CN116410651A - PU coating combination system, coating body and application thereof - Google Patents
PU coating combination system, coating body and application thereof Download PDFInfo
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- CN116410651A CN116410651A CN202111679665.6A CN202111679665A CN116410651A CN 116410651 A CN116410651 A CN 116410651A CN 202111679665 A CN202111679665 A CN 202111679665A CN 116410651 A CN116410651 A CN 116410651A
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- coating
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- 238000000576 coating method Methods 0.000 title claims abstract description 80
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 117
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 108
- 239000004814 polyurethane Substances 0.000 claims abstract description 105
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 63
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 63
- 239000008199 coating composition Substances 0.000 claims abstract description 44
- 239000003973 paint Substances 0.000 claims abstract description 41
- 238000009835 boiling Methods 0.000 claims description 80
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 55
- 239000002904 solvent Substances 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 43
- 229920003023 plastic Polymers 0.000 claims description 33
- 239000004033 plastic Substances 0.000 claims description 33
- 239000012046 mixed solvent Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 23
- 229920000178 Acrylic resin Polymers 0.000 claims description 22
- 239000004925 Acrylic resin Substances 0.000 claims description 22
- 239000003085 diluting agent Substances 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims description 15
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 229920001225 polyester resin Polymers 0.000 claims description 13
- 239000004645 polyester resin Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 229920000180 alkyd Polymers 0.000 claims description 11
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- -1 isooctyl Chemical group 0.000 claims description 10
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 9
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 9
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 230000008033 biological extinction Effects 0.000 claims description 4
- 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 claims description 4
- 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 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 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 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 229920007019 PC/ABS Polymers 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920005669 high impact polystyrene Polymers 0.000 claims description 3
- 239000004797 high-impact polystyrene Substances 0.000 claims description 3
- 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 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 3
- 239000000126 substance Substances 0.000 abstract description 21
- 238000004132 cross linking Methods 0.000 abstract description 10
- 239000000516 sunscreening agent Substances 0.000 abstract description 8
- 229920002635 polyurethane Polymers 0.000 description 84
- 238000012360 testing method Methods 0.000 description 26
- 238000005299 abrasion Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 11
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000006071 cream Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- ODEHMIGXGLNAKK-OESPXIITSA-N 6-kestotriose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(O[C@@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)O1 ODEHMIGXGLNAKK-OESPXIITSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 241001134446 Niveas Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000475 sunscreen effect Effects 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 229920006491 ABS+PC Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- 206010027627 Miliaria Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000669 biting effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- DJGAAPFSPWAYTJ-UHFFFAOYSA-M metamizole sodium Chemical compound [Na+].O=C1C(N(CS([O-])(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 DJGAAPFSPWAYTJ-UHFFFAOYSA-M 0.000 description 1
- 201000004169 miliaria rubra Diseases 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/47—Levelling agents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a PU coating combination system, which adopts polyisocyanate with high functionality and high NCO content (NCO functionality is more than or equal to 10 and NCO content is more than or equal to 25%) as a curing agent, and can be used for synergism with components such as hydroxyl components, flatting agents and the like, so that the density of crosslinking points can be greatly improved under the condition of not increasing or reducing the dosage of the curing agent, thereby obviously improving the compactness of a paint film, obviously improving the chemical resistance of the paint film, particularly the sun cream resistance, improving the hardness and the friction resistance of the paint film to a certain extent, still keeping better adhesiveness, and having no phenomena such as orange peel and the like. The invention also relates to a coating body, which comprises a top-coat film layer and a primer film layer which are prepared from the PU coating combination system. Also relates to the use of the PU coating composition and the coated body.
Description
Technical Field
The invention relates to the technical field of paint, in particular to a PU paint combination system, a paint body and application thereof.
Background
In recent years, products involved in industries such as automobiles, mobile phones, home appliances, and the like often need to be coated on the surface to increase the usability and the aesthetic appearance. The method comprises the steps of firstly coating a primer on the surface of a substrate, and then coating a finish paint for decoration and protection, wherein the Polyurethane (PU) coating can be used for a plastic substrate. The film-coated product (or film-coated product) has certain requirements in terms of scratch resistance, hardness, appearance, adhesion, chemical resistance and other properties.
Taking an automotive interior plastic part as an example, the conventional multilayer coating film of the automotive interior plastic part adopts PU resin as a supporting material in many cases, and a cross-linked network is established between molecular chains of a resin polymer by a diisocyanate curing agent. Specifically, the conventional curing agent for matching PU top coating in the multilayer coating of the traditional automotive interior plastic part is diisocyanate or oligomer thereof (the main component is trimer thereof), for example, the diisocyanate can be Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and the like, and the diisocyanate curing agent carries less than or equal to 3 isocyanate groups (NCO) in the molecule, namely NCO functionality is less than or equal to 3, and can be coupled with side chain hydroxyl groups of resin molecules to form crosslinking points among the resin molecules. Commonly used diisocyanate trimer curing agents such as: kesi wound N3580BA, asahi compound TKA100, kesi wound N3390, diegao T1890E, kesi wound Z4470, kesi wound N75.
However, the multilayer coating film products of the automotive interior plastic parts have poor chemical resistance, particularly sunscreen cream resistance, and the hardness and the abrasion resistance of the coating film are also common, so that the test requirements of various manufacturers cannot be met in a large range.
Therefore, there is a need for further development of PU coatings having improved resistance to chemicals, hardness and abrasion, combined with good adhesion.
Disclosure of Invention
Based on this, it is an object of the present invention to provide PU coating composition systems with improved resistance to chemicals, hardness and abrasion, and also to their coated bodies and applications.
The above object can be achieved by the following technical scheme.
In a first aspect of the present invention, there is provided a PU coating composition system comprising component A1, component B1, and component C1;
the component A1 comprises, in mass percent of 100%:
40% -80% of hydroxyl component;
0.6 to 2.5 percent of leveling agent; and
15% -60% of mixed solvent;
wherein, the hydroxyl content of the hydroxyl component is 3% -8%;
the component B1 comprises polyisocyanate; wherein the NCO functionality of the polyisocyanate is more than or equal to 10, and the NCO content is more than or equal to 25%;
the component C1 is a diluent;
the mass part ratio of the component A1 to the component B1 to the component C1 is 100: (10-50): (50-70).
In some embodiments, in the component A1,
the mass percentage of the hydroxyl component is 60% -70%; and/or the number of the groups of groups,
the weight average molecular weight of the hydroxyl component is 2000Da to 8000Da; and/or the number of the groups of groups,
The viscosity of the hydroxyl component is 5000cps to 20000cps; and/or the number of the groups of groups,
the leveling agent is prepared from the following components in percentage by mass (1-10): the mixture of the polyether modified organosilicon leveling agent and the acrylic leveling agent in the (5-15); and/or the number of the groups of groups,
the mass ratio of the mixed solvent is (1-4): (1-4): (1-4) a mixture of a low boiling point solvent having an initial boiling point of 120 ℃ or less, a medium boiling point solvent having an initial boiling point of 120 ℃ to 150 ℃ and a high boiling point solvent having an initial boiling point of >160 ℃.
In some embodiments, in the component A1,
the hydroxyl component is one or more of hydroxy acrylic resin, polyester resin and alkyd resin; and/or the number of the groups of groups,
the hydroxyl content of the hydroxyl acrylic resin is 4.2% -6%; and/or the number of the groups of groups,
the Tg of the hydroxy acrylic resin is 70-80 ℃; and/or the number of the groups of groups,
the hydroxyl content of the polyester resin is 5% -8%; and/or the number of the groups of groups,
the solid content of the polyester resin is 80% -100%; and/or the number of the groups of groups,
the Tg of the polyester resin is 50-60 ℃; and/or the number of the groups of groups,
the hydroxyl content of the alkyd resin is 5% -6%; and/or the number of the groups of groups,
the solid content of the alkyd resin is 70% -80%; and/or the number of the groups of groups,
the Tg of the alkyd resin is 50-60 ℃; and/or the number of the groups of groups,
The hydroxyl component is selected from one or more of the following resin products: zhan Xin 1198SS-70, zhan Xin SM516, zhan Xin 2803, zuo and HE6790, DIC A859, DIC A862 and Mitsubishi LR7728; and/or the number of the groups of groups,
the polyether modified organosilicon leveling agent is selected from one or more of the following products: BYK-306, BYK-331, TEGO 450, TEGO Glide100 and TEGO 270; and/or the number of the groups of groups,
the acrylic leveling agent is selected from one or more of the following products: EFKA3777, BYK358N, BYK361 and BYK381; and/or the number of the groups of groups,
the initial boiling point of the low boiling point solvent is 75-120 ℃, the initial boiling point of the medium boiling point solvent is 120-160 ℃, and the initial boiling point of the high boiling point solvent is 160-220 ℃;
the low boiling point solvent is one or two of ethyl acetate and isobutyl acetate; and/or the number of the groups of groups,
the medium boiling point solvent is one or two of butyl acetate and methyl isobutyl ketone; and/or the number of the groups of groups,
the high boiling point solvent is one or more of trimethylbenzene, tetramethylbenzene, diisobutyl ketone and diacetone alcohol.
