CN114667306B - 耐候性且耐久性涂料组合物 - Google Patents
耐候性且耐久性涂料组合物 Download PDFInfo
- Publication number
- CN114667306B CN114667306B CN202080079345.4A CN202080079345A CN114667306B CN 114667306 B CN114667306 B CN 114667306B CN 202080079345 A CN202080079345 A CN 202080079345A CN 114667306 B CN114667306 B CN 114667306B
- Authority
- CN
- China
- Prior art keywords
- groups
- amino
- coating composition
- acrylic copolymer
- functional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 40
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 45
- 229920002050 silicone resin Polymers 0.000 claims abstract description 44
- 125000000524 functional group Chemical group 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 150000001414 amino alcohols Chemical class 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- LXQMHOKEXZETKB-UHFFFAOYSA-N 1-amino-2-methylpropan-2-ol Chemical compound CC(C)(O)CN LXQMHOKEXZETKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Chemical group 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003333 secondary alcohols Chemical class 0.000 claims description 3
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 3
- 150000003512 tertiary amines Chemical group 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 150000002924 oxiranes Chemical group 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 27
- 125000003545 alkoxy group Chemical group 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 5
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 20
- -1 polysiloxanes Polymers 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 229920000647 polyepoxide Polymers 0.000 description 13
- 239000003822 epoxy resin Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 239000000049 pigment Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- 229920013731 Dowsil Polymers 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000013523 DOWSIL™ Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 229920006334 epoxy coating Polymers 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- QPKNDHZQPGMLCJ-UHFFFAOYSA-N 1-(3-aminophenyl)ethanol Chemical compound CC(O)C1=CC=CC(N)=C1 QPKNDHZQPGMLCJ-UHFFFAOYSA-N 0.000 description 2
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 2
- FNVOFDGAASRDQY-UHFFFAOYSA-N 3-amino-2,2-dimethylpropan-1-ol Chemical compound NCC(C)(C)CO FNVOFDGAASRDQY-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000937 dynamic scanning calorimetry Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DZGWFCGJZKJUFP-UHFFFAOYSA-N tyramine Chemical compound NCCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- PDNZJLMPXLQDPL-UHFFFAOYSA-N (1-aminocyclopentyl)methanol Chemical compound OCC1(N)CCCC1 PDNZJLMPXLQDPL-UHFFFAOYSA-N 0.000 description 1
- ISBHMJZRKAFTGE-ARJAWSKDSA-N (z)-pent-2-enenitrile Chemical compound CC\C=C/C#N ISBHMJZRKAFTGE-ARJAWSKDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XUSXTHMTOSFZII-UHFFFAOYSA-N 1-(aminomethyl)cyclohexan-1-ol Chemical compound NCC1(O)CCCCC1 XUSXTHMTOSFZII-UHFFFAOYSA-N 0.000 description 1
