CA1126101A - Spray coating process - Google Patents
Spray coating processInfo
- Publication number
- CA1126101A CA1126101A CA308,381A CA308381A CA1126101A CA 1126101 A CA1126101 A CA 1126101A CA 308381 A CA308381 A CA 308381A CA 1126101 A CA1126101 A CA 1126101A
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- microparticles
- diluent
- acrylic
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 24
- 238000005507 spraying Methods 0.000 title abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 117
- 239000011859 microparticle Substances 0.000 claims abstract description 79
- 239000003085 diluting agent Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 24
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000000049 pigment Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 57
- 239000006185 dispersion Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 229920000058 polyacrylate Polymers 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920000578 graft copolymer Polymers 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 abstract description 7
- 238000007665 sagging Methods 0.000 abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000003019 stabilising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- -1 that is to say Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000012704 polymeric precursor Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229940113165 trimethylolpropane Drugs 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 101100130497 Drosophila melanogaster Mical gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 description 1
- 101100345589 Mus musculus Mical1 gene Proteins 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YDSWCNNOKPMOTP-UHFFFAOYSA-N benzenehexacarboxylic acid Natural products OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940063557 methacrylate Drugs 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical compound C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZZSIDSMUTXFKNS-UHFFFAOYSA-N perylene red Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=C(OC=5C=CC=CC=5)C=1)C(=O)C2=CC(OC=1C=CC=CC=1)=C3C(C(OC=1C=CC=CC=1)=CC1=C2C(C(N(C=3C(=CC=CC=3C(C)C)C(C)C)C1=O)=O)=C1)=C2C4=C1OC1=CC=CC=C1 ZZSIDSMUTXFKNS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31699—Ester, halide or nitrile of addition polymer
Abstract
ABSTRACT
SPRAY COATING PROCESS
A process for coating a substrate, especially an automobile body, by spray application whereby improved resistance to "sagging" or "running" on application can be obtained without reduction of the thickness of film which is applied; the process is characterised by the use of a coating composition comprising a film-forming acrylic resin, a volatile organic liquid diluent, a pigment other than a metallic flake pigment, and specified polymer microparticles which are stably dispersed in the combination of the resin and the diluent.
SPRAY COATING PROCESS
A process for coating a substrate, especially an automobile body, by spray application whereby improved resistance to "sagging" or "running" on application can be obtained without reduction of the thickness of film which is applied; the process is characterised by the use of a coating composition comprising a film-forming acrylic resin, a volatile organic liquid diluent, a pigment other than a metallic flake pigment, and specified polymer microparticles which are stably dispersed in the combination of the resin and the diluent.
Description
This invention relates to the application of protective and decorative coatings to surfaces, particularly the surfaces of automobile bodies.
It is well known to formulate coating compositions especially those for use in the automobile industry, upon acrylic resins, that is to say, polymers or copolymers of one or more alkyl esters of acrylic acid or methacrylic acid. Such compositions, however, give rise to certain d~fficulties, especially under the conditions of spray application as normally used in the painting of car bodies. Good flow-out of the coating after application~ which is necessary in order to maximise gloss, may be hard to achieve simultaneously with the avoidance of excessive flow of the composition during the spraying operation, the latter commonly leading to the defect known as "sagging" or "running", particularly at sharp edges or corners of a substrate of complicated shape.
We have now found that these difficulties can be minimised or eliminated if the coating ccmposition contains polymer microparticles of-a specified---t~e.
According to the present invention there is-provided a process for the production of a surface coating upon a substrate which comprises (i) applying by spray to the substrate surface a composition comprising (A) a film-forming acrylic resin as herein defined; (B) a volatile organic liquid diluent in which the acrylic resin is carried; (C) polymer microparticles as hereinafter defined, in an amount of at least 3% of the aggregate weight of the film-forming resin (A) and the micro-particles, which are insoluble in and stably dispersed in the _ 2 ~
:. ~ . . . : , . . - ~ .
iL261~l combination of the acrylic resin (A) and the diluent (B);
(D) a pigment, other than a metallic flake pigment, which is also dispersed in the com~ination of the acrylic resin and the diluent, and (ii) subsequently evaporating the volatile diluent to form a polymer film upon the surface.
The acrylic resin used in the process of the invention may be any film-forming polymer or copolymer of one or more alkyl esters of acrylic acid or methacrylic acid, optionally together with other ~thylenically unsaturated monomers such as vinyl acetate, vinyl propionate, acrylonitrile 7 styrene or vinyl toluene. These polymers may be of either the thermoplastic type or the thermosetting, cross-linking type~ Suitable acrylic or methacrylic esters for either type of polymer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Where the polymer is required to be of the cross-linking type, suitable functional monomers to be used in addition to the latter include acrylic acid, methacrylic acid, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy-propyl methacrylate, N-(alkoxymethyl)acrylamides and N-(alkoxy~
~ethyl)methacrylamides, where the alkoxy group may be, for example, a butoxy group, glycidyl acrylate and glycidyl meth-acrylate. The composition may in such a case contain also a cross-linking agent such as a diisocyanate, a diepoxide or, especially~ a nitrogen resin, that is to say a condensate of ~ormaldehyde with a nitrogenous compOund such as urea, thiourea, melamine or benzoguanamine, or a lower alkyl ether of such a condensate in which the alkyl group contains from 1 to 4 carbon ` ,! - 3 -....
:
, - . . ~
, o~
atoms. Particularly suitable cross-linking a~ents are melamine-formaldehyde condensates in which a substantial proportion of the methylol groups have been etherified by reaction with butanol.
For the purposes of the foregoing general definition of the invention, the cross-linking agent, where present, is considered as ~eing a part of the film-forming polymer (A).
The composition used according to the invention may incorporate a suitable catalyst for the cross-linking reaction between the acrylic polymer and the cross-linking agent, for example an acid-reacting compound such as acid butyl phosphate, acid butyl maleate or p-toluene sulphonic acid. Alte~natively the catalytic action may be supplied by the incorporation of free acid groups in the acr~lic polymer, for example by the use of acrylic acid or methacrylic acid as comonomer in the preparation of the polymer.
Accord1ng to one embodiment of the invention, the acrylic resin (A) is in a state of stable dispersion in the diluent liquid (B), which in such a case will be a non-solvent for the resin. Methods of preparing such polymer dispersions are well known in the art and are further referred to below in co~nection with the production of the polymer microparticles (C)~
In another embodiment~ the acrylic resin (A~ is dissolved in the diluent (B); the polymer may then be prepared by solution polymerisation of the constituent monomer or monomers, in the presence of suitable catalysts or initiators where necessary. Conveniently the polymerisation may be carried out in the same organic liquid that is to provide the diluent (B), ~ .Z~
or in a liquid which is to form part of that diluent.
Alternatively the resin (A) may be prepared in a separate previous operation (e.g. by aqueous emulsion polymerisation of monomer) and then dissolved in a suitable organic liquid~
S In yet another embodiment, the acrylic resin (A) may be partly in dispersion and partly in solution in the diluent (B).
The volatile organic liquid constituent (~) of the composition may be any o~ the liquids, or mixtures of liquids, which are conventionally used as polymer solvents in coating compositions, for example aromatic hydrocarbons such as toluene and xylene and petroleum fractions of various boiling point ranges having a significant~aromatic content, esters such as butyl acetate7 ethylene glycol diacetate and 2-ethoxyethyl acetate, ketones such as acetone and methyl isobutyl ketone, and alcohols such as butyl alcoh~l. The actual liquid~or mixture of liquids selected as the diluent (B) will depend upon the nature of the acrylic resin (A), according to principles which are well known in the coatings art, in order that the resin shall be soluble or insoluble in the diluent as required.
The polymer microparticles (C) present in the composition of the invention are particles of colloidal dimensions, having a diameter of from O.Ol - 10 microns, composed of a polymer which has a glass-liquid transition temperature greater than 0C and is insoluble in the combination of the acryIic resin (A) and the diluent (B), the mlcroparticles being stably dispersed in that combination (in the sense that they do not undergo flocculation or aggregation) as a consequence of the method of their preparation. This method _ 5 _ .
~Z6~t involves two essential stages: (i) the polymerisation of monomer, from which the microparticles are to be derived, in an inert liquid in which the resulting polymer is insolu~le and under conditions such that the polymer is obtained in a state of stable dispersion, and (ii) the subsequent polymer-isation, in the same inert liquid and in the presence of the microparticles formed in the first stage, of ethylenically unsaturated monomer giving rise to a second acrylic polymer which is compatible with the film-forming acrylic resin (A) and is soluble in the combination of polymer (A) and diluent (B).
This second acryliC polymer~ which for convenience will be referred to here as the "auxiliary" polymer, may be either soluble or insoluble in the inert liquid in question, depending on the monomer or monomers from which it is derived.
The insolubility of the microparticles in the - combination of the acrylic resin (A) and the diluent (B~ may be achieved by suitable selection of the composition of the microparticulate polymer, that is to say, the polymer may be one which is inherently insoluble in that combination~ but preferably it is achieved by introducing a sufficient degree of cross-linking into a polymer which, if not cross-linked, would actually he soluble in the combination of the resin (A) and diluent (B). Where insolubility of the microparticles is achie~ed through cross linking, it is preferred that the degree of cross linking should not be greater than that necessary to render the polymer insoluble. Insolubility of the microparticles in the combination of the resin (A) and diluent (B~ may be checked by means of the following test. The microparticles (1 part by weight) are shaken for 30 minutes with the diluent(B~
.: -::
~26~
(100 parts by weight); the suspension is then centrifuged at 17,000 r.p~m. for 30 minutes. The supernatant liquid is decanted off and the residual polymer then dried for 30 minutes at 150C, after which its weight is compared with that of the microparticles originally taken. This test may be difficult to apply where the specific gravity of the diluent is close to or greater than that of the microparticles, but such diluents (e.g. chlorinated solvents) would not normally be used in the compositions under consideration~ Where the result of this test indicates that the microparticles are acceptably insoluble in the diluent (B) alone, it can be assumed that the particles will be at least equally insoluble when the resin (A) is also present in solution in the diluent; there would be practical dif~iculties in carrying out the test actually in the solution o~ the resin (A) in diluent (B). Where ~he resin (A) is in a state of dispersion in the diluent (B), its presence will not normally have any influence on the degree of insolubility o~
the microparticles.
