CC)(C(O)=O)C(O)=O LTMRRSWNXVJMBA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000002444 silanisation Methods 0.000 description 3
- 239000012258 stirred mixture Substances 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 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
- 229940043232 butyl acetate Drugs 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
- 150000002596 lactones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- LJHFIVQEAFAURQ-ZPUQHVIOSA-N (NE)-N-[(2E)-2-hydroxyiminoethylidene]hydroxylamine Chemical compound O\N=C\C=N\O LJHFIVQEAFAURQ-ZPUQHVIOSA-N 0.000 description 1
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical class O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ONIFNICATWBCHW-UHFFFAOYSA-N 1,3-dimethyl-1,2,4-triazole Chemical compound CC=1N=CN(C)N=1 ONIFNICATWBCHW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 101150027068 DEGS1 gene Proteins 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH 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
- 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
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 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
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- PGJJYYADLKWXLJ-UHFFFAOYSA-N isocyanato(trimethoxy)silane Chemical compound CO[Si](OC)(OC)N=C=O PGJJYYADLKWXLJ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- DNYZBFWKVMKMRM-UHFFFAOYSA-N n-benzhydrylidenehydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1=CC=CC=C1 DNYZBFWKVMKMRM-UHFFFAOYSA-N 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- JZORKWZAPJLMOH-UHFFFAOYSA-N phenol triethoxysilane Chemical compound C(C)O[SiH](OCC)OCC.C1(=CC=CC=C1)O JZORKWZAPJLMOH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 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
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 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
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 235000012976 tarts Nutrition 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- 238000012546 transfer Methods 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-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
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to coating formulations (B1) containing a) 20-90 % by weight, in regard to a solid material fraction, a reactive group varnish resin (L), b) 1-90 % by weight, in regard to a solid material fraction, a varnish hardener (H) exhibiting reactive functions by which it reacts with the reactive groups of the varnish resin (L) under heat treatment during a varnish hardening, c) 0.1-40 % by weight, in regard to a solid material fraction, particles containing core consisting of atoms selected from metal, silicon and oxygen atoms or made of a silicon resin, wherein the particles (p) comprises, on the surfaces thereof, at least one isocyanate protected group which releases an isocyanate function by heat treatment associated with a protection group removal, more than 50 % of the isocyanate protected groups are provided with the protection groups whose separation temperature is less than the reaction temperature of the varnish resin (L) functional groups with functional groups of the hardener (H), d) 0-90 % by weight, in regard to the entire coating formulation (B1), a solvent or a solvent mixture and e) optionally, other varnish components and additive.
Description
The present invention relates to the coating preparation, more specifically relate to face coat and transparent coating material, it comprises that there is the particle of protected isocyanate groups on the surface.
The coating system that comprises particle (more specifically being nano particle) is a prior art.This coating all has description in for example EP 1 249 470 or WO 03/16370.Particle in these coating has brought the improvement on the coating property, more specifically is the improvement on its scrath resistance and chemical resistant properties.
The problem that common inorganic particle is used for the appearance of organic coating system regular meeting is included between particle and the paint binder (coating-material matrix) insufficient compatible usually.This will cause particle can not fully disperse in paint binder.And, even finely disseminated particle shelve for a long time or storage process in may take place the precipitation and may form than macro aggregate or aggregate, even this redispersion also can not or be difficult to be separated into original particle.The processing of this nonhomogeneous system under any circumstance all is exceedingly difficult, and in fact normally impossible.In case having the coating of smooth-flat-surface after coating and the curing never prepares in this way usually or only just can prepare down expensive.
Therefore, the particle that uses the surface to have organic group is favourable, and described organic group can improve the consistency with paint binder.The inorganic particle organic shell of one deck of " putting on " in this way.In addition, if the organic functional on the particle surface also have can with the group of paint binder reaction, thereby under the various conditions of cure of the coating that comes into question, they can react with base-material, promptly can obtain good especially coating property herein.In this way, particle successfully is incorporated in the base-material with chemical mode, thereby can not only obtains good especially mechanical properties and can bring improved chemical resistant properties.This class system is for example being described among DE 102 47 359 A1, EP 832 947 A or EP 0 872 500 A1 to some extent.
In addition, it also is well-known using the coating comprise with the binding agent of modified by nano particles.These coating can react with the binding agent that comprises auxiliary functional group by the particle that will have reactive functional group and prepare.Therefore, in this case, be not only the paint solidification stage and even at the preparatory phase of binding agent, the functional organic particle is incorporated in the paint binder with chemical mode.This class system is for example described in EP 1 187 885 A or WO 01/05897 to some extent.
In a kind of situation of coating type of particularly important, use the film-forming resin that comprises the hydroxyl-functional prepolymer, described prepolymer reacts with the isocyanate-functional solidifying agent in paint solidification.This polyurethane coating is with its good especially performance good chemical resistant properties and being celebrated for example, yet special scrath resistance for this system still need improve.Usually they are used for special high value and Application Areas high request: for example, and as the Clear coating and/or the face coat material of OEM japanning system in automobile and the vehicles industry.Most auto repair also is made up of this cured with isocyanates system with refinisher coating.
Typically, have any different between the different polyurethane coating systems that two kinds are called as 2K and 1K system.The former is made up of two components, and one of them component mainly is made up of isocyanate curing agent, and the film-forming resin that contains isocyanate-reactive group is included in second component.Because fully the validity period of mixture is very limited, so two kinds of components must separate storage and transportation, up to processedly not long ago all not mixing at them.Therefore, more advantageously so-called usually 1K system, it only is made up of a component, wherein on the film-forming resin side solidifying agent that comprises protected isocyanate groups is arranged.1K coating is by thermofixation, and the protectiveness group of isocyanate units is eliminated, and de-protected isocyanic ester then can react with film-forming resin.The typical drying temperature of this type of 1K coating is 130-160 ℃.
For these high value coating, wish on its performance, further to be improved.Particularly all the more so to the vehicle surfaces coating.For example, especially, the accessible scrath resistance of conventional automotive coatings is still not enough, and the result is the remarkable damage that the particle in the car carwash washing water causes coating.As time goes on, this will cause the lasting damage to coating gloss.In this case, just need to reach the preparation of higher scrath resistance.
A particularly advantageous mode that realizes this target is the particle that contains protected isocyanate functional group with the surface.When this particle was combined with the 1K polyurethane coating, the isocyanate functional group also discharged in the process of paint solidification, and particle combines by chemical mode with coating.In addition, protected isocyanate groups has increased the consistency between particle and the paint binder.
This class particle that contains protected isocyanate functional group is known basically.Usually this type of particle is by will containing the functional particle of free silicon or metal hydroxides and the polycondensation of alkoxysilyl functional silicoorganic compound prepares, and the organic radical of wherein said silicoorganic compound contains protected isocyanate functional group.This class contains silicoorganic compound existing description in such as DE 34 24 534A1, EP 0 212 058 B1, JP 08-291186 or JP 10-067787 of the isocyanate groups of sheltering.The particle that self contains protected isocyanate functional group with and application in coating, in such as EP 872 500 A, describe to some extent.
By mixing this class particle, in fact the scrath resistance of coating can significantly be strengthened.Yet all of Miao Shuing are used in these particulate methods in the prior art, also do not obtain optimum.
Therefore, an object of the present invention is to provide a kind of surface that comprises and contain the particulate coating of protected NCO group, be intended to make this coating to have the character of further raising, more specifically is the scrath resistance that further improves.
Coating preparation provided by the invention (B1) comprising:
A) based on the film-forming resin that contains reactive group (L) of the 20-90 weight % of solid part (solid fraction),
B) based on the coating curing agent that contains reactive functional (H) of the 1-90 weight % of solid part, by this reactive functional, coating curing agent when thermal treatment and the reaction-ity group reaction of film-forming resin (L) make paint solidification,
C) based on the particle (P) of the 0.1-40 % by weight of solid portion; It comprises by the former molecular nuclear that is selected from metallic atom, silicon atom and oxygen atom; Or the nuclear that is formed by silicones; Described particle (P) has at least one protected isocyanate groups on its surface; Thereby this group is eliminated the protectiveness group through heat treatment and is discharged isocyanate-functional; Surpass 50% protected isocyanate groups with the protectiveness group its eliminate the temperature that temperature is lower than the functional group reactions of the functional group of film-forming resin (L) and curing agent (H)
D) based on the solvent of the 0-90 weight % of whole coating preparations (B1) or solvent mixture and
E) if desired, other coating composition and additive.
Solid part described herein comprises when paint solidification, stays the component in the coating.
The elimination temperature of the isocyanic ester protectiveness group of described particle (P), and the temperature of reaction of the functional group of the functional group of film-forming resin (L) and solidifying agent (H) obtain in the pertinent literature that can be known by those of skill in the art usually.In addition, also can pass through standard technique, dsc (DSC) for example, if perhaps functional group is protected isocyanate functional group, (TG) measures by thermogravimetry.These measuring technologys are prior aries and are that those skilled in that art know.
