CN108192488A - Solvent-type double-component, the clear coat composition of high slipping, Preparation method and use - Google Patents
Solvent-type double-component, the clear coat composition of high slipping, Preparation method and use Download PDFInfo
- Publication number
- CN108192488A CN108192488A CN201711482302.7A CN201711482302A CN108192488A CN 108192488 A CN108192488 A CN 108192488A CN 201711482302 A CN201711482302 A CN 201711482302A CN 108192488 A CN108192488 A CN 108192488A
- Authority
- CN
- China
- Prior art keywords
- solvent
- component
- borne
- varnish composition
- isocyanate
- 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.)
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Links
- 239000000203 mixture Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims description 32
- -1 polysiloxanes Polymers 0.000 claims abstract description 245
- 239000002904 solvent Substances 0.000 claims abstract description 164
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 126
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 114
- 238000006243 chemical reaction Methods 0.000 claims abstract description 113
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000012948 isocyanate Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 62
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 54
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 29
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 18
- 229920003180 amino resin Polymers 0.000 claims abstract description 18
- 239000004645 polyester resin Substances 0.000 claims abstract description 18
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 17
- 229920001225 polyester resin Polymers 0.000 claims abstract description 17
- 238000000518 rheometry Methods 0.000 claims abstract description 7
- 239000002966 varnish Substances 0.000 claims description 131
- 238000000576 coating method Methods 0.000 claims description 99
- 239000011248 coating agent Substances 0.000 claims description 92
- 239000003973 paint Substances 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000003921 oil Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- 239000002981 blocking agent Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 16
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 16
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 16
- 230000000903 blocking effect Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000003495 polar organic solvent Substances 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 12
- VLQZJOLYNOGECD-UHFFFAOYSA-N 2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[SiH]1O[SiH](C)O[SiH](C)O1 VLQZJOLYNOGECD-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 12
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- 239000000113 methacrylic resin Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000008096 xylene Substances 0.000 claims description 12
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000013638 trimer Substances 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- 238000010276 construction Methods 0.000 claims description 9
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- 239000005046 Chlorosilane Substances 0.000 claims description 7
- 230000001588 bifunctional effect Effects 0.000 claims description 7
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 7
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical class O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012974 tin catalyst Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 6
- BYVKCQBOHJQWIO-UHFFFAOYSA-N 2-ethoxyethyl propanoate Chemical compound CCOCCOC(=O)CC BYVKCQBOHJQWIO-UHFFFAOYSA-N 0.000 claims description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 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 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- 229940072049 amyl acetate Drugs 0.000 claims description 6
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 claims description 4
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 claims description 4
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 claims description 4
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 claims description 4
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 claims description 4
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical group O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 4
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 4
- OUJCKESIGPLCRN-UHFFFAOYSA-N 1,5-diisocyanato-2,2-dimethylpentane Chemical group O=C=NCC(C)(C)CCCN=C=O OUJCKESIGPLCRN-UHFFFAOYSA-N 0.000 claims description 4
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical group O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 claims description 4
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 4
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- DLSOILHAKCBARI-UHFFFAOYSA-N n-benzyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NCC1=CC=CC=C1 DLSOILHAKCBARI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 3
- 150000002431 hydrogen Chemical class 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 125000002751 aliphatic alkane group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 150000002596 lactones Chemical class 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000012748 slip agent Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920003270 Cymel® Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- NNFQRKIZFSEFMX-UHFFFAOYSA-N hex-5-enoxy(trimethyl)silane Chemical compound C[Si](C)(C)OCCCCC=C NNFQRKIZFSEFMX-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- MNMVKGDEKPPREK-UHFFFAOYSA-N trimethyl(prop-2-enoxy)silane Chemical compound C[Si](C)(C)OCC=C MNMVKGDEKPPREK-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- FPKBPEZUIZNIJF-UHFFFAOYSA-N CC(C)(CCCCCC=O)N=O Chemical compound CC(C)(CCCCCC=O)N=O FPKBPEZUIZNIJF-UHFFFAOYSA-N 0.000 description 1
- 229920003275 CYMEL® 325 Polymers 0.000 description 1
- 229920003276 CYMEL® NF 2000 Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ZHVVREFXHSWVQF-UHFFFAOYSA-N lithium dimethyl(oxido)silane Chemical compound [Li+].C[SiH](C)[O-] ZHVVREFXHSWVQF-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
- C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of solvent-type double-component, the clear coat composition of high slipping, including：Component A includes：Hydroxylated acrylic resin or hydroxy resin, hydroxy polyester resin, amino resins, rheology control agent, Polycaprolactone modified polysiloxanes, auxiliary agent and the first solvent；Component B includes：It is that polyfunctionality aliphatic isocyanates, and/or polyfunctionality alicyclic isocyanate, and/or part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for polyfunctionality aliphatic and or alicyclic isocyanate；Wherein, curing reaction is participated in baking process for the sealer of blocked isocyanate group or sealer for blocked isocyanate group is sloughed in baking process and releases isocyanate groups, the second solvent again.The solvent-type double-component of the present invention, the clear coat composition of high slipping can effectively improve the slipping of clear coat composition film coated surface, so as to increase the rub resistance of film.
Description
Technical Field
The invention belongs to the technical field of paint preparation, and relates to a varnish composition, a preparation method and application thereof, in particular to a solvent type bi-component high-smoothness varnish composition and a preparation method thereof, and an application method of the solvent type bi-component high-smoothness varnish composition which is coated on a substrate according to different construction processes to form a cured coating or prepare a multi-coating finishing system.
Background
At present, automobiles are the most common daily tool for riding instead of walk for people, and the automobiles are gradually deepened into every family. With the increasing demand of automobiles, the demands for appearance and performance of automobiles are also increasing. The automobile body can be endowed with excellent appearance by spraying automobile paint, and various performances of the automobile body can be improved. In order to keep the car body clean, the car is often sent to a washing shop for washing in daily life. During the washing process, the hard brush and cleaning agent of different materials can act on the surface of the varnish coating film, and the appearance of the varnish coating film can be influenced to a greater or lesser extent, such as: the hard brush can scratch the surface of the varnish coating film in the process of brushing and rubbing, thereby influencing the surface gloss and the flatness of the varnish coating film. In order to improve the abrasion resistance of a varnish coating film, the abrasion resistance of the coating film is generally improved by adjusting the amount of a curing agent used in the varnish composition to increase the crosslinking density and hardness of the coating film; however, if the crosslinking density and hardness of the coating film are increased, negative effects such as: with the continuous increase of the hardness of the paint film, the flexibility of the paint film is gradually reduced, and the impact resistance and the cup-bursting property of the paint film are deteriorated. In recent years, it has been reported that when nanoparticles are added to a varnish composition, the nanoparticles can help to improve the abrasion resistance of a varnish coating film without affecting the performance of the coating film, but the high cost of the nanoparticles also restricts the application of the nanoparticles to the varnish composition.
The organic silicon is an organic polymer containing a large number of repeated Si-O-Si units, the main chain of the organic silicon is very flexible, and the intermolecular action force is much weaker than that of a hydrocarbon compound, so that the organic silicon has the characteristics of weak surface tension, small surface energy, strong film forming capability and the like, and therefore, when the organic silicon polymer is added into a varnish composition, the smoothness of the surface of a varnish coating film can be improved, the surface tension and the friction of the coating film are reduced, and the coating film is endowed with good friction resistance.
US6387519, US6803408, US2003207985 and world patent WO0109261 disclose a process for the preparation of curable varnish compositions capable of improving abrasion resistance. The varnish composition contains nanoparticles prepared from silicone and, when applied to multicoat finish systems, retains good abrasion resistance after prolonged weathering attack.
U.S. Pat. Nos. 8569438, 8679589 and 8805 disclose varnish compositions having high abrasion resistance and weathering stability. The varnish composition consists of a hydroxyl-containing component A, an isocyanate-containing component B and a phosphorus-containing catalyst component which can be used for catalyzing silane groups to carry out crosslinking.
U.S. patent US2002042471 discloses a two-component solvent-based, heat-curable varnish composition having both good abrasion resistance and acid rain resistance, consisting of a polyhydroxy polymer component and a curing agent component. The isocyanate curing agent used in the composition comprises an aliphatic and/or cycloaliphatic polyisocyanate having an isocyanate functionality of at least 2 to 6, about 0.1% to 95% of the isocyanate groups of which are reacted with an N-alkyl-3-aminopropyltrialkoxysilane and/or an N-acyl-3-aminopropyltrialkoxysilane.
U.S. patent US20060217472 discloses a coating composition containing a hydroxyacrylic acid, a low molecular weight polyol component, a polyisocyanate, and an aminoalkoxysilane component. The coating composition can be used as an automotive varnish in a paint/varnish system to impart abrasion resistance to the varnish coating.
World patent WO2006042585 discloses a varnish composition suitable for automotive finishes. The main base component of the varnish composition contains silane-modified polyisocyanate, wherein: more than 90 percent of isocyanate groups in the polyisocyanate react with the bis-alkoxy-silicon-based amine, and the varnish composition has excellent friction resistance and high chemical resistance and weather resistance.
European patent EP1273640 discloses a two-component varnish composition suitable for automobile finishing. The composition is composed of a polyol polymer component and a curing agent component consisting of an aliphatic and/or alicyclic polyisocyanate, wherein: 0.1 to 95 percent of isocyanate groups in the curing agent component react with the bis-alkoxy silicon-based amine. However, when the varnish composition is used for automobile coating, the coating film after being fully cured has good abrasion resistance under the influence of the external environment.
The above patent documents mention that silicone is used for improving the abrasion resistance of a coating film of a varnish composition, and the silicone component for improving the coating film performance is mainly a small-molecular reaction-type group-containing alkylsilane. By means of reactive groups contained in the silane, for example: and (2) reacting amino and hydroxyl with isocyanate to obtain partially or completely blocked silane modified isocyanate, and using the isocyanate as a curing agent component to prepare the two-component varnish.
U.S. Pat. No. 4,430,413 discloses a method for preparing polycaprolactone-polysiloxane block copolymers according to the relevant description in the examples, epsilon-caprolactone and linear α, omega-modified siloxanes were used to prepare the relevant block copolymers, which can be used as surface modifiers for other polymers.
US8729207 discloses a process for the preparation of a novel polycaprolactone-polysiloxane block copolymer. The copolymer contains polysubstituted lactone monomer units, and can be used as an additive in the field of coatings.
US2008255317 discloses a method for preparing a polyester-polysiloxane copolymer. When the main component of the copolymer is a polyester block, the copolymer can be used for intermediate or surface coating of vehicles and also as an additive for various coatings to enhance surface properties, as described in connection with the description, for example: weather resistance, air permeability, abrasion resistance, slip, and the like.
Yilgor et al disclose a method for preparing a novel polycaprolactone-polysiloxane-oxazoline triblock copolymer. The ternary block copolymer can be used as an auxiliary agent for surface modification and modification. The specific content is described in detail as follows: [ "novel triblock siloxane copolymers: synthesis, characterization and application as surface modification aids, journal of polymer science: polymer chemistry, 27 th 1989, P3673～3690。(“Novel TriblockSiloxane Copolymers:Synthesis,Characterization,and Their Use asSurface Modifying Additives.”Journal ofPolymer Science:Part A:Polymer Chemistry,1989,Vol.27,3673-3690.)]
Ekin et al disclose a novel hydroxyalkyl and hydroxyalkyl carbonate terminated polydimethylsiloxane oligomer and a process for preparing copolymers thereof with polycaprolactone. The copolymer can be used as a surface modification auxiliary agent, and can be added into a thermosetting resin system to endow the system with low viscosity, high flexibility, good impact resistance and adhesion. The specific content is described in detail as follows: [ Synthesis and characterization of novel hydroxyalkyl-and bishydroxyalkyl carbonate-terminated polydimethylsiloxane oligomers and their copolymers with polycaprolactone ], [ macromolecules ], [ 39 th 2006, P ]8659～8668。(“Synthesis andCharacterization of Novel HydroxyalkylCarbamate andDihydroxyalkylCarbamateTerminated Poly(dimethylsiloxane)Oligomers and Their Block Copolymers withPoly(ε-caprolactone).”Macromolecular,2006,Vol.39,8659-8668.)]
The above patent documents mention a number of processes for the preparation of polycaprolactone-polysiloxane block copolymers which, after modification, can be used as potential surface modifiers in the field of coatings.
By analyzing the above-mentioned documents, no examples have been found of polycaprolactone-polysiloxane copolymers having both block and graft modification as surface slip agents for coating applications.