In some embodiments, in the component B1,
the NCO functionality of the polyisocyanate is selected from 10 to 100; and/or the number of the groups of groups,
the NCO content of the polyisocyanate is 25% -30%; and/or the number of the groups of groups,
The polyisocyanate has structural units represented by formula (I):
In some embodiments, in the component B1,
the NCO functionality of the polyisocyanate is selected from 10 to 40; and/or the number of the groups of groups,
the polyisocyanate also has structural units of formula (II):
In some embodiments, in the component B1, the polyisocyanate has a general structure of formula (III):
In some embodiments, the component C1 is a mixture of (1-2): (0.5-1): (2.5-5): the mixture of ethyl acetate, butyl acetate, diisobutyl ketone and propylene glycol methyl ether acetate according to (1-2).
In a second aspect of the present invention, there is provided a coated body comprising a top-coat film layer, and further comprising a primer film layer laminated under the top-coat film layer; the finish paint film layer is prepared by coating the surface of the primer film layer with the PU coating composition prepared by the PU coating composition system in the first aspect of the invention.
In some embodiments of the invention, the primer film layer is made from a PU primer composition coating;
the PU primer composition is prepared from a PU primer combination system comprising a component A2, a component B2 and a component C2;
the component A2 comprises the following components in percentage by mass: 35-60% of second hydroxy acrylic resin, 20-50% of second mixed solvent and 10-25% of second additive; wherein the hydroxyl content of the second hydroxyl acrylic resin is 0.5% -1%, and the weight average molecular weight is 1000 Da-5000 Da; the mass ratio of the second mixed solvent is (1-4): 1 and butyl acetate; the second additive is one or more of a dispersing agent, an anti-settling agent, extinction powder, talcum powder, black paste and a second leveling agent;
the component B2 is diisocyanate oligomer, and the polymerization degree is less than or equal to 3;
the composition C2 is a mixture of ethyl acetate, acetone, isobutyl acetate and diacetone alcohol, and the mass ratio of the components is (1-3): (1-3): (1-3): 1.
in a third aspect of the invention, there is provided the use of the PU coating composition system according to the first aspect of the invention or the coated body according to the second aspect of the invention on plastic substrates, including PC substrates, ABS substrates, HIPS substrates, PMMA substrates and plastic substrates of PC/ABS composites.
In a fourth aspect of the present invention, there is provided a PU paint film product comprising a plastic substrate and the coated body according to the second aspect of the present invention, wherein the plastic substrate is laminated under the primer film layer, the primer film layer is made by coating a PU primer composition on the surface of the plastic substrate, and the top film layer is made by coating a PU coating composition formulated by the PU coating composition system according to the first aspect of the present invention on the surface of the primer film layer.
The sun-proof cream resistance, paint film hardness and abrasion resistance of the traditional multilayer coating film for the automotive interior plastic part are closely related to the crosslinking density in the system. The invention introduces synthesized high-functionality polyisocyanate (NCO functionality is more than or equal to 10) as a curing agent to replace conventional diisocyanate curing agents such as HDI, IPDI and the like and oligomers thereof (NCO functionality is less than or equal to 3), and the curing agent and oligomers thereof are synergistic with components such as hydroxyl components, auxiliary agents (such as flatting agents) and the like to greatly improve the density of crosslinking points, thereby obviously improving the compactness of the coating and obviously improving the chemical resistance of the coating, especially the sun cream resistance. Further, as the cross-linking point density increases, the hardness and abrasion resistance of the paint film are also improved to some extent. In addition, as the reaction sites are increased, compared with conventional curing agents such as HDI, IPDI and the like, the reaction speed of coating curing is further accelerated, the baking time is shortened, the film forming time is reduced, the operability is stronger, the energy is saved, and the production efficiency is accelerated.
The diisocyanate curing agent conventionally used has a higher polymerization degree (more NCO groups) after the diisocyanate forms a polymeric structure, and the content of active NCO (reactive NCO) therein is lower, that is, the increase in polymerization degree decreases the content of active NCO, and the six-membered ring in the trimer is a very stable structure, resulting in difficulty in forming a structure with a higher polymerization degree. The polyisocyanate curing agent used in the present invention can achieve both high NCO functionality and high NCO content through structural design, so that sufficient crosslinking of the coating composition can be achieved without increasing the amount of curing agent used, or even with decreasing the amount of curing agent used.
That is, the polyisocyanate of the invention has the characteristics of high functionality (NCO functionality is more than or equal to 10) and high isocyanate content (NCO content is more than or equal to 25%), so that the-NCO in the system can be realized by reducing the addition amount of the curing agent: the relative OH content reaches a ratio (1 to 1.5) of sufficient reaction: 1, while providing particularly improved hardness, friction and chemical resistance properties to the resulting coating.
The PU coating combination system provided by the invention can also form a coating body together with the PU primer, and is coated on the surface of a substrate to provide a multilayer coating film with particularly improved chemical resistance, sun-block resistance, hardness and friction resistance.
Detailed Description
The present invention will be described in further detail with reference to embodiments and examples. It should be understood that these embodiments and examples are provided solely for the purpose of illustrating the invention and are not intended to limit the scope of the invention in order that the present disclosure may be more thorough and complete. It will also be appreciated that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein, but may be modified or altered by those skilled in the art without departing from the spirit of the invention, and equivalents thereof fall within the scope of the present application. Furthermore, in the following description, numerous specific details are set forth in order to provide a more thorough understanding of the invention, it being understood that the invention may be practiced without one or more of these details.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing the embodiments and examples only and is not intended to be limiting of the invention.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
the term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by a combination of at least two conjunctions selected from "and/or", "or/and", "and/or", it should be understood that, in this application, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
The term "plural", and the like in the present invention refers to, unless otherwise specified, a number of 2 or more. For example, "one or more" means one kind or two or more kinds.
As used herein, "a combination thereof," "any combination thereof," and the like include all suitable combinations of any two or more of the listed items.
The "suitable" in the "suitable combination manner", "suitable manner", "any suitable manner" and the like herein refers to the fact that the technical scheme of the present invention can be implemented, the technical problem of the present invention is solved, and the technical effect expected by the present invention is achieved.
Herein, "preferred", "better", "preferred" are merely to describe better embodiments or examples, and it should be understood that they do not limit the scope of the invention. If there are multiple "preferences" in a solution, if there is no particular description and there is no conflict or constraint, then each "preference" is independent of the others.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the present invention, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature being indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics. It should be understood that when the chemical composition of a substance is described in a defined manner, the substance may be provided with impurities present in usual amounts, including but not limited to impurities which are inevitably introduced as a result of the preparation process.
In the present invention, a numerical range (i.e., a numerical range) is referred to, and optional numerical distributions are considered to be continuous within the numerical range and include two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range and each numerical value between the two numerical endpoints unless otherwise specified. Where a numerical range merely refers to integers within the numerical range, including both end integers of the numerical range, and each integer between the two ends, unless otherwise indicated, each integer is recited herein as directly, such as where t is an integer selected from 1 to 10, and where t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
As used herein, the term "alkylene" refers to a hydrocarbon group derived by removal of two hydrogen atoms on an alkyl basis to form a center having two monovalent groups, which may beAnd may be a saturated branched alkyl group or a saturated linear alkyl group. For example, "C 1 ～C 8 Alkylene "or" C 1-8 Alkylene "means that the alkyl moiety contains from 1 to 8 carbon atoms and, at each occurrence, can be independently of each other C 1 Alkylene, C 2 Alkylene, C 3 Alkylene, C 4 Alkylene, C 5 Alkylene, C 6 Alkylene, C 7 Alkylene or C 8 An alkylene group. Suitable examples include, but are not limited to: methylene (-CH) 2 (-), 1-ethyl (-CH (CH) 3 ) (-), 1, 2-ethyl (-CH) 2 CH 2 (-), 1-propyl (-CH (CH) 2 CH 3 ) (-), 1, 2-propyl (-CH) 2 CH(CH 3 ) (-), 1, 3-propyl (-CH) 2 CH 2 CH 2 (-) and 1, 4-butyl (-CH) 2 CH 2 CH 2 CH 2 -)。
All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Unless otherwise contradicted by purpose and/or technical solution of the present application, the cited documents related to the present invention are incorporated by reference in their entirety for all purposes. When reference is made to a cited document in the present invention, the definitions of the relevant technical features, terms, nouns, phrases, etc. in the cited document are also incorporated. In the case of the cited documents, examples and preferred modes of the cited relevant technical features are incorporated into the present application by reference, but are not limited to the embodiments that can be implemented. It should be understood that when a reference is made to the description herein, it is intended to control or adapt the present application in light of the description herein.