Because the difference between the temperature of reaction of the functional group of the elimination temperature of the isocyanic ester protectiveness group of particle (P) and film-forming resin (L) and solidifying agent (H) functional group can't clearly obtain from data in literature at present, and is as follows to these characterizing definitions for purposes of the present invention: the elimination temperature of isocyanic ester protectiveness group is meant the temperature when the protectiveness group elimination speed of measuring with the rate of heating of 1 ℃/min by DSC or TG reaches maximum value.Temperature when the temperature of reaction of the functional group of the functional group of film-forming resin (L) and solidifying agent (H) is meant and measures speed of response between two reactants and reach maximum value by same procedure.
If particle mentioned above (P) is made by following method by particle (P1) and the hydrolyzable organosilane (A) that contains at least one protected isocyanate groups, so the protected isocyanate functional group of particle (P) go to protect temperature determine it is not by measuring particle (P) self but by measuring silane precursor (A).This sharp technology is favourable, because particle (P) is only stable under dissolved state, also is difficult to if possible be separated.
If film-forming resin mentioned above (L) and/or solidifying agent (H) contain the different functional group of two or more reactivities separately, just, if when paint solidification, between film-forming resin (L) and solidifying agent (H), different reactions is arranged, temperature of reaction has nothing in common with each other, then above-mentioned definition indication is (the mole % of the reactive group that participates in the reaction of being discussed just) dominant reaction on the amount in the coating thermoset processes.The elimination temperature of the protectiveness group that at least 70%, preferred especially at least 90%, preferred more especially 100% protected isocyanate groups of the particle (P) that preferred coatings preparation (B1) comprises has is lower than the temperature of reaction of the functional group of the functional group of film-forming resin (L) and solidifying agent (H).In a preferred embodiment of the present invention, coating preparation (B1) comprises the hydroxyl-functional film-forming resin.
Also preferred its coating curing agent of coating preparation (B1) (H) comprises terpolycyantoamino-formaldehyde resin.Yet it coating curing agent that comprises (H) of particularly preferred coating preparation (B1) has protected isocyanate groups as particle (P), can eliminate the protectiveness group and discharge isocyanate-functional when thermal treatment.In this preferred embodiment of the present invention, the film-forming resin (L) and the temperature of reaction of solidifying agent (H) are defined as identical with the elimination temperature of the protectiveness group of solidifying agent (H).This is justified, because by eliminating the meeting and then react with film-forming resin immediately usually of NCO group that the protectiveness group discharges.
That is to say that the present invention preferably comprises the coating preparation (B1) of following component:
A) based on the hydroxyl-functional film-forming resin (L) of the 20-90 weight % of solid part,
B) based on the coating curing agent that contains protected isocyanate groups (H) of the 1-90 weight % of solid part, described isocyanate groups is eliminated the protectiveness group and is discharged the isocyanate functional group through Overheating Treatment,
C) based on the particle (P) of the 0.1-40 % by weight of solid portion; It comprises by the former molecular nuclear that is selected from metallic atom, silicon atom and oxygen atom; Or the nuclear that is formed by silicones; Described particle (P) has at least one protected isocyanate groups on its surface; Thereby this group is eliminated the protectiveness group through heat treatment and is discharged isocyanate-functional; Surpass 50% protected isocyanate groups with the protectiveness group its eliminate the elimination temperature that temperature is lower than in the curing agent (H) the protectiveness group of 6% protected isocyanate groups
D) based on the solvent of the 0-90 weight % of whole coating preparations (B1) or solvent mixture and
E) if desired, other coating composition and additive.
In this case the protectiveness group that protected NCO group at least 70%, preferred especially at least 90% has in the preferred particulates (P) its eliminate the elimination temperature that temperature is lower than 60%, preferred 70%, preferred especially 90% the protectiveness group of protected isocyanate groups in the solidifying agent (H).Particularly preferably, the elimination temperature of the protectiveness group of whole protected isocyanate groups of the middle particle (P) of coating preparation (B1) is lower than whole protectiveness groups of the protected isocyanate groups of solidifying agent (H).
The elimination temperature of the protectiveness group of solidifying agent (H) and particle (P) preferably obtains from documents and materials well-known to those having ordinary skill in the art.Yet,, can measure by aforesaid technology if suspect.
Preferred determine in the deprotection method of temperature that at one the temperature of selecting is meant this class protectiveness group of being discussed of at least 80% was eliminated, discharges the needed temperature of isocyanate functional group in 30 minutes.This eliminates temperature can be by determining such as thermogravimetry.
If particle mentioned above (P) is to be made by following method by particle (P1) and the hydrolyzable organosilane that contains at least one protected isocyanate functional group, so the protected isocyanate functional group of particle (P) go to protect temperature determine it is not by measuring particle (P) self but by measuring silane precursor (A).This technology is favourable, because particle (P) is only stable under dissolved state, if possible also is difficult to be separated.
The present invention is based on following discovery; promptly the scrath resistance that is shown by the coating of the coating preparation (B1) among the present invention preparation is better than the coating that does not satisfy condition accordingly, and wherein said condition is meant that the elimination temperature of the protectiveness group of the protected isocyanate-functional of particle (P) in described coating preparation is lower than the temperature of reaction between film-forming resin (L) and solidifying agent (H) in most cases.This also comprises hydroxyl-functional film-forming resin (L) and is similar to particle (P) that for particle-removing (P) is outer to contain the coating preparation (P1) of solidifying agent (H) of protected isocyanate groups like that all the more so especially.At this; the elimination temperature of particulate protectiveness group at least in most of the cases is lower than (great majority) isocyanate-functional of solidifying agent in the coating preparation of the present invention (B1), and this coating preparation obviously shows better scrath resistance than the identical non-invention coating of protectiveness group of particle and solidifying agent wherein.The reason that this effect produces is, in the process of paint solidification, the coating among the present invention (B1) make particle (P) better chemistry mix in the paint binder.
The present invention also provides the coating preparation that comprises following component (B2):
A) based on the film-forming resin that contains reactive group (L) of the 20-90 weight % of solid part,
B) based on the coating curing agent that contains reactive functional (H) of the 1-90 weight % of solid part, by this reactive functional, the reaction-ity group reaction of coating curing agent and film-forming resin (L) makes paint solidification when thermal treatment,
C) based on the particle (P) of the 0.1-40 % by weight of solid portion; It comprises by the former molecular nuclear that is selected from metallic atom, silicon atom and oxygen atom; Or the nuclear that is formed by silicones; Described particle (P) has at least one protected isocyanate groups on its surface; This group can be eliminated the protectiveness group and discharge isocyanate-functional through heat treatment; Surpass in the particle (P) 50% protected isocyanate groups with the elimination temperature of protectiveness group be lower than butane oxime (butane oxime)
D) based on the solvent of the 0-90 weight % of whole coating preparations (B2) or solvent mixture and
E) if desired, other coating composition and additive.
The elimination temperature of the protectiveness group that at least 70%, especially preferably at least 90% protected isocyanate groups has in the particle that this preferred coatings preparation (B2) comprises is lower than the butane oxime.Particularly preferably, the elimination temperature of the protectiveness group of all protected isocyanate groups all is lower than the butane oxime in the particle (P) of coating preparation (B2).
At least 50%, preferred at least 70% or 90% protected isocyanate groups preferred especially 100% is by Diisopropylamine, 3 or 2 isopropyl imidazole protection in the particle that this preferred coatings preparation (B2) comprises.
In the preferred embodiment in the present invention, coating preparation (B2) comprises hydroxyl-functional film-forming resin (L).
In addition, the coating curing agent (H) of preferred coatings preparation (B2) comprises terpolycyantoamino-formaldehyde resin.Yet the coating curing agent (H) that special preferred coatings preparation (B2) comprises resembles and contains protected isocyanate groups the particle (P), and it is eliminated the protectiveness group and discharges isocyanate-functional when thermal treatment.
That is to say the coating preparation (B2) that preferably includes following component especially:
A) based on the hydroxyl-functional film-forming resin (L) of the 20-90 weight % of solid part,
B) based on the coating curing agent that contains protected isocyanate groups (H) of the 1-90 weight % of solid part, described protected isocyanate groups is eliminated the protectiveness group and is discharged isocyanate-functional through Overheating Treatment,
C) based on the particle (P) of the 0.1-40 weight % of solid part; it comprises the nuclear of being made up of the atom that is selected from atoms metal, Siliciumatom and Sauerstoffatom; or the nuclear of forming by silicone resin; described particle (P) has at least one protected isocyanate groups on its surface; this group can be eliminated the protectiveness group and discharge isocyanate-functional through thermal treatment; the elimination temperature that surpasses the protectiveness group that 50% protected isocyanate groups has in the particle is lower than the butane oxime
D) based on the solvent of the 0-90 weight % of whole coating preparations (B1) or solvent mixture and
E) if desired, other coating composition and additive.