- MBDCOIVZKBMNAT-UHFFFAOYSA-N 1-amino-2-methylpentan-1-ol Chemical compound CCCC(C)C(N)O MBDCOIVZKBMNAT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CUTYBIJPSXIULF-UHFFFAOYSA-N 2,4-bis(methylaminomethyl)phenol Chemical compound CNCC1=C(C=CC(=C1)CNC)O CUTYBIJPSXIULF-UHFFFAOYSA-N 0.000 description 1
- SJYRIEHMQRIBEN-UHFFFAOYSA-N 2-(1-aminopropyl)phenol Chemical compound CCC(N)C1=CC=CC=C1O SJYRIEHMQRIBEN-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- ILDXSRFKXABMHH-UHFFFAOYSA-N 2-(2-aminophenyl)ethanol Chemical compound NC1=CC=CC=C1CCO ILDXSRFKXABMHH-UHFFFAOYSA-N 0.000 description 1
- XALTWITXELVMHP-UHFFFAOYSA-N 2-(2-aminopropylamino)ethanol Chemical compound CC(N)CNCCO XALTWITXELVMHP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MGUMZJAQENFQKN-UHFFFAOYSA-N 2-(cyclohexylamino)ethanol Chemical compound OCCNC1CCCCC1 MGUMZJAQENFQKN-UHFFFAOYSA-N 0.000 description 1
- IOAOAKDONABGPZ-UHFFFAOYSA-N 2-amino-2-ethylpropane-1,3-diol Chemical compound CCC(N)(CO)CO IOAOAKDONABGPZ-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- HCPJEHJGFKWRFM-UHFFFAOYSA-N 2-amino-5-methylphenol Chemical compound CC1=CC=C(N)C(O)=C1 HCPJEHJGFKWRFM-UHFFFAOYSA-N 0.000 description 1
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QWMFKDZIWAENBE-UHFFFAOYSA-N 3-amino-2-methylbenzamide Chemical compound CC1=C(N)C=CC=C1C(N)=O QWMFKDZIWAENBE-UHFFFAOYSA-N 0.000 description 1
- FLROJJGKUKLCAE-UHFFFAOYSA-N 3-amino-2-methylphenol Chemical compound CC1=C(N)C=CC=C1O FLROJJGKUKLCAE-UHFFFAOYSA-N 0.000 description 1
- AGMZSYQMSHMXLT-UHFFFAOYSA-N 3-aminobutan-1-ol Chemical compound CC(N)CCO AGMZSYQMSHMXLT-UHFFFAOYSA-N 0.000 description 1
- FERWBXLFSBWTDE-UHFFFAOYSA-N 3-aminobutan-2-ol Chemical compound CC(N)C(C)O FERWBXLFSBWTDE-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- HDGMAACKJSBLMW-UHFFFAOYSA-N 4-amino-2-methylphenol Chemical compound CC1=CC(N)=CC=C1O HDGMAACKJSBLMW-UHFFFAOYSA-N 0.000 description 1
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 description 1
- DBFYESDCPWWCHN-UHFFFAOYSA-N 5-amino-2-methylphenol Chemical compound CC1=CC=C(N)C=C1O DBFYESDCPWWCHN-UHFFFAOYSA-N 0.000 description 1
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- SUTWPJHCRAITLU-UHFFFAOYSA-N 6-aminohexan-1-ol Chemical compound NCCCCCCO SUTWPJHCRAITLU-UHFFFAOYSA-N 0.000 description 1
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 1
- KVHHMYZBFBSVDI-UHFFFAOYSA-N 8-aminonaphthalen-2-ol Chemical compound C1=C(O)C=C2C(N)=CC=CC2=C1 KVHHMYZBFBSVDI-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- WIVTXBIFTLNVCZ-UHFFFAOYSA-N CC(=C)C(=O)OCCP(=O)=O Chemical compound CC(=C)C(=O)OCCP(=O)=O WIVTXBIFTLNVCZ-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000001825 Polyoxyethene (8) stearate Substances 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 102100029290 Transthyretin Human genes 0.000 description 1