As used herein, PU refers to polyurethane, hydroxyl is OH, VOC refers to a volatile organic compound, tg refers to a glass transition temperature, NCO represents a group-n=c=o, ABS represents a substrate of a terpolymer of three monomers of acrylonitrile (a), butadiene (B), styrene (S), and PC represents a substrate of polycarbonate.
In the present invention, viscosity is referred to as viscosity, and is generally referred to as a brookfield viscosity in cps, unless otherwise specified.
In the invention, the hydroxyl group content of the resin is counted in percentage, which represents the mass percentage of hydroxyl groups in the resin with a certain mass, and can be converted with the hydroxyl value.
In the present invention, NCO content means the percentage by mass of NCO groups in a sample of a certain mass.
The solid content in the present invention is not particularly limited, but is calculated as mass percent.
In the present invention, the term "molecular weight" refers to, unless otherwise specified, average molecular weight. The weight average molecular weight or the number average molecular weight may be used, but is generally referred to as the weight average molecular weight unless otherwise specified.
In the present invention, the term "room temperature" refers to, but is not particularly limited to, usually 15℃to 35℃and may further be 20℃to 30 ℃.
In the present invention, the terms "about", "about" and the like are used, and the terms may be used as long as they are allowed to fluctuate within.+ -. 10%, and may be.+ -. 5%,.+ -. 2%, and the like, unless otherwise specified. For example, about 20℃may be 20.+ -. 2 ℃, 20.+ -. 1 ℃, 20.+ -. 0.5 ℃ and the like. For example, the thickness of about 5 microns may be 5.+ -. 0.5 microns, 5.+ -. 0.2 microns, 5.+ -. 0.1 microns, etc.
The "boiling point" in the present invention means the initial boiling point unless otherwise specified.
In the present invention, the numerical values "above" and "below" include, but are not particularly limited to, the present number.
First aspect of the invention
In a first aspect of the present invention, a polyurethane coating composition system (PU coating composition system) is provided that can be formulated into a PU coating composition for coating (including, but not limited to, spray coating). The PU coating combination system adopts polyisocyanate with high functionality and high NCO content (NCO functionality is more than or equal to 10, NCO content is more than or equal to 25%) as a curing agent with high functionality and high NCO content, replaces conventional diisocyanate curing agents such as HDI, IPDI and the like (curing agent with low functionality, NCO functionality is less than or equal to 3, NCO content is reduced along with the increase of functionality), and cooperates with components such as hydroxyl components, auxiliaries (such as flatting agent) and the like, and greatly improves the crosslinking point density under the condition of reducing the consumption of the curing agent, thereby obviously improving the compactness of a paint film, leading the chemical resistance, especially the sun-proof cream resistance of the paint film to be obviously improved, and simultaneously keeping better paint film adhesion.
In some embodiments of the invention, the PU coating composition system comprises 100 parts by weight: (10-50): (50-70) component A1, component B1 and component C1; the hydroxyl component of component A1 provides a resin component containing hydroxyl groups, component B1 is a curing agent (denoted as a first curing agent), and a polyisocyanate having both high functionality and high NCO content (NCO functionality 10. Gtoreq.25%) and component C1 is a diluent (denoted as a first diluent). The three components cooperate with each other, and under the condition of reducing the dosage of the curing agent, the crosslinking point density of the paint film is improved, so that the comprehensive beneficial effects are realized.
In some embodiments, the PU coating composition system includes component A1, component B1, and component C1;
the component A1 comprises, in mass percent of 100%:
40% -80% of hydroxyl component;
0.6 to 2.5 percent of leveling agent; and
15% -60% of mixed solvent;
wherein, the hydroxyl content of the hydroxyl component is 3% -8%;
the component B1 comprises polyisocyanate; wherein the NCO functionality of the polyisocyanate is more than or equal to 10, and the NCO content is more than or equal to 25%;
the component C1 is a diluent;
the mass part ratio of the component A1 to the component B1 to the component C1 is 100: (10-50): (50-70).
Component A1
Component A1 in the PU coating composition system provides a resin component containing hydroxyl groups.
In some embodiments of the present invention, component A1 comprises a hydroxyl component, a leveling agent (denoted as a first leveling agent), and a mixed solvent (denoted as a first mixed solvent).
In some embodiments, the component A1 comprises, in 100 mass percent:
40% -80% of hydroxyl component;
0.6 to 2.5 percent of leveling agent; and
15% -60% of mixed solvent;
wherein, the hydroxyl content of the hydroxyl component is 3% -8%;
the component B1 comprises polyisocyanate; wherein the NCO functionality of the polyisocyanate is more than or equal to 10, and the NCO content is more than or equal to 25%. In some embodiments, the mixed solvent comprises a low boiling point solvent with an initial boiling point less than or equal to 120 ℃, a medium boiling point solvent with an initial boiling point of 120 ℃ to 150 ℃, and a high boiling point solvent with an initial boiling point of >160 ℃.
In some preferred embodiments of the invention, component A1 comprises the following components in mass percent:
preferably, the method comprises the steps of,
the hydroxyl content of the hydroxyl component is 3% -8%;
the leveling agent A is polyether modified organic silicon;
the leveling agent B is acrylic esters;
the initial boiling point of the low boiling point solvent is 75-120 ℃; the medium boiling point solvent has an initial boiling point of 120 to 160 ℃ (further preferably 120 to 150 ℃); the initial boiling point of the high boiling point solvent is more than or equal to 160 ℃.
Hydroxy component
The hydroxyl component is used as a main supporting material of a paint film crosslinked network, provides appearance fullness, hardness and increases wear resistance.
The hydroxyl component in the invention has higher hydroxyl content, which is beneficial to improving the crosslinking point density. In some embodiments of the invention, the hydroxyl content of the hydroxyl component is 3% to 8%. If the hydroxyl group content is less than 3%, the appearance fullness is affected, and the paint film compactness is lowered, and the chemical resistance, hardness and abrasion resistance are lowered; if the hydroxyl content exceeds 8%, the drying is too slow, which can lead to the prolongation of the reaction time and the influence on the production efficiency, or the paint film is still softer after a certain surface drying time, and the yield is reduced. It is presumed that this is due to the following reasons: as the reaction proceeds, the molecular weight increases, the rotational and kinetic capabilities of the molecular chain decrease, which results in more and more difficult reactions, and thus slower reaction rates, higher hydroxyl content, and longer reaction times required for hydroxyl and isocyanate, whereas a production line using PU coating compositions for coating films typically has a certain surface drying stage, typically less than 15 minutes, and if the film surface is not dried during this time, dust particles are more likely to stick to the surface during transfer, thereby affecting yield. In addition, if the hydroxyl content in the hydroxyl component is too high, the resin content in the formulation may be low, resulting in too low a system solid content, and the film thickness may not be ensured. The hydroxyl group content of the hydroxyl group component may be further 4% to 6%. The hydroxyl group content of the hydroxyl group component is, for example, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.4%, 4.5%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.5%, 5.8%, 6%, 6.2%, 6.4%, 6.5%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.5%, 7.8%, 8%. In some embodiments of the invention, the hydroxyl component is present in component A1 in a mass percent of 40% to 80% and the hydroxyl content is 3% to 8%.
The molecular weight of the hydroxyl component is preferably from 2000Da to 8000Da in weight average molecular weight, so as to provide a suitable degree of polymerization, with a suitable number of hydroxyl groups being introduced in the side chains of the polymer. The molecular weight is too low, which may cause poor compactness of the paint film, and the cured paint film has gaps and is easy to be corroded by chemicals; too high a molecular weight, the system needs to be dissolved by adding more solvent, which may result in too low a solid content of the system and cannot ensure the film thickness. The molecular weight of the hydroxyl group component is exemplified by 2000Da, 3000Da, 4000Da, 5000Da, 6000Da, 7000Da, 8000Da, etc. The molecular weight of the hydroxyl component affects to some extent the viscosity of the resin and thus the viscosity of the coating system, the reaction rate and the film formation time. In some embodiments of the present invention, the viscosity of the hydroxyl component is 5000cps to 20000cps, further exemplified by 5000cps, 6000cps, 7000cps, 8000cps, 9000cps, 10000cps, 11000cps, 12000cps, 15000cps, 16000cps, 18000cps, 20000cps, etc. The molecular weight of the hydroxyl component also affects the glass transition temperature (Tg) of the resin to some extent, thereby affecting the temperature interval at the time of coating.
The hydroxyl component raw material preferably has a relatively high solid content, for example, 70% to 100%, and further, for example, 70%, 72%, 74%, 75%, 76%, 78%, 80%, 82%, 84%, 85%, 86%, 88%, 90%, 92%, 94%, 95%, 96%, 98%, 100%, and the like.