In a preferred embodiment of the present invention, coating preparation (B1) or (B2) comprise following component:
A) based on the film-forming resin (L) of the 30-80 weight % of solid part,
B) based on the coating curing agent (H) of the 10-60 weight % of solid part,
C) based on the particle (P) of the 0.5-30 weight % of solid part; it comprises the nuclear of being made up of the atom that is selected from atoms metal, Siliciumatom and Sauerstoffatom; or the nuclear of forming by silicone resin; described particle (P) has at least one protected isocyanate groups on its surface; this group can be eliminated the protectiveness group and discharge isocyanate-functional through thermal treatment
D) based on one or more solvents of whole coating preparations (B1) or 0-80 weight % (B2) and
E) if desired, other coating composition and additive.
Special preferred coatings preparation (B1) or (B2) comprise following component:
A) based on the film-forming resin (L) of the 40-70 weight % of solid part,
B) based on the coating curing agent (H) of the 15-50 weight % of solid part,
C) based on the particle (P) of the 1-25 weight % of solid part,
D) based on one or more solvents of whole coating preparations (B1) or 20-70 weight % (B2) and
E) if desired, other coating composition and additive.
Preferred especially all coating preparations (B1) or (B2) in the shared ratio of one or more solvents be 30-60 weight %, the more special 35-60 weight % that is preferably.
In the preferred embodiment in the present invention, particle (P) can be by being made up of the atom that is selected from atoms metal, Siliciumatom and Sauerstoffatom, or form by silicone resin, contain the functional particle of free hydroxyl (P1) simultaneously and obtain described organosilane (A) with organosilane (A) reaction:
A) contain at least one hydrolyzable silyl functional or at least one hydroxyl silyl, and
B) comprise at least one protected isocyanate-functional.
In the special preferred embodiment of the present invention, the general formula (I) of the silane of use (A) is
(R
1O)
3-n(R
2)
nSi-A-NH-C(O)-X (I)
Wherein
R
1Be hydrogen, perhaps all contain alkyl, cycloalkyl or the aryl of 1-6 carbon atom, carbochain can be by non-conterminous oxygen, sulphur or NR
3Group interrupts,
R
2Be alkyl, cycloalkyl, the aryl or aralkyl that all contains 1-12 carbon atom, carbochain can be by non-conterminous oxygen, sulphur or NR
3Group interrupts,
R
3Be hydrogen, alkyl, cycloalkyl, aryl, aralkyl, aminoalkyl group or aspartate acid ester radical,
X is the protectiveness group, and it is eliminated with the form of HX under 60-300 ℃ of temperature and discharges isocyanate-functional in this process,
A represent difunctionality alkyl, cycloalkyl or an aryl that contains 1-10 carbon atom and
The value of n is 0,1 or 2.
Radicals R
1Be preferably methyl or ethyl.Radicals R
2Be preferably methyl, ethyl, sec.-propyl or phenyl.R
3Preferably contain and be no more than 10 carbon atoms, more specifically be no more than 4 carbon atoms.A is preferably (CH
2)
3Group also is preferably CH especially
2Group.
The elimination temperature of protectiveness group (more specifically HX) is 80-200 ℃, is preferably 100-170 ℃ especially.Used protectiveness group HX can be secondary alcohol or tertiary alcohol, as the Virahol or the trimethyl carbinol; The CH-acidic cpd is as diethyl malonic acid, methyl ethyl diketone, methyl aceto acetate; Oxime is as formoxime, ethylidenehydroxylamine, butane oxime, cyclohexanone-oxime, acetophenone oxime, diphenylketoxime or diethylidene glyoxime; Lactan is as hexanolactam, Valerolactim, butyrolactam; Phenols is such as phenol, ortho-methyl phenol; The N-alkylamide is as the N-methylacetamide; Imide is as phthalic imidine; Secondary amine is as Diisopropylamine, imidazoles, 2 isopropyl imidazole, pyrazoles, 3,1,2,4-triazole and 2,5-dimethyl-1,2,4-triazole.Preferred protectiveness group such as butane oxime, 3, hexanolactam, diethyl malonic acid, dimethyl malonic acid, methyl aceto acetate, Diisopropylamine, pyrrolidone, 1,2,4-triazole, imidazoles and 2 isopropyl imidazole.The preferred especially protectiveness group that allows low drying temperature, for example diethyl malonic acid, dimethyl malonic acid, butane oxime, Diisopropylamine, 3 and 2 isopropyl imidazole.
In an alternative embodiment of the invention, particle (P) is made by hydroxyl-functional particle (P1) and organosilane (A) reaction of general formula for (II):
(R
1O)
3-n(R
2)
nSi-A-NR
3-C(O)-NH-Y-(NH-C(O)-X)
z (II)
Wherein
R
1, R
2, R
3, A, X and n in the general formula (I) definition,
Y be (z+1)-functional aliphatic radical or aryl and
Z is digital 1-4, preferred 1 or 2.
Particle (P1) preferably directly takes place when reactant mixes with reaction between organosilane (A).It is (I) or silane (II) (A) that the special advantage of this situation is to use general formula, and wherein spacer A represents CH
2Bridge because the feature of this one type of silane (A) is exactly the extra high reactivity of oh group with particle (P1), to such an extent as to particle therewith the functionallization of one type of silane can especially promptly and at low temperatures carry out, more specifically even can at room temperature carry out.Particle (P1) can be used as moisture or do not have dispersion in water proton or the aprotic solvent, perhaps carries out functionalized with solid form.Under latter event, can in as fluidized-bed reactor or other known mixing device such as ploughshear mixer (plowshare mixer), mix.
If used general formula only contains the monoalkoxy silyl functional (just for (I) or silane (II) (A), general formula (I) or (II) in the silane of n=2), in the preparation process of particle (P), do not need to add water, because the monoalkoxy silyl can be directly and the lip-deep hydroxyl-functional reaction of particle (P1).On the other hand, if used silane contain two or trialkoxysilyl group (just, general formula be (I) or (II) in n=0 or 1 silane), so usually, it is favourable adding water in the preparation process of particle (P), because under the sort of situation organoalkoxysilane not only can with the Si-OH functional response of particle (P1), and and then after its hydrolysis, can react to each other.The particle of preparing like this (P) contains the shell of being made up of interior crosslinked silane (A).
When preparation particle (P), not only can use silane (A), and can carry out surface modification with any mixture of wanting of silane (A) and other silane (S1), silazane (S2) or siloxanes (S3).Silane (S1) or contain the hydroxyl silyl or contain hydrolyzable silyl, the preferred latter.This one type of silane also can contain other organic functional, although also can use the silane (S1) that does not contain other organic functional.
Especially preferably use the mixture of the silane (S1) of silane (A) and general formula (III)
(R
1O)
4-a-b(R
2)
aSiR
4 b (III)
Wherein
R
1, R
2And R
3With general formula (I) in the definition identical and
R
4Base is the alkyl of SiC-bonding identical or different, that contain 1-18 carbon atom, can be replaced by halogen atom, amine groups, ether group, ester group, epoxide group, sulfydryl group, cyano group group, isocyanate groups, methacrylic acid group or (gathering) ethylene glycol if desired, the latter is made up of oxygen ethene and/or oxypropylene unit
A be 0,1,2 or 3 and
B is 0,1,2 or 3.
A is preferably 0,1 or 2 herein, and b is preferably 0 or 1.
Used silazane (S2) and/or siloxanes (S3) be hexa methyl silazane and/or hexamethyldisiloxane especially preferably.
Available particle (P1) be all metal oxide particle and mixed metal oxide particle (for example, mixture, titanium oxide, zirconium white, the ferric oxide of aluminum oxide such as corundum, aluminum oxide and other metal and/or silicon), silica dioxide granule (for example, pyrolytic silicon dioxide, precipitated silica, colloided silica) or wherein some silicon valency silicon dioxide compound of carrying (carry) organic radical, just silicone resin.These particles (P1) are celebrated because of the following fact: containing metal hydrogen-oxygen and/or silicon hydrogen-oxygen official on its surface can, (same by this functional group and organosilane (A), if be fit to, with silane (S1), silazane (S2) or siloxanes (S3)) react.The mean diameter of preferred particulates (P1) is 1nm-100 μ m, more preferably 10-200nm.
In the preferred embodiment of the present invention, particle (P1) is made up of pyrolytic silicon dioxide, it makes described silicon compound such as silicon tetrachloride or dimethyl dichlorosilane (DMCS) or trichlorosilane (hydrogentrichlorosilane) or dimethyl dichlorosilane (DMCS) or other methyl chlorosilane or alkyl chlorosilane by the mixture of silicon compound and hydro carbons or the mixture of any volatilizable silicoorganic compound of wanting that maybe can spray in pyrogenic reaction.
Can use by the silicon-dioxide wet chemistry method preparation or preparation under high temperature (being higher than 1000 ℃).Preferred especially silicon-dioxide by the pyrolysis preparation.Hydrophilic can use with silicon-dioxide hydrophobic type.