- 108050000089 Transthyretin Proteins 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000033 alkoxyamino group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- MGFFVSDRCRVHLC-UHFFFAOYSA-N butyl 3-sulfanylpropanoate Chemical compound CCCCOC(=O)CCS MGFFVSDRCRVHLC-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LDTLDBDUBGAEDT-UHFFFAOYSA-N methyl 3-sulfanylpropanoate Chemical compound COC(=O)CCS LDTLDBDUBGAEDT-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005787 opaque polymer Polymers 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- AKPPMPFGSQLQFF-UHFFFAOYSA-M sodium;2-(prop-2-enoylamino)butane-2-sulfonate Chemical compound [Na+].CCC(C)(S([O-])(=O)=O)NC(=O)C=C AKPPMPFGSQLQFF-UHFFFAOYSA-M 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- HTOWLNFYGJZOFV-UHFFFAOYSA-N triaminomethanol Chemical compound NC(N)(N)O HTOWLNFYGJZOFV-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 229960003732 tyramine Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
- Silicon Polymers (AREA)
Abstract
提供了一种可固化涂料组合物,其具有多官能化丙烯酸共聚物和氨基官能硅酮树脂固化剂。可固化涂料组合物的丙烯酸共聚物具有聚合形式的环氧官能化基团和固化相容性基团,并且氨基官能硅酮树脂是烷氧基官能硅氧烷,其任选地衍生自空间位阻醇‑胺前体部分。所述涂料组合物可用于优良耐候性和耐久性的涂料领域,并且可用于代替含异氰酸酯的聚氨酯类涂料。还提供了由所述可固化组合物产生的经涂布制品。
Description
本发明涉及具有多官能化丙烯酸共聚物和氨基官能硅酮树脂固化剂的可固化涂料组合物。更特别地,丙烯酸共聚物具有聚合形式的环氧官能化基团和固化相容性基团,并且氨基官能硅酮树脂是烷氧基官能硅氧烷,其任选地衍生自空间位阻的醇-胺前体部分。所述涂料组合物可用于优良耐候性和耐久性的涂料领域,并且可用于代替含异氰酸酯的聚氨酯类涂料。
含异氰酸酯的聚氨酯类涂料用于需要优良耐候性和耐久性的应用。然而,制造商和消费者的需要移向不含异氰酸酯的涂料,以限制暴露于此类材料;同时提供耐候性外加耐化学性和耐腐蚀性。在使用环氧涂层保护金属但需要良好颜色和光泽度保持性的应用中,环氧涂层上还进一步涂布顶涂层(通常是聚氨酯)。衍生自环氧树脂的其它涂料(如聚硅氧烷-环氧树脂涂料)取决于固化的湿度,且通常随着涂料继续固化而变得脆性。
具有通过Si-OC键连接的胺官能团的氨基官能聚硅氧烷通常在水分存在下表现出稳定性问题,因为SiOC键易于水解,从而导致原始胺醇和硅烷醇的再生。水解会影响保护涂层的外观,因为醇胺通常与主体硅氧烷树脂和有机环氧固化剂不相容,并且会影响保护涂层的性能,因为如果SiOC键断裂,则化学交联水平将受到很大限制。
美国专利公开案2005/0148752 A1公开了在聚合物主链和官能团之间具有Si-OC键的氨基官能聚硅氧烷;并且包括环氧-聚硅氧烷组合物。US2005/0148752A1未能认识到包含丙烯酸共聚物的涂料。此外,US2005/0148752 A1未能区分与使用衍生自空间位阻醇-胺前体部分的硅氧烷相关的益处和与使用衍生自非空间位阻部分的硅氧烷相关的益处。
美国专利8,193,293公开了一种低温环境可固化涂料组合物,其包含氨基官能聚硅氧烷;聚硅氧烷树脂,其是含有硅氢化物的聚硅氧烷与具有两个或更多个能够进行氢化硅烷化反应的不饱和键的含羟基官能团的材料的反应产物;以及聚环氧化物。
美国专利8,871,888公开了一种高固含量、单组分、储存稳定的涂料组合物,其包含每个分子包含超过一个1,2-环氧基团的环氧树脂;具有软化点50℃至140℃的烃化合物;烷氧基官能和/或硅烷醇官能硅酮;以及包含反应物的反应产物的酮亚胺固化剂,所述反应物包含聚烷基二胺组分和酮组分。
国际专利公开案WO 01/51575 A1公开了一种环境温度固化涂料组合物,其包含具有烷基、芳基、烷氧基、反应性缩水甘油氧基和OSi(OR)3基团的聚硅氧烷;缩水甘油基官能的丙烯酸聚合物;以及硬化剂。聚硅氧烷不含胺官能团。
日本专利公开案2002-167546 A公开了一种用于单涂层饰面的防腐蚀涂料材料组合物,其包含(A)丙烯酸树脂、(B)具有至少两个环氧基的环氧树脂、(C)有机硅烷化合物和(D)含氨基硅烷的胺固化剂,并且关于丙烯酸树脂(A)、环氧树脂(B)和有机硅烷化合物(C)的混配比率,各自基于这些树脂的固体含量的总量,组分(A)为5-65wt.%;组分(B)为30-90wt.%;并且组分(C)为5-65wt.%。
需要一种具有成本效益的涂料组合物,它在水分存在下表现出良好稳定性,并提供包括UV防护、耐腐蚀、良好干燥时间和耐化学性在内的性质的良好平衡;同时使用最少的材料。
本发明提供一种可固化涂料组合物,其包含:
(1)氨基官能硅酮树脂,其包含聚合形式的以下结构单元:
(i)(R3SiO1/2)a;
(ii)(R2Si(OR’)xO(2-x)/2)b;
(iii)(RSi(OR’)y,O(3-y)/2)c;和
(iv)(Si(OR’)zO(4-z)/2)d
其中每个R'是氢、烷基或官能化烷基,条件是所有R'基团的至少5摩尔%是下式的含胺基团:-Ra-NHRb;其中,Ra为衍生自氨基醇的烷基或含芳基基团,并且Rb为氢、烷基或芳基;其中a+b+c+d=1.00(100摩尔百分比);x为0或1;y为0、1或2;并且z为0、1、2或3;其中每个R独立地为氢、烷基或芳基;氨基官能硅酮树脂的-NH-当量质量为50至750;和(2)丙烯酸共聚物,其具有聚合形式的环氧官能化基团和固化相容性基团;其中涂料组合物的胺NH官能团与环氧官能团的摩尔比在0.5到1.3范围内。本发明还提供一种经涂布的制品,其包含经固化涂料组合物的一个或多个层。
术语“摩尔百分比”也可以表示为“摩尔分数”,由此1摩尔百分比等于0.01的摩尔分数。术语“摩尔百分比”和“摩尔分数”基于总计100摩尔%(即1.00摩尔分数)的材料中的Si含量。对于本发明中提出的每个范围,范围的下限和范围的上限是可分离的,并且可与其它下限或上限以任何方式组合;包括与本发明中确定的额外组分的范围的下限和上限组合。所有个别值和子范围都包括于本文中并且公开于本文中。
氨基官能硅酮树脂
本发明的氨基官能硅酮树脂可以描述为具有硅氧烷键(-Si-O-Si-)的硅氧烷结构,其中胺官能团通过Si-OC键连接到硅氧烷结构上的Si单元上,并且包含聚合形式的以下结构单元:
(i)(R3SiO1/2)a;
(ii)(R2Si(OR’)xO(2-x)/2)b;
(iii)(RSi(OR’)y,O(3-y)/2)c;和
(iv)(Si(OR’)zO(4-z)/2)d
其中每个R'是氢、烷基或官能化烷基,条件是所有R'基团的至少5摩尔%是下式的含胺基团:-Ra-NHRb;