The PU coating combination system can be used for being matched with a PU primer combination system to form a surface paint film of a plastic piece together. The resin component in the primer combination system can be one or more selected from the group consisting of hydroxy acrylic resin, polyester resin and alkyd resin, which is beneficial to improving the adhesion between the primer and the substrate layer. In some embodiments of the invention, the hydroxyl component is one or more of hydroxyl acrylic resin, polyester resin and alkyd resin, which is beneficial to promoting the compatibility between the top-coat film layer and the primer film layer, improving the binding force between the top-coat film layer and the primer film layer, forming matched contractility between the top-coat film layer and the primer film layer, maintaining the flatness of the paint surface and playing a role in avoiding the occurrence of orange peel phenomenon.
The hydroxyl group content of the hydroxy acrylic resin used in the component A1 may be 4.2% to 6%, and further examples thereof include 4.4%, 4.5%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.5%, 5.8%, 6%, and the like. The Tg may be 70℃to 80℃and further includes, for example, 70℃71℃72℃73℃74℃75℃76℃77℃78℃79℃80 ℃.
The hydroxyl group content of the polyester resin used in the component A1 may be 5% to 8%, and further, for example, 5%, 5.2%, 5.4%, 5.5%, 5.8%, 6%, 6.2%, 6.4%, 6.5%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.5%, 7.8%, 8% and the like. The solid content may be 80% to 100%, and further, for example, 80%, 82%, 84%, 85%, 86%, 88%, 90%, 92%, 94%, 95%, 96%, 98%, 100% and the like. The Tg may be 50℃to 60℃and further includes, for example, 50℃51℃52℃53℃54℃55℃56℃57℃58℃59℃60 ℃.
The hydroxyl group content of the alkyd resin used in the component A1 may be 5% to 6%, and further examples thereof include 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, and the like. The solid content may be 70% to 80%, and further examples thereof include 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, and the like. The Tg may be 50℃to 60℃and further includes, for example, 50℃51℃52℃53℃54℃55℃56℃57℃58℃59℃60 ℃.
In some embodiments of the invention, the mass percent of hydroxyl component in component A1 is 40% to 80%. If the hydroxyl component accounts for less than 40%, the solvent content of the system is too high, VOC exceeds standard, and the solid content of the system is too low, so that the film thickness cannot be ensured; if the hydroxyl component accounts for more than 80 percent, the viscosity is too large, which is unfavorable for dispersion and even stirring, and affects construction. The mass percentage of the hydroxyl group component in the component A1 may be further 50% to 70%, and may be further 60% to 70%, specifically, for example, 40%, 42%, 44%, 45%, 46%, 48%, 50%, 52%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 78%, 80%, and the like.
In some embodiments of the invention, the hydroxyl component is selected from one or more of the following resin products: zhan Xin 1198SS-70, zhan Xin SM516, zhan Xin 2803, zuo and HE6790, DIC A859, DIC A862, mitsubishi LR7728, and the like.
First leveling agent
The leveling agent in component A1 is denoted as the first leveling agent. The leveling agent used in the first aspect of the present invention may be any suitable leveling agent known in the art.
In some embodiments of the present invention, the first leveling agent is in a mass ratio of (1 to 10): and (5-15) a mixture of polyether modified organosilicon leveling agent and acrylic leveling agent.
In some embodiments, the first leveling agent includes leveling agent a and leveling agent B.
In some embodiments, the first leveling agent consists of leveling agent a and leveling agent B; wherein the leveling agent A is polyether modified organic silicon, so that the appearance leveling property and the smoothness can be improved; the leveling agent B is acrylic esters, can improve leveling property, reduce shortwaves and reduce orange marks.
The leveling agent A is used for improving the appearance leveling property and increasing the smoothness. The leveling agent A is preferably polyether modified organic silicon, and further can be selected from one or more of the following types of products: BYK-306, BYK-331, TEGO 450, TEGO Glide100, TEGO 270, and the like. The mass percentage of the leveling agent A in the component A1 is 0.1% -1%, and further can be 0.1% -0.5%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% and the like.
The leveling agent B is used for improving leveling property, reducing shortwaves and reducing orange peel. The leveling agent B is preferably acrylic esters, and further can be selected from one or more of the following types of products: EFKA3777, BYK358N, BYK361, BYK381, and the like. The mass percentage of the leveling agent B in the component A1 is 0.5% -1.5%, and further can be 0.5% -1%, such as 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc.
In the component A1, the total mass fraction of the leveling agent A and the leveling agent B is preferably 0.8 to 2.5%, and more preferably 1 to 2%. Examples thereof include 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, and 2.5%.
In the component A1, the mass part ratio of the leveling agent A to the leveling agent B is preferably 1 (1.5-2.5), for example, 1:2.
First mixed solvent
The mixed solvent in the component A1 is denoted as a first mixed solvent.
In some embodiments, the first mixed solvent in component A1 employs a mixed solvent of low boiling point, medium boiling point, and high boiling point. The solvent with a low boiling point provides a faster volatilization rate, so that the surface drying speed of a paint film is higher, the film is easier to form, the adhesion of dust is reduced, and the yield of products is improved. The medium boiling point solvent plays a role in balancing the volatilization rate, and a small part of residual paint film has slight biting property on the primer, so that better adhesive force can be provided. The volatilization rate of the high-boiling point solvent is low, so that the wet film fluidity of the paint film can be ensured, better appearance leveling property is brought, the volatilization rate can be balanced, and paint film defects such as prickly heat, pinholes and the like caused by too high volatilization are reduced.
The mass percentages of the low boiling point solvent, the medium boiling point solvent and the high boiling point solvent in the component A1 may each independently be 5 to 20%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 16%, 18%, 20%, etc. The total mass percent of the low boiling point solvent, the medium boiling point solvent, and the high boiling point solvent may be 25% to 50%, such as, for example, 25%, 26%, 27%, 28%, 28.5%, 30%, 32%, 33.5%, 35%, 38%, 38.5%, 40%, 45%, 46%, 48%, 48.5%, 50%, etc.
The low boiling point solvent in component A1 has an initial boiling point of 120℃or less, preferably 75℃to 120℃such as 75℃80℃85℃90℃95℃100℃105℃110 ℃. In some embodiments of the invention, the low boiling point solvent in component A1 is one or more of ethyl acetate, isobutyl acetate, and the like. In some embodiments of the invention, the mass percentage of low boiling point solvent in component A1 is 5-20%, such as, for example, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 16%, 18%, 20%, etc.
The medium boiling point solvent in component A1 has an initial boiling point selected from 120℃to 160℃and preferably 120℃to 150℃such as 120℃and 125℃and 130℃and 135℃and 140℃and 145℃and 150℃for example. In some embodiments of the invention, the mid-boiling solvent in component A1 is one or more of butyl acetate, diisobutyl ketone, and the like, and in some embodiments of the invention the mass percent of mid-boiling solvent in component A1 is 7.5-15%, such as, for example, 7.5%, 8%, 8.5%, 9%, 10%, 12%, 13%, 14%, 13.5%, 15%, 16%, 18%, 20%, and the like.
The high boiling point solvent in component A1 has an initial boiling point of not less than 160 ℃, preferably 160℃to 220 ℃, for example 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ and the like. The high boiling point solvent in component A1 in some embodiments of the present invention is preferably one or more of trimethylbenzene, tetramethylbenzene, diisobutylketone, diacetone alcohol, and the like. In some embodiments of the invention, the low boiling point solvent is present in component A1 in a mass percentage of 10 to 20%, such as, for example, 10%, 12%, 14%, 15%, 16%, 18%, 20%, etc.
In some embodiments of the present invention, the low boiling point solvent has an initial boiling point of less than or equal to 120 ℃ (preferably 75 ℃ to 120 ℃), the medium boiling point solvent has an initial boiling point selected from 120 ℃ to 160 ℃ (preferably 120 ℃ to 150 ℃), and the high boiling point solvent has an initial boiling point of more than or equal to 160 ℃ (preferably 160 ℃ to 220 ℃).
In some embodiments, the first mixed solvent is in a mass ratio of (1-4): (1-4): (1-4) a mixture of a low boiling point solvent having an initial boiling point of not more than 120 ℃, a medium boiling point solvent having an initial boiling point of 120 ℃ -160 ℃ (further, for example, 120 ℃ -150 ℃), and a high boiling point solvent having an initial boiling point of >160 ℃.
In some embodiments of the present invention, the first mixed solvent is a mixture of ethyl acetate, butyl acetate and diacetone alcohol, and the mass part ratio of the foregoing components is 1: (0.4-2): (1-3), further may be 1:0.85:1.5, 1:1.35:1.5, 1 (0.4-0.5): 1, 1:0.425:1, 1:1.7:3, etc.