In view of the above, it is necessary to provide a coating material having high slip and high abrasion resistance, and particularly a solvent-based two-component varnish having abrasion resistance as a coating film.
Disclosure of Invention
In view of the drawbacks of the prior art, it is an object of the present invention to provide a solvent-based two-component, high-slip varnish composition having a coating film with abrasion resistance.
The invention also aims to provide a preparation method of the solvent type two-component high-slip varnish composition, and particularly relates to a method for preparing the solvent type two-component high-slip varnish composition from hydroxy acrylic resin or hydroxy methacrylic resin, hydroxy polyester resin, amino resin, a rheological control agent, a polycaprolactone modified polysiloxane slip agent and a curing agent by a specific preparation method.
The invention further aims to provide application of the solvent-based two-component high-slip varnish composition, in particular to an application method for coating the solvent-based two-component high-slip varnish composition on a substrate according to different construction processes to form a cured varnish coating and prepare a multi-coating finishing system.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
one aspect of the present invention provides a solvent-borne two-component, high-slip varnish composition comprising:
component A, comprising:
at least one hydroxy acrylic resin or hydroxy methacrylic resin;
at least one hydroxy polyester resin;
at least one amino resin;
at least one rheology control agent;
at least one polycaprolactone-modified polysiloxane;
at least one auxiliary agent; and
at least one first solvent;
component B, comprising:
at least one polyfunctional aliphatic isocyanate;
and/or at least one polyfunctional cycloaliphatic isocyanate;
and/or polyfunctional aliphatic and/or cycloaliphatic isocyanates in which at least a portion of the isocyanate groups are blocked, but free isocyanate groups are still present; wherein the blocking agent for blocking the isocyanate groups participates in a curing reaction during baking, or the blocking agent for blocking the isocyanate groups is removed during baking to release the isocyanate groups again; and
at least one second solvent.
Preferably, one aspect of the present invention provides a solvent-type two-component, high-slip varnish composition comprising the following components in parts by weight:
component A, comprising:
20-50 parts of at least one hydroxyl acrylic resin or hydroxyl methacrylic resin;
10-30 parts of at least one hydroxyl polyester resin;
10-20 parts of at least one amino resin;
5-30 parts of at least one rheological control agent;
0.1-5 parts of at least one polycaprolactone modified polysiloxane;
0.1-7 parts of at least one auxiliary agent; and
1-40 parts of at least one first solvent;
component B, comprising:
10-50 parts of at least one polyfunctional aliphatic isocyanate;
and/or 0-20 parts of at least one polyfunctional alicyclic isocyanate;
and/or 0 to 10 parts of polyfunctional aliphatic and/or alicyclic isocyanate of which at least one part of isocyanate groups is blocked and free isocyanate groups exist; wherein the blocking agent for blocking the isocyanate groups participates in a curing reaction during baking, or the blocking agent for blocking the isocyanate groups is removed during baking to release the isocyanate groups again; and
5-50 parts of at least one second solvent.
The component A and the component B are in a ratio of (1-18) in parts by weight: 3.
in the solvent-based bi-component high-slip varnish composition, the solid content of the component A is between 40 and 70 percent, and the solid content of the component B is between 50 and 90 percent; at the time of application, the ratio of the amount of substance of hydroxyl groups in component a to the amount of substance of isocyanate groups in component B is 1: (0.2-5).
The number average molecular weight of the hydroxyl acrylic resin or the hydroxyl methacrylic resin is 2000-20000 g/mol, the hydroxyl value is 60-250 mg KOH/g, the glass transition temperature (Tg) is-40 ℃ to +60 ℃, and the solid content is 50-90%.
The hydroxyl functionality of the hydroxyl polyester resin is between 2 and 5, the number average molecular weight is between 500 and 8000g/mol, the hydroxyl value is between 60 and 250mg KOH/g, and the solid content is between 70 and 90 percent.
The amino resin is butylated melamine formaldehyde resin containing imino group and existing in polymer form, and/or mixed etherified melamine formaldehyde resin containing imino group and existing in oligomer form, and/or mixed etherified melamine formaldehyde resin containing total etherified modified melamine formaldehyde resin existing in monomer form, and/or amino resin with carbamate functional group; in the present invention, the butylated, imino-containing, polymeric, and/or mixed etherified, imino-containing, oligomeric, and/or mixed etherified, fully etherified, monomeric melamine-formaldehyde resin may be selected from any of the following commercial products available from nepesin (su) co, basf co, and jjm (shanghai) co, including but not limited to the following products known to those skilled in the art: setalux US138 BB70 and Setalux US146 BB72 by Nepets resins (Suzhou) Ltd, Luwipol 072 and Luwipol 052 by Pasteur Co, Cymel 325, CYMEL 1158, Cymel 1168 and Cymel 303 by Zhan New resins (Shanghai) Ltd; the amino resin having carbamate functional groups may be selected from all relevant brands of commercial products manufactured by basf and Zhan new resins (Shanghai) Inc., including but not limited to the following products known to those skilled in the art: larotact 150 from Pasteur, Cymel NF2000 from New resins (Shanghai) Inc.
The rheology control agent is a compound containing urea bonds, a polymer and derivatives thereof; and/or high-molecular fine particles having a crosslinked structure; and/or fine silica particles having a surface treated, preferably polyurea or a derivative thereof, which is prepared by modifying mainly polyester or polyacrylic resin. For the purposes of the present invention, the rheology control agent may be chosen from all relevant brands of commercial products manufactured by nepes resins (suzhou) limited, such as: setalux 61767, Setalux 91796, Setalux 91757 and Setalux 91760 from Nepetes resin, Inc., and similar products from other companies may be selected.
The polycaprolactone modified polysiloxane has a structure shown as a formula (I) or (II):
in the formula (I), R1Has at least one of the structures shown in formula (III):
in the formula (II), R5Has at least one of the structures shown in formula (IV):
R2、R3and R4The groups may be the same or different, and each group has at least one of the structures shown in formula (V):
m>0，n>0，o>0，p>0，q>0，r>0，x>0，y>0，z>0。
the auxiliary agent is at least one of a leveling control agent, an ultraviolet absorbent and a hindered amine light stabilizer.
The leveling control agent may be selected from all relevant brands of commercial products manufactured by the company nikk, germany, for example: BYK 310, BYK 315, BYK 320, BYK 325, BYK 331, BYK 358N, BYK 3550, and BYK 3560, and similar products from other companies may be selected.
The ultraviolet absorber can be referred to as commercial products of all relevant brands selected from basf corporation, for example: tinuvin 292, Tinuvin 1130 may also be selected from similar products produced by other companies.
The hindered amine light stabilizer may be referred to as a commercial product selected from all relevant grades produced by basf corporation, for example: tinuvin 384-2, Tinuvin 123, and similar products produced by other companies can be selected.
The auxiliary agent can also further comprise an antioxidant and/or an anti-settling agent.
The antioxidant and/or anti-settling agent may be referred to as a commercial product selected from all relevant brands produced by basf corporation, for example: irgafos168 and963S; similar products from other companies may also be selected. Wherein the amount of the antioxidant depends on the resin used for different purposes, and the amount of the anti-settling agent depends on the amount of the pigment. When it is desired to use the aforementioned antioxidants and anti-settling agents, it is also desirable to uniformly mix them with the other components of the adjuvant.
The first solvent is at least one of aliphatic ester, ketone, glycol ether, glycol ester and aromatic hydrocarbon solvent, including but not limited to the following compounds known to those skilled in the art: toluene, xylene, S-100# solvent oil, trimethylbenzene solvent oil, S-150# solvent oil, durene solvent oil, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol butyl ether acetate, amyl acetate, ethylene glycol ethyl ether propionate and propylene glycol methyl ether acetate.
The polyfunctional aliphatic isocyanate has a functionality of at least 2 isocyanate groups, specifically 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane (HDI, hexamethylene diisocyanate), 2-methyl-1, 5-diisocyanatopentane, 1, 5-diisocyanato-2, 2-dimethyl-pentane, 2, 4-trimethyl-1, 6-diisocyanatohexane, 2,4, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, and/or trimers, pentamers and multimers formed from the above aliphatic diisocyanate monomers.
The polyfunctional alicyclic isocyanate has a functionality of at least 2 of isocyanate groups, specifically 1, 3-diisocyanatocyclohexane, 1, 4-diisocyanatocyclohexane, 2, 6-diisocyanato-1-methylcyclohexane, 2, 4-diisocyanato-1-methylcyclohexane, 1, 3-bis- (isocyanatomethyl) cyclohexane, 1, 4-bis- (isocyanatomethyl) cyclohexane, isophorone diisocyanate (IPDI), 2,4 '-diisocyanatodicyclohexylmethane, 4' -diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4 (3) isocyanatomethylcyclohexane, bis (isocyanatomethyl) -norbornane, and/or trimers formed from the above alicyclic diisocyanate monomers, Pentamers and multimers.
The polyfunctional aliphatic and/or cycloaliphatic isocyanate in which some of the isocyanate groups are blocked but free isocyanate groups are still present has a functionality of at least 1.
The second solvent is at least one of aliphatic ester, ketone, glycol ether, glycol ester, and aromatic hydrocarbon solvent, including but not limited to the following compounds known to those skilled in the art: toluene, xylene, S-100# solvent oil, trimethylbenzene solvent oil, S-150# solvent oil, durene solvent oil, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol butyl ether acetate, amyl acetate, ethylene glycol ethyl ether propionate and propylene glycol methyl ether acetate.
The invention also provides a preparation method of the solvent-based two-component high-slip varnish composition, which is specifically characterized in that a component A is prepared by firstly preparing hydroxy acrylic resin or hydroxy methacrylic resin, hydroxy polyester resin, amino resin, a rheological control agent, polycaprolactone modified polysiloxane, an auxiliary agent and a solvent, and then the component A and the component B are mixed to prepare the solvent-based two-component high-slip varnish composition, and the preparation method comprises the following steps (taking 1kg of varnish sample as an example):
step one, stirring and mixing a first part of first solvent, hydroxy acrylic resin or hydroxy methacrylic resin and hydroxy polyester resin uniformly;
secondly, under the condition of keeping the stirring speed unchanged, sequentially adding amino resin, a rheological control agent, polycaprolactone modified polysiloxane, an auxiliary agent and a second part of first solvent, and uniformly stirring and mixing to obtain the component A;
thirdly, keeping the stirring speed unchanged, and adding polyfunctional aliphatic isocyanate, and/or polyfunctional alicyclic isocyanate, and/or polyfunctional aliphatic and/or alicyclic isocyanate with part of isocyanate groups being blocked and free isocyanate groups still existing; wherein the blocking agent for blocking the isocyanate groups participates in a curing reaction during baking, or the blocking agent for blocking the isocyanate groups is removed during baking to release the isocyanate groups again; and a second solvent to obtain the component B;
and fourthly, adding the component B into the component A, and uniformly stirring to obtain the solvent type bi-component high-smoothness varnish composition.
The stirring and mixing are uniform, namely the stirring speed is 400-1000 revolutions per minute (r/min), and the stirring time is 10-60 min.
And in the second step, the amino resin, the rheological control agent, the polycaprolactone modified polysiloxane, the assistant and the second part of the first solvent are sequentially added for 5-10 min.
The preparation method of the polycaprolactone modified polysiloxane comprises the following steps:
firstly, mixing unsaturated monohydric alcohol and hexamethyldisilazane, heating to react, and obtaining a trimethylsiloxy unsaturated compound after the reaction is completed;
secondly, under the protection of nitrogen, adding a catalyst into the trimethylsiloxy unsaturated compound obtained in the first step, mixing, heating for reaction, and dropwise adding trimethylcyclotrisiloxaneObtaining trimethylsiloxy alkyl modified cyclotrisiloxane after the reaction is finished
Thirdly, under the anhydrous and oxygen-free conditions, mono-functional alkyl lithium or bi-functional alkyl lithium and trimethylsiloxy alkyl modified cyclotrisiloxane obtained in the second stepHexamethylcyclotrisiloxane D3Mixing with a solvent, heating for reaction, adding dimethyl hydrogen chlorosilane for termination of reaction, and performing aftertreatment to obtain polysiloxane with a side chain having a hydroxyl protecting group and a single end or double ends having a hydrosilyl group;
fourthly, under the protection of nitrogen, mixing the polysiloxane with the side chain having the hydroxyl protecting group and the hydrosilyl group at one end or both ends obtained in the third step with a catalyst, heating for reaction, dropwise adding the trimethylsiloxy unsaturated compound obtained in the first step for reaction, and carrying out post-treatment to obtain the polysiloxane with the side chain, one end or both ends having the hydroxyl protecting group;
fifthly, mixing the polysiloxane with the hydroxyl protecting group at the side chain, single end or double end obtained in the fourth step, an alcohol solvent and a weak acid catalyst, and heating for reaction to obtain the polysiloxane with the hydroxyl group at the side chain, single end or double end;
and sixthly, mixing the polysiloxane with the side chain, single end or double ends all provided with the hydroxyl alkyl, caprolactone and organic tin catalyst obtained in the fifth step, heating to react, and carrying out post-treatment to obtain the polycaprolactone modified polysiloxane.