其中Ra为衍生自氨基醇的烷基或含芳基基团,并且Rb为氢、烷基或芳基;
其中a+b+c+d=1.00(100摩尔百分比);x为0或1;y为0、1或2;并且z为0、1、2或3;
其中每个R独立地为氢、烷基或芳基;并且
氨基官能硅酮树脂的-NH-当量质量为50到1000,优选地50到750,更优选80到900,甚至更优选100到800,以及最优选100-700。
作为下式的含胺基团的所有R'基团的量:-Ra-NHRb,可以低至5摩尔百分比、10摩尔百分比或20摩尔百分比,并且可以独立地高达100摩尔百分比、50摩尔百分比或30摩尔百分比,优选范围为5至42摩尔百分比和20至30摩尔百分比;条件是氨基官能硅酮树脂的-NH-当量质量在确定的范围内。Ra衍生自由式HO-Ra-NHRb表示的氨基醇,其中Ra是烷基或含芳基基团。优选地,Ra衍生自氨基醇,其选自以下氨基醇的组:(a)在COH部分周围具有空间位阻;(b)是仲醇或叔醇;(c)是其混合物。
在描述硅酮树脂时,R3SiO1/2也称为M,R2SiO2/2也称为D,RSiO3/2也称为T,并且SiO4/2也称为Q。如果在M、D、T或Q名称旁边使用上标,那么它指示存在的一个或多个R基团的类型。例如,DPh意指两个R基团中的一个是苯基。除非聚合物的特定描述另外指示,否则本领域的技术人员将未由上标描述的任何R基团理解为甲基。通过获得氨基官能硅酮树脂的已知量溶液或纯净样品的13C-NMR光谱,并相对于与已知量内标物(通常为1,4-二噁烷)相关的那些峰对氨基官能硅酮树脂的氨基官能Si单元相关的峰进行定量,接着调节样品中存在的溶剂(如果存在)含量(如通过气相色谱法所确定),确定氨基官能硅酮树脂的-NH-当量质量。氨基官能硅酮树脂呈纯净液体、溶液或可熔固体的形式。每个下标a、b、c或d是构成材料的单元分布的平均值,并且对于任何给定的材料,均通过使用基于NMR光谱数据(通常为29Si-NMR和13C-NMR、或者29Si-NMR和1H-NMR)的计算来测定。
本发明的氨基官能硅酮树脂可以通过使(1)具有羟基、烷氧基或芳氧基官能团的硅酮树脂与(2)氨基醇反应来产生。具有羟基、烷氧基或芳氧基官能团的硅酮树脂可以衍生自聚硅氧烷、烷氧基硅烷或氯硅烷。硅酮树脂(1)组合物的羟基、烷氧基或芳氧基官能团有时称为“OZ”含量并以摩尔百分比表示。合适的硅酮树脂的非限制性实例包括可从陶氏化学公司(The Dow Chemical Company)获得的DOWSILTM 3074和DOWSILTM 3037;从信越化学株式会社(Shin-Etsu Chemical Co.,Ltd.)获得的Shin-Etsu Silicone KR-213和KR-510;和从瓦克化学公司(Wacker Chemie AG)获得的IC232和/>SY231。
如先前所述,氨基醇可由式HO-Ra-NHRb表示。合适的氨基醇的非限制性实例包括2-氨基-1-乙醇、1-氨基-2-丙醇、1-氨基-2-甲基丙-2-醇、2-氨基-1-丙醇、3-氨基-1-丙醇、2-氨基-1-丁醇、3-氨基-1-丁醇、新戊醇胺(3-氨基-2,2-二甲基-1-丙醇)、2-氨基-1-甲基-1-丙醇、2-氨基-2-甲基-1-丙醇、2-氨基-2-乙基丙烷-1,3-二醇、2-氨基-2-甲基丙烷-1,3-二醇、5-氨基-1-戊醇、1,2-二甲基乙醇胺、3-烷氧基-2-羟基-丙胺、1-氨基-2-甲基-戊醇、N-甲基乙醇胺、N-羟乙基丙二胺、N-环己基乙醇胺、p-(β-羟乙基)-苯胺、N-(β-羟丙基)-N'-(β-氨基乙基)哌嗪、2-羟基-3-(间乙基苯氧基)丙胺、2-羟基-2-苯乙胺、三(羟甲基)氨基甲烷、2-氨基苯甲醇、3-氨基苯甲醇、3-氨基-邻-甲酚、4-氨基-邻-甲酚、5-氨基-邻-甲酚、2-氨基-对-甲酚、4-氨基-间-甲酚、6-氨基-间-甲酚、1-氨基-1-环戊烷甲醇、2-(2-氨基乙氧基)乙醇、2-(2-氨基乙基氨基)乙醇、6-氨基-1-己醇、3-(1-羟乙基)苯胺、2-氨基-1-苯基乙醇、1-氨基甲基-1-环己醇、8-氨基-2-萘酚、2-氨基-苯乙醇、4-氨基苯乙醇、3-(α-羟乙基)苯胺、曼尼希碱、氨基醇与顺式-2-戊烯腈然后进行氢化步骤的反应产物、氨基苯酚(如对氨基苯酚)、酪氨酸、酪胺和类似物、环氧-胺加合物及其混合物。优选的氨基醇包括但不限于1-氨基-2-丙醇和1-氨基-2-甲基丙-2-醇。
NMR:利用NMR确定各种含烷氧基氨基官能硅酮树脂组合物的组成。使用Mercury400MHz超导光谱仪进行核磁共振(NMR)分析。所述仪器使用无硅探头。
烷氧基含量-烷氧基含量通过两种方法之一计算。方法一使用从13C NMR测量的烷氧基与苯基的比率,并且然后将该比率乘以从29Si NMR测量的苯基含量。所获得结果以摩尔百分比(mol%)表示。方法2在13C NMR中使用内标氘代氯仿。使用添加到NMR样品中的树脂和氯仿的重量,确定烷氧基的重量%。然后使用该信息结合从29Si NMR获得的组成来计算烷氧基的摩尔量。
分子量-使用凝胶渗透色谱分析树脂的分子量(Mn和Mw)。以THF制备浓度为0.5%的样品,用乙酸酐封端,过滤并使用RI检测针对聚苯乙烯标准进行分析。柱是两个300mm 5微米的混合C和50mm保护柱。流速为l ml/min。
烷基由以下例示但不限于:甲基、乙基、丙基、丁基、己基、辛基、癸基、十二烷基、十六烷基和十八烷基,其中烷基通常为甲基。芳基由以下例示但不限于:苯基、萘基、苯甲基、甲苯基、二甲苯基、联苯基、甲基苯基、2-苯基乙基、2-苯基-2-甲基乙基、氯苯基、溴苯基和氟苯基,其中芳基通常为苯基。
具有羟基、烷氧基或芳氧基官能团的硅酮树脂根据本领域已知的聚合方法合成。非限制性的说明性聚合方法在美国专利公开案2005/0148752A1中公开。
多官能化丙烯酸共聚物描述
多官能化丙烯酸共聚物是指包含大部分量的共聚(甲基)丙烯酸酯的共聚物,所述共聚物包括通过丙烯酸酯键连的呈聚合形式的环氧官能化基团和固化相容性基团,其在丙烯酸共聚物的主链上保留其官能团。优选地,部分地由于固化相容性基团的存在,多官能化丙烯酸共聚物为极性材料,尽管不受任何理论的束缚,但据信所述固化相容性基团有助于与极性氨基官能硅酮树脂的相容性。这种相容性通过减少固化涂料组合物中的雾度而最好地表现出来。如本文所使用,在术语“(甲基)”之后紧跟另一个术语如丙烯酸酯的使用是指丙烯酸酯和甲基丙烯酸酯两者。例如,术语“(甲基)丙烯酸酯”是指丙烯酸酯或甲基丙烯酸酯。类似地,术语“(甲基)丙烯酸”是指甲基丙烯酸或丙烯酸。丙烯酸共聚物通过在溶剂(如二甲苯)中的自由基聚合制备,其中单体、引发剂、任选地链转移剂和溶剂可装入容器中并且在约60℃到175℃下反应约1到6小时以形成聚合物。可用于制备丙烯酸共聚物的典型溶剂为以下:甲苯、乙酸乙酯、乙酸丁酯、丙酮、甲基异丁基酮、甲基乙基酮、乙醇、矿油精、乙二醇单乙醚乙酸酯和其它适宜使用的脂肪族、环脂肪族和芳香族烃、酯、醚、酮和醇。或者,丙烯酸共聚物可通过自由基乳液或悬浮液加成聚合或通过在剪切下将预形成的聚合物分散到水性介质中来制备。优选地,本发明的丙烯酸共聚物为溶剂型(solvent-borne)。