The microparticulate polymer may be of various types~
It may, for example9 be an acr~lic addition polymer, derived from one or more of the same monomers as have been described above in connection with the acrylic resin constituent (A).
Where it is desired that such a polymer should be cross-linked, this may be achieved by either of two general methods: firstly, by including in the ~onomers from which the polymer is derived a minor proportion of a monomer which is polyfunctional with respect to the polymerisation reaction, e.g. ethylene glycol dimethacrylate or divinylbenzene; or secondly, by including in :
: ' ~ ~' ' a126101 those monomers minor proportions of two other monomers carrying pairs of chemical groupings which can be caused to react with one another either during or after the polymerisation reaction, such as epoxy and carboxyl (e.g. glycidyl methacrylate and methacrylic acid), anhydride and hydroxyl or isocyanate and hydroxyl. Alternatively, the microparticles may be composed of a condensation polymer, for example a polyester prepared from a polyhydric alcohol and a polycarboxylic acid. Suitable polyhydric alcohols include ethylene glycol, propylene glycol~ hutylene glycol, 1:6-hexylene glycol, neopentyl glyco~, diethyl~ne glycol, triethylene glycol, tetraethylene glycol, glycerol, trimethylol-propane, trimethylolethane, pentaerythritol, dipentaerythritol, tripentaerythritol, hexane triol, oligomers of styrene and allyl alcohol ~for example that sold by Monsan~o Chemical Company under the designation RJ 100) and the condensation products of trimethylolpropane with ethylene oxide or propylene oxide (such *
as the products known commercially as "Niax" triolsj. Suitable polycarboxylic acids include succinic acid ~or its anhydride), adipic acid, azelaic acid~ sebacic acid, maleic acid (or its anhydride), fumaric acid5 muconic acid, itaconic acid, phthalic acid (or its anhydride), isoph~halic acid, terephthalic acid, tr}mellitic acid (or its anhydride) and pyromellitic acid (or its anhydride). Where it is desired that the polyester should be cross-linked, this may again be achieved by incorporating in the starting composition materials of functionality ~reater than two, although in this case, because of the characteristic-ally broad distribution of molecular species formed in a condensation polymerisation, it may be difficult to ensure that all those species are .in fact cross-linked.
* Trade Marks _ 8 --13 :
The ch~mical compositions and degree of cross-linking of the microparticulate polymer are so chosen as to ensure that the polymer per se has a glass-liquid transition temperature (Tg~
greater than 0C, that is to say, under normal conditions of use S of the composition which is spray-applied according to the invention, the microparticles are hard and glassy.
As already stated, it is necessary that the polymer microparticles be sta~ly dispersed in the combination of the acryli~ resin (A) and the liquid diluent. ~y '9stably dispersed"
is meant that the particles are prevented from flocculating or aggregating by means of a sterîc barrier around the particles~
of polymer chains which are solvated by the said combination and hence are in a chain-extended configuration. In this context the term "solvated" implies that the polymer chains in lS question, if they were independent molecules, would be actually soluble in the combination in question; however, because the chains are in fact attached to the microparticles at one or more points along their length, the steric barrier remains permanently attached to the particles. It will be understood that the stabilising polymer chains to be u ed in any particular instance will be selected with reference to the nature of the li~uid diluent and fil~-forming acrylic resin concerned. In general terms this means that the chains will be of a degree of polarity similar to that of the diluent and film~formin~ resin, so that the combination of the latter will be inherently a solvent for the polymer of whlch the chains are composec~ Since, in the automobile finishes to which the present invention is primarily directed, the liquid diluent will conventionally be of a : .: :. -.
~L~26~
relatively high degree of polarity (containing, for example, a substantial proportion OI' "strong" ester and ketone solvents) it follows that the stabilising chains on the microparticles will usually require to be of a composition such that they are inherently soluble in that type of liquid.
The mode of anchoring of the stabilising chains to the microparticles is conveniently discussed in connection with methods of making the particles, as follows.
The polymer microparticles may be produced in various ways. Prefera~ly they are produced by a process of dispersion polymerisation of monomers, in an organic liquid in which the resul'cing polymer is insoluble, in the presence of an amphipathic steric stabilising agent. Suitable processes OIC dispersion polymerisation are well known and extensively described in the literature. Thus, so far as the dispersion polymerisation of ethylenically unsaturated monomers such as acrylic or methacrylic acid esters, vinyl esters and styrene or its derivatives is concerned, the procedure is basically one of polymerising the monomers in an inert liquid in which the monomers are soluble but the resulting polymer is not soluble~ in the presence dissolved in the liquid of an amphipathic stabilising agent or of a polymeric precursor which, by copolymerisation or grafting with a portion of the monomers, can give rise in situ to such a stabilising agent. Reference may be made, for example, to British Patent Specifications Nos. 941,305; 1,052,241; 1,1229397 and 1~2317614 for a general desc:ription of the principles involved, as wel~ as to "Dispersion Polymerisation in Organic Media", ed K.E. J. Barrett (John Wiley and Sons, 1975)~
: -; , - - .
, ~ . . .
Th~ choice of suitable unsaturated monomers for the production of microparticles having the required Tg and other characteristics will present no difficulty to those skilled in the polymer art. Amongst suitable monomers, there may be mentioned methyl methacrylate, styrene and vinyl acetate, the homopolymers of which have Tg values of about 105, 100 and 32C respectively. Where a lower Tg than that of the homopolymer is desired, these "hard't monomers may be copolymerised with a suitably chosen proportion of a "soft" monomer, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or butyl meth-acrylate~ In the case where the microparticle polymer is produced by a process of dispersion polymerisation of the monomer or monomers in an organic medium, there may be a limit imposed upon the proportion of "soft" monomers which can be included by the need to ensure that the resulting copolymer is not too soluble, even in organic liquids of low polarity such as hydrocarbons, ~or the formation of a stable dispersion of the microparticles to take place. The skilled person will, howe~er, readily be a~le to find, if necessary with the aid of simple experimentation, suitable monomer compositions to satis~y the given requirements.
The production specifically of dispersion of cross-linked addition polymer particles can be achieved by including, in the monomers selected, pairs of monomers containing (in addition to the polymerisable unsaturated groups) groups capable of enter'ng into chemical reaction with each other; for example, the epoxide and carboxyl groups contained in glycidyl methacrylate and methacrylic acid. By ollowing the procedure particularly .
described in British Patent Specifications NosO 1,095,288 and 1,156,012, for example, particles are obtained in which there are present such complementary groups which, although not at that stage co-reacted, can be caused to co-react and so for~
crosslinks by subsequently heating the dispersion to a suitably elevated temperature. Cross-linked add.ition polymers may also be prepared in dispersion by including in the monomers under-going dispersion polymerisation a minor proportion of a monomer which is difunctional with respect to the polymerisation reaction, such as ethyleneglycol dimethacrylate or divinyl~enzene. Small propartions of comonomers incorporating carboxyl groups, e~g.
acrylic acid or methacrylic acid may be included (where the microparticles are to be cross-linked, such propo~tions would be in excess of those used in order to achleve cross-linking by reaction with a co-reactive monomer such as glycidyl methacrylate).
Conversely, small (additional) proportions of an epoxide monomer, e~g. glycidyl methacrylate, may be included. Other functional monomers, such as hydroxyethyl acrylate or acrylamide, may also be included in minor proportions in the monomers from which the microparticles are to be derived.
The production of dispersions of condensation polymers is described, for example, in British Patent Specifications Nos~
1,373,531; 1,403,794 and 1,413,199, and methods of obtaining cross-linked polymer particles are included in these descriptions.
The general principles in~olved here are the same as those referred to above in connection with addition polymer dispersions, but there is a difference of detail arising from the commonly more highly polar nature of the monomers or starting materials . . ..
from which condensation polymers are derived. This is, namely, that the mono~ers in question are usually insoluble in the inert liquid in which the polymerisation is to be carried out.
Accordingly the first step in the dispersion polymerisation of the monomers is to bring them into a state of colloidal dispersion in the inert llquid, either as liquid or as solid particles. In the second step, polymerîsation of the monomers takes place within those same particlesO An amphipathic sta~ilising agent is required in each stage, firstly in order to stabilise the particles of monomer and secondly in order to s~abilise the particles of polymer formed, but in suitable cases a single stabilising agent can be found which w}ll perform both these functions. In place of using a preformed amphipathic stabilising agent in this process, ther-e may be e~ployed instead a suitable polymeric precursor which, by copolymeris2tion or grafting with a portion of the monomers being polymerised, can give rise to such a stabilising agent in situ. Reference may be made in this connection to British Patent Seria~ No-. 1583142, published ~anuary 21, 1981 Suitable monomeric starting materials for preparin~
condensation polymer microparticles are those which are well known for use in making such polymers by melt or solution polymerisation techniquesO For example, in the case of polyester microparticles, suitable materials in general are the polyhydric alcohols and polycarboxylic acids, and here, as with the pol~mers of the aclc31tic)n type discussed above, it will be evident to the skilled person which particular reactants are to be selected in arder to produce a m~croparticulate polymer having the requisite Tg and other characteristics.
, .~. . .
,..... .. .. ..
: :.......... ~ .. . ...
~2~
It will, of course, be understood that, in the case of both polyester and polyamide microparticles, the mixture to be polymerised must incorporate some proportion of a starting monomer which has a functionality greater than two, where it is desired that the microparticles should be cross-linked.