The temperature of the heating reaction in the first step is 90-120 ℃, and the time is 4-8 h.
The molar ratio of the unsaturated monohydric alcohol to the hexamethyldisilazane in the first step is 2 (1-2), preferably 2 (1-1.1).
The unsaturated monohydric alcohol in the first step is at least one of the following structures:
A1)CH2＝CHCH2OH A2)CH2＝CHCH2CH2OH A3)CH2＝CHCH2CH2CH2OH
A4)CH2＝CHCH2CH2CH2CH2OH A5)CH2＝CHCH2NHC(O)OCH2CH2OH。
in the first step, the trimethylsiloxy unsaturated compound is at least one of the following structures:
B1)CH2＝CHCH2OSi(CH3)3B2)CH2＝CHCH2CH2OSi(CH3)3B3)CH2＝CHCH2CH2CH2OSi(CH3)3
B4)CH2＝CHCH2CH2CH2CH2OSi(CH3)3B5)CH2＝CHCH2NHC(O)OCH2CH2OSi(CH3)3。
the temperature of the temperature rise reaction in the second step is 80-110 ℃, and the time is 4-12 hours.
The mass of the catalyst in the second step accounts for trimethylcyclotrisiloxane0.05-1% of the mass.
In the second step, trimethyl siloxy unsaturated compound and trimethyl cyclotrisiloxaneThe molar ratio of (3-6): 1, preferably (3-3.3): 1.
The catalyst in the second step is chloroplatinic acid.
In the second step, trimethylsiloxyalkyl modified cyclotrisiloxaneIs at least one of the following structures:
in the third step, the temperature of the heating reaction is-70 ℃ to 50 ℃ and the time is 4 to 12 hours.
And in the third step, the molar ratio of the monofunctional alkyl lithium or the bifunctional alkyl lithium to the dimethyl hydrogen chlorosilane is 1 (1-2.2).
And the solvent in the third step comprises a non-polar organic solvent and a polar organic solvent, wherein the mass ratio of the non-polar organic solvent to the polar organic solvent is 1 (1-5).
In the third step, the solvent and trimethylsiloxyalkyl modified cyclotrisiloxaneHexamethylcyclotrisiloxane D3The total mass ratio of the monofunctional alkyllithium to the bifunctional alkyllithium is (0.25 to 4): 1.
In the third step, trimethylsiloxyalkyl modified cyclotrisiloxaneHexamethylcyclotrisiloxane D3And monofunctional alkyllithium or bifunctional alkyllithium, depending on the molecular weight of the product obtained after anionic polymerization.
Referring to the polysiloxane obtained after anionic polymerization in example 7 and having hydroxyl protecting groups on the side chains and hydrosilyl groups at the single ends, the molecular weight design formula (taking n-butyllithium as an initiator and 1mol as an example) is as follows:
the designed molecular weight of the polysiloxane is n-butyl (57) + DT 3Molecular weight XDT 3Amount of substance (n/3) + D3Molecular weight of (2) XD3Amount of substance (m/3) + (CH)3)2The molecular weight of SiH (59), i.e., M57 +60M +190n + 59.
If the molecular weight is about 1000, n and m in the above reaction formula are 1 and 12 respectively, that is, 1mol of n-butyl lithium initiator and 1/3mol of D are required to prepare polysiloxane with molecular weight of about 1000, wherein the side chain of the polysiloxane has a hydroxyl protecting group and the single end of the polysiloxane has a hydrosilyl groupT 3And 4mol of D3。
The designed molecular weight of the polysiloxane with the side chain having the hydroxyl protecting group and the single end having the hydrosilyl group is MRemoval of lithium molecular weight from mono-or bi-functional alkyllithium+DT 3Molecular weight XDT 3Amount of substance (c) + D3Molecular weight of (2) XD3Amount of substance(s) + MDimethyl hydrogen chlorosilane。
Referring to the polysiloxane obtained after anionic polymerization in example 8 and having hydroxyl protecting groups on the side chains and hydrosilyl groups at both ends, the molecular weight design formula (taking lithium dimethylsiloxy as an initiator and 1mol as an example) is as follows:
the designed molecular weight of the polysiloxane is that of dimethylsiloxy (90) + DT 3Molecular weight XDT 3Amount of substance(s) ((p + q)/3) + D3Molecular weight of (2) XD3Amount of substance(s) ((o + r)/3) +2 × (CH)3)2The molecular weight of SiH (118), i.e., M57 +60(o + r) +204(p + q) + 118.
If the molecular weight is about 1000, the (p + q) and (o + r) in the above reaction formula are respectively 1 and 10, namely, 1mol of dimethyl silicon oxygen lithium initiator and 1/3mol of D are needed to prepare polysiloxane with the molecular weight of about 1000, wherein the side chain of the polysiloxane has a hydroxyl protecting group and the two ends of the polysiloxane have hydrosilyl groupsT 3And 10/3mol of D3。
The designed molecular weight of the polysiloxane with the side chain having the hydroxyl protecting group and the two ends having the hydrosilyl group is MRemoval of lithium molecular weight from mono-or bi-functional alkyllithium+DT 3Molecular weight XDT 3Amount of substance (c) + D3Molecular weight of (2) XD3Amount of substance(s) +2 XMDimethyl hydrogen chlorosilane。
The monofunctional alkyl lithium or difunctional alkyl lithium in the third step is at least one of the following structures:
the non-polar organic solvent in the third step is selected from at least one of aliphatic, alicyclic and aromatic hydrocarbon solvents, including but not limited to the following compounds known to those skilled in the art: isopentane, n-pentane, petroleum ether, n-hexane, cyclohexane, isooctane, cyclopentane, trimethylpentane, cyclopentane, heptane, toluene, benzene, xylene.
The polar organic solvent in the third step is at least one selected from aliphatic ketones, alicyclic ketones, aromatic ketones, amides, sulfoxides, nitriles and heterocyclic solvents, including but not limited to the following compounds known to those skilled in the art: tetrahydrofuran, formamide, acetonitrile, N-dimethylformamide, hexamethylphosphoramide, butanone, dimethyl sulfoxide, acetone, 1, 4-dioxane and pyridine.
And in the third step, the dimethyl hydrochlorosilane is dimethyl chlorosilane.
In the third step, the number average molecular weight (Mn) of polysiloxane with a side chain having a hydroxyl protecting group and a hydrosilyl group at a single end or double ends is 200-10000, preferably 500-3000; the Polymerization Degree Index (PDI) is between 1 and 1.2; has at least one of the following structures,
wherein: m >0, n >0, o >0, p >0, q >0, r > 0;
R1has at least one of the structures shown in formula (III):
R2has at least one of the structures shown as formula (V):
R5has at least one of the structures shown in formula (IV):
the reaction temperature in the fourth step is 80-110 ℃, and the reaction time is 4-12 h.
And the catalyst in the fourth step is chloroplatinic acid.
The mass of the catalyst in the fourth step accounts for 0.05-1% of that of the polysiloxane with a side chain with a hydroxyl protecting group and a hydrosilyl group at one end or both ends.
In the fourth step, the molar ratio of the trimethylsiloxy unsaturated compound to the hydrosilyl (Si-H) contained in the polysiloxane with a side chain having a hydroxyl protecting group and a hydrosilyl group at one end or both ends is (1-2): 1, preferably (1.01-1.05): 1.
The polysiloxane having a hydroxyl protecting group at either side chain, single end or both ends in the fourth step has at least one of the following structures:
wherein: m >0, n >0, o >0, p >0, q >0, r > 0;
R1has at least one of the structures shown in formula (III):
R5has at least one of the structures shown in formula (IV):
R2、R3and R4The groups may be the same or different, and each group has at least one of the structures shown in formula (V):
and in the fifth step, the temperature of the heating reaction is 65-100 ℃, and the reaction time is 4-12 h.
And in the fifth step, the alcohol solvent is at least one of methanol, ethanol, n-propanol and isopropanol.
And in the fifth step, the weak acid catalyst is at least one of formic acid, acetic acid, propionic acid, lactic acid, dimethylolpropionic acid and dimethylolbutyric acid.
In the fifth step, the mass ratio of the polysiloxane with the hydroxyl protecting group at the side chain, single end or double ends to the alcohol solvent is 1 (1-4).
And in the fifth step, the mass of the weak acid catalyst accounts for 0.5-5% of that of the polysiloxane with hydroxyl protecting groups at the side chain, single end or double ends.
The polysiloxane having a hydroxyalkyl group at each of the side chain, the single end and the double end in the fifth step has at least one of the following structures:
wherein: m >0, n >0, o >0, p >0, q >0, r > 0;
R1has at least one of the structures shown in formula (III):
R5has at least one of the structures shown in formula (IV):
R2、R3and R4The groups may be the same or different, and each group has at least one of the structures shown in formula (V):
and in the sixth step, the temperature for raising the temperature to carry out the reaction is 80-140 ℃ and the time is 5-20 hours.
And in the sixth step, the number average molecular weight (Mn) of a polycaprolactone chain segment in the polycaprolactone modified polysiloxane is 200-5000, preferably 500-3500.
And in the sixth step, the organic tin catalyst is at least one of stannous isooctanoate, dibutyltin dilaurate, dioctyltin oxide, dibutyltin oxide, tributyltin and dibutyltin acetate.
In the sixth step, the mass of the organic tin catalyst accounts for 0.01-5% of that of caprolactone.
The feeding molar ratio of the polysiloxane with the side chain, single end or double end provided with the hydroxyl alkyl and the caprolactone depends on the molecular weight of the polycaprolactone chain segment, wherein: the molecular weight of each polycaprolactone chain segment is 200-5000.
Referring to the polycaprolactone-modified polysiloxane of example 7 having the structural formula (I), the molecular weight of each polycaprolactone segment is: nxx x molecular weight of caprolactone (114) and yxy molecular weight of caprolactone (114), wherein: 200< nxx x 114<5000, 200<114y <5000, the total molecular weight of the polyhexamethylene lactone segments is: 400< (3x + y) × 114< 10000.
If n, x and y in the final product formula are 1, 1.8 and 1.9, respectively, the molecular weight of each polyhexamethylene lactone segment is: 205.2 and 216.6.
Referring to the polycaprolactone-modified polysiloxane of example 8 having the structural formula (II), the molecular weight of each polycaprolactone segment is: (p + q). times.x.hexanolide (114) and (y + z). times.hexanolide (114), wherein: 200< (p + q) × x 114<5000, 200<114(y + z) <5000, the total molecular weight of the polyhexamethylene lactone segments is: 400< [ (p + q) × x + (y + z) ] × 114< 10000.
If (p + q), x, y and z in the final product formula are 1, 2.7, 2 and 2, respectively, the molecular weight of each polycaprolactone segment is: 307.8, 228, and 228.
The preparation method of the multifunctional aliphatic and/or alicyclic isocyanate with part of the isocyanate groups being blocked and free isocyanate groups still existing comprises the following steps:
mixing polyfunctional aliphatic isocyanate and/or polyfunctional alicyclic isocyanate with a catalyst, heating a reaction system to 60-80 ℃, slowly dropwise adding a mixed solution of a sealing agent and a solvent after the temperature is constant, controlling the reaction temperature in the dropwise adding process, keeping the temperature not more than 80 ℃, continuously reacting for 4-5 hours at the temperature after the dropwise adding is finished, controlling the content of residual isocyanate groups, stopping the reaction, and discharging to obtain the polyfunctional aliphatic and/or alicyclic isocyanate with part of the isocyanate groups being sealed and still having free isocyanate groups.
The catalyst is an organic tin compound or an organic alkali compound.
The organic tin compound is at least one of stannous isooctanoate, dibutyltin dilaurate, dioctyltin oxide, dibutyltin oxide, tributyltin and dibutyltin acetate.
The organic alkali compound is at least one of sodium methoxide and sodium ethoxide.