适合于制备丙烯酸共聚物的单体包括(甲基)丙烯酸酯,如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯和其组合。额外单体可以用于制备丙烯酸共聚物,所述额外单体包括羧酸单体,如(甲基)丙烯酸和衣康酸,以及其盐;磺酸单体,如苯乙烯磺酸钠和丙烯酰胺基-甲基-丙烷磺酸钠,以及其盐;以及磷酸单体,如甲基丙烯酸磷酸乙酯和其盐。如苯乙烯、丙烯腈、甲基丙烯酸乙酰乙酰氧基乙酯(AAEM)和烷氧基硅烷官能(甲基)丙烯酸酯的单体以及能够赋予可共固化官能团的单体(如(甲基)丙烯酸缩水甘油酯和(甲基)丙烯酸羟烷基酯)也可以用于制备丙烯酸共聚物。在某些实施例中,有利的是将少量的共聚多烯系不饱和单体基团并入到丙烯酸共聚物中,所述共聚多烯系不饱和单体基团包括(甲基)丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、1,4-丁二醇二(甲基)丙烯酸酯、1,2-乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯和二乙烯基苯。将此类单体基团不均匀地并入到聚合物中以形成多相聚合物粒子从而产生核-壳、半球面或闭塞形态也可以是有利的。可以使用链转移剂制备这些丙烯酸共聚物,所述链转移剂的实例包括十二烷基硫醇、2-巯基乙醇、巯基三烷氧基硅烷、巯基丙酸丁酯、巯基丙酸甲酯和巯基丙酸。引发剂可用于制备这些丙烯酸共聚物,所述引发剂的实例包括过氧基化合物和偶氮化合物。
丙烯酸共聚物的环氧官能化基团包含缩水甘油基,如甲基丙烯酸缩水甘油酯(GMA)或丙烯酸缩水甘油酯;其中GMA为优选。诸如在聚合中使用OH官能链转移剂时,丙烯酸共聚物的固化相容性基团包含呈聚合形式的单体基团,所述单体基团含有侧接到主链(如丙烯酸单体)或作为端基连接的醇(OH)官能团、酚基、叔胺或酸基团中的一个或多个,诸如使用单体3-(三甲氧基甲硅烷基)丙基甲基丙烯酸酯(MATS)、叔胺或酸基。优选地,固化相容性基团是(甲基)丙烯酸羟乙酯(HEMA或HEA)。优选地,丙烯酸共聚物由包括GMA、HEMA、甲基丙烯酸甲酯(MMA)和丙烯酸2-乙基己酯(EHA)的单体合成。
按添加产生共聚物的总单体单元的重量计,丙烯酸共聚物含有30重量%到80重量%的(甲基)丙烯酸缩水甘油酯单体单元;优选地40重量%到60重量%的(甲基)丙烯酸缩水甘油酯单体;并且最优选地在所述范围的底部之上大于30重量%的(甲基)丙烯酸缩水甘油酯单体。按添加产生共聚物的总单体单元的重量计,丙烯酸共聚物含有至多20重量%的固化相容性基团单体单元;优选地至多10重量%的固化相容性基团单体单元;优选地至多8重量%的固化相容性基团单体单元;并且优选地大于到2重量%的固化相容性基团单体单元,其中优选范围为5重量%到10重量%。当将HEMA与GMA官能团并入时,固化相容性基团的上限主要由共聚物的粘度决定。理论上,当使用其它单体(如用HEA和丙烯酸缩水甘油酯的组合)时,有可能具有较高含量的固化相容性基团。如根据ASTM D1652所测定,丙烯酸共聚物含有的环氧当量(EEW)在200-600g/mol环氧树脂的范围内;优选地下限大于250g/mol环氧树脂,更优选地大于275g/mol环氧树脂;并且优选地上限小于500g/mol环氧树脂,更优选地小于450g/mol环氧树脂;并且其中优选范围为300-400g/mol环氧树脂。
丙烯酸共聚物的经计算的玻璃化转变温度(“Tg”)为八十摄氏度(80℃)或更低,优选地30℃或更低,最优选地15℃或更低,其中优选范围为-40℃到10℃。如本领域众所周知的,Tg通过选择单体和单体的量达到,从而实现所需聚合物Tg。使用动态扫描量热法(Dynamic Scanning Calorimetry)测量聚合物的Tg。
丙烯酸共聚物溶液为粘性液体,其在室温(25℃)下以约70%固体具有500厘泊(cP)到8,000cP范围内粘度。如通过凝胶渗透色谱法使用聚苯乙烯标准物所测量,本发明的丙烯酸共聚物的数目平均分子量为500到10,000g/mol,优选地1,000到5,000g/mol或更大,或更优选地4,000g/mol或更小。
涂料组成描述
本发明的涂料组合物包含丙烯酸共聚物和氨基官能硅酮树脂。胺NH官能团与环氧官能团的摩尔比在0.5到1.3的范围内;优选地在0.8到1的范围内。优选地,最好避免过量的胺基,因为这可能产生对于外部耐久性来说不良的胺致异色(amine blush)。胺致异色在暴露于水之后会导致光泽度损失。尽管可以加速固化,但是通常使涂料组合物经受环境固化。
本发明的涂料组合物可含有额外组合物,其包括但不限于:加速剂/增塑剂,如苯甲醇、水杨酸和三-2,4,6-二甲基氨基甲基酚;填料,如细粉状的矿物,包括二氧化硅、氧化铝、氧化锆、滑石、硫酸盐、TiO2、碳黑、石墨、硅酸盐等;其它固化剂;其它环氧树脂;增强剂;流变改性剂;溶剂;加速剂;表面活性剂;紫外线(UV)稳定剂;抗氧化剂;润湿剂;溶剂;消泡剂;增韧剂;和着色剂,包括颜料、染料和色料。
本发明的可固化涂料组合物可以是未着色的澄清透明涂料,或用于底漆、底涂层和顶涂层应用的着色系统。颜料可以是任何典型的有机或无机颜料。可能需要几种不同的颜料来达成特定应用所需的颜色。合适颜料的实例包括但不限于二氧化钛,不透明聚合物,重晶石,粘土,碳酸钙,氧化铁红,CI颜料黄(Pigment Yellow)42,CI颜料蓝(Pigment Blue)15,15:1、15:2、15:3、15:4(铜酞菁)(copper phthalocyanines)、CI颜料红(Pigment Red)49:1、CI颜料红57:1以及碳黑。
可使用本领域中已知的技术将所得涂料组合物涂覆到基板上;例如通过喷涂、刷涂、刮涂(draw-down)、辊涂。涂层的标称干膜厚度(DFT)大于或等于1密耳,优选地大于或等于2密耳,优选地大于或等于2.5密耳并且更优选地大于或等于3密耳。1密耳等于1/1000英寸。可以涂布的基板的实例包括但不限于塑料、木材、金属(如铝、钢或镀锌薄板)、镀锡钢、混凝土、玻璃、复合材料、氨基甲酸酯弹性体、涂底漆(喷漆)的基板等。可以在室温下或在高温下于强制空气烘箱中或用其它类型的加热源固化涂层。
以下实例是对本发明的说明。
实例和实验方法:
丙烯酸共聚物
将二甲苯添加到装备有搅拌轴、冷凝器、热电偶端口和添加端口的500mL 4颈圆底烧瓶中。用加热罩使二甲苯的温度升至回流温度(140℃)。将由甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯酸甲酯(MMA)、丙烯酸2-乙基己酯(EHA)和甲基丙烯酸2-羟乙酯(HEMA)组成的单体共混物称重,并且在500mL玻璃罐中混合,接着用鲁尔锁(Luer Lock)连接器分入50mL塑料进料注射器。将引发剂,即过氧乙酸叔丁基酯(TBPA,在矿油精中50%)添加到单个50mL塑料注射器中,并且通过带有长进料针连接物(long feed needle attachment)的鲁尔锁连接器连接到进料管。使用双注射泵以恒定进料速率添加单体混合物,并使用单个进料注射泵以进料引发剂。当溶剂处于回流时开始进料。进料速率时间和温度取决于溶剂,和引发剂的半衰期。一旦进料耗尽,就用少量溶剂冲洗管线。继续再运行一小时以将残余单体和引发剂减少到可接受水平。表1示出制得的丙烯酸共聚物。
丙烯酸共聚物的表征
GPC