Also can use the different metal oxides or the mixture of silicon-dioxide, for example have the mixture of the metal oxide of different B ET surface-area or silicon-dioxide or have different hydrophobic degs or the silica mixture of silanization degree.
The operation of surface modification preferably is made up of following three steps: (1) adds silicon-dioxide in silane, (2) reaction, and (3) purifying silicon dioxide is to remove excessive silane and/or by product or split product.
Surface treatment is preferably carried out in the atmosphere that does not cause the silanized silica oxidation, and just, preferred oxygen is lower than 10 volume %, especially preferably is lower than 2.5 volume %, can reach optimum when being lower than 1 volume %.
Coating, reaction and purifying can interval or operate continuouslys.For the preferred successive reaction of technical reason.
Apply preferably under-30-150 ℃, preferred 20-100 ℃ temperature and carry out, preferred especially coating step carries out under 30-50 ℃ temperature.
Residence time is 1 minute-24 hours, preferred 15-240 minute, and for the reason of space time yield, preferred 15-90 minute especially.
The pressure range that applies operation is preferably standard pressure from being low to moderate 0.2 slight underpressure of clinging to the overpressures up to 100 crust for technical reason, promptly relates to the atmospheric operation of outside/barometric point.
Silane (A) mixture of other silane (S1), silazane (S2) or siloxanes (S3) (when being fit to) preferably with the fluid form adding, is particularly sneaked in pulverous silicon-dioxide.Compound can mix with pure state, perhaps sneaks into the solution form in the solvent of knowing in this area, and described solvent is alcohols for example, more specifically is the alkanol that contains 1-6 carbon atom, as methyl alcohol, ethanol or Virahol; Ethers is as ether, THF or dioxane; Or hydro carbons, as hexanaphthene or toluene.Strength of solution is 5-95 weight % in this case, is preferably 30-95 weight %, is preferably 50-95 weight % especially.
Mixing process is preferably undertaken by nozzle technology or comparable technology such as effective atomization technique, for example use single fluid nozzle (preferred 5-20 crust) atomizing under certain pressure, with two-fluid spray nozzle (preferred gas and liquid 2-20 crust) spraying under certain pressure, Gu by making silane and the equally distributed atomizer of Powdered silicon-dioxide or having mobile, rotation or the gas/transfer equipment of static internals reaches high dispersing.
Silane (A) mixture of other silane (S1), silazane (S2) or siloxanes (S3) (when being fit to) preferably with the aerosol form adding of high dispersing, is characterized in that described aerocolloidal settling velocity is the 0.1-20 cel.The filling of silicon-dioxide and preferably carry out with the fluidisation of mechanical fluidisation or gas load (gas-supported) with the reaction of silane.Special preferred mechanical fluidisation.
The fluidisation of gas load can with the rare gas element that silane, silicon-dioxide and silanized silica react not be with all, described rare gas element can not cause second order reaction, DeR, oxidation or burning or explosion phenomenon, preferably as nitrogen, argon gas, other rare gas, carbonic acid gas etc.Fluidizing agent preferably is the 0.05-5 cel, is preferably the zone supply of 0.5-2.5 cel especially in airflow on surface speed.
Especially preferably need not the other mechanical fluid of using the gas except that the gas that is used for inerting to take place, it is undertaken by paddle stirrer, anchor agitator and other whipping appts that is fit to.
Temperature of reaction is lower than the elimination temperature of the corresponding protectiveness radicals X of the silane A on the silica sphere, and preferred 0-200 ℃, preferred 20-100 ℃, more preferred 20-80 ℃, and in a specific embodiment, be 20-40 ℃.
Reaction times is 5 minutes-48 hours, preferred 10 minutes-4 hours.
Randomly, can add protonic solvent, as liquid or transpirable alcohol or water; Typical alcohol is Virahol, ethanol and methyl alcohol.The mixture that also can add above-mentioned protonic solvent.The preferred adding with respect to protonic solvent silica 1-50 weight %, preferred especially 5-25 weight %.Special preferably water.Randomly, can be added on Lewis acid or the Br nsted acid meaning to the tart an acidic catalyst, hydrogenchloride for example, or be alkaline basic catalyst, for example ammonia or amine such as triethylamine on Lewis alkali or Br nsted alkali meaning.Preferred trace adds, and just, add-on is less than 1000ppm.Especially preferably do not add catalyzer.
Preferred cleansing temp is lower than the elimination temperature of the corresponding protectiveness radicals X of the silane A on the silica sphere, and it is 20-200 ℃, is preferably 50-150 ℃, is preferably 50-100 ℃ especially.The purification step preferred feature is to stir, and especially preferably stirs at a slow speed and low-level mixing.Installation that agitation means is favourable and move mode make and mix and the fluidisation generation, but not exclusively form vortex.
The feature of purification step also can be to increase gas and feed, and corresponding superficial gas velocity is preferably the 0.001-10 cel, more preferably the 0.01-1 cel.Can be with not carrying out this step with all rare gas elementes of silane A, silicon-dioxide or alkylation alkali silica reaction, promptly, described rare gas element can not cause second order reaction, DeR, oxidation or burning or explosion phenomenon, preferably as nitrogen, argon gas, other rare gas, carbonic acid gas etc.
In addition, at the mechanical ramming that can the employing method during the silanization or behind the purifying be used for silicon-dioxide, for example pressure roller machine, the grinding equipment such as wheel roller and ball mill, screw or Worm type kneading machine, Worm type compactor, briquetting press or the air or the gas that exist with suitable vacuum method suction and pumping carry out compacting.In addition, in the particularly preferred process, can adopt the method for deagglomeration silicon-dioxide after granules preparation and the purification process, rotating disk peg type runner milling (pinned-disk mill) or mill/sorting equipment for example is as rotating disk peg type runner milling, hammer mill, opposed air-flow runner milling (opposed-jet mill), impact mill or mill/sorting equipment.
The silanization pyrolytic silicon dioxide feature that can be used as particle (P1) less than 100nm, is preferably 5-50nm particularly in its preferred average primary particle diameter.In a preferred embodiment of the present invention, these primary particles can independently not exist usually, but are the part of the big aggregate of diameter 50-1000nm.
In another preferred embodiment of the present invention, particle (P1) is as the starting point of preparation particle (P), it comprises the particle of being made up of silica colloidal or metal oxide, and described particle occurs with dispersion form discussed oxide particle, sub-micron in moisture or anhydrous solvent usually.Wherein, used oxide compound can be the oxide compound of metallic aluminium, titanium, zirconium, tantalum, tungsten, hafnium or tin.Especially preferably use the organic solution of colloidal silica sol.
Can be undertaken by the whole bag of tricks by silica colloidal or preparation of metal oxides particle (P).Yet, preferably by in aqueous sol or organosol, adding silane (A) (suitably the time and the mixture of other silane (S1), silane (S2) or silane (S3)).In the time of suitably, described colloidal sol for example passes through hydrochloric acid or trifluoroacetic acid by acid stable, is perhaps for example stablized by alkalescence by ammoniacal liquor.Usually the temperature of reaction generation is 0-200 ℃, preferred 20-80 ℃, and preferred 20-60 ℃ especially.Reaction times was generally 5 minutes-48 hours, preferred 1-24 hour.Randomly, can add acidity, alkalescence or heavy metal catalyst.The preferred trace that uses less than 1000ppm, yet, more preferably do not add independent catalyzer.
Because silica colloidal or metal oxide sol are generally the form of water or pure dispersion, during preparation particle (P) or afterwards, changing solvent or mixed solvent may be favourable for other solvent or mixed solvent.This can be for example removes original solvents by distillation and finish, can before the distillation, during or add new solvent or mixed solvent by a step or multistep afterwards.Suitable solvent mentioned above can be, for example water; Aromatics or fatty alcohol, preferred aliphat alcohol in this case more preferably contains the fatty alcohol (as the various regional isomers (regioisomer) of methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol and hexanol) of 1-6 carbon atom; Ester (as ethyl acetate, propyl acetate, butylacetate, Diethylene Glycol monobutyl ether acetate, 1-Methoxy-2-propyl acetate); Ketone (as acetone, methylethylketone); Ether (as ether, t-butyl methyl ether, THF); Aromatic solvent (the various regional isomers of toluene, dimethylbenzene and mixture such as solvent naphtha); Lactone (as butyrolactone etc.) or lactan (for example, N-Methyl pyrrolidone).Preferred aprotic solvent and only by or the mixed solvent formed by aprotic solvent to small part.The advantage of aprotic solvent is that any dissolvent residual of staying in the coating is an inert to eliminating the isocyanate functional group who discharges after the protectiveness group in solidification process.Except the preparation particle dispersion, the particle under the separate solid (P) also is possible.