The sealant has one of the structures shown as formula (VI), (VII) or (VIII):
wherein R is6And R7The groups can be the same or different and are respectively selected from aliphatic alkyl containing 1-8 carbon atoms;
R8(CH2)aSi(OR9)(OR10)(OR11)
(VII)
HN[(CH2)aSi(OR9)(OR10)(OR11)]
(VIII)
wherein R is8Is at least one of primary amino group, hydroxyl group and sulfhydryl group, a is an integer more than or equal to 1, R9、R10And R11The groups can be the same or different and are respectively selected from aliphatic alkyl containing 1-8 carbon atoms and/or aliphatic acyl containing 1-8 carbon atoms;
or, the blocking agent is a compound containing active hydrogen, specifically at least one of monohydric alcohols, mono-substituted alcohol ethers, ketoximes, monoamines, pyrazoles and alicyclic amides, including but not limited to the following compounds known to those skilled in the art: methanol, ethanol, propanol, N-butanol, isobutanol, N-hexanol, N-octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, methyl ethyl ketoxime, acetone oxime, cyclohexanone ketoxime, diisopropyl amine, N-tert-butyl benzylamine, 3, 5-dimethyl pyrazole, caprolactam.
The solvent is at least one of aliphatic ester, ketone, glycol ether, glycol ester and aromatic hydrocarbon solvent, including but not limited to the following compounds known to those skilled in the art: toluene, xylene, S-100# solvent oil, trimethylbenzene solvent oil, S-150# solvent oil, durene solvent oil, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol butyl ether acetate, amyl acetate, ethylene glycol ethyl ether propionate and propylene glycol methyl ether acetate.
The polyfunctional aliphatic isocyanate has a functionality of at least 2 isocyanate groups, specifically 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane (HDI, hexamethylene diisocyanate), 2-methyl-1, 5-diisocyanatopentane, 1, 5-diisocyanato-2, 2-dimethyl-pentane, 2, 4-and/or 2,4, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, and/or trimers, pentamers and multimers formed from the above aliphatic diisocyanate monomers.
The polyfunctional alicyclic isocyanate has a functionality of at least 2 of isocyanate groups, specifically 1, 3-diisocyanatocyclohexane, 1, 4-diisocyanatocyclohexane, 2, 6-diisocyanato-1-methylcyclohexane, 2, 4-diisocyanato-1-methylcyclohexane, 1, 3-bis- (isocyanatomethyl) cyclohexane, 1, 4-bis- (isocyanatomethyl) cyclohexane, isophorone diisocyanate (IPDI), 2,4 '-diisocyanatodicyclohexylmethane, 4' -diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4 (3) isocyanatomethylcyclohexane, bis (isocyanatomethyl) -norbornane, and/or trimers formed from the above alicyclic diisocyanate monomers, Pentamers and multimers.
The mass of the catalyst accounts for 0.01-1% of the mass of the polyfunctional aliphatic isocyanate and/or the polyfunctional alicyclic isocyanate.
The mass of the blocking agent accounts for 20-50% of the mass of the polyfunctional aliphatic isocyanate and/or the polyfunctional alicyclic isocyanate.
The mass of the solvent accounts for 40-50% of the mass of the polyfunctional aliphatic isocyanate and/or the polyfunctional alicyclic isocyanate.
In a further aspect, the invention provides a use of the solvent-based two-component, high-slip varnish composition, in particular a use of the solvent-based two-component, high-slip varnish composition for forming a cured coating on a substrate; the method comprises the following steps:
applying a primer or basecoat to a substrate and curing it, applying a basecoat to the substrate with the primer or basecoat already cured, then applying the solvent-borne two-component, high slip, clearcoat composition to the uncured basecoat surface, and finally curing both coats simultaneously to obtain the multi-coat finish system, which can be used in a three-coat two-bake system;
or,
applying a primer or a basecoat to a substrate, applying a basecoat to the surface of the uncured primer or basecoat, applying the solvent-borne two-component, high slip clearcoat composition to the surface of the uncured basecoat, and simultaneously curing the three-part coating to obtain the multi-coat finishing system, which can be used in a three-coat one-bake system or an integrated spray process (IPP) system;
or,
applying two coats of pigmented paint to a substrate without a primer and a basecoat, then spraying the solvent-borne two-component, high slip clear coat composition over the second coat of pigmented paint and simultaneously curing the three coats to obtain the multi-coat finish system, which can be used in a compact spray process (CCT) system;
or,
applying a primer or basecoat to a substrate and curing the same, applying a basecoat or basecoat to the substrate with the primer or basecoat cured, applying a pearlescent paint to the uncured surface of the basecoat, applying the solvent-borne two-component, high slip clear coat composition to the uncured surface of the pearlescent paint, and simultaneously curing the three-part coating to obtain the multi-coat finishing system, which can be used in a four-coat two-bake system;
or,
the method comprises the steps of firstly applying a primer or a middle coat on a substrate, then applying a single-color paint on the surface of an uncured primer or middle coat, then applying a pearlescent color paint on the surface of an uncured single-color paint, then applying the solvent-based two-component high-smoothness varnish composition on the surface of the uncured pearlescent color paint, and finally simultaneously curing the four parts of coatings to obtain the multi-coat finishing system which can be used in a four-coat one-bake system.
The substrate is a standard automobile body or a component assembly of the automobile body and is prepared by cold-rolled sheets which are subjected to chemical pretreatment and covered with an electrophoretic coating; the curing temperature is 100-180 ℃; the curing time is 10-40 min.
The primer and the colored paint used in the three-coating two-drying, three-coating one-drying, integrated spraying process, tightening spraying process, four-coating two-drying and four-coating one-drying system are water-based paints, the construction solid content of the primer is between 35% and 55%, the cured film thickness is between 10 and 50 mu m, the construction solid content of the colored paint is between 20% and 40%, and the cured film thickness is between 6 and 20 mu m.
The outermost coating layer of the multi-coating finishing system is prepared from the solvent-based bi-component high-slip varnish composition; the dry film thickness of the multi-coat coating system is 10 to 80 μm, preferably 20 to 70 μm, and more preferably 30 to 60 μm; the curing temperature is 100-180 ℃, and preferably 120-160 ℃; the curing time is 10-40 min.
The solvent-based two-component high-slip varnish composition can be used as finishing varnish for automobile coating.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the solvent-type bi-component high-slip varnish composition disclosed by the invention uses the polycaprolactone modified polysiloxane with a special structure, and when the polycaprolactone modified polysiloxane is added into a solvent-type coating, particularly a solvent-type varnish, the surface performance of a coating film can be improved, the slip property is increased, and the friction resistance is improved.
The solvent type two-component high-slip varnish composition provided by the invention can effectively improve the slip of the surface of a coating film of the varnish composition, thereby increasing the friction resistance of the coating film.
In the solvent-based two-component high-smoothness varnish composition provided by the invention, polycaprolactone in the polycaprolactone-modified polysiloxane modifies polysiloxane through block and grafting, and the solvent-based two-component high-smoothness varnish composition has the advantages of a polycaprolactone block-modified polysiloxane copolymer and a polycaprolactone graft-modified grafted polysiloxane copolymer.
In the solvent-based two-component high-smoothness varnish composition provided by the invention, the polycaprolactone modified polysiloxane can be used as a solvent-based paint auxiliary agent, and when the solvent-based paint composition is added into a solvent-based paint, particularly a solvent-based varnish, the surface performance of a coating film can be improved, the smoothness is increased, and the friction resistance is improved.
In the solvent-based bi-component high-slip varnish composition provided by the invention, the polycaprolactone modified polysiloxane is composed of a special polysiloxane chain segment and a polycaprolactone chain segment, has excellent miscibility with solvent-based paint, can be used as a paint auxiliary agent, and can be particularly used as a surface slip agent; after the polycaprolactone modified polysiloxane is used as a surface slip agent and added into a solvent type coating, the surface tension of the coating can be reduced, so that good wettability and good anti-cratering property are provided; particularly, when added to a solvent-based varnish, the varnish does not cause turbidity, and the surface smoothness and scratch resistance of the varnish coating can be further enhanced.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the case where the objects of the present invention are illustrated and explained by the following examples, the components of the composition are all explained on the general standard of parts by weight. In the present invention, the terms "part by weight" and "part" are used synonymously in the examples for the sake of brevity without specific mention.
Example 1
Hydroxy (meth) acrylic resin
Firstly, 3000g of a mixed solvent of xylene and propylene glycol monomethyl ether acetate (mass ratio of 1:1) is added into a 10L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, dropwise adding a reaction mixture consisting of 500g of styrene, 2250g of n-butyl acrylate, 1750g of hydroxyethyl methacrylate, 50g of acrylic acid, 450g of methyl methacrylate and 310g of tert-butyl peroxy-2-ethyl hexanoate into the reaction kettle by a peristaltic pump, maintaining the reaction temperature at 130-140 ℃ in the dropwise adding process, and controlling the dropwise adding speed to ensure that the dropwise adding of the reaction mixture is completed within 2-4 hours. After the dropwise addition, continuously keeping the temperature at 130-140 ℃ for 2-4 h, and terminating the reaction to obtain the hydroxyl acrylic resin with the solid content of 62.5%, the hydroxyl value of 150mgKOH/g, the glass transition temperature (Tg) of 0 ℃ and the number average molecular weight of 3500 or so.
Example 2
Hydroxy (meth) acrylic resin
Firstly, 3000g of a mixed solvent of xylene and propylene glycol monomethyl ether acetate (mass ratio of 1:1) is added into a 10L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, dropwise adding a reaction mixture consisting of 500g of styrene, 1750g of n-butyl acrylate, 1750g of hydroxyethyl methacrylate, 50g of acrylic acid, 950g of methyl methacrylate and 432g of tert-butyl peroxy-2-ethyl hexanoate into the reaction kettle by a peristaltic pump, maintaining the reaction temperature between 130 and 140 ℃ in the dropwise adding process, and controlling the dropwise adding speed to ensure that the dropwise adding of the reaction mixture is completed within 2 to 4 hours. After the dropwise addition, continuously keeping the temperature at 130-140 ℃ for 2-4 h, and terminating the reaction to obtain the hydroxyl acrylic resin with the solid content of 62.5%, the hydroxyl value of 150mgKOH/g, the glass transition temperature (Tg) of 15 ℃ and the number average molecular weight of 2500 or so.
Example 3
Hydroxy polyester resin
In a 5L reactor, 708g of 1, 6-hexanediol (M ═ 118), 312g of neopentyl glycol (M ═ 104), 804g of trimethylolpropane (M ═ 134), 216g of 1, 4-cyclohexanedimethanol (M ═ 144), 1752g of adipic acid (M ═ 146), 516g of 1, 6-cyclohexanedicarboxylic acid (M ═ 172) and 2.5g of dibutyltin oxide were added in this order. Starting stirring, slowly heating the reaction kettle to 120 ℃, and preserving heat for 15-30 min at the temperature. After the materials are completely dissolved, heating the reaction kettle to 150 ℃, preserving heat for 2-2.5 hours at the temperature, then heating the reaction kettle to 180 ℃, preserving heat for 2-2.5 hours at the temperature, and finally heating the reaction kettle to 220 ℃. The reaction kettle is kept at 220 ℃ for continuous heat preservation, when the temperature of the fractionating column is reduced to 80 ℃, xylene is added for refluxing with water, and samples are taken every 3 hours to measure the acid value. When the acid value is less than 3, stopping heating, cooling the reaction system to 110 ℃, and then adding 1572g of butyl acetate for dilution to obtain the hydroxyl polyester resin with the solid content of 70%, the hydroxyl value of 134mgKOH/g, the hydroxyl functionality of 3 and the number average molecular weight of 2500 or so.
Example 4
Hydroxy polyester resin
In a 5L reactor, 708g of 1, 6-hexanediol (M ═ 118), 312g of neopentyl glycol (M ═ 104), 804g of trimethylolpropane (M ═ 134), 216g of 1, 4-cyclohexanedimethanol (M ═ 144), 1752g of adipic acid (M ═ 146), 567.6g of 1, 6-cyclohexanedicarboxylic acid (M ═ 172) and 2.5g of dibutyltin oxide were added in this order. Starting stirring, slowly heating the reaction kettle to 120 ℃, and preserving heat for 15-30 min at the temperature. After the materials are completely dissolved, heating the reaction kettle to 150 ℃, preserving heat for 2-2.5 hours at the temperature, then heating the reaction kettle to 180 ℃, preserving heat for 2-2.5 hours at the temperature, and finally heating the reaction kettle to 220 ℃. The reaction kettle is kept at 220 ℃ for continuous heat preservation, when the temperature of the fractionating column is reduced to 80 ℃, xylene is added for refluxing with water, and samples are taken every 3 hours to measure the acid value. When the acid value is less than 3, stopping heating, cooling the reaction system to 110 ℃, and then adding 1230g of butyl acetate for dilution to obtain the hydroxyl polyester resin with the solid content of 75%, the hydroxyl value of 82mgKOH/g, the hydroxyl functionality of 3.25 and the number average molecular weight of 3000 or so.
Example 5
Polyfunctional aliphatic and/or cycloaliphatic isocyanates in which part of the isocyanate groups are blocked but free isocyanate groups are still present, wherein the blocking agents used to block the isocyanate groups are removed during baking to liberate isocyanate groups again;
964g of hexamethylene diisocyanate trimer (trade name: Desmodur N3300 available from Bayer Co.) and 1g of dibutyltin dilaurate were charged into a 2L reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, and then the reaction system was heated to 70 ℃. When the temperature is constant, slowly dripping a mixed solution of 288g of 3, 5-dimethylpyrazole dissolved in 410g of butyl acetate, and controlling the reaction temperature in the dripping process to keep the temperature not to exceed 80 ℃. And (3) continuously reacting for 4-5 h at the temperature after the dropwise adding is finished, stopping the reaction and discharging when the content of the residual isocyanate groups reaches 5.05% of a theoretical value, thus obtaining the polyfunctional aliphatic and/or alicyclic isocyanate which has a solid content of 75%, is closed by partial isocyanate groups and still has free isocyanate groups.
Example 6
Polyfunctional aliphatic and/or cycloaliphatic isocyanates in which part of the isocyanate groups are blocked but free isocyanate groups are still present, wherein the blocking agents used for blocking the isocyanate groups participate in the curing reaction during the baking process;
964g of hexamethylene diisocyanate trimer (trade name: Desmodur N3300 available from Bayer Co.), 222g of isophorone diisocyanate and 1g of dibutyltin dilaurate were charged into a 2L reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, and then the reaction system was heated to 70 ℃. When the temperature is constant, slowly adding 270g of hydroxypropyl trimethoxy silane and 261g of methyl ethyl ketoxime dropwise, and controlling the reaction temperature during the dropwise adding process to keep the temperature not to exceed 80 ℃. And (3) continuously reacting for 4-5 h at the temperature after the dropwise adding is finished, stopping the reaction when the content of the residual isocyanate groups reaches 7.34% of a theoretical value, and adding 570g of butyl acetate to obtain the polyfunctional aliphatic and/or alicyclic isocyanate which has a solid content of 75%, is closed by partial isocyanate groups and still has free isocyanate groups.
Example 7
Polycaprolactone-modified polysiloxanes of the formula (I), R1Is CH3CH2CH2CH2，R2And R3Are all CH2CH2CH2，n＝1，m＝12，x＝1.8，y＝1.9；
The reaction equation for polycaprolactone-modified polysiloxanes having the structural formula (I) is shown below:
step one, hydroxyl protection: 338.1g (2.1mol) of hexamethyldisilazane were slowly added dropwise to 232g (4mol) of allyl alcohol A in a 1L reactor at room temperature1(molar ratio of unsaturated monohydric alcohol to hexamethyldisilazane is 2: 1.05). After the dropwise addition, the reaction system was heated to 100 ℃ and continued to react at this temperature for 6 hours, and then the reaction was stopped. The 98-100 ℃ fraction was collected under normal pressure to obtain 473.2g of allyloxytrimethylsilane (91% yield).
Step two, primary hydrosilylation: 393.9g (3.03mol) of allyloxytrimethylsilane obtained in the first step and 0.5g of chloroplatinic acid catalyst (the mass of the catalyst accounts for 0.28% of that of trimethylcyclotrisiloxane) are sequentially added into a 1L reaction kettle, after nitrogen is introduced for 20min, the reaction system is heated to 100 ℃, 180g (1mol) of trimethylcyclotrisiloxane (the molar ratio of the trimethylsiloxy unsaturated compound to the trimethylcyclotrisiloxane is 3.03:1) is dropwise added at the temperature, and the reaction is terminated after 8h of reaction. The low boiling point substance was distilled off under reduced pressure to obtain 553g of trimethylsiloxyalkyl-modified cyclotrisiloxane in a yield of 97.0%.
Third step, anionic polymerization: and sequentially adding 64g (1mol) of n-butyllithium, 740g of hexamethylcyclotrisiloxane and 190g of mixed solution of trimethylsiloxy alkyl modified cyclotrisiloxane obtained in the second step and 500g of n-hexane and tetrahydrofuran (the mass ratio is 1:1) (the total mass ratio of the solvent to trimethylsiloxy alkyl modified cyclotrisiloxane, hexamethylcyclotrisiloxane, monofunctional alkyl lithium or bifunctional alkyl lithium is 0.33:1) into a 2L reaction kettle which is subjected to anhydrous and anaerobic treatment, stirring and reacting for 8 hours at 25 ℃, and adding 1.1mol of dimethylchlorosilane (the molar ratio of n-butyllithium to dimethylchlorosilane is 1:1.1) to terminate the reaction. The reaction solution was filtered to remove the generated lithium chloride, and the low boiling point substance was removed by distillation under reduced pressure, whereby 987g of polysiloxane having a hydroxyl-protecting group at the side chain and a hydrosilyl group at the single end and having a number average molecular weight of 1026 or so and a Polymerization Degree Index (PDI) of 1.12 was obtained with a yield of 96.2%.
Trimethyl in the preparation processSiloxane-based modified cyclotrisiloxanesHexamethylcyclotrisiloxane D3And monofunctional alkyllithium or bifunctional alkyllithium, depending on the molecular weight of the product obtained after anionic polymerization.
In this example, the molecular weight design formula of the polysiloxane having a hydroxyl protecting group on a side chain and a hydrosilyl group at a single end obtained after anionic polymerization (taking n-butyllithium as an initiator and the amount of 1mol as an example) is as follows:
the designed molecular weight of the polysiloxane is n-butyl (57) + DT 3Molecular weight XDT 3Amount of substance (n/3) + D3Molecular weight of (2) XD3Amount of substance (m/3) + (CH)3)2The molecular weight of SiH (59), i.e., M57 +60M +190n + 59.
If the molecular weight is about 1000, n and m in the above reaction formula are 1 and 12 respectively, that is, 1mol of n-butyl lithium initiator and 1/3mol of D are required to prepare polysiloxane with molecular weight of about 1000, wherein the side chain of the polysiloxane has a hydroxyl protecting group and the single end of the polysiloxane has a hydrosilyl groupT 3And 4mol of D3。
Step four, secondary hydrosilylation: 615.6g (0.6mol) of polysiloxane with a hydroxyl protecting group on a side chain and a hydrosilyl group at a single end and obtained in the third step and 1g of chloroplatinic acid catalyst (the mass of the catalyst accounts for 0.16% of that of the polysiloxane with a hydroxyl protecting group on a side chain and a hydrosilyl group at a single end) are sequentially added into a 1L reaction kettle, after nitrogen is introduced for 20min, the reaction system is heated to 100 ℃, 78g (0.6mol) of allyloxytrimethylsilane (the molar ratio of the trimethylsiloxy unsaturated compound and the hydrosilyl group (Si-H) contained in the polysiloxane with a hydroxyl protecting group on a side chain and a hydrosilyl group at a single end obtained in the first step is 1:1) is dropwise added at the temperature, and the reaction is terminated after 5H. The low boiling point compound was distilled off under reduced pressure to obtain 657g of polysiloxane having a hydroxyl protecting group at both the side chain and the terminal end and having a number average molecular weight of 1156, in a yield of 94.8%.
Fifthly, alcoholysis reaction: 345g of the polysiloxane having a hydroxyl protecting group at both side chains and at a single end, which was obtained in the fourth step, 500g of methanol (the mass ratio between the polysiloxane having a hydroxyl protecting group at both side chains and at a single end and the alcohol solvent is 1:1.45) and 3g of acetic acid (the mass of the weak acid catalyst accounts for 0.87% of the mass of the polysiloxane having a hydroxyl protecting group at both side chains and at a single end) were sequentially added to a 1L reaction kettle, and the reaction was stopped after 9 hours of reaction under a heating reflux condition at 65 ℃. Acetic acid, excessive methanol and low-boiling-point substances are removed by reduced pressure distillation, 320g of polysiloxane with the number average molecular weight of about 1000 and both side chains and single ends having hydroxyl alkyl is obtained, and the yield is 92.7%.
Sixth step, ring-opening polymerization: and (2) adding 300g of polysiloxane with a hydroxyalkyl group at the side chain and the single end obtained in the fifth step, 228g of caprolactone and 0.3g of stannous isooctanoate (the mass of the organic tin catalyst accounts for 0.13% of that of the caprolactone) into a 1L reaction kettle at one time, heating the reaction system to 80 ℃ under the stirring state, reacting for 6 hours at the temperature, heating the reaction system to 120 ℃, continuing to react for 6 hours, and terminating the reaction to obtain the polycaprolactone modified polysiloxane with the structural formula (I).
The charging molar ratio between the polysiloxane with hydroxyl alkyl at the side chain, single end or double end and the caprolactone depends on the molecular weight of the polycaprolactone chain segment, wherein: the molecular weight of each polycaprolactone chain segment is 200-5000.
Referring to the polycaprolactone-modified polysiloxane of the present example having the structural formula (I), the molecular weight of each polycaprolactone segment is: nxx x molecular weight of caprolactone (114) and yxy molecular weight of caprolactone (114), wherein: 200< nxx x 114<5000, 200<114y <5000, the total molecular weight of the polyhexamethylene lactone segments is: 400< (3x + y) × 114< 10000.
In the final product formula, n, x and y are 1, 1.8 and 1.9, respectively, then the molecular weight of each polyhexamethylene lactone segment is: 205.2 and 216.6.
Example 8
A polycaprolactone-modified polysiloxane having the structural formula (II): r5Is OSi (CH)3)2O，R2、R3And R4Are all CH2CH2CH2CH2，(p+q)＝1，(o+r)＝10，x＝2.7，y＝2，z＝2；
o>0，p>0，q>0，r>0，x>0，y>0，z>0。
Step one, hydroxyl protection: 338.1g (2.1mol) of hexamethyldisilazane were slowly added dropwise to 288g of 3-buten-1-ol (4mol) A in a 1L reactor at room temperature3(molar ratio of unsaturated monohydric alcohol to hexamethyldisilazane is 2: 1.05). After the dropwise addition, the reaction system was heated to 100 ℃ and continued to react at this temperature for 6 hours, and then the reaction was stopped. The 110 ℃ and 115 ℃ fractions were collected at atmospheric pressure to give 558g of vinylbutoxytrimethylsilane in a 96.9% yield.
Step two, primary hydrosilylation: 436.3g (3mol) of vinylbutoxytrimethylsilane obtained in the first step and 0.2g of chloroplatinic acid catalyst (the mass of the catalyst accounts for 0.11% of that of trimethylcyclotrisiloxane) are sequentially added into a 1L reaction kettle, nitrogen is introduced for 20min, the reaction system is heated to 100 ℃, 180g (1mol) of trimethylcyclotrisiloxane (the molar ratio of the trimethylsiloxy unsaturated compound to the trimethylcyclotrisiloxane is 3:1) is dropwise added at the temperature, and the reaction is terminated after 8 h. The low boiling point substance was distilled off under reduced pressure to obtain 601g of trimethylsiloxyalkyl-modified cyclotrisiloxane in a yield of 98.2%.
Third step, anionic polymerization: and (2) adding a mixed solution of 104g (1mol) of lithium dimethylsiloxy, 592g of hexamethylcyclotrisiloxane and 204g of trimethylsiloxy alkyl modified cyclotrisiloxane obtained in the second step and 500g of n-hexane and tetrahydrofuran (the mass ratio is 1:1) (the total mass ratio of the solvent to the trimethylsiloxy alkyl modified cyclotrisiloxane, the hexamethylcyclotrisiloxane, the monofunctional lithium alkyl or the difunctional lithium alkyl is 0.56:1) into a 2L reaction kettle after anhydrous and anaerobic treatment, stirring and reacting for 8 hours at 25 ℃, and adding 2.1mol of dimethylchlorosilane (the molar ratio of the lithium dimethylsiloxy to the dimethylchlorosilane is 1:2.1) to terminate the reaction. The reaction mixture was filtered to remove the lithium chloride produced, and the low boiling point substance was distilled off under reduced pressure to obtain 961g of polysiloxane having a number average molecular weight of about 1004 and a PDI of 1.15, which had a hydroxyl-protecting group at the side chain and a silylhydride group at both ends, at a yield of 95.7%.