In all the above-described dispersion polymerisation processes, the amphipathic steric stabilising agent is a substance the molecule of which contains a polymeric component which is solvatable by the liquid in which the di.spersion is made and another component which is relatively non-solvatable by that liquid and is capable of associating with the polymer particles produced. Such a stabilising agent will be soluble as a whole in the dispersion liquid, but the resulting solution will usually cont~in both individual molecules and micellar aggregates or molecules, in equili~rium with each other. The type of sta~ilising agent preferred for use in the invention is a block or graft copolymer containing two types of polymeric component: one type consists, as stated above, of polymer chains which are solvatable by the dispersion liquid and the other type consists of polymer chains of different polarity from the first type which accordingly are not solvatable by that liquid and are capable of becoming anchored to the polymer microparticles.
A particularly useful form of such a stabilising agent is a graft copolymer comprising a polymer backbone, which is the non-solvatable or "anchor" component, and a plùrality of solvatable polymer chains pendant from the backbone. Specific examples of such graft copolymers include those in which the backbone is an ,: .
- ~4 -.
acrylic polymer chain, derived predominantly from methyl methacrylate, and the pendant chains are residues of poly -(12-hydroxystearic acid) which are readily solvatable by an aliphatic hydrocarbon medium. These copolymers may be made, for example, by first reacting poly-(lZ-hydroxystearic acid) with glycidyl acrylate or glycidyl methacrylate, whereby the terminal - COOH group in the polymeric acid is converted to an ester derivative containing a polymerisable unsaturated grouping, and then copolymerising that derivative with methyl methaorylate, optionally together with minor proportions of other copolymeric monomers. By employing acrylic acid or methacrylic acid as such minor comonomers, it is possible to introduce carboxyl groups into the ~ackbone chain of the graft copolymer with beneficial results inasmuoh as the backbone is thereby rendered more polar than it is if composed of methyl methacrylate units alone. This increased polarity causes the -backbone to be even less solvatable by a non-polar diluent such as an aliphatic hydrocarbon, and in consequence enhances the force whereby it becomes anchored to the microparticle.
The foregoing patent and literature references, and the foregoing description, relating to dispersion polymerisation processes suitable for the production of the polymer micro-particles are equally applicable to the production of the film-forming acrylic polymer (A), where this is to be in a state of stable dispersion in the diluent (B), except that the polymer (A) will not normally be cross-linked at this stage even though it may become cross-linked as the result of a curing operation following application of the composition to a substrate.
.
,:
~6~
After formation of the polymer microparticles in dispersion in the manner just described, tne acrylic auxiliary poly~er is then formed by polymerisation of ethyl-enically unsaturated monomer in the presence of the mi~ro-S particles. This further polymerisation is accomplished byfeeding in a charge of suitable monomer to the sa~e reaction mixture in which the microparticles have been produced under essentially the same conditions as were operated in the first stage, but with the differences that the monomer or monomers involved will overall be of a different composition to those used in the first stage and that the acrylic auxiliary polymer, unlike the microparticles, will not necessarily be wholly insoluble in the inert liquid in which the polymerisation is c~rried out.
lS In general, the auxiliary polymer will be required to have a composition such that it is compatible with the film-forming acrylic polymer (A~; indeed, it may be identical with that polymer and, in certain circumstances as described below, even wholly replace it. The monomer or monomers from which the auxiliary polymer is to be derived will be chosen with this requirement in mind, from the ran~e of ethylenically unsaturated monomers already described in connection with the production o~
the polymer (A~, or other suitable monomers, as will be apparent to those skilled in the art.
On introducing the microparticles, associated wit.h auxiliary polymer in the way described above, into the dispersion or solution of the acrylic polymer (A) in the diluent (B), part o~ the auxiliary polymer may be dissolved away by that ~ore ~12~
polar medium, but it is believed that a substantial proportion of the auxiliary polymer chains remain attached to the microparticles (albeit now solvated by the mediu~), for example by virtue of their having become entangled with the chains of the microparticle polymer during their formation, or as a result of actual grafting on to those chains. Whatever the mechanism may be, the effect of the presence of the auxiliary polymer is to stabilise the microparticles in the new, more polar environment. If desired, this stability may be enhanced by ensuriny that covalent linkages are developed between the chains of the auxiliary polymer and those of the microparticlesO This ~ay be done, for example, by including an unsaturated ~arboxyllc acid in the monomers from which the auxiliary polymer is deriv~d~ The carboxyl groups so introduced are able to react with epoxide groups, present in the microparticle polymer as the result of the use of a slight excess of the latter groups for the purpose of cross-linking that polymer by reaction with carboxyl groups in the manner described above. The incorporation of the microparticles, associated with auxiliary polymer, into the composition of the invention may be achieved either by blendin~ the dispersion obtained after formation of the auxiliary polymer directly with the dispersion or solution of the film-forming acrylic polymer (A) in the diluent (~), or, in the extreme case, by simply adding to the microparticle dispersion sufficient strong solvent to dlssolve away enough of the acrylic auxiliary polymer from the microparticles to provide itself the whole of the film-forming polymer constituent (A), whilst still leaving a residue . .. ~
.
of the auxiliary polymer associated with the microparticles which will ensure their continued stabilisation. Another possi~ility is to separate the microparticles from the dispersion in which they are made, for example by centrifuging, filtration or spray-drying, and then to blend the microparticles with the dispersion or solution of the film-forming acrylic polymer (A). It will be understood from the foregoing description that, for the purposes of the definition of the invention hereinbefore given, the film~forming resin (A) is considered to comprise that portion of the auxiliary polymer which is dissolved away from the microparticles when the latter are incorporated into the coating composition.
As an alternative to the use in organic media of dispersion polymerisation methods, the polymer microparticles rnay, for example, be produced by aqueous emulsion polymerisation of suitable unsaturated monomers, using procedures well known in the art. The microparticles are then obtained in the form of a charge-stabilised dispersion, from which the particles -- themselves can be separated, e.g. by spray drying. For incorporation into the coating composition, the microparticles are then re-dispersed in the solution or dispersion in the diluent of the film-forming polymer, preferably by methods imparting high shear to the mixture such as pug milling or triple roll milling, in an analagous fashion to the dispersion of a pigrnent. By further analogy to pigment dispersion, the requisite steric stability of the microparticles may then be achieved simply as a result of an innate tendency of the film-forming polymer (especially where it is soluble in, and therefore solvated by, the diluent) to associate with the particles, for example through the interaction of polar groups present in the film-forming polymer and in the microparticle respectively. In producing the microparticles by aqueous emulsion polymerisation, some difunctional unsaturated compounds may be included in the polymerising rnonomers in order to give rise to a cross-linked polymer which will be insoluble in the solution or dispersion of the film-forming acrylic polymer (A) in the diluent (B), whatever the nature of the latter. Here again, as in the case of microparticles made by dispersion polymerisation in inorganic media, it is essential to continue the emulsion polymerisation with a second feed of monomers which does not include any difunc~ional (i.e. cross-lin~ing) material and which gives rise to an acrylic polymer which is compatible with the polymer (A) and is soluble in the solution or dispersion of polymer (A) in diluent ~B), in other words to associate with the microparticles an auxiliary polymer having the same function as that previously described.
The polymer microparticles (C) used in the process of the invention are preferably present in proportions of from
It is well known to formulate coating compositions especially those for use in the automobile industry, upon acrylic resins, that is to say, polymers or copolymers of one or more alkyl esters of acrylic acid or methacrylic acid. Such compositions, however, give rise to certain d~fficulties, especially under the conditions of spray application as normally used in the painting of car bodies. Good flow-out of the coating after application~ which is necessary in order to maximise gloss, may be hard to achieve simultaneously with the avoidance of excessive flow of the composition during the spraying operation, the latter commonly leading to the defect known as "sagging" or "running", particularly at sharp edges or corners of a substrate of complicated shape.
We have now found that these difficulties can be minimised or eliminated if the coating ccmposition contains polymer microparticles of-a specified---t~e.
According to the present invention there is-provided a process for the production of a surface coating upon a substrate which comprises (i) applying by spray to the substrate surface a composition comprising (A) a film-forming acrylic resin as herein defined; (B) a volatile organic liquid diluent in which the acrylic resin is carried; (C) polymer microparticles as hereinafter defined, in an amount of at least 3% of the aggregate weight of the film-forming resin (A) and the micro-particles, which are insoluble in and stably dispersed in the _ 2 ~
:. ~ . . . : , . . - ~ .
iL261~l combination of the acrylic resin (A) and the diluent (B);
(D) a pigment, other than a metallic flake pigment, which is also dispersed in the com~ination of the acrylic resin and the diluent, and (ii) subsequently evaporating the volatile diluent to form a polymer film upon the surface.
The acrylic resin used in the process of the invention may be any film-forming polymer or copolymer of one or more alkyl esters of acrylic acid or methacrylic acid, optionally together with other ~thylenically unsaturated monomers such as vinyl acetate, vinyl propionate, acrylonitrile 7 styrene or vinyl toluene. These polymers may be of either the thermoplastic type or the thermosetting, cross-linking type~ Suitable acrylic or methacrylic esters for either type of polymer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Where the polymer is required to be of the cross-linking type, suitable functional monomers to be used in addition to the latter include acrylic acid, methacrylic acid, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy-propyl methacrylate, N-(alkoxymethyl)acrylamides and N-(alkoxy~
~ethyl)methacrylamides, where the alkoxy group may be, for example, a butoxy group, glycidyl acrylate and glycidyl meth-acrylate. The composition may in such a case contain also a cross-linking agent such as a diisocyanate, a diepoxide or, especially~ a nitrogen resin, that is to say a condensate of ~ormaldehyde with a nitrogenous compOund such as urea, thiourea, melamine or benzoguanamine, or a lower alkyl ether of such a condensate in which the alkyl group contains from 1 to 4 carbon ` ,! - 3 -....
:
, - . . ~
, o~
atoms. Particularly suitable cross-linking a~ents are melamine-formaldehyde condensates in which a substantial proportion of the methylol groups have been etherified by reaction with butanol.
For the purposes of the foregoing general definition of the invention, the cross-linking agent, where present, is considered as ~eing a part of the film-forming polymer (A).
The composition used according to the invention may incorporate a suitable catalyst for the cross-linking reaction between the acrylic polymer and the cross-linking agent, for example an acid-reacting compound such as acid butyl phosphate, acid butyl maleate or p-toluene sulphonic acid. Alte~natively the catalytic action may be supplied by the incorporation of free acid groups in the acr~lic polymer, for example by the use of acrylic acid or methacrylic acid as comonomer in the preparation of the polymer.
Accord1ng to one embodiment of the invention, the acrylic resin (A) is in a state of stable dispersion in the diluent liquid (B), which in such a case will be a non-solvent for the resin. Methods of preparing such polymer dispersions are well known in the art and are further referred to below in co~nection with the production of the polymer microparticles (C)~
In another embodiment~ the acrylic resin (A~ is dissolved in the diluent (B); the polymer may then be prepared by solution polymerisation of the constituent monomer or monomers, in the presence of suitable catalysts or initiators where necessary. Conveniently the polymerisation may be carried out in the same organic liquid that is to provide the diluent (B), ~ .Z~
or in a liquid which is to form part of that diluent.
Alternatively the resin (A) may be prepared in a separate previous operation (e.g. by aqueous emulsion polymerisation of monomer) and then dissolved in a suitable organic liquid~
S In yet another embodiment, the acrylic resin (A) may be partly in dispersion and partly in solution in the diluent (B).
The volatile organic liquid constituent (~) of the composition may be any o~ the liquids, or mixtures of liquids, which are conventionally used as polymer solvents in coating compositions, for example aromatic hydrocarbons such as toluene and xylene and petroleum fractions of various boiling point ranges having a significant~aromatic content, esters such as butyl acetate7 ethylene glycol diacetate and 2-ethoxyethyl acetate, ketones such as acetone and methyl isobutyl ketone, and alcohols such as butyl alcoh~l. The actual liquid~or mixture of liquids selected as the diluent (B) will depend upon the nature of the acrylic resin (A), according to principles which are well known in the coatings art, in order that the resin shall be soluble or insoluble in the diluent as required.
The polymer microparticles (C) present in the composition of the invention are particles of colloidal dimensions, having a diameter of from O.Ol - 10 microns, composed of a polymer which has a glass-liquid transition temperature greater than 0C and is insoluble in the combination of the acryIic resin (A) and the diluent (B), the mlcroparticles being stably dispersed in that combination (in the sense that they do not undergo flocculation or aggregation) as a consequence of the method of their preparation. This method _ 5 _ .
~Z6~t involves two essential stages: (i) the polymerisation of monomer, from which the microparticles are to be derived, in an inert liquid in which the resulting polymer is insolu~le and under conditions such that the polymer is obtained in a state of stable dispersion, and (ii) the subsequent polymer-isation, in the same inert liquid and in the presence of the microparticles formed in the first stage, of ethylenically unsaturated monomer giving rise to a second acrylic polymer which is compatible with the film-forming acrylic resin (A) and is soluble in the combination of polymer (A) and diluent (B).
This second acryliC polymer~ which for convenience will be referred to here as the "auxiliary" polymer, may be either soluble or insoluble in the inert liquid in question, depending on the monomer or monomers from which it is derived.
The insolubility of the microparticles in the - combination of the acrylic resin (A) and the diluent (B~ may be achieved by suitable selection of the composition of the microparticulate polymer, that is to say, the polymer may be one which is inherently insoluble in that combination~ but preferably it is achieved by introducing a sufficient degree of cross-linking into a polymer which, if not cross-linked, would actually he soluble in the combination of the resin (A) and diluent (B). Where insolubility of the microparticles is achie~ed through cross linking, it is preferred that the degree of cross linking should not be greater than that necessary to render the polymer insoluble. Insolubility of the microparticles in the combination of the resin (A) and diluent (B~ may be checked by means of the following test. The microparticles (1 part by weight) are shaken for 30 minutes with the diluent(B~
.: -::
~26~
(100 parts by weight); the suspension is then centrifuged at 17,000 r.p~m. for 30 minutes. The supernatant liquid is decanted off and the residual polymer then dried for 30 minutes at 150C, after which its weight is compared with that of the microparticles originally taken. This test may be difficult to apply where the specific gravity of the diluent is close to or greater than that of the microparticles, but such diluents (e.g. chlorinated solvents) would not normally be used in the compositions under consideration~ Where the result of this test indicates that the microparticles are acceptably insoluble in the diluent (B) alone, it can be assumed that the particles will be at least equally insoluble when the resin (A) is also present in solution in the diluent; there would be practical dif~iculties in carrying out the test actually in the solution o~ the resin (A) in diluent (B). Where ~he resin (A) is in a state of dispersion in the diluent (B), its presence will not normally have any influence on the degree of insolubility o~
the microparticles.
The microparticulate polymer may be of various types~
It may, for example9 be an acr~lic addition polymer, derived from one or more of the same monomers as have been described above in connection with the acrylic resin constituent (A).
Where it is desired that such a polymer should be cross-linked, this may be achieved by either of two general methods: firstly, by including in the ~onomers from which the polymer is derived a minor proportion of a monomer which is polyfunctional with respect to the polymerisation reaction, e.g. ethylene glycol dimethacrylate or divinylbenzene; or secondly, by including in :
: ' ~ ~' ' a126101 those monomers minor proportions of two other monomers carrying pairs of chemical groupings which can be caused to react with one another either during or after the polymerisation reaction, such as epoxy and carboxyl (e.g. glycidyl methacrylate and methacrylic acid), anhydride and hydroxyl or isocyanate and hydroxyl. Alternatively, the microparticles may be composed of a condensation polymer, for example a polyester prepared from a polyhydric alcohol and a polycarboxylic acid. Suitable polyhydric alcohols include ethylene glycol, propylene glycol~ hutylene glycol, 1:6-hexylene glycol, neopentyl glyco~, diethyl~ne glycol, triethylene glycol, tetraethylene glycol, glycerol, trimethylol-propane, trimethylolethane, pentaerythritol, dipentaerythritol, tripentaerythritol, hexane triol, oligomers of styrene and allyl alcohol ~for example that sold by Monsan~o Chemical Company under the designation RJ 100) and the condensation products of trimethylolpropane with ethylene oxide or propylene oxide (such *
as the products known commercially as "Niax" triolsj. Suitable polycarboxylic acids include succinic acid ~or its anhydride), adipic acid, azelaic acid~ sebacic acid, maleic acid (or its anhydride), fumaric acid5 muconic acid, itaconic acid, phthalic acid (or its anhydride), isoph~halic acid, terephthalic acid, tr}mellitic acid (or its anhydride) and pyromellitic acid (or its anhydride). Where it is desired that the polyester should be cross-linked, this may again be achieved by incorporating in the starting composition materials of functionality ~reater than two, although in this case, because of the characteristic-ally broad distribution of molecular species formed in a condensation polymerisation, it may be difficult to ensure that all those species are .in fact cross-linked.
* Trade Marks _ 8 --13 :
The ch~mical compositions and degree of cross-linking of the microparticulate polymer are so chosen as to ensure that the polymer per se has a glass-liquid transition temperature (Tg~
greater than 0C, that is to say, under normal conditions of use S of the composition which is spray-applied according to the invention, the microparticles are hard and glassy.
As already stated, it is necessary that the polymer microparticles be sta~ly dispersed in the combination of the acryli~ resin (A) and the liquid diluent. ~y '9stably dispersed"
is meant that the particles are prevented from flocculating or aggregating by means of a sterîc barrier around the particles~
of polymer chains which are solvated by the said combination and hence are in a chain-extended configuration. In this context the term "solvated" implies that the polymer chains in lS question, if they were independent molecules, would be actually soluble in the combination in question; however, because the chains are in fact attached to the microparticles at one or more points along their length, the steric barrier remains permanently attached to the particles. It will be understood that the stabilising polymer chains to be u ed in any particular instance will be selected with reference to the nature of the li~uid diluent and fil~-forming acrylic resin concerned. In general terms this means that the chains will be of a degree of polarity similar to that of the diluent and film~formin~ resin, so that the combination of the latter will be inherently a solvent for the polymer of whlch the chains are composec~ Since, in the automobile finishes to which the present invention is primarily directed, the liquid diluent will conventionally be of a : .: :. -.
~L~26~
relatively high degree of polarity (containing, for example, a substantial proportion OI' "strong" ester and ketone solvents) it follows that the stabilising chains on the microparticles will usually require to be of a composition such that they are inherently soluble in that type of liquid.
The mode of anchoring of the stabilising chains to the microparticles is conveniently discussed in connection with methods of making the particles, as follows.
The polymer microparticles may be produced in various ways. Prefera~ly they are produced by a process of dispersion polymerisation of monomers, in an organic liquid in which the resul'cing polymer is insoluble, in the presence of an amphipathic steric stabilising agent. Suitable processes OIC dispersion polymerisation are well known and extensively described in the literature. Thus, so far as the dispersion polymerisation of ethylenically unsaturated monomers such as acrylic or methacrylic acid esters, vinyl esters and styrene or its derivatives is concerned, the procedure is basically one of polymerising the monomers in an inert liquid in which the monomers are soluble but the resulting polymer is not soluble~ in the presence dissolved in the liquid of an amphipathic stabilising agent or of a polymeric precursor which, by copolymerisation or grafting with a portion of the monomers, can give rise in situ to such a stabilising agent. Reference may be made, for example, to British Patent Specifications Nos. 941,305; 1,052,241; 1,1229397 and 1~2317614 for a general desc:ription of the principles involved, as wel~ as to "Dispersion Polymerisation in Organic Media", ed K.E. J. Barrett (John Wiley and Sons, 1975)~
: -; , - - .
, ~ . . .
Th~ choice of suitable unsaturated monomers for the production of microparticles having the required Tg and other characteristics will present no difficulty to those skilled in the polymer art. Amongst suitable monomers, there may be mentioned methyl methacrylate, styrene and vinyl acetate, the homopolymers of which have Tg values of about 105, 100 and 32C respectively. Where a lower Tg than that of the homopolymer is desired, these "hard't monomers may be copolymerised with a suitably chosen proportion of a "soft" monomer, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or butyl meth-acrylate~ In the case where the microparticle polymer is produced by a process of dispersion polymerisation of the monomer or monomers in an organic medium, there may be a limit imposed upon the proportion of "soft" monomers which can be included by the need to ensure that the resulting copolymer is not too soluble, even in organic liquids of low polarity such as hydrocarbons, ~or the formation of a stable dispersion of the microparticles to take place. The skilled person will, howe~er, readily be a~le to find, if necessary with the aid of simple experimentation, suitable monomer compositions to satis~y the given requirements.
The production specifically of dispersion of cross-linked addition polymer particles can be achieved by including, in the monomers selected, pairs of monomers containing (in addition to the polymerisable unsaturated groups) groups capable of enter'ng into chemical reaction with each other; for example, the epoxide and carboxyl groups contained in glycidyl methacrylate and methacrylic acid. By ollowing the procedure particularly .
described in British Patent Specifications NosO 1,095,288 and 1,156,012, for example, particles are obtained in which there are present such complementary groups which, although not at that stage co-reacted, can be caused to co-react and so for~
crosslinks by subsequently heating the dispersion to a suitably elevated temperature. Cross-linked add.ition polymers may also be prepared in dispersion by including in the monomers under-going dispersion polymerisation a minor proportion of a monomer which is difunctional with respect to the polymerisation reaction, such as ethyleneglycol dimethacrylate or divinyl~enzene. Small propartions of comonomers incorporating carboxyl groups, e~g.
acrylic acid or methacrylic acid may be included (where the microparticles are to be cross-linked, such propo~tions would be in excess of those used in order to achleve cross-linking by reaction with a co-reactive monomer such as glycidyl methacrylate).
Conversely, small (additional) proportions of an epoxide monomer, e~g. glycidyl methacrylate, may be included. Other functional monomers, such as hydroxyethyl acrylate or acrylamide, may also be included in minor proportions in the monomers from which the microparticles are to be derived.
The production of dispersions of condensation polymers is described, for example, in British Patent Specifications Nos~
1,373,531; 1,403,794 and 1,413,199, and methods of obtaining cross-linked polymer particles are included in these descriptions.
The general principles in~olved here are the same as those referred to above in connection with addition polymer dispersions, but there is a difference of detail arising from the commonly more highly polar nature of the monomers or starting materials . . ..
from which condensation polymers are derived. This is, namely, that the mono~ers in question are usually insoluble in the inert liquid in which the polymerisation is to be carried out.
Accordingly the first step in the dispersion polymerisation of the monomers is to bring them into a state of colloidal dispersion in the inert llquid, either as liquid or as solid particles. In the second step, polymerîsation of the monomers takes place within those same particlesO An amphipathic sta~ilising agent is required in each stage, firstly in order to stabilise the particles of monomer and secondly in order to s~abilise the particles of polymer formed, but in suitable cases a single stabilising agent can be found which w}ll perform both these functions. In place of using a preformed amphipathic stabilising agent in this process, ther-e may be e~ployed instead a suitable polymeric precursor which, by copolymeris2tion or grafting with a portion of the monomers being polymerised, can give rise to such a stabilising agent in situ. Reference may be made in this connection to British Patent Seria~ No-. 1583142, published ~anuary 21, 1981 Suitable monomeric starting materials for preparin~
condensation polymer microparticles are those which are well known for use in making such polymers by melt or solution polymerisation techniquesO For example, in the case of polyester microparticles, suitable materials in general are the polyhydric alcohols and polycarboxylic acids, and here, as with the pol~mers of the aclc31tic)n type discussed above, it will be evident to the skilled person which particular reactants are to be selected in arder to produce a m~croparticulate polymer having the requisite Tg and other characteristics.
, .~. . .
,..... .. .. ..
: :.......... ~ .. . ...
~2~
It will, of course, be understood that, in the case of both polyester and polyamide microparticles, the mixture to be polymerised must incorporate some proportion of a starting monomer which has a functionality greater than two, where it is desired that the microparticles should be cross-linked.
In all the above-described dispersion polymerisation processes, the amphipathic steric stabilising agent is a substance the molecule of which contains a polymeric component which is solvatable by the liquid in which the di.spersion is made and another component which is relatively non-solvatable by that liquid and is capable of associating with the polymer particles produced. Such a stabilising agent will be soluble as a whole in the dispersion liquid, but the resulting solution will usually cont~in both individual molecules and micellar aggregates or molecules, in equili~rium with each other. The type of sta~ilising agent preferred for use in the invention is a block or graft copolymer containing two types of polymeric component: one type consists, as stated above, of polymer chains which are solvatable by the dispersion liquid and the other type consists of polymer chains of different polarity from the first type which accordingly are not solvatable by that liquid and are capable of becoming anchored to the polymer microparticles.
A particularly useful form of such a stabilising agent is a graft copolymer comprising a polymer backbone, which is the non-solvatable or "anchor" component, and a plùrality of solvatable polymer chains pendant from the backbone. Specific examples of such graft copolymers include those in which the backbone is an ,: .
- ~4 -.
acrylic polymer chain, derived predominantly from methyl methacrylate, and the pendant chains are residues of poly -(12-hydroxystearic acid) which are readily solvatable by an aliphatic hydrocarbon medium. These copolymers may be made, for example, by first reacting poly-(lZ-hydroxystearic acid) with glycidyl acrylate or glycidyl methacrylate, whereby the terminal - COOH group in the polymeric acid is converted to an ester derivative containing a polymerisable unsaturated grouping, and then copolymerising that derivative with methyl methaorylate, optionally together with minor proportions of other copolymeric monomers. By employing acrylic acid or methacrylic acid as such minor comonomers, it is possible to introduce carboxyl groups into the ~ackbone chain of the graft copolymer with beneficial results inasmuoh as the backbone is thereby rendered more polar than it is if composed of methyl methacrylate units alone. This increased polarity causes the -backbone to be even less solvatable by a non-polar diluent such as an aliphatic hydrocarbon, and in consequence enhances the force whereby it becomes anchored to the microparticle.
The foregoing patent and literature references, and the foregoing description, relating to dispersion polymerisation processes suitable for the production of the polymer micro-particles are equally applicable to the production of the film-forming acrylic polymer (A), where this is to be in a state of stable dispersion in the diluent (B), except that the polymer (A) will not normally be cross-linked at this stage even though it may become cross-linked as the result of a curing operation following application of the composition to a substrate.
.
,:
~6~
After formation of the polymer microparticles in dispersion in the manner just described, tne acrylic auxiliary poly~er is then formed by polymerisation of ethyl-enically unsaturated monomer in the presence of the mi~ro-S particles. This further polymerisation is accomplished byfeeding in a charge of suitable monomer to the sa~e reaction mixture in which the microparticles have been produced under essentially the same conditions as were operated in the first stage, but with the differences that the monomer or monomers involved will overall be of a different composition to those used in the first stage and that the acrylic auxiliary polymer, unlike the microparticles, will not necessarily be wholly insoluble in the inert liquid in which the polymerisation is c~rried out.
lS In general, the auxiliary polymer will be required to have a composition such that it is compatible with the film-forming acrylic polymer (A~; indeed, it may be identical with that polymer and, in certain circumstances as described below, even wholly replace it. The monomer or monomers from which the auxiliary polymer is to be derived will be chosen with this requirement in mind, from the ran~e of ethylenically unsaturated monomers already described in connection with the production o~
the polymer (A~, or other suitable monomers, as will be apparent to those skilled in the art.
On introducing the microparticles, associated wit.h auxiliary polymer in the way described above, into the dispersion or solution of the acrylic polymer (A) in the diluent (B), part o~ the auxiliary polymer may be dissolved away by that ~ore ~12~
polar medium, but it is believed that a substantial proportion of the auxiliary polymer chains remain attached to the microparticles (albeit now solvated by the mediu~), for example by virtue of their having become entangled with the chains of the microparticle polymer during their formation, or as a result of actual grafting on to those chains. Whatever the mechanism may be, the effect of the presence of the auxiliary polymer is to stabilise the microparticles in the new, more polar environment. If desired, this stability may be enhanced by ensuriny that covalent linkages are developed between the chains of the auxiliary polymer and those of the microparticlesO This ~ay be done, for example, by including an unsaturated ~arboxyllc acid in the monomers from which the auxiliary polymer is deriv~d~ The carboxyl groups so introduced are able to react with epoxide groups, present in the microparticle polymer as the result of the use of a slight excess of the latter groups for the purpose of cross-linking that polymer by reaction with carboxyl groups in the manner described above. The incorporation of the microparticles, associated with auxiliary polymer, into the composition of the invention may be achieved either by blendin~ the dispersion obtained after formation of the auxiliary polymer directly with the dispersion or solution of the film-forming acrylic polymer (A) in the diluent (~), or, in the extreme case, by simply adding to the microparticle dispersion sufficient strong solvent to dlssolve away enough of the acrylic auxiliary polymer from the microparticles to provide itself the whole of the film-forming polymer constituent (A), whilst still leaving a residue . .. ~
.
of the auxiliary polymer associated with the microparticles which will ensure their continued stabilisation. Another possi~ility is to separate the microparticles from the dispersion in which they are made, for example by centrifuging, filtration or spray-drying, and then to blend the microparticles with the dispersion or solution of the film-forming acrylic polymer (A). It will be understood from the foregoing description that, for the purposes of the definition of the invention hereinbefore given, the film~forming resin (A) is considered to comprise that portion of the auxiliary polymer which is dissolved away from the microparticles when the latter are incorporated into the coating composition.
As an alternative to the use in organic media of dispersion polymerisation methods, the polymer microparticles rnay, for example, be produced by aqueous emulsion polymerisation of suitable unsaturated monomers, using procedures well known in the art. The microparticles are then obtained in the form of a charge-stabilised dispersion, from which the particles -- themselves can be separated, e.g. by spray drying. For incorporation into the coating composition, the microparticles are then re-dispersed in the solution or dispersion in the diluent of the film-forming polymer, preferably by methods imparting high shear to the mixture such as pug milling or triple roll milling, in an analagous fashion to the dispersion of a pigrnent. By further analogy to pigment dispersion, the requisite steric stability of the microparticles may then be achieved simply as a result of an innate tendency of the film-forming polymer (especially where it is soluble in, and therefore solvated by, the diluent) to associate with the particles, for example through the interaction of polar groups present in the film-forming polymer and in the microparticle respectively. In producing the microparticles by aqueous emulsion polymerisation, some difunctional unsaturated compounds may be included in the polymerising rnonomers in order to give rise to a cross-linked polymer which will be insoluble in the solution or dispersion of the film-forming acrylic polymer (A) in the diluent (B), whatever the nature of the latter. Here again, as in the case of microparticles made by dispersion polymerisation in inorganic media, it is essential to continue the emulsion polymerisation with a second feed of monomers which does not include any difunc~ional (i.e. cross-lin~ing) material and which gives rise to an acrylic polymer which is compatible with the polymer (A) and is soluble in the solution or dispersion of polymer (A) in diluent ~B), in other words to associate with the microparticles an auxiliary polymer having the same function as that previously described.
The polymer microparticles (C) used in the process of the invention are preferably present in proportions of from
2% to 30~ of the aggregate weight of the film-forming acrylic resin (A) and the microparticIes. More preferably, the proportion of microparticles is from 5% to 20% of that aggregate weight. The precise proportion which is used will depend upon the particular application properties which it is des~red that the coating composition should possess. For the purposes of this definition, the term "polymer microparticles"
is to be understood as referring to the microparticles proper ' : :
:
:
L26~
together with that part of the auxiliary polymer associated therewith which cannot be dissolved away from the particles by the diluent (B), under the conditions of the insolubility test described above.
The compositions used in the process of the invention incorporate, in addition to the acrylic resin (A), the diluent (B) and the polymer microparticles (C), pigments (D~ as conventionally used in the coatings art7 other than metallic flake pigments. Such pigments may range in particle size from 1 to 50 microns and may be inorganic in nature7 for example titanium dioxide, iron oxide, chromium oxide, lead chromate or carbon black, or organic in nature, for example phthalo-cyanine blue, phthalocyanine green, carbazole violet, anthra-pyrimidine yellow, flavanthrone yellow, isoindoline yellow, indanthrone blue, quinacridone violet and perylene red. Any of these pigments may be present in the compositions in a proportion of from 2~o to 50% of the a~gregate weight of the acrylic resin (A) and the microparticles (C). The term "pigment"
is here meant to embrace also conventional fillers and extenders, such as talc or kaolin. Such pigments may be incorporated into the compositions with the aid of known dispersants, for example with the aid of an acrylic polymer which is compatible with the acrylic film-forming polymer (A). Any such polymeric dispersant is also considered to be part of the film-forming constituent (A~.
If desired, the compositions may additionally incorporate other known additives, for example viscosity modifiers such as bentone or cellulose acetate butyrate.
_ 20 -.
. .
.
In the case where the film-forming acrylic polymer (A) is of the thermosetting or cross-linking type, there may, as already stated, be incorporated in the composition used according to the invention a cross-linking agent. The proportion of cross-linking agent to cross-linkable acrylic polymer in the composition may vary widely, but in general a ratio of from 50:50 to 90:10 by weight of polymer to cross-linking agent is satisfactory. The precise proportion to be employed depends upon the properties required in the ~inal film, but a preferred range affording a good balance of properties is from 60:40 to 85:15 by weight of polymer to cross-linking agent. Where it is of particular importance that the film should exhibit good resistance towards acid corrosion induced by severe atmospheric pollution, an especially preferred rang~ of ratios of polymer to cross-linking agent is ~rom 70:30 to 85:15 by weight.
~ As already indicated, the composition may also incorporate a suitable catalyst for the cross linking reaction, for example an acid-reacting compound, or the film-forming . . . .. , ~ ~ .
acrylic polymer-(A) of the composition may be arranged to - _ _ contain ~ree acid groups.
The coating compositions may be applied to a substrate according to the invention by any of the known spraying procedures, such as compressed air spraying, electrostatic spraying, hot spraying and airless spraying, and either manual or automatic methods are suitable. By these proc~dures there can be achieved an improvement o~ 15-20% in the thickness o~
paint which can be applied before sagging occurs, without the loss of gloss, poor appearance or lower spray solids which result from attempts to improve sag resistance by other methods _ 21 -.,: ,., .. . , ~
~12~
~for example, by increasing the average molecular wei~ht of the film-forming polymer or by including in the composition inorganic sag-control aids~.
EXAMPLE
' (a) Preparation of Polymer Micro~articles To a vessel fitted with stirrer, thermometer, reflux condenser and provision for adding a liquid feed to the returning condensate was charged - - -Aliphatic hydrocarbon (boilin~ range 12.081 parts :--.
170 - 210~C; aromatic content 5%) Hexane 2.~59 parts ~ :
: Heptane 15.821 parts The vessel and contents were purged with inert gas;~the temperature of the reactants was raised to 100C.
The following prem1xed ingredients were added as a : : :single rapid addition:to the refluxing solvents:-~ Methyl methacrylate 0.972 parts :: 20 Methacrylic acid 0.020 parts Azodiisobutyronitrile 0.077 parts ~raft copoly.~er sta~iliser 0.362 parts : (33% solution; as described below) ~ ~ ~ The contents of the vessel were then held at reflux 25 : for 30 minutes to form a seed-polymer dispersion~ The followlng ingredients were premixed and fed into the hydrocarbon returning rom the condenser at a uniorm rate over a period of 3 hours:
..j , "
~ 22 - ~ ;
.
z~
Methyl methacrylate 18.460 parts Methacrylic acid 0.188 parts Glycidyl methacrylate 0O188 parts Azodiisobutyronitrile 0.247 parts Graft copolymer stabiliser solution 3.885 parts (as described below) Dimethylamino ethanol 0.036 parts After completion of the feed, the reaction mixture was maintained under reflux for 3 hours, when a fine ~ispersion of insoluble gel microparticles was obtainedO The total solids content of the dispersion was 38-4Q%; the content of insoluble microparticles was 26.0% and the polymer of which the micro-particles were composed had a glass-liquid transition temperature ~ o~ 80 - 100C.
The grat copolymer stabiliser used in the above : procedure was obtained as follows. 12-Hydroxystearic acid was ~ self-condensed to an acid~value of about 31 - 34 mg KOH/g ; (corresponding to a molecular weight of 1650 - 1800) and then reacted with an equivalent amount of glycidyl methacrylate. The 20 resulting unsaturated ester was copolymerised at a weight ratio of 2:1 with a mixture of methyl methacrylate and acrylic acid in the proportions of 95:5.
(b) ~
To a vessel fitted as descrlbed in step (a) there was charged:~-Microparticle dispersion obtained 55.296 partsin step (a) Xylene 14.640 parts This charge was heated to recycling temperature in an inert gas atrnosphere and 2.5 - 3.9 parts of distillate . were removed until the temperature reached 115~C. The following - ~6~
ingredients were premîxed and fed at a constant rate over a period of 3 hours to the hydrocarbon returning ~rom the condenser~
Methyl methacrylate 2.894 parts Hydroxyethyl acrylate 1.651 parts Methacrylic acid . 0.429 parts Butyl methacrylate 3.197 parts 2-Ethylhexyl acrylate 3.301 parts : Styrene 4,946 parts tert-8utyl perbenzoate a. 392 parts prim-Octyl mercaptan 0.183 parts Graft copolymer stabiliser solution 1.294 parts (as descrîbed in step (a).) On completion of the feed, the reaction mixture was : ~15 held at recycle temperature for 2 hours, then cooled; the following solvent mixture was added:-n Butanol 2.944 parts ~;Butyl acetate 8.833 parts --The~.compo~sltion ~h~s~ obta~-ned-had a total sollds:
.
~: 20 content o~,:40%;:the content of insoIuble"'yel microparticles 'was 23%.
( c ) ~ ~
~) White compositions of hiqh piqment content :The following :series of ingredients i:denti~ied in columns I and II respectiveIy were blended:-:
~ I II
8utylated melamine formaldehyde ~ 10.97 10.97 parts ~ resin (65% solution in butanol) : Titanium dioxide millbase29~.9 29.19 parts ' : 30 (68.7% Titanium dioxide) ~ , ~- ~
z~
I II
Thermosetting acrylic copolymer 30.09 22.62 parts resin solution (~5% solution in xylene) Modified microparticle - 12.15 parts dispersion from step (b) Flow-promoting polymer 0.800.80 parts t10% solution in xylene) Dipentene 6.006.00 parts The white paints thus obtained had the ~ollowing characteristics:-Viscosity (B.S. B4 Cup at 25C) 61 seconds 44 seconds Non volatile content : 64% 61%
The acrylic copolymer resin had the composition :
Styrene 30 parts, methyl methacrylate lS parts, but~l methacrylate 17 parts, 2-ethylhexyl acrylate 20 parts, hydroxyethyl acrylate 15 pa~ts, methacrylic acid 3 parts. The resin had a welght average molecular weight of 6000-7000.
Primed metal panels were sprayed with each of the :
20 ~ two compositions without further thinning so as to give a "wedge" coat of varying f1lm thickness. Each panel was allowed to stand for 30 m~nutes vertically and was then stoved, again ln a vertical position, for 15 minutes at 130C.
The film thickness at which "sagging" first occurred ; 2S was then determined in each case.
The panel finished with composition I sagged at a film thickness oE 60-65 microns and above, but the panels finished with composition II sagged only at a ~ilm thickrless of 70-75 microns and above.
This improvement in sag resistance occurred even though sample I was at a higher viscosity and contained less solvent when sprayed than sample II~
:
i (ii) Blue compositions of low piqment content .
The following series of ingredients identified in columns I and II respectively were blended:- ~
I II
Butylated melamine formaldehyde 18.1 18.1 parts resin ~65% solution in butanol) Dispersion of Prussian Blue 12.0 12.0 parts (30% in xylene) Dispersion of Titanium Dioxide 0.4 0.4 parts (68.7% in xylene) Dispersion of Ph~halocyanine Green 0~2 0.2 parts (16.4% in xylene) Thermosetting acrylic resin 40.7 29.6 parts solution (65% solution in xylene) Modified microparticle - 18.3 parts dispersion from step (b) Flow-promoting polymer 0.60.6 parts (10% solution in xylene) Xylene 8.08.0 parts Dipentene 6.06.0 parts The blue paints thus obtained had the following characteristics:-I II
Viscosity (B.S.B3 Cup at 25C) 91 secs~ 99 secsq Non-volatile content 51% 46%
The acrylic resln solution USed was the same~as that descrlbed for the white paint in (i) above. Panels were sprayed and stoved in an identical manner to that described in (i) above.
The panel finished with composition I sagged at a film thickness of 66 microns, whereas the panel finished with composition II sagged~only at a film thickness of ~reater than 80 microns.
26 _ ~: ~ ' ' ' ' :
is to be understood as referring to the microparticles proper ' : :
:
:
L26~
together with that part of the auxiliary polymer associated therewith which cannot be dissolved away from the particles by the diluent (B), under the conditions of the insolubility test described above.
The compositions used in the process of the invention incorporate, in addition to the acrylic resin (A), the diluent (B) and the polymer microparticles (C), pigments (D~ as conventionally used in the coatings art7 other than metallic flake pigments. Such pigments may range in particle size from 1 to 50 microns and may be inorganic in nature7 for example titanium dioxide, iron oxide, chromium oxide, lead chromate or carbon black, or organic in nature, for example phthalo-cyanine blue, phthalocyanine green, carbazole violet, anthra-pyrimidine yellow, flavanthrone yellow, isoindoline yellow, indanthrone blue, quinacridone violet and perylene red. Any of these pigments may be present in the compositions in a proportion of from 2~o to 50% of the a~gregate weight of the acrylic resin (A) and the microparticles (C). The term "pigment"
is here meant to embrace also conventional fillers and extenders, such as talc or kaolin. Such pigments may be incorporated into the compositions with the aid of known dispersants, for example with the aid of an acrylic polymer which is compatible with the acrylic film-forming polymer (A). Any such polymeric dispersant is also considered to be part of the film-forming constituent (A~.
If desired, the compositions may additionally incorporate other known additives, for example viscosity modifiers such as bentone or cellulose acetate butyrate.
_ 20 -.
. .
.
In the case where the film-forming acrylic polymer (A) is of the thermosetting or cross-linking type, there may, as already stated, be incorporated in the composition used according to the invention a cross-linking agent. The proportion of cross-linking agent to cross-linkable acrylic polymer in the composition may vary widely, but in general a ratio of from 50:50 to 90:10 by weight of polymer to cross-linking agent is satisfactory. The precise proportion to be employed depends upon the properties required in the ~inal film, but a preferred range affording a good balance of properties is from 60:40 to 85:15 by weight of polymer to cross-linking agent. Where it is of particular importance that the film should exhibit good resistance towards acid corrosion induced by severe atmospheric pollution, an especially preferred rang~ of ratios of polymer to cross-linking agent is ~rom 70:30 to 85:15 by weight.
~ As already indicated, the composition may also incorporate a suitable catalyst for the cross linking reaction, for example an acid-reacting compound, or the film-forming . . . .. , ~ ~ .
acrylic polymer-(A) of the composition may be arranged to - _ _ contain ~ree acid groups.
The coating compositions may be applied to a substrate according to the invention by any of the known spraying procedures, such as compressed air spraying, electrostatic spraying, hot spraying and airless spraying, and either manual or automatic methods are suitable. By these proc~dures there can be achieved an improvement o~ 15-20% in the thickness o~
paint which can be applied before sagging occurs, without the loss of gloss, poor appearance or lower spray solids which result from attempts to improve sag resistance by other methods _ 21 -.,: ,., .. . , ~
~12~
~for example, by increasing the average molecular wei~ht of the film-forming polymer or by including in the composition inorganic sag-control aids~.
EXAMPLE
' (a) Preparation of Polymer Micro~articles To a vessel fitted with stirrer, thermometer, reflux condenser and provision for adding a liquid feed to the returning condensate was charged - - -Aliphatic hydrocarbon (boilin~ range 12.081 parts :--.
170 - 210~C; aromatic content 5%) Hexane 2.~59 parts ~ :
: Heptane 15.821 parts The vessel and contents were purged with inert gas;~the temperature of the reactants was raised to 100C.
The following prem1xed ingredients were added as a : : :single rapid addition:to the refluxing solvents:-~ Methyl methacrylate 0.972 parts :: 20 Methacrylic acid 0.020 parts Azodiisobutyronitrile 0.077 parts ~raft copoly.~er sta~iliser 0.362 parts : (33% solution; as described below) ~ ~ ~ The contents of the vessel were then held at reflux 25 : for 30 minutes to form a seed-polymer dispersion~ The followlng ingredients were premixed and fed into the hydrocarbon returning rom the condenser at a uniorm rate over a period of 3 hours:
..j , "
~ 22 - ~ ;
.
z~
Methyl methacrylate 18.460 parts Methacrylic acid 0.188 parts Glycidyl methacrylate 0O188 parts Azodiisobutyronitrile 0.247 parts Graft copolymer stabiliser solution 3.885 parts (as described below) Dimethylamino ethanol 0.036 parts After completion of the feed, the reaction mixture was maintained under reflux for 3 hours, when a fine ~ispersion of insoluble gel microparticles was obtainedO The total solids content of the dispersion was 38-4Q%; the content of insoluble microparticles was 26.0% and the polymer of which the micro-particles were composed had a glass-liquid transition temperature ~ o~ 80 - 100C.
The grat copolymer stabiliser used in the above : procedure was obtained as follows. 12-Hydroxystearic acid was ~ self-condensed to an acid~value of about 31 - 34 mg KOH/g ; (corresponding to a molecular weight of 1650 - 1800) and then reacted with an equivalent amount of glycidyl methacrylate. The 20 resulting unsaturated ester was copolymerised at a weight ratio of 2:1 with a mixture of methyl methacrylate and acrylic acid in the proportions of 95:5.
(b) ~
To a vessel fitted as descrlbed in step (a) there was charged:~-Microparticle dispersion obtained 55.296 partsin step (a) Xylene 14.640 parts This charge was heated to recycling temperature in an inert gas atrnosphere and 2.5 - 3.9 parts of distillate . were removed until the temperature reached 115~C. The following - ~6~
ingredients were premîxed and fed at a constant rate over a period of 3 hours to the hydrocarbon returning ~rom the condenser~
Methyl methacrylate 2.894 parts Hydroxyethyl acrylate 1.651 parts Methacrylic acid . 0.429 parts Butyl methacrylate 3.197 parts 2-Ethylhexyl acrylate 3.301 parts : Styrene 4,946 parts tert-8utyl perbenzoate a. 392 parts prim-Octyl mercaptan 0.183 parts Graft copolymer stabiliser solution 1.294 parts (as descrîbed in step (a).) On completion of the feed, the reaction mixture was : ~15 held at recycle temperature for 2 hours, then cooled; the following solvent mixture was added:-n Butanol 2.944 parts ~;Butyl acetate 8.833 parts --The~.compo~sltion ~h~s~ obta~-ned-had a total sollds:
.
~: 20 content o~,:40%;:the content of insoIuble"'yel microparticles 'was 23%.
( c ) ~ ~
~) White compositions of hiqh piqment content :The following :series of ingredients i:denti~ied in columns I and II respectiveIy were blended:-:
~ I II
8utylated melamine formaldehyde ~ 10.97 10.97 parts ~ resin (65% solution in butanol) : Titanium dioxide millbase29~.9 29.19 parts ' : 30 (68.7% Titanium dioxide) ~ , ~- ~
z~
I II
Thermosetting acrylic copolymer 30.09 22.62 parts resin solution (~5% solution in xylene) Modified microparticle - 12.15 parts dispersion from step (b) Flow-promoting polymer 0.800.80 parts t10% solution in xylene) Dipentene 6.006.00 parts The white paints thus obtained had the ~ollowing characteristics:-Viscosity (B.S. B4 Cup at 25C) 61 seconds 44 seconds Non volatile content : 64% 61%
The acrylic copolymer resin had the composition :
Styrene 30 parts, methyl methacrylate lS parts, but~l methacrylate 17 parts, 2-ethylhexyl acrylate 20 parts, hydroxyethyl acrylate 15 pa~ts, methacrylic acid 3 parts. The resin had a welght average molecular weight of 6000-7000.
Primed metal panels were sprayed with each of the :
20 ~ two compositions without further thinning so as to give a "wedge" coat of varying f1lm thickness. Each panel was allowed to stand for 30 m~nutes vertically and was then stoved, again ln a vertical position, for 15 minutes at 130C.
The film thickness at which "sagging" first occurred ; 2S was then determined in each case.
The panel finished with composition I sagged at a film thickness oE 60-65 microns and above, but the panels finished with composition II sagged only at a ~ilm thickrless of 70-75 microns and above.
This improvement in sag resistance occurred even though sample I was at a higher viscosity and contained less solvent when sprayed than sample II~
:
i (ii) Blue compositions of low piqment content .
The following series of ingredients identified in columns I and II respectively were blended:- ~
I II
Butylated melamine formaldehyde 18.1 18.1 parts resin ~65% solution in butanol) Dispersion of Prussian Blue 12.0 12.0 parts (30% in xylene) Dispersion of Titanium Dioxide 0.4 0.4 parts (68.7% in xylene) Dispersion of Ph~halocyanine Green 0~2 0.2 parts (16.4% in xylene) Thermosetting acrylic resin 40.7 29.6 parts solution (65% solution in xylene) Modified microparticle - 18.3 parts dispersion from step (b) Flow-promoting polymer 0.60.6 parts (10% solution in xylene) Xylene 8.08.0 parts Dipentene 6.06.0 parts The blue paints thus obtained had the following characteristics:-I II
Viscosity (B.S.B3 Cup at 25C) 91 secs~ 99 secsq Non-volatile content 51% 46%
The acrylic resln solution USed was the same~as that descrlbed for the white paint in (i) above. Panels were sprayed and stoved in an identical manner to that described in (i) above.
The panel finished with composition I sagged at a film thickness of 66 microns, whereas the panel finished with composition II sagged~only at a film thickness of ~reater than 80 microns.
26 _ ~: ~ ' ' ' ' :
Claims (10)
1. A process for the production of a surface coating upon a substrate which comprises (i) applying by spray to the substrate surface a composition comprising (A) a film-forming acrylic resin which is derived from one or more alkyl esters of acrylic acid or methacrylic acid, (B) a volatile organic liquid diluent in which the polymer (A) is carried, and (C) a pigment, other than a metallic flake pigment, which is dispersed in the combination of the film-forming resin (A) and the diluent (B), and (ii) subsequently evaporating the volatile diluent to form a polymer film upon the surface, characterised in that the composition applied to the substrate further comprises (D) microparticles having a diameter of from 0.01 to 10 microns composed of a polymer which has a glass-liquid transition temperature greater than 0°C, and which are insoluble in and stably dispersed in the combination of the resin (A) and the diluent (B), the microparticles being obtained by (a) polymerisation of monomer in an inert-liquid in which the resulting polymer is insoluble and under conditions such that the polymer is obtained in a state of stable dispersion and (b) subsequent polymerisation, in the same inert liquid and in the presence of the particles formed in stage (a), of ethylenically unsaturated monomer giving rise to a second acrylic polymer or copolymer which is compatible with the acrylic resin (A) and is soluble in the combination of the resin (A) and the diluent (B), and the microparticles (D) being present in an amount of at least 3% of the aggregate weight of the resin (A) and the microparticles.
2. A process according to claim 1, wherein the acrylic resin is a polymer or copolymer of one or more alkyl esters of acrylic acid or methacrylic acid, optionally together with other ethylenically unsaturated monomers.
3. A process according to claim 1 or claim 2, wherein the acrylic resin is of the thermosetting, cross-linking type and the composition contains in addition a cross-linking agent.
4. A process according to Claim 1 or Claim 2, wherein the microparticulate polymer is an acrylic polymer.
5. A process according to Claim 1 or Claim 2, wherein the microparticulate polymer is a condensation polymer.
6. A process according to Claim 1, wherein the microparticles are obtained by dispersion polymer-isation of monomers, in an organic liquid in which the resulting polymer is insoluble, in the presence of an amphipathic steric stabilising agent, the molecule of which contains a polymeric component which is solvatable by the liquid in which the dispersion is made and another component which is relatively non-solvatable by that liquid and is capable of associating with the polymer particles produced.
7. A process according to claim 6, wherein the amphipathic stabilising agent is a graft copolymer comprising a polymer backbone, which is the non-solvatable or "anchor"
component, and a plurality of solvatable polymer chains pendant from the backbone.
component, and a plurality of solvatable polymer chains pendant from the backbone.
8. A process according to claim 7, wherein the polymer backbone is an acrylic polymer chain derived predominant-ly from methyl methacrylate and the pendant chains are residues of poly (12-hydroxy-stearic acid).
9. A process according to claim 6, wherein the monomers from which the auxiliary polymer is formed are such that during their polymerisation covalent linkages are developed between the chains of the auxiliary polymer and those of the microparticles.
10. A process according to Claim 1 or Claim 2, wherein the polymer microparticles are present in a proportion of from 2% to 30% of the aggregate weight of the acrylic resin (A) and the microparticles.
20th June 1978
20th June 1978
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB20096/78A GB1598419A (en) | 1978-05-17 | 1978-05-17 | Coating process |
GB20096/78 | 1978-05-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1126101A true CA1126101A (en) | 1982-06-22 |
Family
ID=10140319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA308,381A Expired CA1126101A (en) | 1978-05-17 | 1978-07-28 | Spray coating process |
Country Status (12)
Country | Link |
---|---|
US (1) | US4242384A (en) |
EP (1) | EP0005428B1 (en) |
JP (1) | JPS54150439A (en) |
BE (1) | BE870092A (en) |
CA (1) | CA1126101A (en) |
DE (1) | DE2861934D1 (en) |
ES (1) | ES474505A1 (en) |
FR (1) | FR2426073A1 (en) |
GB (1) | GB1598419A (en) |
IT (1) | IT1101522B (en) |
NZ (1) | NZ187822A (en) |
ZA (1) | ZA783923B (en) |
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US4413084A (en) * | 1980-10-23 | 1983-11-01 | Ford Motor Company | Paint composition comprising hydroxy functional film former and improved stabilized flow control additive |
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US4396680A (en) * | 1981-03-04 | 1983-08-02 | E. I. Du Pont De Nemours And Co. | Substrate coated with crater resistant acrylic enamel |
US4391858A (en) * | 1981-11-20 | 1983-07-05 | Glasurit America, Inc. | Coating process |
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US4528317A (en) * | 1983-01-05 | 1985-07-09 | Ford Motor Company | Non-aqueous dispersions based on capped stabilizers and reactants comprising polyfunctional monomers II |
US4533695A (en) * | 1983-01-05 | 1985-08-06 | Ford Motor Company | Non-aqueous dispersions based on capped stabilizers and reactants comprising polyfunctional monomers II |
US4530957A (en) * | 1983-01-05 | 1985-07-23 | Ford Motor Company | Non-aqueous dispersions based on capped stabilizers and reactants comprising polyfunctional monomers I |
US4605720A (en) * | 1983-02-23 | 1986-08-12 | Ford Motor Company | Preparation of nonaqueous dispersions with the use of monofunctional stabilizer |
US4533681A (en) * | 1983-02-23 | 1985-08-06 | Ford Motor Company | Crosslinked flow control additives for high solids paints I |
US4493914A (en) * | 1983-02-23 | 1985-01-15 | Ford Motor Company | Stabilized dispersion of cross-linked polymer particles |
US4558075A (en) * | 1984-03-30 | 1985-12-10 | Ppg Industries, Inc. | High-solids coating composition for improved rheology control containing organo-modified clay |
US4620994A (en) * | 1984-03-30 | 1986-11-04 | Ppg Industries, Inc. | Color plus clear coating system utilizing organo-modified clay |
US4620993A (en) * | 1984-03-30 | 1986-11-04 | Ppg Industries, Inc. | Color plus clear coating system utilizing organo-modified clay in combination with organic polymer microparticles |
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GB1242054A (en) | 1967-06-08 | 1971-08-11 | Ici Ltd | Improved coating compositions |
GB1319781A (en) | 1969-08-14 | 1973-06-06 | Ici Ltd | Coating compositions comprising polymer dispersions |
FR2118667A5 (en) * | 1970-12-15 | 1972-07-28 | Mitsubishi Rayon Co | |
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US3862062A (en) * | 1972-12-20 | 1975-01-21 | Du Pont | Thermosetting acrylic powder of an acrylic polymer having low glass transition temperature, cellulose acetate butyrate and a cross-linking agent |
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US4055530A (en) * | 1975-02-27 | 1977-10-25 | Standard Oil Company (Indiana) | Aqueous dispersion of addition polymer of an alpha-beta-ethylenically unsaturated monomer and suspended polypropylene particles |
US4025474A (en) * | 1975-06-02 | 1977-05-24 | Ppg Industries, Inc. | Polyester coating compositions comprising cross-linked polymeric microparticles |
US4115472A (en) * | 1975-03-19 | 1978-09-19 | Ppg Industries, Inc. | Urethane coating compositions |
US4064294A (en) * | 1975-06-02 | 1977-12-20 | Ppg Industries, Inc. | In-situ production of microcapsules on a substrate |
JPS52112630A (en) * | 1976-03-12 | 1977-09-21 | Nippon Paint Co Ltd | Leveling agent for high-solid paint |
JPS6011755B2 (en) * | 1976-04-26 | 1985-03-27 | 関西ペイント株式会社 | Room temperature curing high solids coating composition |
NZ186925A (en) * | 1977-04-25 | 1979-12-11 | Ici Ltd | Top-coating based on a basecoat and top-coat compositions not requiring an intermediate baking operation |
-
1978
- 1978-05-17 GB GB20096/78A patent/GB1598419A/en not_active Expired
- 1978-06-28 DE DE7878300095T patent/DE2861934D1/en not_active Expired
- 1978-06-28 EP EP78300095A patent/EP0005428B1/en not_active Expired
- 1978-07-07 ZA ZA00783923A patent/ZA783923B/en unknown
- 1978-07-07 US US05/922,847 patent/US4242384A/en not_active Expired - Lifetime
- 1978-07-10 NZ NZ187822A patent/NZ187822A/en unknown
- 1978-07-28 CA CA308,381A patent/CA1126101A/en not_active Expired
- 1978-08-15 JP JP9873778A patent/JPS54150439A/en active Pending
- 1978-08-30 BE BE190171A patent/BE870092A/en not_active IP Right Cessation
- 1978-09-04 FR FR7825384A patent/FR2426073A1/en active Granted
- 1978-10-25 ES ES474505A patent/ES474505A1/en not_active Expired
- 1978-12-04 IT IT7830516A patent/IT1101522B/en active
Also Published As
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---|---|
FR2426073B1 (en) | 1983-09-09 |
US4242384A (en) | 1980-12-30 |
GB1598419A (en) | 1981-09-23 |
IT1101522B (en) | 1985-10-07 |
ES474505A1 (en) | 1979-03-16 |
EP0005428B1 (en) | 1982-06-30 |
IT7830516A0 (en) | 1978-12-04 |
ZA783923B (en) | 1979-12-27 |
BE870092A (en) | 1979-02-28 |
EP0005428A1 (en) | 1979-11-28 |
JPS54150439A (en) | 1979-11-26 |
NZ187822A (en) | 1980-08-26 |
DE2861934D1 (en) | 1982-08-19 |
FR2426073A1 (en) | 1979-12-14 |
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