In addition, preparation same and particle (P) is relevant is the silicone resin that preferably uses general formula (IV) as particle (P1):
(R
5 3SiO
1/2)
e(R
5 2SiO
2/2)
f(R
5SiO
3/2)
g(SiO
4/2)
h (IV)
Wherein
R
5Be an OR
1Sense, OH official can, be contained the alkyl non-replacement or that halogen, hydroxyl, amino, epoxy group(ing), thiol group, (methyl) acryl or NCO replace of 1-18 carbon atom,
E is the numerical value more than or equal to 0,
F is the numerical value more than or equal to 0,
G is the numerical value more than or equal to 0,
H is the numerical value more than or equal to 0, and
E+f+g+h is at least 1, preferably is at least 5.
Preferably whole at least R
570 moles of % of base are methyl, ethyl, sec.-propyl or phenyl.
In a preferred embodiment, under the situation of the silicone resin of logical formula V, e+h is at least 90 moles of % of e+f+g+h.
Can be by the aforesaid method silicone resin of general formula (IV) and the particle (P) among silane (A) preparation the present invention.
Another method that preferably prepares particle (P) is not from the particle (P1) of hydroxyl.But the cohydrolysis by silane (A) and other silane (S4) prepares particle (P).Used silane (S4) can be all hydrolyzable silane and the silane that contains the hydroxyl silyl.Also can be with siloxanes or silazane.Preferably use the silane of general formula (III).The representative instance of suitable silane (S4) has tetraethoxysilane, tetramethoxy-silicane, methyltrimethoxy silane, trimethoxy phenol silane (phenoltrimethoxysilane), Union carbide A-162, triethoxy phenolic silanes (phenoltriethoxysilane), dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylammonium methoxy silane or trimethylethoxysilane.Can certainly use the mixture of different silane (S4).Be not only the mixture of the silane (A) that only contains the silane (S4) that has or not other organic functional, and be the mixture that contains the silane (S4) that has or not other organo-functional group and contain the silane (A) of the silane (S4) with other organic functional, all can use in this case.When preparing particle (P) by cohydrolysis, various silane can add jointly and continuously.Another method for preparing particle (P) comprises with the saturated organopolysiloxane resin of silane (A).Cohydrolysis and saturated (equilibration) can carry out in the presence of catalyzer.Be generally used for preparing cohydrolysis and saturation process all descriptions to some extent in many documents of resin.
Among the present invention coating preparation (B1) or (B2) in the other film-forming resin (L) of particle (P) preferably by the prepolymer of hydroxyl, preferred especially polypropylene provided with hydroxyl group acid esters or polyester.Polypropylene provided with hydroxyl group acid esters and polyester that this class is suitable for the coating preparation are well-known for those skilled in the art, and in relative literature description are arranged all.
Similarly; among the present invention coating preparation (B1) or (B2) in coating curing agent (H) also be well-known in the prior art; and in relative literature, describe to some extent, it preferably includes terpolycyantoamino-formaldehyde resin or preferably contains the protected isocyanate groups of eliminating the protectiveness group and discharge isocyanate-functional when thermal treatment.The solidifying agent (H) that wherein especially preferably contains protected isocyanate groups.Usually use common vulcabond and/or the polymeric polyisocyanate that has had each self-protective group for this purpose.The protectiveness group that is fit under this sharp situation is the same with relevant general formula (I) and the protectiveness group HX described in general formula (I) paragraph afterwards, though must be complementary according to the protectiveness group of particle provided by the invention (P) and solidifying agent (H).For isocyanic ester, can use all conventional isocyanic ester of in lot of documents, describing in principle.Common vulcabond is crude product or technical grade MDI form and pure 4 of for example diphenylmethanediisocyanate (MDI), 4 ' and/or 2,4 ' isomer or their form of mixtures, the various regional isomer forms of tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), isophorone diisocyanate (IPDI), perhydro-MDI (H-MDI), tetramethylene diisocyanate, 2-methyl pentamethylene diisocyanate, 2,2, the 4-trimethyl hexamethylene diisocyanate, ten dimethylene diisocyanates, hexanaphthene 1, the 4-vulcabond, 4-methylcyclohexane 1, the 3-vulcabond, or hexamethylene diisocyanate (HDI).The example of polymeric polyisocyanate is the diisocyanate trimer or the biuret tripolymer of poly-MDI (P-MDI), triphenylmethane triisocyanate and all above-mentioned isocyanic ester.In addition, can also use the above-mentioned oligopolymer that has the isocyanic ester of end-blocking NCO group.All two and/polymeric polyisocyanate can use or mix use separately.Preferably to the diisocyanate trimer and the biuret tripolymer of the aliphatic isocyanates of UV stable, the tripolymer of preferred especially HDI and IPDI.
The blocked isocyanate groups of solidifying agent (H) and particle (P) is generally 0.5-2 with respect to the ratio of the isocyanate-reactive group of film-forming resin (L), is preferably 0.8-1.5, is preferably 1.0-1.2 especially.
In addition, coating preparation (B1) or (B2) also may comprise typical conventional solvent and adjuvant and additive in the coating preparation.The example that can mention for described solvent has aromatics and aliphatic hydrocarbon; Ester is as butylacetate, Diethylene Glycol monobutyl ether acetate, ethyl acetate or 1-Methoxy-2-propyl acetate; Ether; Alcohol is as Virahol or isopropylcarbinol; Ketone is as acetone or butyl methyl ketone; And heterocycle, as lactone or lactan.Also having important solvent is water.Water-based paint is special in its low VOC ratio (volatile organic compound) receives much attention.Additive comprises flow control auxiliary agent, surfactant, adhesion promotor, light stabilizer such as uv-absorbing agent and/or free-radical scavengers, thixotropic agent and other solid.In order to produce coating preparation (B1) in all cases or (B2) and the coating material solidified character of wanting, this class adjuvant is normally indispensable.Coating preparation (B1) or (B2) can also comprise pigment.
In the preferable methods, coating preparation of the present invention (B1) or (B2) particle (P) prepares by adding with the form of the dispersion in powder or the appropriate solvent during the married operation process.Yet it is preferred also having the another one method, and wherein initial masterbatch is by particle (P) with by one or more coating composition preparations, and the granule density that masterbatch contains is preferably greater than 25% greater than 15%, is preferably greater than 35% especially.Under the coating preparation (B1) or situation (B2) that prepare like this among the present invention, then described masterbatch is mixed with other coating composition.Masterbatch is by the initial preparation of particle dispersion, if in the process of preparation masterbatch by for example distilation steps or to replace the solvent of removing particle dispersion with different solvents or solvent mixture may be favourable.
Coating preparation (B1) that obtains or the substrate that (B2) can be used for applying any needs are to improve scrath resistance, wearability or chemical resistant properties.Preferred substrate is plastics, and for example polycarbonate, polybutylene terephthalate, polymethylmethacrylate, polystyrene or polyvinyl chloride and other are applied to the coating of prior step.
Special preferred coatings preparation (B1) or (B2) can be used as the Clear coating or the face coat material of scrath resistance more specifically is used for automotive industry.The coating preparation can be by any method of wanting, and the method for for example submergence, spraying and cast applies.The wet method coating also is feasible.Curing is undertaken by heating under the necessary condition of blocked isocyanate, certainly comes acceleration by adding catalyzer.
More than the definition of symbol in all general formulas be independent of each other.Siliciumatom all is a tetravalence in all general formulas.
Except as otherwise noted, all number and percentage numbers all are based on weight, and all pressure is that 0.10MPa (abs.) and all temperature are 20 ℃.
Embodiment
Synthetic embodiment 1: contain the preparation (silane 1) of organoalkoxysilane of the isocyanate groups of butane oxime protection
Get the 2-butane oxime of 74.0g and the Borchi catalyzer of 0.12g (originating from the catalyst V P 0244 of Borchers GmbH) and be heated 80 ℃.The isocyanato Trimethoxy silane (isocyanatotrimethoxysilane) that dropwise added 150.00g in 1 hour then stirred mixture 1 hour under 80 ℃ of temperature.
1H NMR and IR spectrum demonstrate the fully reaction of isocyanato silane.
Synthetic embodiment 2: contain the preparation (silane 2) of organoalkoxysilane of the isocyanate groups of Diisopropylamine protection
Get the Diisopropylamine of 86.0g and the Borchi catalyzer of 0.12g (originating from the catalyst V P 0244 of Borchers GmbH) and be heated 80 ℃.The isocyanato Trimethoxy silane that dropwise added 150.00g in 1 hour then stirred mixture 1 hour under 60 ℃ of temperature.
1H NMR and IR spectrum demonstrate the fully reaction of isocyanato silane.
Synthetic embodiment 3: contain the preparation (silane 3) of organoalkoxysilane of the isocyanate groups of Diisopropylamine protection
((originating from the catalyst V P 0244 of Borchers GmbH) also is heated 80 ℃ to get the Diisopropylamine of 74.5g and the Borchi catalyzer of 0.12g.The 3-isocyanato propyl trimethoxy silicane that dropwise added 150.00g in 1 hour then stirred mixture 1 hour under 60 ℃ of temperature.