Component B1 (first curing agent)
Component B1 of the PU coating composition is a curing agent, denoted as first curing agent, and mainly consists of polyisocyanates having a high functionality and a high NCO content (NCO functionality preferably. Gtoreq.10, more preferably 10 to 100, further still 10 to 40; NCO content. Gtoreq.25%), it being understood that high functionality here means a higher NCO functionality, which is numerically equal to the number of reactive NCO groups contained in one molecule. It should also be understood that it is permissible to carry impurities or other components which are present in conventional amounts, including but not limited to impurities which are inevitably introduced as a result of the preparation process. The content of polyisocyanate in component B1 is preferably not less than 90%, more preferably not less than 95%, more preferably not less than 96%, more preferably not less than 97%, more preferably not less than 98%, more preferably not less than 99%. In a preferred embodiment, the polyisocyanate content in component B1 is 100%.
The diisocyanate curing agent conventionally used has a higher polymerization degree (more NCO groups) after the diisocyanate forms a polymeric structure, and the content of active NCO (reactive NCO) therein is lower, that is, the increase in polymerization degree decreases the content of active NCO, and the six-membered ring in the trimer is a very stable structure, resulting in difficulty in forming a structure with a higher polymerization degree. The polyisocyanate curing agent used in the present invention can achieve both high NCO functionality and high NCO content through structural design, so that sufficient crosslinking of the coating composition can be achieved without increasing the amount of curing agent used, or even with decreasing the amount of curing agent used.
In some embodiments of the invention, component B1 is a polyisocyanate, further having an NCO functionality of 10 or more, further selected from 10 to 100, further 10 to 40, and further 15 to 35; examples of NCO functionalities are 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, etc. The NCO functionality in the present invention means, without particular limitation, an average value. The invention makes it possible to achieve high NCO functionality and also high NCO contents. In some embodiments of the invention, the NCO content of the polyisocyanate in component B1 is not less than 25%, further may be 25% to 30%; examples of NCO contents are 25%, 26%, 27%, 28%, 29%, 30% and the like.
In some embodiments of the invention, the polyisocyanates in component B1 have an NCO functionality of 10 (independently preferably 10 to 100, further preferably 10 to 40) and an NCO content of 25% (independently preferably 25% to 30%).
In some preferred embodiments of the invention, the NCO functionality of the polyisocyanates in component B1 is > 10 and the NCO content is 25% to 30%, in which case the coating film can also have a better compactness with reduced amounts of curing agent. In order to avoid excessively brittle films, the NCO functionality of the polyisocyanates is preferably less than or equal to 100, more preferably from 10 to 40. That is, by controlling the NCO functionality of the polyisocyanate in the component B1 to 10 to 100, preferably 10 to 40, the resulting coating film can be better made to have both improved abrasion resistance, chemical resistance and good flexibility.
The solids content of the polyisocyanates in component B1 is preferably 100%.
The polyisocyanates in component B1 are preferably in the liquid state. In this case, the solid content is preferably 100%. Here, the solid content of 100% means that the curing agent is directly used as a stock solution without dilution with a solvent.
The polyisocyanates in component B1 consist essentially of polyisocyanate compounds.
In some embodiments of the invention, the polyisocyanate in component B1 has structural units of formula (I):
In some embodiments, the polyisocyanate in component B1 further has structural units of formula (II):
In some embodiments, the polyisocyanate in component B1 has a general structure of formula (III):
In some embodiments, the end groups in formula (III) are selected from
End groups formed by polymerization, or->
And->
End groups formed upon copolymerization. When m=0, formula (III) is +.>
The definition of two "×" is consistent with the above, further, both terminal groups may be attached.
In some preferred embodiments of the invention, the polyisocyanate in component B1 has the general structure of formula (IV):
wherein n is equal in value to the NCO functionality of the polyisocyanate and n is selected from 10 to 40; r is R 3 、R 1 Is defined in (a) and one of the aboveSo that. Preferably, R 3 Is- (CH) 2 ) p -; wherein p is 1, 2, 3, 4, 5 or 6, further p is 2, 4 or 6, further 2.
In some embodiments of the invention, the polyisocyanate in component B1 is of the general structure of formula (V):
wherein either "×" is independently a terminal group allowed to form by polymerization of acrylic monomer, and both "×" may be the same or different; n, R 3 、R 1 And (including preferences and examples) are consistent with the foregoing.
The polyisocyanate curing agent used in component B may be prepared by polymerization of an acrylic isocyanate. Acrylic isocyanate refers to a molecule having c=c-C (=o) -, at one end, an isocyanate group, such as for example
R 1 、R 3 And (including preferences and examples) are consistent with the foregoing. Specific examples of the acrylic isocyanate include ethyl acrylate and ethyl methacrylate. The polymerization may also be carried out without or with a small amount of +.>
The monomer can obtain the polyisocyanate with the structure shown in the formula (III).
By controlling the degree of polymerization and R 3 、R 1 Group size (especially R) 3 The group size) of the polyisocyanate curing agent, the NCO functionality and the NCO content of the polyisocyanate curing agent may be controlled. The greater the degree of polymerization, the higher the NCO functionality; if R is 3 Too long a segment may lead to a decrease in NCO content.
Component C1 (diluent)
Component C1 in the PU coating combination system is a diluent (marked as a first diluent), and the viscosity of the PU coating combination system can be adjusted to adjust the film forming process, such as film forming time and the like.
In some embodiments of the invention, component C1 is selected from one or more of ethyl acetate, butyl acetate, diisobutyl ketone, propylene glycol methyl ether acetate, and the like.
In some embodiments of the invention, component C1 is a mixture of ethyl acetate, butyl acetate, diisobutyl ketone, and propylene glycol methyl ether acetate. The mass portion ratio of the four components can be (1-2): (0.5-1): (2.5-5): (1-2). The mass ratio of the four components can be (1.5-2.5): 1 (2.5-7.5): (1-3). The diluent in the mixed form is convenient for promoting the components of the PU coating combination system to be fully dissolved, so that the PU coating combination prepared by the PU coating combination system is more uniform, and the comprehensive performance of a paint film is improved. In some embodiments of the invention, the parts by weight of ethyl acetate, butyl acetate, diisobutyl ketone, and propylene glycol methyl ether acetate are as follows, for example, 2:1:5:2.
component A1, component B1 and component C1
In some embodiments of the present invention, the ratio of the parts by weight of component A1, component B1 and component C1 in the PU coating composition system is 100: (10-50): (50-70), for example, 100: (15-30): (50-70), further such as 100:25:60, 100:25:65, 100:15:55, 100:24:70, 100:24.75:60, 100:26.14:60, 100:25.34:65, 100:15.6:55, 100:23.65:70, etc.
The component B1 may be used in an amount of 10 to 50 parts by weight, further 15 to 30 parts by weight, based on 100 parts by weight of the component A1, and the component B1 may be used in an amount of, for example, 10, 12, 15, 20, 25, 30, 35, 40, 45, 50, etc., based on 100 parts by weight of the component A1.
The component C1 may be used in an amount of 50 to 70 parts by weight based on 100 parts by weight of the component A1, and the component C1 may be used in an amount of, for example, 50, 55, 60, 65, 70, etc., based on 100 parts by weight of the component A1.
The mass ratio of the component A1 to the component B1 is reasonably controlled, the molar ratio of-NCO to-OH can be controlled at a proper ratio, the full reaction between hydroxyl components and curing agents is facilitated, the compactness, chemical resistance, sunscreen cream resistance, hardness and other performances of a paint film are improved, and meanwhile, the good paint film adhesiveness is maintained. In some embodiments of the invention, the molar ratio of-NCO to-OH in the PU coating composition system is from (1 to 1.5): 1, further may be (1.1 to 1.5): 1, further may be (1.4 to 1.5): 1. such molar ratios are exemplified by (1.1:1), (1.2:1), (1.3:1), (1.4:1), (1.5:1), and the like.
Too little diluent can result in an inability to adjust to the desired viscosity, too much diluent can result in a coating system with a low solids content that is detrimental to film formation.
Packaging mode and use mode
In the PU coating combination system, the component A1, the component B1 and the component C1 can be respectively and independently packaged, or can be packaged in a combined way, and preferably, the component A1 and the component B1 are packaged separately.
When the PU coating combination system is used, the components are mixed according to the corresponding mass percentages and uniformly dispersed to prepare the PU coating combination with proper viscosity, and the PU coating combination can be used for coating. The PU coating composition for coating has a viscosity of 8.5 to 11s (cup No. 2, 25 ℃ C.). Known suitable coating means may be employed including, but not limited to, spraying. The film thickness may be about 30 to 35. Mu.m, for example, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, etc. Before coating, sieving treatment can be carried out to remove insoluble particles; the mesh number of the screen is, for example, 300 mesh.