Referring to the polysiloxane obtained after anionic polymerization in this example and having a hydroxyl protecting group on a side chain and a hydrosilyl group at both ends, the molecular weight design formula (taking dimethylsiloxy lithium as an initiator and the amount of 1mol as an example) is as follows:
the designed molecular weight of the polysiloxane is that of dimethylsiloxy (90) + DT 3Molecular weight XDT 3Amount of substance(s) ((p + q)/3) + D3Molecular weight of (2) XD3Amount of substance(s) ((o + r)/3) +2 × (CH)3)2The molecular weight of SiH (118), i.e., M57 +60(o + r) +204(p + q) + 118.
If the molecular weight is about 1000, the (p + q) and (o + r) in the above reaction formula are respectively 1 and 10, namely, 1mol of dimethyl silicon oxygen lithium initiator and 1/3mol of D are needed for preparing polysiloxane with the molecular weight of about 1000 and with a hydroxyl protecting group on the side chain and a hydrosilyl group at the both endsT 3And 10/3mol of D3。
The designed molecular weight of the polysiloxane with the side chain having the hydroxyl protecting group and the two ends having the hydrosilyl group is MRemoval of lithium molecular weight from mono-or bi-functional alkyllithium+DT 3Molecular weight XDT 3Amount of substance (c) + D3Molecular weight of (2) XD3Amount of substance(s) +2 XMDimethyl hydrogen chlorosilane。
Step four, secondary hydrosilylation: adding 500g (1mol of Si-H group) of polysiloxane with a hydroxyl protecting group on a side chain and a hydrosilyl group at both ends obtained in the third step and 0.5g of chloroplatinic acid catalyst (the mass of the catalyst accounts for 0.1% of that of the polysiloxane with a hydroxyl protecting group on a side chain and a hydrosilyl group at both ends) in sequence into a 1L reaction kettle, introducing nitrogen for 20min, heating the reaction system to 100 ℃, dropwise adding 150g (1.04mol) of vinylbutoxytrimethylsilane (the molar ratio of trimethylsiloxy unsaturated compound obtained in the first step to the hydrosilyl group (Si-H) contained in the polysiloxane with a hydroxyl protecting group on a side chain and a hydrosilyl group at one end or both ends) at the temperature is 1.04:1), and stopping the reaction after 5H. The low boiling point compound was distilled off under reduced pressure to obtain 621g of polysiloxane having a number average molecular weight of about 1292 and both side chains and hydroxyl protecting groups, with a yield of 96.4%.
Fifthly, alcoholysis reaction: 581.4g of the polysiloxane having a hydroxyl protecting group at both ends and a side chain obtained in the fourth step, 600g of methanol (the mass ratio of the polysiloxane having a hydroxyl protecting group at both ends and the alcoholic solvent is 1:1.03) and 3.6g of acetic acid (the mass of the weak acid catalyst is 0.62% of the mass of the polysiloxane having a hydroxyl protecting group at both ends and a side chain) were sequentially added into a 1L reaction kettle. The reaction was stopped after 9h at 65 ℃ under reflux. Acetic acid, excessive methanol and low boiling point substances are removed by reduced pressure distillation, 479g of polysiloxane with the side chain of which the number average molecular weight is about 1124 and the both ends of which have hydroxyl alkyl are obtained, and the yield is 94.7 percent.
Sixth step, ring-opening polymerization: 337.2g of the polysiloxane having a hydroxyalkyl group at both the side chain and the terminal obtained in the fifth step, 228g of caprolactone and 0.3g of stannous isooctanoate (the mass of the organotin catalyst is 0.13% of that of caprolactone) were charged in one portion in a 1L reactor. And (3) heating the reaction system to 80 ℃ under the stirring state, reacting for 6 hours at the temperature, heating the reaction system to 120 ℃, continuing to react for 6 hours, and terminating the reaction to obtain the polycaprolactone modified polysiloxane with the structural formula (II).
The charging molar ratio between the polysiloxane with hydroxyl alkyl at the side chain, single end or double end and the caprolactone depends on the molecular weight of the polycaprolactone chain segment, wherein: the molecular weight of each polycaprolactone chain segment is 200-5000.
Referring to the polycaprolactone-modified polysiloxane of the present example having the structural formula (II), the molecular weight of each polycaprolactone segment is: (p + q). times.x.hexanolide (114) and (y + z). times.hexanolide (114), wherein: 200< (p + q) × x 114<5000, 200<114(y + z) <5000, the total molecular weight of the polyhexamethylene lactone segments is: 400< [ (p + q) × x + (y + z) ] × 114< 10000.
When (p + q), x, y and z are 1, 2.7, 2 and 2, respectively, in the final product formula, the molecular weight of each polycaprolactone segment is: 307.8, 228, and 228.
The components and preparation method of the solvent-based two-component, high-slip varnish composition of the present invention are illustrated in examples 9 to 18 and further illustrated in conjunction with the specific applications thereof.
The solvent-based two-component high-slip varnish composition for automobile finishing and other related fields mentioned in examples 9 to 18 of the present invention was prepared by preparing a component a from a hydroxy acrylic resin or a hydroxy methacrylic resin, a hydroxy polyester resin, an amino resin, a rheology control agent, a polycaprolactone-modified polysiloxane, an auxiliary agent and a solvent according to the amounts of the different resin components set forth in tables 1 and 2, and then mixing the component a with the curing agent of the component B to prepare the solvent-based two-component high-slip varnish composition.
In order to ensure the uniformity of quality and performance of the solvent-based two-component, high-slip varnish composition, the preparation method comprises the following steps of stirring and mixing the components at normal pressure and room temperature according to the following specific feeding sequence (taking 1kg of a sample of the solvent-based two-component, high-slip varnish composition as an example for preparation):
firstly, stirring and uniformly mixing 0.5-30 parts of a first solvent, 20-50 parts of hydroxyl acrylic resin or hydroxyl methacrylic resin and 10-30 parts of hydroxyl polyester resin;
secondly, under the condition that the stirring speed is kept unchanged, sequentially adding 10-20 parts of amino resin, 5-30 parts of rheological control agent, 0.1-5 parts of polycaprolactone modified polysiloxane, 0.1-7 parts of auxiliary agent and 0.5-10 parts of first solvent, and uniformly stirring and mixing to obtain a component A;
thirdly, under the condition of keeping the stirring speed unchanged, 10-50 parts of polyfunctional aliphatic isocyanate, and/or 0-20 parts of polyfunctional alicyclic isocyanate, and/or 0-10 parts of polyfunctional aliphatic and/or alicyclic isocyanate with partial isocyanate groups being blocked and free isocyanate groups still existing are added; wherein the blocking agent for blocking the isocyanate groups participates in a curing reaction during baking, or the blocking agent for blocking the isocyanate groups is removed during baking to release the isocyanate groups again; and 5-50 parts of a second solvent to obtain the component B;
fourthly, adding the component B into the component A, and uniformly stirring to obtain the solvent type bi-component high-smoothness varnish composition;
the ratio of the component A to the component B in parts by weight is (1-18): 3.
the solvent-borne two-component, high-slip clear coat compositions were subjected to the following performance tests, in which the composite coating films concerned (3C1B system) were prepared in the following manner. Firstly, selecting a cold rolling test board which is subjected to chemical pretreatment and covered with an electrophoretic coating, wherein the test board is prepared on an automobile OEM production line according to a standard processing technology; then, respectively spraying an aqueous dark gray middle coat (Nippon product) with the mark of AR800N2 and an aqueous black colored paint (Nippon product) with the mark of AR 3500731P according to a wet-on-wet process, and pre-drying the sprayed coating film for 8min at 85 ℃; then, spraying the varnish composition of the invention on the surface of the uncured colored paint again according to a wet-on-wet process in a construction state; finally, the composite coating, namely the multiple coating consisting of the water-based middle coating, the water-based colored paint and the varnish composition, is baked for 25min at 145 ℃ to form a composite coating consisting of the multiple coating; wherein the film thickness of each coating in the composite coating is respectively as follows: middle coating 20 +/-2 microns, colored paint 12 +/-1 microns and varnish 45 +/-5 microns.
The components and formulations of the solvent-borne two-component, high-slip varnish compositions prepared in examples 9-18 are shown in tables 1 and 2 (in parts by weight):
TABLE 1
Abrasion resistance of the coating film after curing was measured by using sandpaper of type P2400 on an abrasion tester, and the retention of 20 ° gloss of the coating film after abrasion for 15 cycles was examined.
In examples 9 to 13, the solvent in the first step of the preparation method in component A was 3 parts of butyl acetate, and the solvent in the second step of the preparation method in component A was 3 parts of S-100# solvent oil.
As can be seen from the data in Table 1, the dry rub resistance data of the paint film gradually increased with the increase in the amount of the polycaprolactone-modified polysiloxane used as compared with the comparative example, indicating that the addition of the polycaprolactone-modified polysiloxane to the varnish composition can improve the rub resistance of the paint film.
TABLE 2
Example 14: the solvent in the first step of the preparation method in component A is 17 parts of butyl acetate, and the solvent in the second step of the preparation method in component A is 8.6 parts of S-100# solvent oil.
Example 15: the solvent in the first step of the preparation method in the component A is 1 part of butyl acetate, and the solvent in the second step of the preparation method in the component A is 1 part of S-100# solvent oil.
Example 16: the solvent in the first step of the preparation method in component A is 10 parts of butyl acetate, and the solvent in the second step of the preparation method in component A is 10 parts of S-100# solvent oil.
Example 17: the solvent in the first step of the preparation method in component A is 12.5 parts of butyl acetate, and the solvent in the second step of the preparation method in component A is 14 parts of S-100# solvent oil.
Example 18: the solvent in the first step of the preparation method in component A is 20 parts of butyl acetate, and the solvent in the second step of the preparation method in component A is 20 parts of S-100# solvent oil.
In examples 14 to 18, the ratio of BYK 315, BYK 358N, Tinuvin 292 and Tinuvin 384-2 was 1:1:1: 1.
The solvent type bi-component high-smoothness varnish composition can be used as finishing varnish for automobile.
The invention relates to application of a solvent type bi-component high-slip varnish composition, in particular to application of the solvent type bi-component high-slip varnish composition in forming a cured coating on a substrate; the method comprises the following steps:
applying a primer or basecoat to a substrate and curing it, applying a basecoat to the substrate with the primer or basecoat already cured, then applying the solvent-borne two-component, high slip, clearcoat composition to the uncured basecoat surface, and finally curing both coats simultaneously to obtain the multi-coat finish system, which can be used in a three-coat two-bake system;
or,
applying a primer or a basecoat to a substrate, applying a basecoat to the surface of the uncured primer or basecoat, applying the solvent-borne two-component, high slip clearcoat composition to the surface of the uncured basecoat, and simultaneously curing the three-part coating to obtain the multi-coat finishing system, which can be used in a three-coat one-bake system or an integrated spray process (IPP) system;
or,
applying two coats of pigmented paint to a substrate without a primer and a basecoat, then spraying the solvent-borne two-component, high slip clear coat composition over the second coat of pigmented paint and simultaneously curing the three coats to obtain the multi-coat finish system, which can be used in a compact spray process (CCT) system;
or,
applying a primer or basecoat to a substrate and curing the same, applying a basecoat or basecoat to the substrate with the primer or basecoat cured, applying a pearlescent paint to the uncured surface of the basecoat, applying the solvent-borne two-component, high slip clear coat composition to the uncured surface of the pearlescent paint, and simultaneously curing the three-part coating to obtain the multi-coat finishing system, which can be used in a four-coat two-bake system;
or,
the method comprises the steps of firstly applying a primer or a middle coat on a substrate, then applying a single-color paint on the surface of an uncured primer or middle coat, then applying a pearlescent color paint on the surface of an uncured single-color paint, then applying the solvent-based two-component high-smoothness varnish composition on the surface of the uncured pearlescent color paint, and finally simultaneously curing the four parts of coatings to obtain the multi-coat finishing system which can be used in a four-coat one-bake system.
The substrate is a standard automobile body or a component assembly of the automobile body and is prepared by cold-rolled sheets which are subjected to chemical pretreatment and covered with an electrophoretic coating; the curing temperature is 100-180 ℃; the curing time is 10-40 min.
The primer and the colored paint used in the three-coating two-drying, three-coating one-drying, integrated spraying process, tightening spraying process, four-coating two-drying and four-coating one-drying system are water-based paints, the construction solid content of the primer is between 35% and 55%, the cured film thickness is between 10 and 50 mu m, the construction solid content of the colored paint is between 20% and 40%, and the cured film thickness is between 6 and 20 mu m.