1H NMR and IR spectrum demonstrate the fully reaction of isocyanato silane.
Synthetic embodiment 4: use the preparation of the pyrolytic silicon dioxide of the end capped isocyanate groups modification of butane oxime
At 25 ℃ of temperature and N
2Moisture content with 100g under the inert atmosphere is lower than 1%, HCl content is lower than 100ppm and specific surface area is 300m
2/ g (the BET method according to DIN 66131 and 66132 is measured) is (commercially available from Wacker-Chemie GmbH; Munich; D; commodity are called WACKER HDK T30) pyrolysis wetting ability silicon-dioxide, isocyanato silane and the 10ml water protected through the single fluid nozzle (pressure: 5 crust) and the butane oxime of the description in synthetic embodiment 1 (silane 1) of 70g mix with the form of high dispersing.Then at N
2With silicon-dioxide in the fluidisation institute load under 25 ℃ of temperature 2 hours, then at N
2Under 80 ℃ of temperature, reaction is 2 hours in the loft drier of 100l.Obtain containing the white SiO 2 powder (KP-1) of silylating reagent homogeneous layer.
Synthetic embodiment 5: contain the preparation of the pyrolytic silicon dioxide of the end capped isocyanate groups of Diisopropylamine
At 25 ℃ of temperature and N
2Moisture content with 100g under the inert atmosphere is lower than 1%, HCl content is lower than 100ppm and specific surface area is 300m
2/ g (the BET method according to DIN 66131 and 66132 is measured) is (commercially available from Wacker-Chemie GmbH; Munich; D; commodity are called WACKER HDK T30) pyrolysis wetting ability silicon-dioxide, isocyanato silane and the 10ml water protected through the single fluid nozzle (pressure: 5 crust) and the Diisopropylamine of the description in synthetic embodiment 2 (silane 2) of 70g mix with the form of high dispersing.Then at N
2With silicon-dioxide in the fluidisation institute load under 25 ℃ of temperature 2 hours, then at N
2Under 80 ℃ of temperature, reaction is 2 hours in the loft drier of 100l.Obtain containing the white SiO 2 powder (KP-2) of silylating reagent homogeneous layer.
Synthetic embodiment 6: with the SiO of the end capped isocyanate groups modification of butane oxime
2The preparation of Nano sol particulate
The isocyanato silane (silane 1) that the butane oxime according to synthetic embodiment 1 preparation of 1.33g is protected is dissolved in the Virahol of 1g.Then, the SiO that in 30 minutes, dropwise adds 20g
2Organosol (IPA-ST, from Nissan Chemicals, 30 weight %SiO
2, median size 12nm), and adjust pH to 3.5 with trifluoroacetic acid.Stirred 3 hours under 60 ℃ of temperature dispersions obtained, at room temperature stirred then 18 hours.Add the 18.0g 1-Methoxy-2-propyl acetate then.This mixture is stirred several minutes under 70 ℃ of temperature, distill out most of Virahol then.That is to say, continue distillation and be concentrated to 28.0 grams until nano particle colloidal sol.
The solid content of the dispersion that obtains is 26.2%.SiO
2Content is 21.4%, and the amount of protected isocyanate groups is 0.18mmol/g in the dispersion.This dispersion is slightly muddy and demonstrate Tyndall effect.
Synthetic embodiment 7: with the SiO of the end capped isocyanate groups modification of Diisopropylamine
2The preparation of Nano sol particulate
The isocyanato silane (silane 2) that the butane oxime according to synthetic embodiment 2 preparations of 1.40g is protected is dissolved in the Virahol of 1g.Then, the SiO that in 30 minutes, dropwise adds 20g
2Organosol (IPA-ST, from Nissan Chemicals, 30 weight %SiO
2, median size 12nm), and adjust pH to 3.5 with trifluoroacetic acid.Stirred 3 hours under 60 ℃ of temperature dispersions obtained, at room temperature stirred then 18 hours.Add the 18.1g 1-Methoxy-2-propyl acetate then.This mixture is stirred several minutes under 70 ℃ of temperature, distill out most of Virahol then.That is to say, continue distillation and be concentrated to 29.4 grams until nano particle colloidal sol.
The solid content of the dispersion that obtains is 25.5%.SiO
2Content is 20.8%, and the amount of protected isocyanate groups is 0.17mmol/g in the dispersion.This dispersion is slightly muddy and demonstrate Tyndall effect.
Synthetic embodiment 8: with the SiO of the end capped isocyanate groups modification of Diisopropylamine
2The preparation of Nano sol particulate
Get the isocyanato silane (silane 3) of 1.54g according to the Diisopropylamine protection of synthesizing embodiment 3 preparations.Then, the SiO that in 30 minutes, dropwise adds 20g
2Organosol (IPA-ST, from Nissan Chemicals, 30 weight %SiO
2, median size 12nm), and adjust pH to 3.0 with trifluoroacetic acid.Stirred 3 hours under 60 ℃ of temperature dispersions obtained, at room temperature stirred then 24 hours.
SiO
2Content is 27.9%, and the amount of protected isocyanate groups is 0.23mmol/g in the dispersion.This dispersion is slightly muddy and demonstrate Tyndall effect.
Embodiment 1: comprise solidifying agent with the end capped isocyanate groups of butane oxime and by the preparation of the onepot coating preparation of the pyrolytic silicon dioxide of the end capped isocyanate groups modification of Diisopropylamine
In order to prepare coating preparation of the present invention, the Desmophen A365 BA/X from Bayer (the acrylate-based coating polyvalent alcohol of hydroxy radical content 1.71mmol OH/g) of 8.56g and the Desmodur BL3175 SN from Bayer (the end capped polymeric polyisocyanate of butane oxime, end-blocking NCO content about 11%) of 6.33g are mixed.This is 1.1: 1 corresponding to protected isocyanate-functional to the mol ratio of oh group.And, the concentration of sneaking into 0.05g is 50% dibutyl tin laurate solution (in methyl ethyl ketone) and the ADDID 100 from TEGO AG (based on the flow control auxiliary agent of polydimethylsiloxane) of 0.01g and the methyl ethyl ketone of 3.15g, obtains solid content and is about 50% coating preparation.
1.8g is mixed in the resulting mixture by dissolver by the pyrolytic silicon dioxide with the end capped isocyanate groups of Diisopropylamine (KP-2) modification that synthetic embodiment 5 obtains, obtain the Clear paint preparation.
Comparative Examples 1 (non-invention): comprise solidifying agent and by the preparation of the onepot coating preparation of the pyrolytic silicon dioxide of the end capped isocyanate groups modification of butane oxime with the end capped isocyanate groups of butane oxime
In order to prepare contrast coating, Desmophen A 365 BA/X from Bayer (the acrylate-based coating polyvalent alcohol of hydroxy radical content 1.71mmol OH/g) of 8.56g and the Desmodur BL3175 SN from Bayer (the end capped polymeric polyisocyanate of butane oxime, end-blocking NCO content about 11%) of 6.33g are mixed.This is 1.1: 1 corresponding to protected isocyanate-functional to the mol ratio of oh group.And, the concentration of sneaking into 0.05g is 50% dibutyl tin laurate solution (in methyl ethyl ketone) and the ADDID 100 from TEGO AG (based on the flow control auxiliary agent of polydimethylsiloxane) of 0.01g and the methyl ethyl ketone of 3.15g, obtains solid content and is about 50% coating preparation.
1.8g is mixed in the resulting mixture by dissolver by the pyrolytic silicon dioxide with the end capped isocyanate groups of butane oxime (KP-1) modification that synthetic embodiment 4 obtains, obtain the Clear paint preparation.
The preparation and the evaluation of the paint film in embodiment 1 and the Comparative Examples 1
Employing from Erichsen, have the Coatmaster 509MC membrane equipment that slit height is the scraper of 100 μ m, with the coating preparation in embodiment 1 and the Comparative Examples 1 respectively blade coating on sheet glass.Then with the paint film that obtains in air dry oven under 160 ℃ of temperature dry 30 minutes.The coating that obtains from the coating preparation of embodiment and Comparative Examples visually all is smooth flawless.Use the glossiness of measuring coating from 20 ° of glossmeters of Micro gloss of Byk, find to be about 144 gloss unit, and be about 131 gloss unit for the coating preparation of Comparative Examples 1 for the coating preparation coating gloss of embodiment 1.
Measure the scrath resistance of prepared curing coating film with Peter-Dahn wear testing instrument.For this reason, with the area of heavy 500g be the Scotch Brite 2297 non-woven emery cloths scrapings 50 times of 45 * 45mm.Before scraping experiment beginning and after finishing, use the glossiness of measuring coating from 20 ° of glossmeters of Micro gloss of Byk respectively.Determine with respect to the loss of initial value glossiness as the measurement result of coating scrath resistance separately:
| Coating sample | The loss of glossiness |
| Embodiment 1 | 22％ |
| Comparative Examples 1 * | 55％ |
The loss of glossiness in the table 1:Peter-Dahn scraping experiment
*Non-invention
Embodiment 2: comprise the solidifying agent of the end capped isocyanate groups of butane oxime and by the SiO of the end capped isocyanate groups modification of Diisopropylamine
2The preparation of Nano sol particulate onepot coating preparation
In order to prepare coating preparation of the present invention, with the 4.50g solid content is that 52.4 weight %, oh group content are that 1.46mmol/g resin solution, acid number are the many alcohol of the acrylate-based coating (solvent: solvent naphtha of 10-15mg KOH/g, 1-Methoxy-2-propyl acetate (10: 1)) the Desmodur BL3175 SN from Bayer (the end capped polymeric polyisocyanate of butane oxime, end-blocking NCO content 2.64mmol/g) with 2.69g mixes.Add the SiO that contain useful Diisopropylamine end capped isocyanate groups modification of 0.76g subsequently according to synthetic embodiment 7 preparations
2Nano sol particulate dispersion.This is 1.1: 1 corresponding to protected isocyanate-functional to the mol ratio of oh group.And, sneak into the dibutyl tin laurate of 0.01g and 0.03g concentration and be the aqueous isopropanol of 10% the ADDID 100 from TEGO AG (based on the flow control auxiliary agent of polydimethylsiloxane), obtain solid content and be about 50% coating preparation.This mixture is still muddy slightly at first, stirs after 48 hours under the room temperature, obtains transparent coating preparation.
Embodiment 3: comprise the solidifying agent that contains the end capped isocyanate groups of butane oxime and by the SiO of the end capped isocyanate groups modification of Diisopropylamine
2The preparation of Nano sol particulate onepot coating preparation
In order to prepare coating preparation of the present invention, with the 4.50g solid content is 52.4 weight % (solvents: solvent naphtha, 1-Methoxy-2-propyl acetate (10: 1)), oh group content is that 1.46mmol/g, acid number are the Desmodur BL3175 SN from Bayer (the end capped polymeric polyisocyanate of butane oxime, the end-blocking NCO content 2.64mmol/g) mixing of the many alcohol of acrylate-based coating with the 2.60g of 10.15mg KOH/g.Add the SiO that contain useful Diisopropylamine end capped isocyanate groups modification of 2.11g subsequently according to synthetic embodiment 7 preparations
2Nano sol particulate dispersion.This is 1.1: 1 corresponding to protected isocyanate-functional to the mol ratio of oh group.And, sneak into the dibutyl tin laurate of 0.01g and 0.03g concentration and be the aqueous isopropanol of 10% the ADDID 100 from TEGO AG (based on the flow control auxiliary agent of polydimethylsiloxane), obtain solid content and be about 50% coating preparation.This mixture is still muddy slightly at first, stirs after 48 hours under the room temperature, obtains transparent coating preparation.
Embodiment 4: comprise the solidifying agent of the end capped isocyanate groups of butane oxime and by the SiO of the end capped isocyanate groups modification of Diisopropylamine
2The preparation of Nano sol particulate onepot coating preparation
In order to prepare coating preparation of the present invention, with the 4.50g solid content is 52.4 weight % (solvents: solvent naphtha, 1-Methoxy-2-propyl acetate (10: 1)), oh group content is that 1.46mmol/g, acid number are the Desmodur BL3175 SN from Bayer (the end capped polymeric polyisocyanate of butane oxime, the end-blocking NCO content 2.64mmol/g) mixing of the many alcohol of acrylate-based coating with the 2.69g of 10-15mg KOH/g.Add the SiO that contain useful Diisopropylamine end capped isocyanate groups modification of 0.57g subsequently according to synthetic embodiment 8 preparations
2Nano sol particulate dispersion.This is 1.1: 1 corresponding to protected isocyanate-functional to the mol ratio of oh group.And, sneak into 0.05g concentration and be 50% dibutyl tin laurate (in methyl ethyl ketone) and 0.01g from the ADDID 100 (based on the flow control auxiliary agent of polydimethylsiloxane) of TEGO AG, obtain solid content and be about 50% coating preparation.This mixture is still muddy slightly at first, stirs after 24 hours under the room temperature, obtains transparent coating preparation.
Comparative Examples 2 (non-invention): comprise the solidifying agent of the end capped isocyanate groups of butane oxime and by the SiO of the end capped isocyanate groups modification of butane oxime
2The preparation of Nano sol particulate onepot coating preparation
In order to prepare coating, with the 4.50g solid content is 52.4 weight % (solvents: solvent naphtha, 1-Methoxy-2-propyl acetate (10: 1)), oh group content is that 1.46mmol/g, acid number are the Desmodur BL3175SN from Bayer (the end capped polymeric polyisocyanate of butane oxime, the end-blocking NCO content 2.64mmol/g) mixing of the many alcohol of acrylate-based coating with the 2.69g of 10-15mgKOH/g.Add the SiO that contain useful butane oxime end capped isocyanate groups modification of 0.75g subsequently according to synthetic embodiment 6 preparations
2Nano sol particulate dispersion.This is 1.1: 1 corresponding to protected isocyanate-functional to the mol ratio of oh group.And, sneak into 0.05g concentration and be 50% dibutyl tin laurate (in methyl ethyl ketone) and 0.01g from the ADDID 100 (based on the flow control auxiliary agent of polydimethylsiloxane) of TEGO AG, obtain solid content and be about 50% coating preparation.This mixture is still muddy slightly at first, stirs after 24 hours under the room temperature, obtains transparent coating preparation.
The preparation of the paint film of embodiment 2-4 and Comparative Examples 2 and 3 and evaluation
The Coatmaster 509MC membrane equipment that slit height is the scraper of 120 μ m that has of Erichsen is originated from employing, and the coating preparation in embodiment 2-4 and Comparative Examples 2 and 3 is distinguished blade coating on sheet glass.Then with the paint film that obtains in air dry oven under 70 ℃ of temperature dry 30 minutes, then under 150 ℃ of temperature dry 30 minutes.The coating that obtains from the coating preparation of embodiment and Comparative Examples visually all is smooth flawless.Use the glossiness of measuring coating from 20 ° of glossmeters of Micro gloss of Byk, be the 160-164 gloss unit for all the coating preparation glossiness in embodiment 2-4 and Comparative Examples 1 and 2.
Measure the scrath resistance of prepared curing coating film with the Peter-Dahn abrasion meter.For this reason, with the areas of heavy 500 grams be the non-woven emery cloths scraping of Scotch Brite 2297 samples 40 times of 45 * 45mm.Before scraping experiment beginning and after finishing, use the glossiness of measuring coating from 20 ° of glossmeters of Micro gloss of Byk respectively.Determine with respect to the loss of initial value glossiness as the scrath resistance measurement result of coating separately:
| Coating sample | The loss of glossiness |
| Embodiment 2 | 28％ |
| Embodiment 3 | 24％ |
| Embodiment 4 | 30％ |
| Comparative Examples 2 * | 54％ |
The loss of glossiness in the table 1:Peter-Dahn scraping experiment
*Non-invention
Claims (12)
1. coating preparation (B1), it comprises following component:
A) based on the film-forming resin that contains reactive group (L) of the 20-90 weight % of solid part,
B) based on the coating curing agent that contains reactive functional (H) of the 1-90 weight % of solid part, by this reactive functional, coating curing agent when thermal treatment and the reaction-ity group reaction of film-forming resin (L) make paint solidification,
C) based on the particle (P) of the 0.1-40 % by weight of solid portion; It comprises by the former molecular nuclear that is selected from metallic atom, silicon atom and oxygen atom; Or the nuclear that is formed by silicones; Described particle (P) has at least one protected isocyanate groups on its surface; Thereby this group is eliminated the protectiveness group through heat treatment and is discharged isocyanate-functional; Surpass 50% protected isocyanate groups with the elimination temperature of protectiveness group be lower than the temperature of the functional group reactions of the functional group of film-forming resin (L) and curing agent (H)
D) based on the solvent of the 0-90 weight % of whole coating preparations (B1) or solvent mixture and
E) if desired, other coating composition and additive.
2. the coating preparation (B1) of claim 1, it comprises following component:
A) based on the hydroxyl-functional film-forming resin (L) of the 20-90 weight % of solid part,
B) based on the coating curing agent that contains protected isocyanate groups (H) of the 1-90 weight % of solid part, described isocyanate groups is eliminated the protectiveness group and is discharged the isocyanate functional group through Overheating Treatment,
C) based on the particle (P) of the 0.1-40 % by weight of solid portion; It comprises by the former molecular nuclear that is selected from metallic atom, silicon atom and oxygen atom; Or the nuclear that is formed by silicones; Described particle (P) has at least one protected isocyanate groups on its surface; Thereby this group is eliminated the protectiveness group through heat treatment and is discharged isocyanate-functional; Surpass 50% protected isocyanate groups with the protectiveness group its eliminate the elimination temperature that temperature is lower than in the curing agent (H) the protectiveness group of at least 55% protected isocyanate groups
D) based on the solvent of the 0-90 weight % of whole coating preparations (B1) or solvent mixture and
E) if desired, other coating composition and additive.