It should be understood that, since the component A1, the component B1 and the component C1 may be mixed after being weighed according to the required total mass and mass fraction ratio at the time of use, the mass fraction ratio of each component need not be strictly in accordance with the mass fraction ratio of the foregoing guidance when individually packaging each component, so long as the packaging provided can provide the PU coating composition system for formulating the foregoing mass fraction ratio.
Second aspect of the invention
In a second aspect of the present invention, there is provided a coated body comprising a top-coat film layer, and further comprising a primer film layer laminated under the top-coat film layer; the finish paint film layer is prepared from a PU coating composition prepared by the PU coating composition system in the first aspect of the invention.
The PU coating composition is coated on the surface of the primer film layer to prepare the coating body.
In some embodiments of the invention, the primer film layer is coated with a primer composition formulated from a PU primer composition system.
In some embodiments of the present invention, the PU primer composition is formulated from a PU primer composition system comprising component A2, component B2, and component C2, wherein component A2 provides the resin component, component B2 is the curing agent (denoted as the second curing agent), and component C2 is the diluent (denoted as the second diluent).
Component A2
In some embodiments of the invention, component A2 comprises the following components in mass percent: 35% -60% of hydroxy acrylic resin (marked as second hydroxy acrylic resin), 20% -50% of mixed solvent (marked as second mixed solvent) and 10% -25% of additive (marked as second additive).
In some embodiments of the invention, the mass percent of the second hydroxy acrylic resin in component A2 is 35% to 60%, such as 35%, 40%, 45%, 50%, 55%, 60%, etc.
In some embodiments of the invention, the mass percentage of the second mixed solvent in component A2 is 20% to 50%, such as, for example, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.
In some embodiments of the invention, the mass percentage of the second additive in component A2 is 10% to 25%, such as, for example, 10%, 11%, 12%, 13%, 14%, 15%, 20%, 21%, 22%, 23%, 24%, 25%, etc.
In some embodiments of the invention, the second hydroxy acrylic resin has a hydroxyl content of 0.5% to 1% (e.g., 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.); and/or the weight average molecular weight of the second hydroxy acrylic resin is 1000Da to 5000Da (e.g., 1000Da, 2000Da, 3000Da, 4000Da, 5000Da, etc.).
In some embodiments of the present invention, the second mixed solvent is a mixture of (1 to 4): 1, such as 1:1, 1.5:1, 2:1, 3:1, 3.5: 1. 4:1, etc.
In some embodiments of the invention, the second additive is one or more of a dispersant, an anti-settling agent, a matting powder, talc, black paste, a leveling agent (denoted as a second leveling agent), and the like. In some embodiments, the second additive comprises 5% to 10% matting powder and 1% to 6% black paste; and/or the second additive further comprises 0.5-1% of anti-settling agent and 0.1-0.5% of leveling agent; and/or the second additive further comprises 3-8% of talcum powder and 2-4% of dispersing agent.
Component B2
In some embodiments of the invention, component B2 (the second curative) is a diisocyanate oligomer (the degree of polymerization is generally. Ltoreq.3, for example the degree of polymerization is 3, i.e., trimer). In some preferred embodiments of the invention, component B2 is selected from one or more of kestose N3580BA, asahi TKA100, di-high T1890E, kestose Z4470, kestose N75, and the like.
Component C2
In some embodiments of the invention, component C2 is selected from one or more of ethyl acetate, acetone, isobutyl acetate, diacetone alcohol, and the like.
In some embodiments of the present invention, component C2 is a mixture of ethyl acetate, acetone, isobutyl acetate and diacetone alcohol, the aforementioned components being in parts by weight (1-3): (1-3): (1-3): 1.
In some embodiments of the invention, in component A2, the second hydroxy acrylic resin has a hydroxyl content of 0.5% to 1% and a weight average molecular weight of 1000Da to 5000Da; the mass ratio of the second mixed solvent is (1-4): 1 and butyl acetate; the second additive is one or more of dispersing agent, anti-settling agent, extinction powder, talcum powder, black paste and second leveling agent; and/or the number of the groups of groups,
component B2 is diisocyanate oligomer; and/or the number of the groups of groups,
the component C2 is a mixture of ethyl acetate, acetone, isobutyl acetate and diacetone alcohol, and the mass part ratio of the components is (1-3): (1-3): (1-3): 1, for example 3:3:3:1.
in some embodiments of the invention, component A2: component B2 (curing agent): component C2 (diluent) =100: (5-10): (80-100), for example, 100:5:80.
third aspect of the invention
In a third aspect of the invention, there is provided the use of the PU coating composition system according to the first aspect of the invention or the coated body according to the second aspect of the invention.
In some embodiments of the invention, the application includes, but is not limited to, application to plastic substrates. Further, the plastic substrate comprises PC substrate, ABS substrate, HIPS substrate, PMMA substrate, PC/ABS composite material plastic substrate and the like.
In some embodiments of the invention, the application is the preparation of a multilayer coating film on a plastic substrate.
In some embodiments of the invention, the application includes, but is not limited to, application in automotive interior materials, preferably with plastic substrates.
In some embodiments of the present invention, the application is in the preparation of an automotive interior plastic part, preferably an automotive interior plastic part comprising a plastic substrate and a topcoat film layer formed from the PU coating composition, further comprising a primer film layer between the plastic substrate and the topcoat film layer, further wherein the primer film layer is a primer film layer formed from the PU primer composition of the present invention. The PU primer composition may be selected from any of the PU primer compositions described herein (including, but not limited to, primer compositions formulated with any of the primer combination systems).
In some embodiments of the present invention, the application includes coating the PU coating composition formulated from the PU coating composition provided in the first aspect of the present invention onto the PU primer film layer surface, and drying to form a PU topcoat film layer.
Fourth aspect of the invention
In a fourth aspect of the present invention, there is provided a PU paint film article comprising a plastic substrate and the coated body of the second aspect of the present invention, wherein the plastic substrate is laminated under a primer film layer, further wherein the primer film layer is made by coating a PU primer composition onto the surface of the plastic substrate, and wherein the topcoat film layer is made by coating a PU coating composition formulated from the PU coating composition of the first aspect of the present invention onto the surface of the primer film layer. .
Wherein the PU primer composition is formulated from a PU primer composition system, and may be selected from any suitable primer composition system, including but not limited to the primer composition systems described herein.
In some embodiments of the invention, the primer film layer is prepared by: the PU primer composition is sprayed on a plastic substrate, the sprayed film thickness is about 15-25 mu m, and then the film is cured and formed by baking for 30 minutes under the heating condition (such as 80 ℃), so that a cured primer layer, namely the primer film layer, is obtained, and the primer film layer is directly laminated on the surface of the plastic substrate. The spraying can be performed by using a W-100 spray gun in the rock field. The material of the plastic substrate is, for example, an abs+pc composite material.
In some embodiments of the invention, the PU coating composition is applied to the primer film layer surface by: adding the raw materials in the PU coating combination system into a batching tank according to the preparation proportion, stirring for 5-10 min by using a dispersing stirrer according to 600-800 r/min to obtain a component A1, mixing the component A1, the component B1 (first curing agent) and the component C1 (first diluent) according to the proper mass proportion, for example, the method comprises the following steps of: (25-50): (50-70), then placing the mixture into a dispersing mixer to stir for 2-5 min at the speed of 200-400 r/min, uniformly dispersing, and then filtering the mixture by a 300-mesh filter screen to obtain the PU coating composition with the viscosity (8.5-11 s, a cup No. 2 in a rock field, and 25 ℃). Spraying the prepared PU coating composition onto the surface of the solidified primer layer by using a W-100 spray gun in a rock field, wherein the thickness of the sprayed film is about 30-35 mu m, standing for 5-8 min at room temperature in a wet film state, and then placing into a baking oven at 70-80 ℃ for baking for 1-1.5 h to obtain a PU paint film product with black matte texture. The thickness of the coating after drying and film forming is basically consistent with that of the sprayed film. In some embodiments, the film thickness of the coating after film formation is 30 microns, 35 microns, etc.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples, in which specific conditions are not noted, are preferably referred to the guidelines given in the present invention, and may be according to the experimental manual or conventional conditions in the art, the conditions suggested by the manufacturer, or the experimental methods known in the art.
In the specific examples described below, the measurement parameters relating to the raw material components, unless otherwise specified, may have fine deviations within the accuracy of weighing. Temperature and time parameters are involved, allowing acceptable deviations from instrument testing accuracy or operational accuracy.
In the examples described below, the room temperature was 20℃to 30℃unless otherwise indicated.
1. Raw materials and reagents
1.1. Preparation of high functionality polyisocyanates
Some exemplary high functionality polyisocyanates have the structure of formula (V) or formula (III):
in formula (V), two "×" are each independently
End groups, R, formed during the polymer reaction 1 Is H or methyl, R 3 Ethylene, n is 15, 23, 25, 30, 35, respectively. The polyisocyanate structure represented by formula (V) in the following examples is shown in Table 2.