The outermost coating layer of the multi-coating finishing system is prepared from the solvent-based bi-component high-slip varnish composition; the dry film thickness of the multi-coat coating system is 10 to 80 μm, preferably 20 to 70 μm, and more preferably 30 to 60 μm; the curing temperature is 100-180 ℃, and preferably 120-160 ℃; the curing time is 10-40 min.
The solvent-type bi-component high-slip varnish composition disclosed by the invention uses the polycaprolactone modified polysiloxane with a special structure, and when the polycaprolactone modified polysiloxane is added into a solvent-type coating, particularly a solvent-type varnish, the surface performance of a coating film can be improved, the slip property is increased, and the friction resistance is improved.
The solvent type two-component high-slip varnish composition provided by the invention can effectively improve the slip of the surface of a coating film of the varnish composition, thereby increasing the friction resistance of the coating film.
In the solvent-based two-component high-smoothness varnish composition provided by the invention, polycaprolactone in the polycaprolactone-modified polysiloxane modifies polysiloxane through block and grafting, and the solvent-based two-component high-smoothness varnish composition has the advantages of a polycaprolactone block-modified polysiloxane copolymer and a polycaprolactone graft-modified grafted polysiloxane copolymer.
In the solvent-based two-component high-smoothness varnish composition provided by the invention, the polycaprolactone modified polysiloxane can be used as a solvent-based paint auxiliary agent, and when the solvent-based paint composition is added into a solvent-based paint, particularly a solvent-based varnish, the surface performance of a coating film can be improved, the smoothness is increased, and the friction resistance is improved.
In the solvent-based bi-component high-slip varnish composition provided by the invention, the polycaprolactone modified polysiloxane is composed of a special polysiloxane chain segment and a polycaprolactone chain segment, has excellent miscibility with solvent-based paint, can be used as a paint auxiliary agent, and can be particularly used as a surface slip agent; after the polycaprolactone modified polysiloxane is used as a surface slip agent and added into a solvent type coating, the surface tension of the coating can be reduced, so that good wettability and good anti-cratering property are provided; particularly, when added to a solvent-based varnish, the varnish does not cause turbidity, and the surface smoothness and scratch resistance of the varnish coating can be further enhanced.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (34)
1. A solvent-based two-component, high-slip varnish composition characterized by: the method comprises the following steps:
component A, comprising:
at least one hydroxy acrylic resin or hydroxy methacrylic resin;
at least one hydroxy polyester resin;
at least one amino resin;
at least one rheology control agent;
at least one polycaprolactone-modified polysiloxane;
at least one auxiliary agent; and
at least one first solvent;
component B, comprising:
at least one polyfunctional aliphatic isocyanate;
and/or at least one polyfunctional cycloaliphatic isocyanate;
and/or polyfunctional aliphatic and/or cycloaliphatic isocyanates in which at least a portion of the isocyanate groups are blocked, but free isocyanate groups are still present; wherein the blocking agent for blocking the isocyanate groups participates in a curing reaction during baking, or the blocking agent for blocking the isocyanate groups is removed during baking to release the isocyanate groups again; and
at least one second solvent.
2. The solvent-borne two-component, high slip varnish composition according to claim 1, wherein: the paint comprises the following components in parts by weight:
component A, comprising:
20-50 parts of at least one hydroxyl acrylic resin or hydroxyl methacrylic resin;
10-30 parts of at least one hydroxyl polyester resin;
10-20 parts of at least one amino resin;
5-30 parts of at least one rheological control agent;
0.1-5 parts of at least one polycaprolactone modified polysiloxane;
0.1-7 parts of at least one auxiliary agent; and
1-40 parts of at least one first solvent;
component B, comprising:
10-50 parts of at least one polyfunctional aliphatic isocyanate;
and/or 0-20 parts of at least one polyfunctional alicyclic isocyanate;
and/or 0 to 10 parts of polyfunctional aliphatic and/or alicyclic isocyanate of which at least one part of isocyanate groups is blocked and free isocyanate groups exist; wherein the blocking agent for blocking the isocyanate groups participates in a curing reaction during baking, or the blocking agent for blocking the isocyanate groups is removed during baking to release the isocyanate groups again; and
5-50 parts of at least one second solvent.
3. The solvent-borne two-component, high-slip varnish composition according to claim 1 or 2, characterized in that: the component A and the component B are in a ratio of (1-18) in parts by weight: 3;
in the solvent-based bi-component high-slip varnish composition, the solid content of the component A is between 40 and 70 percent, and the solid content of the component B is between 50 and 90 percent; at the time of application, the ratio of the amount of substance of hydroxyl groups in component a to the amount of substance of isocyanate groups in component B is 1: (0.2-5).
4. The solvent-borne two-component, high-slip varnish composition according to claim 1 or 2, characterized in that: the number average molecular weight of the hydroxyl acrylic resin or the hydroxyl methacrylic resin is 2000-20000 g/mol, the hydroxyl value is 60-250 mg KOH/g, the glass transition temperature is-40 ℃ to +60 ℃, and the solid content is 50-90%;
the hydroxyl functionality of the hydroxyl polyester resin is between 2 and 5, the number average molecular weight is between 500 and 8000g/mol, the hydroxyl value is between 60 and 250mg KOH/g, and the solid content is between 70 and 90 percent;
the amino resin is butylated melamine formaldehyde resin containing imino group and existing in polymer form, and/or mixed etherified melamine formaldehyde resin containing imino group and existing in oligomer form, and/or mixed etherified melamine formaldehyde resin containing total etherified modified melamine formaldehyde resin existing in monomer form, and/or amino resin with carbamate functional group;
the rheology control agent is a compound containing urea bonds, a polymer and derivatives thereof; and/or high-molecular fine particles having a crosslinked structure; and/or surface-treated fine silica particles.
5. The solvent-borne two-component, high-slip varnish composition according to claim 1 or 2, characterized in that: the polycaprolactone modified polysiloxane has a structure shown as a formula (I) or (II):
in the formula (I), R1Has at least one of the structures shown in formula (III):
in the formula (II), R5Has at least one of the structures shown in formula (IV):
R2、R3and R4Respectively have at least one of the structures shown in formula (V):
m>0，n>0，o>0，p>0，q>0，r>0，x>0，y>0，z>0。
6. the solvent-borne two-component, high-slip varnish composition according to claim 1 or 2, characterized in that: the auxiliary agent is at least one of a leveling control agent, an ultraviolet absorber and a hindered amine light stabilizer;
the first solvent is at least one of aliphatic ester, ketone, dihydric alcohol ether, dihydric alcohol ester and aromatic hydrocarbon solvent.
7. The solvent-borne two-component, high slip varnish composition according to claim 6, wherein: the auxiliary agent also comprises an antioxidant and/or an anti-settling agent;
the first solvent includes the following compounds: toluene, xylene, S-100# solvent oil, trimethylbenzene solvent oil, S-150# solvent oil, durene solvent oil, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol butyl ether acetate, amyl acetate, ethylene glycol ethyl ether propionate and propylene glycol methyl ether acetate.
8. The solvent-borne two-component, high-slip varnish composition according to claim 1 or 2, characterized in that: the polyfunctional aliphatic isocyanate has a functionality of at least 2 of isocyanate groups such as 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane, 2-methyl-1, 5-diisocyanatopentane, 1, 5-diisocyanato-2, 2-dimethyl-pentane, 2, 4-trimethyl-1, 6-diisocyanatohexane, 2,4, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, and/or trimers, pentamers, and multimers formed from the above aliphatic diisocyanate monomers;
the polyfunctional alicyclic isocyanate has a functionality of at least 2 of the isocyanate group of 1, 3-diisocyanatocyclohexane, 1, 4-diisocyanatocyclohexane, 2, 6-diisocyanato-1-methylcyclohexane, 2, 4-diisocyanato-1-methylcyclohexane, 1, 3-bis- (isocyanatomethyl) cyclohexane, 1, 4-bis- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,4 '-diisocyanatodicyclohexylmethane, 4' -diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4- (3) isocyanatomethylcyclohexane, bis (isocyanatomethyl) -norbornane, and/or a trimer formed from the above alicyclic diisocyanate monomers, Pentamers and multimers.
9. The solvent-borne two-component, high-slip varnish composition according to claim 1 or 2, characterized in that: the functionality of the polyfunctional aliphatic and/or alicyclic isocyanate in which part of the isocyanate groups are blocked but free isocyanate groups are still present is at least 1;
the second solvent is at least one of aliphatic ester, ketone, dihydric alcohol ether, dihydric alcohol ester and aromatic hydrocarbon solvent.
10. The solvent-borne two-component, high slip varnish composition according to claim 9, wherein: the second solvent comprises the compound: toluene, xylene, S-100# solvent oil, trimethylbenzene solvent oil, S-150# solvent oil, durene solvent oil, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol butyl ether acetate, amyl acetate, ethylene glycol ethyl ether propionate and propylene glycol methyl ether acetate.
11. A method for preparing a solvent-borne two-component, high-slip varnish composition according to any one of claims 1 to 10, wherein: the method comprises the following steps:
step one, stirring and mixing a first part of first solvent, hydroxy acrylic resin or hydroxy methacrylic resin and hydroxy polyester resin uniformly;
secondly, under the condition of keeping the stirring speed unchanged, sequentially adding amino resin, a rheological control agent, polycaprolactone modified polysiloxane, an auxiliary agent and a second part of first solvent, and uniformly stirring and mixing to obtain the component A;
thirdly, keeping the stirring speed unchanged, and adding polyfunctional aliphatic isocyanate, and/or polyfunctional alicyclic isocyanate, and/or polyfunctional aliphatic and/or alicyclic isocyanate with part of isocyanate groups being blocked and free isocyanate groups still existing; wherein the blocking agent for blocking the isocyanate groups participates in a curing reaction during baking, or the blocking agent for blocking the isocyanate groups is removed during baking to release the isocyanate groups again; and a second solvent to obtain the component B;
and fourthly, adding the component B into the component A, and uniformly stirring to obtain the solvent type bi-component high-smoothness varnish composition.
12. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 11, wherein: the stirring and mixing are uniform, namely the stirring speed is 400-1000 revolutions per minute (r/min), and the stirring time is 10-60 min;
and in the second step, the amino resin, the rheological control agent, the polycaprolactone modified polysiloxane, the assistant and the second part of the first solvent are sequentially added for 5-10 min.
13. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 11, wherein: the preparation method of the polycaprolactone modified polysiloxane comprises the following steps:
firstly, mixing unsaturated monohydric alcohol and hexamethyldisilazane, heating to react, and obtaining a trimethylsiloxy unsaturated compound after the reaction is completed;
secondly, under the protection of nitrogen, adding a catalyst into the trimethylsiloxy unsaturated compound obtained in the first step, mixing, heating for reaction, and dropwise adding trimethylcyclotrisiloxaneObtaining trimethylsiloxy alkyl modified cyclotrisiloxane after the reaction is finished
Third, in the absence of waterUnder oxygen condition, mono-functional alkyl lithium or bi-functional alkyl lithium, and trimethylsiloxy alkyl modified cyclotrisiloxane obtained in the second stepHexamethylcyclotrisiloxane D3Mixing with a solvent, heating for reaction, adding dimethyl hydrogen chlorosilane for termination of reaction, and performing aftertreatment to obtain polysiloxane with a side chain having a hydroxyl protecting group and a single end or double ends having a hydrosilyl group;
fourthly, under the protection of nitrogen, mixing the polysiloxane with the side chain having the hydroxyl protecting group and the hydrosilyl group at one end or both ends obtained in the third step with a catalyst, heating for reaction, dropwise adding the trimethylsiloxy unsaturated compound obtained in the first step for reaction, and carrying out post-treatment to obtain the polysiloxane with the side chain, one end or both ends having the hydroxyl protecting group;
fifthly, mixing the polysiloxane with the hydroxyl protecting group at the side chain, single end or double end obtained in the fourth step, an alcohol solvent and a weak acid catalyst, and heating for reaction to obtain the polysiloxane with the hydroxyl group at the side chain, single end or double end;
and sixthly, mixing the polysiloxane with the side chain, single end or double ends all provided with the hydroxyl alkyl, caprolactone and organic tin catalyst obtained in the fifth step, heating to react, and carrying out post-treatment to obtain the polycaprolactone modified polysiloxane.
14. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 13, wherein: the temperature of the heating reaction in the first step is 90-120 ℃, and the time is 4-8 hours (h);
in the first step, the molar ratio of the unsaturated monohydric alcohol to the hexamethyldisilazane is 2 (1-2);
the unsaturated monohydric alcohol in the first step is at least one of the following structures:
A1)CH2＝CHCH2OHA2)CH2＝CHCH2CH2OHA3)CH2＝CHCH2CH2CH2OH
A4)CH2＝CHCH2CH2CH2CH2OHA5)CH2＝CHCH2NHC(O)OCH2CH2OH。
15. the method of preparing a solvent-borne two-component, high slip varnish composition according to claim 13, wherein: the temperature of the temperature rise reaction in the second step is 80-110 ℃, and the time is 4-12 h;
the mass of the catalyst in the second step accounts for trimethylcyclotrisiloxane0.05-1% of the mass;
in the second step, trimethyl siloxy unsaturated compound and trimethyl cyclotrisiloxaneThe molar ratio of (3-6) to (1);
the catalyst in the second step is chloroplatinic acid.
16. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 13, wherein: the temperature of the heating reaction in the third step is-70 ℃ to 50 ℃, and the time is 4 to 12 hours;
in the third step, the molar ratio of the monofunctional alkyl lithium or the bifunctional alkyl lithium to the dimethyl hydrogen chlorosilane is 1 (1-2.2);
the solvent in the third step comprises a non-polar organic solvent and a polar organic solvent, and the mass ratio of the non-polar organic solvent to the polar organic solvent is 1 (1-5);
in the third step, the solvent and trimethylsiloxyalkyl modified cyclotrisiloxaneSix-layer armorCyclotrisiloxane D3The total mass ratio of the monofunctional alkyllithium to the bifunctional alkyllithium is (0.25 to 4): 1.
17. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 13, wherein: the side chain is provided with a hydroxyl protecting group,
The side chain is provided with a hydroxyl protecting group,
The monofunctional alkyl lithium or difunctional alkyl lithium in the third step is at least one of the following structures:
in the third step, the dimethyl hydrochlorosilane is dimethyl chlorosilane;
in the third step, the number average molecular weight of polysiloxane with a side chain having a hydroxyl protecting group and a hydrosilyl group at a single end or double ends is 200-10000; the polymerization degree index is between 1 and 1.2.
18. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 16, wherein: the nonpolar organic solvent in the third step is selected from at least one of aliphatic, alicyclic and aromatic hydrocarbon solvents;
the polar organic solvent in the third step is at least one selected from aliphatic ketones, alicyclic ketones, aromatic ketones, amides, sulfoxides, nitriles and heterocyclic solvents.
19. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 18, wherein: the non-polar organic solvent in the third step includes the following compounds: at least one of isopentane, n-pentane, petroleum ether, n-hexane, cyclohexane, isooctane, cyclopentane, trimethylpentane, cyclopentane, heptane, toluene, benzene and xylene;
the polar organic solvent in the third step includes the following compounds: at least one of tetrahydrofuran, formamide, acetonitrile, N-dimethylformamide, hexamethylphosphoramide, butanone, dimethyl sulfoxide, acetone, 1, 4-dioxane and pyridine.
20. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 13, wherein: the reaction temperature in the fourth step is 80-110 ℃, and the reaction time is 4-12 h;
the catalyst in the fourth step is chloroplatinic acid;
the mass of the catalyst in the fourth step accounts for 0.05-1% of that of polysiloxane with a side chain having a hydroxyl protecting group and a single end or double ends having a hydrosilyl group;
in the fourth step, the molar ratio of the trimethylsiloxy unsaturated compound to the hydrosilyl group contained in the polysiloxane with a side chain having a hydroxyl protecting group and a hydrosilyl group at one end or both ends is (1-2): 1.
21. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 13, wherein: the temperature of the heating reaction in the fifth step is 65-100 ℃, and the reaction time is 4-12 h;
in the fifth step, the alcohol solvent is at least one of methanol, ethanol, n-propanol and isopropanol;
the weak acid catalyst in the fifth step is at least one of formic acid, acetic acid, propionic acid, lactic acid, dimethylolpropionic acid and dimethylolbutyric acid;
in the fifth step, the mass ratio of the polysiloxane with the hydroxyl protecting group at the side chain, single end or double ends to the alcohol solvent is 1 (1-4);
and in the fifth step, the mass of the weak acid catalyst accounts for 0.5-5% of that of the polysiloxane with hydroxyl protecting groups at the side chain, single end or double ends.
22. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 13, wherein: the temperature for heating and reacting in the sixth step is 80-140 ℃, and the time is 5-20 h;
in the sixth step, the number average molecular weight of a polycaprolactone chain segment in the polycaprolactone modified polysiloxane is 200-5000;
in the sixth step, the organic tin catalyst is at least one of stannous isooctanoate, dibutyltin dilaurate, dioctyltin oxide, dibutyltin oxide, tributyltin and dibutyltin acetate;
in the sixth step, the mass of the organic tin catalyst accounts for 0.01-5% of that of caprolactone.
23. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 11, wherein: the preparation method of the multifunctional aliphatic and/or alicyclic isocyanate with part of the isocyanate groups being blocked and free isocyanate groups still existing comprises the following steps:
mixing polyfunctional aliphatic isocyanate and/or polyfunctional alicyclic isocyanate with a catalyst, heating a reaction system to 60-80 ℃, slowly dropwise adding a mixed solution of a sealing agent and a solvent after the temperature is constant, controlling the reaction temperature in the dropwise adding process, keeping the temperature not more than 80 ℃, continuously reacting for 4-5 hours at the temperature after the dropwise adding is finished, controlling the content of residual isocyanate groups, stopping the reaction, and discharging to obtain the polyfunctional aliphatic and/or alicyclic isocyanate with part of the isocyanate groups being sealed and free isocyanate groups still existing.
24. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 23, wherein: the catalyst is an organic tin compound or an organic alkali compound;
the sealant has one of the structures shown as formula (VI), (VII) or (VIII):
wherein R is6And R7Respectively selected from aliphatic alkyl containing 1-8 carbon atoms;
R8(CH2)aSi(OR9)(OR10)(OR11)
(VII)
HN[(CH2)aSi(OR9)(OR10)(OR11)]
(VIII)
wherein R is8Is at least one of primary amino group, hydroxyl group and sulfhydryl group, a is an integer more than or equal to 1, R9、R10And R11Respectively selected from aliphatic alkane group containing 1 to 8 carbon atoms and/or aliphatic acyl group containing 1 to 8 carbon atoms;
or the sealing agent is a compound containing active hydrogen and is at least one of monohydric alcohols, monosubstituted alcohol ethers, ketoximes, monoamines, pyrazoles and alicyclic amides.
25. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 24, wherein: the organic tin compound is at least one of stannous isooctanoate, dibutyltin dilaurate, dioctyltin oxide, dibutyltin oxide, tributyltin and dibutyltin acetate;
the organic alkali compound is at least one of sodium methoxide and sodium ethoxide;
the blocking agent comprises the following compounds: at least one of methanol, ethanol, propanol, N-butanol, isobutanol, N-hexanol, N-octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, methyl ethyl ketoxime, acetone oxime, cyclohexanone ketoxime, diisopropyl amine, N-tert-butyl benzyl amine, 3, 5-dimethyl pyrazole, and caprolactam.
26. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 23, wherein: the solvent is at least one of aliphatic ester, ketone, dihydric alcohol ether, dihydric alcohol ester and aromatic hydrocarbon solvent;
the polyfunctional aliphatic isocyanate has a functionality of at least 2, and is 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane, 2-methyl-1, 5-diisocyanatopentane, 1, 5-diisocyanato-2, 2-dimethyl-pentane, 2, 4-trimethyl-1, 6-diisocyanatohexane, 2,4, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, and/or a trimer, pentamer, multimer formed from the above aliphatic diisocyanate monomers.
27. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 23, wherein: the polyfunctional alicyclic isocyanate has a functionality of at least 2 of the isocyanate group of 1, 3-diisocyanatocyclohexane, 1, 4-diisocyanatocyclohexane, 2, 6-diisocyanato-1-methylcyclohexane, 2, 4-diisocyanato-1-methylcyclohexane, 1, 3-bis- (isocyanatomethyl) cyclohexane, 1, 4-bis- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,4 '-diisocyanatodicyclohexylmethane, 4' -diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4- (3) isocyanatomethylcyclohexane, bis (isocyanatomethyl) -norbornane, and/or a trimer formed from the above alicyclic diisocyanate monomers, Pentamers and multimers.
28. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 26, wherein: the solvent includes the following compounds: toluene, xylene, S-100# solvent oil, trimethylbenzene solvent oil, S-150# solvent oil, durene solvent oil, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol butyl ether acetate, amyl acetate, ethylene glycol ethyl ether propionate and propylene glycol methyl ether acetate.
29. The method of preparing a solvent-borne two-component, high slip varnish composition according to claim 23, wherein: the mass of the catalyst accounts for 0.01-1% of the mass of the polyfunctional aliphatic isocyanate and/or the polyfunctional alicyclic isocyanate;
the mass of the blocking agent accounts for 20-50% of the mass of the polyfunctional aliphatic isocyanate and/or the polyfunctional alicyclic isocyanate;
the mass of the solvent accounts for 40-50% of the mass of the polyfunctional aliphatic isocyanate and/or the polyfunctional alicyclic isocyanate.
30. Use of a solvent-borne two-component, high slip varnish composition according to any one of claims 1 to 10, wherein: the method comprises the following steps:
applying a primer or basecoat to a substrate and curing it, applying a basecoat to the substrate with the primer or basecoat already cured, then applying the solvent-borne two-component, high slip, clearcoat composition to the uncured basecoat surface, and finally curing both coats simultaneously to obtain the multi-coat finish system, which can be used in a three-coat two-bake system;
or,
firstly, applying a primer or a middle coating on a substrate, then applying a color paint on the surface of an uncured primer or middle coating, applying the solvent-based two-component high-smoothness varnish composition on the surface of the uncured color paint, and finally curing the three parts of coatings simultaneously to obtain the multi-coating finishing system, wherein the multi-coating finishing system can be used for a three-coating one-baking system or an integrated spraying process system;
or,
applying two coats of pigmented paint to a substrate without a primer and a basecoat, then spraying the solvent-borne two-component, high slip clear coat composition over the second coat of pigmented paint and simultaneously curing the three coats to obtain the multi-coat finish system, which can be used in a compact spray process system;
or,
applying a primer or basecoat to a substrate and curing the same, applying a basecoat or basecoat to the substrate with the primer or basecoat cured, applying a pearlescent paint to the uncured surface of the basecoat, applying the solvent-borne two-component, high slip clear coat composition to the uncured surface of the pearlescent paint, and simultaneously curing the three-part coating to obtain the multi-coat finishing system, which can be used in a four-coat two-bake system;
or,
the method comprises the steps of firstly applying a primer or a middle coat on a substrate, then applying a single-color paint on the surface of an uncured primer or middle coat, then applying a pearlescent color paint on the surface of an uncured single-color paint, then applying the solvent-based two-component high-smoothness varnish composition on the surface of the uncured pearlescent color paint, and finally simultaneously curing the four parts of coatings to obtain the multi-coat finishing system which can be used in a four-coat one-bake system.
31. Use of the solvent-borne two-component, high slip varnish composition according to claim 30, characterised in that: the substrate is a standard automobile body or a component assembly of the automobile body and is prepared by cold-rolled sheets which are subjected to chemical pretreatment and covered with an electrophoretic coating;
the curing temperature is 100-180 ℃;
the curing time is 10-40 min.
32. Use of the solvent-borne two-component, high slip varnish composition according to claim 30, characterised in that: the primer and the colored paint used in the three-coating two-drying, three-coating one-drying, integrated spraying process, tightening spraying process, four-coating two-drying and four-coating one-drying system are water-based paints, the construction solid content of the primer is between 35% and 55%, the cured film thickness is between 10 and 50 mu m, the construction solid content of the colored paint is between 20% and 40%, and the cured film thickness is between 6 and 20 mu m.
33. Use of the solvent-borne two-component, high slip varnish composition according to claim 30, characterised in that: the outermost coating layer of the multi-coating finishing system is prepared from the solvent-based bi-component high-slip varnish composition; the dry film thickness of the multi-coating finishing system is 10-80 mu m; the curing temperature is 100-180 ℃; the curing time is 10-40 min.
34. Use of a solvent-borne two-component, high slip varnish composition according to any one of claims 1 to 10, wherein: the coating is used as finishing varnish for automobiles.
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