将样品在四氢呋喃(THF)中溶解达到2mg/mL;注射前,将溶液通过0.2μmPTFE针筒式过滤器过滤。在35℃下,以1.0mL/分钟的流动速率,用在带有MIXED-D管柱的安捷伦(Agilent)1100系列(300×7.5mm)上所进行测量的GPC来进行分子量测量。安捷伦折射率检测器由安捷伦GPC/SEC软件使用。使用聚合物实验室(Polymer labs)的17种窄PS标准物进行校准,在3,742kg/mol到0.580kg/mol的范围内拟合成3阶多项式曲线。
EEW
根据ASTM D1652测量EEW。将环氧树脂溶解于二氯甲烷中,并且在乙酸中存在过量溴化四乙基铵(TEAB)的情况下用含标准化0.1N过氯酸(HClO4)的冰乙酸滴定。使用经配置用于EEW测定的瑞士万通(Metrohm)905滴定器和相关的Tiamo滴定软件进行测量。
固体百分比
给小型铝盘的底部贴上标签,将所述盘放置在秤上并记录其重量,精确到0.0001克。使用移液管将约0.5g-1.5g的样品均匀分布在所述盘中。将所述重量记录为初始重量(盘+样品)。在将样品放入烘箱之前,将其放在烘烤盘上并用绑定夹向下夹住,接着使用移液管将树脂用约2克的甲苯覆盖,接着小心地放入预加热的A类烘箱。2小时后,从烘箱中移出烘烤盘和样品。调整天平,并且将样品(和盘)放置在天平上并记录最终重量,并通过以下式计算固体含量:
固体%=(最终重量-盘重量)/(初始重量-盘重量)*100
玻璃化转变温度
Tg是根据ASTM D7426用差示扫描量热法DSC Q2000 V24.10测量的,其中样品大小为约5-10mg。如下进行温度分布:在10℃下等温持续5分钟。以10℃/分钟升温至-50℃,等温5分钟,以10℃/分钟升温至150℃,等温5分钟,使用TA软件分析Tg。
粘度
使用具有小样品适配器(SSA)的布氏DV-III超粘度计(Brookfield DV-III Ultraviscometer)进行粘度测量。小样品适配器的流变学上正确的圆柱几何形状提供极其精确的粘度测量和剪切速率测定。对于这些样品,将9mL的材料沉积到圆柱体中,并使用#31或#34轴,并改变转速以获得约25牛顿米(N*m)的扭矩。以厘泊(cP)为单位报告测量值。
氨基官能硅酮树脂
氨基官能硅酮树脂S1至S13如表2所示,并且各自是硅酮树脂与醇胺的反应产物。根据以下程序通过使硅酮树脂试剂/反应物与NMR确定的结构D0.337T环己基 0.010TPh 0.653(OZ=68.64mol%,FW~126.5g/mol Si)和1-氨基-2-丙醇(Mw=75.11,TCI牌号,bp=160℃)反应来制备代表性硅酮树脂S1:向250mL1-颈圆底烧瓶中装入硅酮树脂反应物(94.19g,0.745mol Si.0.511mol OZ)和1-氨基-2-丙醇(16.52g,0.220mol,0.440mol NH)。烧瓶配备有磁力搅拌棒和连接到水冷冷凝器的迪恩斯塔克(Dean Stark)装置。该混合物在室温下是浑浊的。将混合物在140℃的铝块温度下加热2小时。第一小时收集的挥发物量为3.35g,并且第二小时为0.31g。反应混合物在加热至140℃时变澄清。铝块温度增加至180℃并在该温度下保持2小时。第一小时收集的挥发物量为1.85g,并且第二小时为0.13g。最终产物在115℃油浴温度和约1mm Hg压力下在旋转蒸发仪上汽提。
所得产物在室温下为澄清粘稠液体。产物的分离产率为100.9g,并且它具有从13CNMR光谱计算的256g/mol NH的胺氢当量。产物的NMR分析表明它是:D0.333T环己基 0.007TPh 0.660,其中OZ含量为61.95mol%(26.9mol%OR和33.5mol%OMe)。通过取得OR积分值之比并将其除以苯基的积分值来由13C NMR计算OR和OMe值。
根据以下程序通过使衍生自烷氧基硅烷的硅酮树脂试剂/反应物与乙醇胺反应来制备代表性硅酮树脂S6:
试剂:
·苯基三甲氧基硅烷–DowsilTMZ-6124硅烷(可从陶氏公司或其附属公司获得)–
·甲基三甲氧基硅烷–SilasticTMZ-6070硅烷(可从陶氏公司或其附属公司获得),实验室蒸馏;Mw=136.22
·乙醇胺,从阿克洛斯有机物公司(Acros Organics)获得
向250mL 2颈圆底烧瓶中装入苯基三甲氧基硅烷(106.28g,0.536mol)、甲基三甲氧基硅烷(35.96g,0.264mol)和乙醇胺(12.91g,0.21mol,0.42mol NH)。使用磁力搅拌棒进行混合并将混合物加热至50℃铝块温度。缓慢添加去离子水(14.83g,0.823mol)并将混合物在70℃铝块温度下加热1小时。将铝块温度增加至120℃,并且然后在该温度下保持1小时。除去的挥发物的量为55.8g。将产物在旋转蒸发仪上在80℃油浴温度、约1.0mm Hg下汽提45分钟。所得产物在室温下为澄清粘稠液体,从13C NMR光谱计算的胺当量为304g/molNH。产物的NMR分析表明它是:TMe 0.300T环己基 0.010TPh 0.690;其中OZ含量为83.4mol%。
表2
涂料配制物:澄清涂料
表3的澄清涂料组合物通过以下方式制备:将丙烯酸共聚物放置于MAX40SpeedMixerTM杯中,并添加氨基官能硅酮树脂且在FlackTekTM DAC150SpeedMixerTM中以2000rpm混合2分钟。在配制涂料组合物时,丙烯酸共聚物和氨基官能硅酮树脂的添加量应使环氧/NH摩尔比为1∶1。
表3
/>
DOWSILTM 3055为具有SiC键合胺官能团的胺官能硅氧烷树脂,与SiOC键合胺官能团不同,并且可从陶氏公司或其附属公司获得。
用于澄清涂层涂覆的刮涂涂覆方法
根据ASTM D4147,将涂料涂覆至Q-Panel R-412-I(磷酸盐处理的冷轧钢)和AL412(铬酸盐处理的铝)面板。使用磁性卡盘或夹具将面板固定在坚固的水平表面上。使用多间隙正方形涂敷器将涂料涂敷到面板上,将5到6密耳润湿厚度定为目标以达到约2.5密耳的所需干膜厚度。
涂料的涂覆和测试方法
喷涂涂覆:在研究中使用了三种类型的面板(磷酸盐处理的冷轧钢(CRS)、喷砂钢和铬酸盐处理的铝面板),在喷涂之前用脱脂剂或车间溶剂清洁磷酸盐处理和喷砂的钢面板。将油漆放入配备有200μm过滤器的一次性喷雾容器中,并使用1.4mm或1.8mm的雾化头。将面板放置在金属丝支架上,并使用传统的空气辅助涂覆技术,用3MTM AccusprayTMSystem工业喷涂器进行喷涂。在实验室中以受控的温度和湿度为72°F和50%相对湿度的情况下,使得面板进行固化。
干燥时间:将涂料刮涂到湿膜厚度为76微米(μm)的1”x12”玻璃基板上,并置于毕克干燥时间记录器(BYK drying time recorder)上。根据ASTM D5895-03使用毕克干燥时间记录器,通过拖动针通过涂层来测量设定触摸、无粘性时间和干燥硬化。
摆锤硬度:摆锤硬度是使用来自BYK Gardner的配备了摆锤的摆锤硬度测试仪测量的。根据ISO 1522运行测试仪且设定为以秒为单位测量硬度。
铅笔硬度
根据ASTM D3363方法测量涂膜的铅笔硬度。将涂料组合物施涂在玻璃板上以形成120微米厚的湿膜并在室温下固化7天。然后用中华铅笔测试所得薄膜。所用铅笔的硬度为:9H、8H、7H、6H、5H、4H、3H、2H、H、F、HB、B、2B、3B、4B、5B、6B,其中9H最硬,6B最软。