To be used for
The high functionality polyisocyanate is prepared by polymerizing a monomer (the monomer used herein is ethyl acrylate). The length of time for which the polymerization reaction is carried out can be monitored by infrared detection of the residual amount of carbon-carbon double bonds. The carbon-carbon double bond referred to herein is CH 2 =ch-or CH 2 -C(CH 3 ). Detection 1640cm -1 Infrared characteristic peaks of the locations.
The preparation process for n of about 23 is as follows: 20g of ethyl acetate (the solvent is dehydrated) was added to the reactor, stirring was started, and the temperature was slowly raised to 70 ℃. 20g of ethyl acrylate was dissolved in ethyl acetate, 0.3g of initiator AIBN was added and slowly added dropwise to the reactor. Testing infrared 1640cm after finishing dripping -1 After confirming the positions of all double bonds, finishing the reaction to obtain a polyisocyanate product P0a.
Structural confirmation of product P0a by hydrogen spectrum nuclear magnetism: chemical shift units with deuterated chloroform as solvent and ppm as characteristic peak, 1 in the H NMR spectrum: the delta 1.92-2.00,2.28-2.45 position is hydrogen on the main chain of the polymer, which proves that the polymer is formed; delta 3.57-3.63,4.06-4.15 is a continuous CH2 characteristic peak.
In formula (III), two "+" are each independently 
And->
End groups formed during copolymerization, m is 1, 2, 3, 4, 5; r1 is H methyl, R2 is H or methyl, R3 is ethylene, R4 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, hexyl, n-octyl, isooctyl, decyl, lauryl or isobornyl, and n is 12, 18, 30 respectively. The polyisocyanate structure represented by formula (III) in the following examples is shown in Table 2.
To be used for
The high-functionality polyisocyanate is prepared by polymerization of monomers (the monomers used in the process are ethyl acrylate monomers and acrylic ester monomers). The length of time for which the polymerization reaction is carried out can be monitored by infrared detection of the residual amount of carbon-carbon double bonds. The carbon-carbon double bond referred to herein is CH 2 =ch-or CH 2 -C(CH 3 ). The carbon-carbon double bond being CH 2 When=ch-, 1640cm was detected -1 Infrared characteristic peaks of the locations.
The preparation process with n about 12 and m 1 is as follows: 20g of ethyl acetate (the solvent is dehydrated) was added to the reactor, stirring was started, and the temperature was slowly raised to 70 ℃. 18g of ethyl acrylate and 2g of butyl methacrylate were dissolved in ethyl acetate, 1g of initiator AIBN was added and slowly added dropwise to the reactor. Testing infrared 1640cm after finishing dripping -1 After confirming the positions of all the double bonds, the reaction was terminated to obtain a polyisocyanate product P0b.
The structure of the product P0b by hydrogen spectrum nuclear magnetism was confirmed as follows: chemical shift units with deuterated chloroform as solvent and ppm as characteristic peak, 1 in the H NMR spectrum: the delta 1.92-2.00,2.28-2.45 position is hydrogen on the main chain of the polymer, which proves that the polymer is formed; structurally continuous CH at position n of delta 3.57-3.63,4.06-4.15 2 Characteristic peaks; the delta 4.06-4.09 position is CH which is close to O atom on m unit structure 2 Characteristic peaks; the δ1.36-1.59 positions are structurally continuous CH of m units 2 Characteristic peaks;
delta 0.95-0.99 position is terminal CH 3 Characteristic peaks.
Raw materials of PU Top-coat (corresponding to PU coating composition System)
1.2.1. Raw materials of component A1
The raw materials and parts by weight of the PU top-coat main agent (component A1) used in the following examples and comparative examples are shown in Table 1. The total mass of component A1 in each example was 100g.
The hydroxyl component was selected from commercially available Zhan Xin SM516/70BAC, zhan Xin 2803/78BAC, zuo and HE6790, DSM CY472, worle epol 1181/03.
Zhanxin SM516/70BAC: a hydroxy acrylic resin having a hydroxyl group content of 5.5% and a solid content of 70%;
zhanxin 2803/78BAC: a polyester resin having a hydroxyl group content of 6.0% and a solid content of 80%;
Android and HE6790: a hydroxy acrylic resin having a hydroxyl group content of 4.5% and a solid content of 70%;
DSM CY472: a hydroxy acrylic resin having a hydroxyl group content of 1.7% and a solid content of 57%;
woriepol 1181/03: polyester resin with 10% hydroxyl and 100% solid content.
Wherein the "hydroxyl group content" is the mass content of hydroxyl groups in the solid resin, and the actual hydroxyl group content of each resin raw material is the hydroxyl group content x solid content in the solid resin; the hydroxyl value of the resin raw material was actual hydroxyl content×33. Taking the example of Zhanxin SM516/70BAC, the hydroxyl number is 5.5X133X 0.7= 127.05mgKOH/g.
TABLE 1 raw materials and parts by weight of PU topcoat Main agent (component A1)
1.2.2. the proportion of the components in the PU finishing paint
The formulation of component A1 (main agent) and component B1 (curing agent), component C1 (diluent) in the examples and comparative examples is shown in Table 2.
The calculation formula of the usage amount of the curing agent is as follows: m is M NCO = (7.5× (ratio of-NCO to-OH in the system) ×hydroxyl value× (percent resin content))/(NCO content×100).
Table 2. Matching relationship of component A1 (main agent) and component B1 (curing agent), component C1 (diluent) in PU top-coat paint.
Wherein the PU paint diluent is prepared from the following components in percentage by mass: 1:5:2, butyl acetate, diisobutyl ketone and propylene glycol methyl ether acetate.
Raw materials for preparing PU primer composition
The raw materials and the mass ratios of the component A2 in the PU primer composition are shown in Table 3.
Table 3.
| Raw materials | Mass percent (%) |
| Mitsubishi LR-7791 | 40 |
| Dispersant BYK: P-104S | 5 |
| Polyamide wax slurry: dis barone 6900-HV | 5 |
| Extinction powder OK520 | 10 |
| Talc powder | 5 |
| Black paste | 5 |
| Leveling agent BYK-306 | 0.2 |
| Acetic acid ethyl ester | 20 |
| Butyl acetate | 9.8 |
| Totalizing | 100 |
The mass ratio of the diluent in the PU primer composition is 3:3:3:1, acetone, isobutyl acetate and diacetone alcohol.
2. Preparation of coating systems
The coating systems of the examples and comparative examples were prepared as follows:
after the primer component A2 (Table 3) and the component B2 (N3390) are mixed according to the mass ratio of 100:5, 80% of diluent (component C2) of the mass of the component A2 is added, and after the mixture is stirred uniformly, the mixture is sprayed onto an ABS+PC plastic substrate by a field W-100 spray gun and baked at 80 ℃ for 30 minutes to prepare a primer film with the thickness of about 20 mu m.
And then coating PU finishing paint on the cured primer film: the top coat raw materials in the examples and the comparative examples in table 1 are added into a batching tank according to the preparation proportion, and the component A1 is prepared after uniform dispersion. Component A1 (Table 1), component B1 (Table 2) and diluent (component C1) in the finish paint are uniformly mixed according to the mass ratio, then (the viscosity is 9s, a W-100 spray gun and 25 ℃) are sprayed on the surface of a primer film, the sprayed film thickness is about 32 mu m, the system is fully leveled after standing for 6min at room temperature in a wet film state, and the system is fully cured by baking in a baking oven at 70 ℃ to obtain a PU film (film to be tested), and the adhesive force to be tested is obtained.
3. Test item (TL 226 automobile inner decoration test standard)
After the adhesion of the PU coating film was tested, the film was baked at 60℃to 80℃for 48 hours, and then other items were tested, and the test results are shown in Table 4.
3.1. Adhesion test: ISO 2409-2013: after 1mm cross-cuts, the test was performed with tape, with a rating of 0.
3.2. Hardness testing: GB T6739-2006 Chinese pencil, load 500g, need not less than H.
3.3. Abrasion resistance test: and (3) carrying out a dry cloth abrasion resistance color-removing test on the coating to be tested, and judging the abrasion resistance of the coating according to the abrasion times and the abrasion grades and the abrasion cloth gray card grades. The more the number of friction times, the smaller the abrasion grade, the larger the friction cloth ash card grade, which shows that the smaller the appearance friction trace, the better the coating film friction resistance. The abrasion grade is required to be less than or equal to grade 2, and the white cloth has no color change (the gray card grade of the friction cloth used for testing according to DIN EN 20105-A03 standard is required to be more than or equal to grade 4).
3.4. Chemical resistance test: the chemical resistance of the coating film was characterized by a drip test and a face cream test, respectively.