3. coating preparation (B2), it comprises following component:
A) based on the film-forming resin that contains reactive group (L) of the 20-90 weight % of solid part,
B) based on the coating curing agent that contains reactive functional (H) of the 1-90 weight % of solid part, by this reactive functional, the reaction-ity group reaction of coating curing agent and film-forming resin (L) makes paint solidification when thermal treatment,
C) based on the particle (P) of the 0.1-40 weight % of solid part; it comprises the nuclear of being made up of the atom that is selected from atoms metal, Siliciumatom and Sauerstoffatom; or the nuclear of forming by silicone resin; described particle (P) has at least one protected isocyanate groups on its surface; this group can be eliminated the protectiveness group and discharge isocyanate-functional through thermal treatment; the elimination temperature that surpasses the protectiveness group that 50% protected isocyanate groups has in the particle (P) is lower than the butane oxime
D) based on the solvent of the 0-90 weight % of whole coating preparations (B2) or solvent mixture and
E) if desired, other coating composition and additive.
4. the coating preparation (B2) of claim 3, it comprises following component:
A) based on the hydroxyl-functional film-forming resin (L) of the 20-90 weight % of solid part,
B) based on the coating curing agent that contains protected isocyanate groups (H) of the 1-90 weight % of solid part, described protected isocyanate groups is eliminated the protectiveness group and is discharged isocyanate-functional through Overheating Treatment,
C) based on the particle (P) of the 0.1-40 weight % of solid part; it comprises the nuclear of being made up of the atom that is selected from atoms metal, Siliciumatom and Sauerstoffatom; or the nuclear of forming by silicone resin; described particle (P) has at least one protected isocyanate groups on its surface; this group can be eliminated the protectiveness group and discharge isocyanate-functional through thermal treatment; the elimination temperature that surpasses the protectiveness group that 50% protected isocyanate groups has in the particle is lower than the butane oxime
D) based on the solvent of the 0-90 weight % of whole coating preparations (B1) or solvent mixture and
E) if desired, other coating composition and additive.
5. the coating preparation (B1) of one of claim 1-4 or (B2), it comprises following component:
A) based on the film-forming resin (L) of the 30-80 weight % of solid part,
B) based on the coating curing agent (H) of the 10-60 weight % of solid part,
C) based on the particle (P) of the 0.5-30 weight % of solid part,
D) based on one or more solvents of whole coating preparations (B1) or 0-80 weight % (B2) and
E) if desired, other coating composition and additive.
6. the coating preparation (B1) of one of claim 1-5 or (B2); wherein particle (P) is by particle (P1) and organosilane (A) reaction are made; described particle (P1) is formed or is made up of silicone resin by the atom that is selected from atoms metal, Siliciumatom, Sauerstoffatom; and have the free hydroxyl official can; described organosilane (A): a) contain at least one hydrolyzable silyl functional or at least one hydroxyl silyl, and b) contains at least one protected isocyanate groups.
7. the coating preparation (B1) of one of claim 1-6 or (B2), wherein use the organosilane (A) of following general formula (I):
(R
1O)
3-n(R
2)
nSi-A-NH-C(O)-X (I)
Wherein
R
1For hydrogen, all contain alkyl, cycloalkyl or the aryl of 1-6 carbon atom, carbochain can be by non-conterminous oxygen, sulphur or NR
3Group interrupts,
R
2Be alkyl, cycloalkyl, the aryl or aralkyl that all contains 1-12 carbon atom, carbochain can be by non-conterminous oxygen, sulphur or NR
3Group interrupts,
R
3Be hydrogen, alkyl, cycloalkyl, aryl, aralkyl, aminoalkyl group or aspartate acid ester radical,
X is the protectiveness group, and it is eliminated with the HX form under 60-300 ℃ of temperature, and discharges isocyanate-functional in this process,
A representative contain 1-10 carbon atom difunctionality alkyl, cycloalkyl or aryl and
The value of n is 0,1 or 2.
8. the coating preparation (B1) of one of claim 1-6 or (B2), wherein use the organosilane (A) of following general formula (II):
(R
1O)
3-n(R
2)
nSi-A-NR
3-C (O)-NH-Y-(NH-C (O)-X)
z(II) wherein
R
1, R
2, R
3, A, X and n be with the definition of mutual-through type in the claim 6 (I),
Y be (z+1)-functional aliphatics or aromatic group and
Z is digital 1-4, is preferably 1 or 2.
9. the coating preparation (B1) of one of claim 6-8 or (B2), wherein particle (P1) mixed oxide, titanium oxide, zirconium white, ferric oxide, silicon oxide and some the silicon valencys that are selected from aluminum oxide, aluminium and other metal and/or silicon carries the silicon oxide compounds of organic radical.
10. the coating preparation (B1) of one of claim 6-8 or (B2), wherein with the silicone resin of following general formula (IV) as particle (P1):
(R
5 3SiO
1/2)
e(R
5 2SiO
2/2)
f(R
5SiO
3/2)
g(SiO
4/2)
h(IV) wherein
R
5Be OR
1Sense, hydroxyl-functional, contain the alkyl non-replacement or that halogen, hydroxyl, amino, epoxy group(ing), thiol group, (methyl) acryl or NCO replace of 1-18 carbon atom,
E is the numerical value more than or equal to 0,
F is the numerical value more than or equal to 0,
G is the numerical value more than or equal to 0,
H is at least more than or equal to 0 numerical value and e+f+g+h.
11. the coating preparation (B1) of one of claim 1-10 or (B2), wherein the end capped isocyanate groups of solidifying agent (H) and particle (P) is 0.5-2 to the ratio of the isocyanate-reactive group of film-forming resin (L).
12. the coating preparation (B1) of one of claim 1-11 or (B2) as the purposes of scrath resistance Clear coating or face coat material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005006187.7 | 2005-02-10 | ||
| DE102005006187 | 2005-02-10 | ||
| DE102005026699.1 | 2005-06-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101115812A true CN101115812A (en) | 2008-01-30 |
Family
ID=39023447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800045311A Pending CN101115812A (en) | 2005-02-10 | 2006-02-02 | Varnish containing particles with protected isocyanate groups |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101115812A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909318A (en) * | 2020-08-21 | 2020-11-10 | 万华化学集团股份有限公司 | Alkyl silyl ether modified hydroxy acrylic emulsion, preparation method and application |
| CN116851627A (en) * | 2023-07-14 | 2023-10-10 | 东亚科技(苏州)有限公司 | Adhesive for cast aluminum resin and coating for cast aluminum resin sand mold |
-
2006
- 2006-02-02 CN CNA2006800045311A patent/CN101115812A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909318A (en) * | 2020-08-21 | 2020-11-10 | 万华化学集团股份有限公司 | Alkyl silyl ether modified hydroxy acrylic emulsion, preparation method and application |
| CN111909318B (en) * | 2020-08-21 | 2022-07-12 | 万华化学集团股份有限公司 | Alkyl silyl ether modified hydroxy acrylic emulsion, preparation method and application |
| CN116851627A (en) * | 2023-07-14 | 2023-10-10 | 东亚科技(苏州)有限公司 | Adhesive for cast aluminum resin and coating for cast aluminum resin sand mold |
| CN116851627B (en) * | 2023-07-14 | 2024-04-12 | 东亚科技(苏州)有限公司 | Coating for cast aluminum resin sand mold |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101248131B (en) | Paints comprising particles | |
| CN101006116B (en) | Particles with protected isocyanate groups | |
| CN101993521B (en) | Curable material comprising silylated polymers containing urethane groups, and use thereof in sealants and binders | |
| CN101182378A (en) | Nanoparticle Modified Polyisocyanates | |
| CN103180376A (en) | Polyurethane coating composition, multilayer surface coatings having a matt surface produced therefrom and processes for producing the multilayer surface coatings | |
| CN101168631A (en) | Film-forming binders containing nanoscale particles and featuring enhanced scratch resistance and flexibility, processes for their preparation, and high-transparency coating materials containing them | |
| KR20070104460A (en) | Lacquers containing particles with protected isocyanate groups | |
| CN101855265A (en) | Nanoparticle Modified Polyisocyanates | |
| JP5038910B2 (en) | Paint containing particles having a protected isocyanate group | |
| CN101228239A (en) | Paints containing particles | |
| CN101228225A (en) | Particle-containing coats | |
| CN101115812A (en) | Varnish containing particles with protected isocyanate groups | |
| CN101522777A (en) | Compositions containing phosphonate-functional particles | |
| DE102005026699A1 (en) | Coating formulation, useful as scratch-proof clear- or finish coatings, comprises varnish resin; varnish hardener; particles containing core consisting of atoms (e.g. metal); solvent; and optionally, varnish components and additives | |
| CN101115806A (en) | Lacquers containing particles with protected isocyanate groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080130 |