光泽度:涂层的20°、60°和85°光泽度是根据ASTM D-523-89使用毕克加德纳的micro-TRI光泽度仪测量的。
雾度:澄清涂料配制物中的雾度是根据ASTM E430测试方法B用毕克的微雾度加仪(micro-haze plus meter)测量的。将涂料以76微米在玻璃面板上拉拽,并且通过黑色伦塔图(Lenta chart)进行测量。测量是利用亮度补偿的对数缩放。
甲基乙基酮双摩擦测试:使用DJH设计公司(DJH DESIGNS INC)制造的半自动MEK摩擦测试机,根据ASTM D5402进行甲基乙基酮(MEK)双摩擦测试。测试一直进行到涂层被磨擦至基板为止或完成最多200次双磨擦而没有穿透。
涂料组合物的性能特征示出在表4和表5中。与Ctg 14和Ctg 15相比,Ctg12和Ctg13分别说明了丙烯酸共聚物中固化相容性基团(例如HEMA)对提供改进的铅笔硬度、改进的干燥时间、改进的光泽读数、改进的硬度和改进的MEK抗性的重要性。表4和5说明了具有多官能化丙烯酸共聚物和氨基官能硅酮树脂固化剂的涂料组合物以成本效益的方式改进了涂料组合物的性质。当丙烯酸共聚物具有聚合形式的环氧官能化基团和固化相容性基团并且氨基官能硅酮树脂是烷氧基官能硅氧烷时,涂层性能得到改善。此外,当氨基官能硅酮树脂具有衍生自空间位阻醇-胺前体部分的烷氧基官能硅氧烷时或当醇-胺前体是仲醇或叔醇时,涂料性能得到最大改善。
表4
表5
/>
Claims (11)
1.一种可固化涂料组合物,其包含:
(1)氨基官能硅酮树脂,其包含聚合形式的以下结构单元:
(i)(R3SiO1/2)a;
(ii)(R2Si(OR’)xO(2-x)/2)b;
(iii)(RSi(OR’)y,O(3-y)/2)c;和
(iv)(Si(OR’)zO(4-z)/2)d
其中每个R'是氢、烷基或官能化烷基,条件是所有R'基团的至少5摩尔%是下式的含胺基团:-Ra-NHRb;
其中Ra为衍生自氨基醇的烷基或含芳基基团,并且Rb为氢、烷基或芳基;
其中a+b+c+d=1.00,其中1.00代表100摩尔百分比;x为0或1;y为0、1或2;并且z为0、1、2或3;
其中每个R独立地为氢、烷基或芳基;并且
所述氨基官能硅酮树脂的-NH-当量质量为50至750;和
(2)具有呈聚合形式的环氧官能化基团和固化相容性基团的丙烯酸共聚物;并且
其中所述涂料组合物的胺NH官能团与环氧官能团的摩尔比在0.5到1.3范围内;
其中所述丙烯酸共聚物的环氧官能化基团衍生自选自以下的群组的一种或多种单体:甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯和其混合物;并且其中所述丙烯酸共聚物的环氧当量在200到600的范围内。
2.根据权利要求1所述的涂料组合物,其中胺NH官能团与环氧官能团的摩尔比在0.8到1的范围内。
3.根据权利要求1所述的涂料组合物,其中所述氨基官能硅酮树脂的所有R'基团的至少20摩尔%是下式的含胺基团:-Ra-NHRb。
4.根据权利要求1所述的涂料组合物,其中所述氨基官能硅酮树脂的所有R'基团的5至42摩尔%是下式的含胺基团:-Ra-NHRb。
5.根据权利要求1所述的涂料组合物,其中所述氨基醇选自下组:(a)在COH部分周围具有空间位阻;(b)为仲醇或叔醇;或(c)其混合物。
6.根据权利要求1所述的涂料组合物,其中所述氨基醇是1-氨基-2-丙醇或1-氨基-2-甲基丙-2-醇。
7.根据权利要求4所述的涂料组合物,其中按所述丙烯酸共聚物的总单体单元的重量计,所述丙烯酸共聚物包含呈聚合形式的30重量%到60重量%的(甲基)丙烯酸缩水甘油酯单体单元。
8.根据权利要求1所述的涂料组合物,其中按所述丙烯酸共聚物的总单体单元的重量计,所述丙烯酸共聚物包含呈聚合形式的2重量%到20重量%的固化相容性基团单体单元。
9.根据权利要求1所述的涂料组合物,其中所述丙烯酸共聚物的固化相容性基团包含呈聚合形式的单体基团,所述单体基团含有侧接到主链或作为端基连接的醇官能团、酚基、叔胺或酸基中的一个或多个。
10.根据权利要求1所述的涂料组合物,其中所述固化相容性基团衍生自甲基丙烯酸羟乙酯。
11.一种经涂布的制品,其包含根据权利要求1所述的固化涂料组合物的一个或多个层。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201962944005P | 2019-12-05 | 2019-12-05 | |
US62/944,005 | 2019-12-05 | ||
PCT/US2020/060078 WO2021113042A1 (en) | 2019-12-05 | 2020-11-12 | Weatherable and durable coating compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114667306A CN114667306A (zh) | 2022-06-24 |
CN114667306B true CN114667306B (zh) | 2023-12-19 |
Family
ID=73790215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202080079345.4A Active CN114667306B (zh) | 2019-12-05 | 2020-11-12 | 耐候性且耐久性涂料组合物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20220380626A1 (zh) |
EP (1) | EP4069766A1 (zh) |
JP (1) | JP2023504240A (zh) |
KR (1) | KR20220107262A (zh) |
CN (1) | CN114667306B (zh) |
BR (1) | BR112022009465A2 (zh) |
MX (1) | MX2022006253A (zh) |
WO (1) | WO2021113042A1 (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1662581A (zh) * | 2002-05-03 | 2005-08-31 | 式玛卡龙服务股份有限公司 | 氨基-官能化聚硅氧烷及其在涂料中的用途 |
CN101376792A (zh) * | 2007-08-28 | 2009-03-04 | 赢创德固赛有限责任公司 | 用于处理纸或膜的涂料的含贫挥发性有机化合物的氨基烷基官能的硅化合物的组合物 |
CN106381084A (zh) * | 2016-10-17 | 2017-02-08 | 哈尔滨工业大学无锡新材料研究院 | 一种无转移有机硅改性丙烯酸酯离型剂及其制备方法 |