3.4.1. Drop test: synthetic sweat A (0.75% acetic acid by volume ratio, prepared by adding distilled water into 7.5mL 100% acetic acid to 1L), dropping 0.1mL solution (sweat A) on the surface of the coating film to be tested by a pipette, exposing for 10min, drying in a high temperature box at 60 ℃ for 30min, observing the surface of the coating film after 24h, and requiring no visible change of appearance of the coating film.
3.4.2. Face cream resistance test (popular, curiosity): generally, the higher the SPF value of the face cream, the higher the test temperature, the longer the time, and the harder the coating film is to withstand. The method comprises the steps of respectively adopting Thierry GmbH sun cream (popular type) and Nivea (NIVEA) SPF50++ sun cream, respectively placing the sun cream in a high-temperature box at 100 ℃ for 2 hours (test one) and placing the sun cream in a high-temperature box at 80 ℃ for 24 hours (test two), requiring no appearance and touch change (such as lines, swelling, cracks, softening and viscosity) of a coating film, then testing the gray card grade of the coating film according to DIN EN 20105-A02 standard, wherein the gray card grade is more than or equal to 4, indicating that the color of the coating film is free from parallax before and after the test, no fading and bloom phenomena exist, and further testing the adhesive force and hardness of a base material of the coating film.
3.5. Appearance leveling test: the DOI orange-peel instrument requirement is more than or equal to 90.
3.6. Surface drying speed: baking at 80 ℃ and recording the touch dry time, wherein the touch dry time is required to be less than or equal to 15min.
3.7. Real dry speed: baking at 80 ℃, and recording the actual drying time; the film provided by the invention is judged whether to be dried or not according to a cotton ball pressing method in GB/T1728-1979 (1989) paint film and putty drying time measuring method. "hr" means "hour".
TABLE 4 test results
As is clear from tables 2 and 4, the high-functionality polyisocyanate curing agent having NCO content of 25% -30% and functionality of 10 or more was changed while keeping other conditions unchanged in example 1 and comparative example 3, and the compactness of the coating film was greatly improved even with a reduced amount of curing agent, thereby producing a coating film having improved hardness, dry speed, abrasion resistance and chemical resistance, in particular, the resistance of the coating film to a face cream was greatly improved, and a face cream test having more strict conditions could be tolerated. Meanwhile, the component A1 is preferable, and the matching functionality is preferably more than 10 and less than 100 (more preferably 10-40) and has high NCO content, so that the prepared coating film has good substrate adhesiveness, leveling effect and surface drying speed.
The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Further, it is understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the above teachings, and equivalents thereof fall within the scope of the present application. It should also be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent of the invention should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.
Claims (11)
1. A PU coating composition system comprising component A1, component B1, and component C1;
the component A1 comprises, in mass percent of 100%:
40% -80% of hydroxyl component;
0.6 to 2.5 percent of leveling agent; and
15% -60% of mixed solvent;
wherein, the hydroxyl content of the hydroxyl component is 3% -8%;
the component B1 comprises polyisocyanate; wherein the NCO functionality of the polyisocyanate is more than or equal to 10, and the NCO content is more than or equal to 25%;
the component C1 is a diluent;
the mass part ratio of the component A1 to the component B1 to the component C1 is 100: (10-50): (50-70).
2. The PU coating composition system of claim 1, wherein, in said component A1,
the mass percentage of the hydroxyl component is 60% -70%; and/or the number of the groups of groups,
the weight average molecular weight of the hydroxyl component is 2000Da to 8000Da; and/or the number of the groups of groups,
the viscosity of the hydroxyl component is 5000cps to 20000cps; and/or the number of the groups of groups,
the leveling agent is prepared from the following components in percentage by mass (1-10): the mixture of the polyether modified organosilicon leveling agent and the acrylic leveling agent in the (5-15); and/or the number of the groups of groups,
the mass ratio of the mixed solvent is (1-4): (1-4): (1-4) a mixture of a low boiling point solvent having an initial boiling point of 120 ℃ or less, a medium boiling point solvent having an initial boiling point of 120 ℃ to 160 ℃ and a high boiling point solvent having an initial boiling point of >160 ℃.
3. The PU coating composition system of claim 2, wherein, in said component A1,
the hydroxyl component is one or more of hydroxy acrylic resin, polyester resin and alkyd resin; and/or the number of the groups of groups,
the hydroxyl content of the hydroxyl acrylic resin is 4.2% -6%; and/or the number of the groups of groups,
the Tg of the hydroxy acrylic resin is 70-80 ℃; and/or the number of the groups of groups,
the hydroxyl content of the polyester resin is 5% -8%; and/or the number of the groups of groups,
the solid content of the polyester resin is 80% -100%; and/or the number of the groups of groups,
the Tg of the polyester resin is 50-60 ℃; and/or the number of the groups of groups,
the hydroxyl content of the alkyd resin is 5% -6%; and/or the number of the groups of groups,
the solid content of the alkyd resin is 70% -80%; and/or the number of the groups of groups,
the Tg of the alkyd resin is 50-60 ℃; and/or the number of the groups of groups,
the hydroxyl component is selected from one or more of the following resin products: zhan Xin 1198SS-70, zhan Xin SM516, zhan Xin 2803, zuo and HE6790, DIC A859, DIC A862 and Mitsubishi LR7728; and/or the number of the groups of groups,
the polyether modified organosilicon leveling agent is selected from one or more of the following products: BYK-306, BYK-331, TEGO 450, TEGO Glide100 and TEGO 270; and/or the number of the groups of groups,
the acrylic leveling agent is selected from one or more of the following products: EFKA3777, BYK358N, BYK361 and BYK381; and/or the number of the groups of groups,
The initial boiling point of the low boiling point solvent is 75-120 ℃, the initial boiling point of the medium boiling point solvent is 120-160 ℃, and the initial boiling point of the high boiling point solvent is 160-220 ℃;
the low boiling point solvent is one or two of ethyl acetate and isobutyl acetate; and/or the number of the groups of groups,
the medium boiling point solvent is one or two of butyl acetate and methyl isobutyl ketone; and/or the number of the groups of groups,
the high boiling point solvent is one or more of trimethylbenzene, tetramethylbenzene, diisobutyl ketone and diacetone alcohol.
4. The PU coating composition system of claim 1, wherein, in said component B1,
the NCO functionality of the polyisocyanate is selected from 10 to 100; and/or the number of the groups of groups,
the NCO content of the polyisocyanate is 25% -30%; and/or the number of the groups of groups,
the polyisocyanate has structural units represented by formula (I):
5. The PU coating composition system of claim 4, wherein, in said component B1,
the NCO functionality of the polyisocyanate is selected from 10 to 40; and/or the number of the groups of groups,
the polyisocyanate also has structural units of formula (II):
6. The PU coating composition system according to claim 5, wherein in component B1, the polyisocyanate has a general structure of formula (III):
7. The PU coating composition system of claim 1 to 6, wherein the component C1 is a mixture of (1 to 2): (0.5 to 1): (2.5 to 5): the mixture of ethyl acetate, butyl acetate, diisobutyl ketone and propylene glycol methyl ether acetate according to (1-2).
8. A coated body comprising a top-coat film layer, and further comprising a primer film layer laminated under the top-coat film layer; wherein the topcoat film layer is prepared from the PU coating composition formulated by the PU coating composition system of any one of claims 1 to 7.
9. The coated body of claim 8, wherein the primer film layer is coated with a PU primer composition;
the PU primer composition is prepared from a PU primer combination system comprising a component A2, a component B2 and a component C2;
The component A2 comprises, in mass percent of 100%: 35-60% of second hydroxy acrylic resin, 20-50% of second mixed solvent and 10-25% of second additive; wherein the hydroxyl content of the second hydroxyl acrylic resin is 0.5% -1%, and the weight average molecular weight is 1000 Da-5000 Da; the mass ratio of the second mixed solvent is (1-4): 1 and butyl acetate; the second additive is one or more of a dispersing agent, an anti-settling agent, extinction powder, talcum powder, black paste and a second leveling agent;
the component B2 is diisocyanate oligomer, and the polymerization degree is less than or equal to 3;
the component C2 is a mixture of ethyl acetate, acetone, isobutyl acetate and diacetone alcohol, and the mass ratio of the components is (1-3): (1-3): (1-3): 1.
10. use of the PU coating composition system according to any one of claims 1 to 7, or the coated body according to any one of claims 9 to 10, on plastic substrates, including PC substrates, ABS substrates, HIPS substrates, PMMA substrates and plastic substrates of PC/ABS composites.
11. A PU paint film article comprising a plastic substrate and the coated body of any one of claims 9 to 10, wherein the plastic substrate is laminated under the primer film layer, the primer film layer is made by coating a PU primer composition on the surface of the plastic substrate, and the topcoat film layer is made by coating a PU paint composition formulated with the PU paint composition system of any one of claims 1 to 7 on the surface of the primer film layer.
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