CN108431149A (zh) * | 2015-12-30 | 2018-08-21 | 陶氏环球技术有限责任公司 | 基于环氧树脂和胺官能聚硅氧烷的抗生物污垢涂料 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2238416T3 (es) | 2000-01-12 | 2005-09-01 | Akzo Nobel Coatings International B.V. | Composicion de revestimiento de curado a temperatura ambiente. |
JP3497814B2 (ja) | 2000-12-01 | 2004-02-16 | 関西ペイント株式会社 | 一回塗装仕上げ用防食塗料組成物 |
US6639025B2 (en) * | 2002-02-01 | 2003-10-28 | Ameron International Corporation | Elastomer-modified epoxy siloxane compositions |
US8193293B2 (en) | 2008-03-17 | 2012-06-05 | Ppg Industries Ohio, Inc. | Low temperature curable coating compositions and related methods |
US8871888B2 (en) | 2009-05-22 | 2014-10-28 | Ppg Industries Ohio, Inc | One-component epoxy coating compositions |
-
2020
- 2020-11-12 JP JP2022529105A patent/JP2023504240A/ja active Pending
- 2020-11-12 WO PCT/US2020/060078 patent/WO2021113042A1/en unknown
- 2020-11-12 US US17/775,918 patent/US20220380626A1/en active Pending
- 2020-11-12 MX MX2022006253A patent/MX2022006253A/es unknown
- 2020-11-12 CN CN202080079345.4A patent/CN114667306B/zh active Active
- 2020-11-12 EP EP20821472.6A patent/EP4069766A1/en active Pending
- 2020-11-12 BR BR112022009465A patent/BR112022009465A2/pt unknown
- 2020-11-12 KR KR1020227022214A patent/KR20220107262A/ko active Search and Examination
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1662581A (zh) * | 2002-05-03 | 2005-08-31 | 式玛卡龙服务股份有限公司 | 氨基-官能化聚硅氧烷及其在涂料中的用途 |
CN101376792A (zh) * | 2007-08-28 | 2009-03-04 | 赢创德固赛有限责任公司 | 用于处理纸或膜的涂料的含贫挥发性有机化合物的氨基烷基官能的硅化合物的组合物 |
CN108431149A (zh) * | 2015-12-30 | 2018-08-21 | 陶氏环球技术有限责任公司 | 基于环氧树脂和胺官能聚硅氧烷的抗生物污垢涂料 |
CN106381084A (zh) * | 2016-10-17 | 2017-02-08 | 哈尔滨工业大学无锡新材料研究院 | 一种无转移有机硅改性丙烯酸酯离型剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2023504240A (ja) | 2023-02-02 |
WO2021113042A1 (en) | 2021-06-10 |
US20220380626A1 (en) | 2022-12-01 |
CN114667306A (zh) | 2022-06-24 |
KR20220107262A (ko) | 2022-08-02 |
MX2022006253A (es) | 2022-06-23 |
BR112022009465A2 (pt) | 2022-08-16 |
EP4069766A1 (en) | 2022-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1335909C (en) | Automotive coating compositions | |
US4684697A (en) | Compositions based on silane hydrolyzates and vinyl polymers containing hydrolyzable silyl groups | |
TW557320B (en) | Ambient temperature curing coating composition | |
JP6294941B2 (ja) | 塗装材料組成物および成形材料における変性ポリシロキサンの使用 | |
US4614766A (en) | Compositions containing resins having air-oxidizable groups and epoxy groups and epoxy-reactive silicon-containing compounds having hydrolyzable groups | |
CN104125992A (zh) | 室温可固化的涂料组合物 | |
CN114667306B (zh) | 耐候性且耐久性涂料组合物 | |
JPH09302286A (ja) | 塗膜形成方法 | |
CN114729127B (zh) | 耐候性且耐久性涂料组合物 | |
CN112352026B (zh) | 耐候性且耐久性涂料组合物 | |
CN112368347B (zh) | 耐候性且耐久性涂料组合物 | |
JP7229860B2 (ja) | 3-グリシジルオキシプロピルアルコキシシランオリゴマーを含有する組成物、その製造方法及びその使用 | |
US4808663A (en) | Method of preparing acrylic polymers containing hydrolyzable moieties from organosilane compounds | |
JP4182368B2 (ja) | 塗料用樹脂組成物 | |
JP4398605B2 (ja) | 無溶剤液状型の硬化性樹脂組成物及び硬化皮膜形成用の塗料組成物 | |
JP2001279161A (ja) | 上塗り塗料組成物 | |
JP2004107469A (ja) | 無機鏡面基材用硬化性組成物 | |
JPH11310724A (ja) | 硬化性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |