JP6481332B2 - Coating composition and coating film formed therefrom - Google Patents
Coating composition and coating film formed therefrom Download PDFInfo
- Publication number
- JP6481332B2 JP6481332B2 JP2014224562A JP2014224562A JP6481332B2 JP 6481332 B2 JP6481332 B2 JP 6481332B2 JP 2014224562 A JP2014224562 A JP 2014224562A JP 2014224562 A JP2014224562 A JP 2014224562A JP 6481332 B2 JP6481332 B2 JP 6481332B2
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- JP
- Japan
- Prior art keywords
- mass
- coating film
- parts
- resin particles
- crosslinked 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.)
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- 239000011248 coating agent Substances 0.000 title claims description 95
- 238000000576 coating method Methods 0.000 title claims description 95
- 239000008199 coating composition Substances 0.000 title claims description 61
- 239000011347 resin Substances 0.000 claims description 121
- 229920005989 resin Polymers 0.000 claims description 121
- 239000002245 particle Substances 0.000 claims description 104
- 239000000178 monomer Substances 0.000 claims description 89
- 230000009477 glass transition Effects 0.000 claims description 38
- 239000011230 binding agent Substances 0.000 claims description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 23
- 230000000379 polymerizing effect Effects 0.000 claims description 20
- 239000004925 Acrylic resin Substances 0.000 claims description 11
- 229920000178 Acrylic resin Polymers 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000516 sunscreening agent Substances 0.000 description 49
- 230000000475 sunscreen effect Effects 0.000 description 44
- -1 acrylic polyol Chemical class 0.000 description 36
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 24
- 239000003995 emulsifying agent Substances 0.000 description 21
- 239000004816 latex Substances 0.000 description 18
- 229920000126 latex Polymers 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003505 polymerization initiator Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
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- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 9
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
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- 239000010452 phosphate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
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- 238000010790 dilution Methods 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
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- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000005282 brightening 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- XDSGMUJLZDSCPA-UHFFFAOYSA-N diazanium;phenoxybenzene;sulfate Chemical class [NH4+].[NH4+].[O-]S([O-])(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 XDSGMUJLZDSCPA-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- CKAOXDUSLQBRSY-UHFFFAOYSA-N dodecyl(2-phenylethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH2+]CCC1=CC=CC=C1 CKAOXDUSLQBRSY-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VIDXETATLKBUBY-UHFFFAOYSA-M lithium;benzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=CC=C1 VIDXETATLKBUBY-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- OGRPJZFGZFQRHZ-UHFFFAOYSA-M sodium;4-octoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].CCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O OGRPJZFGZFQRHZ-UHFFFAOYSA-M 0.000 description 1
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、塗料組成物とそれより形成される塗膜に関する。 The present invention relates to a coating composition and a coating film formed therefrom.
自動車の内外装部品や各種成形品の基材表面には、意匠性付与や保護などを目的として塗装が施される場合が多い。
自動車の内外装部品や各種成形品は人の手に触れる機会が多いため、人の皮脂や汗が付着しやすく、塗膜が劣化することがある。特に、夏場など紫外線の強い時期は日焼け止め剤を使用する機会が増えるが、日焼け止め剤が付着した手で自動車の内外装部品や各種成形品を触ると、日焼け止め剤によって塗膜が膨れ・膨潤などして外観が悪くなったり、塗膜の耐摩耗性が低下したりしやすくなる。よって、塗膜には日焼け止め剤に対する耐性（以下、「耐日焼け止め剤性」という。）が要求される。
In many cases, the interior and exterior parts of automobiles and the base material surfaces of various molded products are coated for the purpose of imparting design properties and protection.
Since interior and exterior parts of automobiles and various molded products have many opportunities to touch human hands, human sebum and sweat are likely to adhere to them, and the coating film may be deteriorated. In particular, sunscreens are used more frequently in the summer, such as in the summer, but if you touch the interior / exterior parts of automobiles or various molded parts with sunscreen, the sunscreen will swell the coating. It tends to deteriorate due to swelling and the like, and the wear resistance of the coating film tends to decrease. Therefore, the coating film is required to have resistance to the sunscreen (hereinafter referred to as “sunscreen resistance”).
そこで、塗料にセルロース誘導体を配合して塗膜に耐日焼け止め剤性を付与する方法が提案されている（例えば、特許文献１参照）。 In view of this, a method has been proposed in which a cellulose derivative is blended in a paint to impart sunscreen resistance to a coating film (see, for example, Patent Document 1).
しかしながら、特許文献１に記載のように、セルロース誘導体を配合した塗料より形成される塗膜は、耐日焼け止め剤性試験後において塗膜の外観および耐摩耗性の両方を必ずしも満足するものではなかった。 However, as described in Patent Document 1, a coating film formed from a coating containing a cellulose derivative does not necessarily satisfy both the appearance and the abrasion resistance of the coating film after the sunscreen resistance test. It was.
本発明は、上記事情に鑑みてなされたものであり、耐日焼け止め剤性試験後においても、外観が良好で、耐摩耗性に優れる塗膜を形成できる塗料組成物と、それより形成される塗膜の提供を目的とする。 The present invention has been made in view of the above circumstances, and is a coating composition that can form a coating film that has a good appearance and excellent wear resistance even after a sunscreen resistance test, and is formed from the coating composition. The purpose is to provide a coating film.
本発明は、以下の態様を有する。
［１］ バインダー樹脂と、架橋樹脂粒子とを含有する塗料組成物であって、前記架橋樹脂粒子が、共重合性単官能モノマーとアクリル系多官能モノマーとを共重合した共重合体であり、前記共重合性単官能モノマーを重合して得られる重合体のガラス転移温度が５０〜１３０℃であり、前記架橋樹脂粒子の平均粒子径が１０〜５００ｎｍであり、前記架橋樹脂粒子の含有量が、前記バインダー樹脂１００質量部に対して１０〜４００質量部である、塗料組成物。
［２］ ［１］に記載の塗料組成物より形成される、塗膜。
The present invention has the following aspects.
[1] A coating composition containing a binder resin and crosslinked resin particles, wherein the crosslinked resin particles are a copolymer obtained by copolymerizing a copolymerizable monofunctional monomer and an acrylic polyfunctional monomer, The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer is 50 to 130 ° C., the average particle diameter of the crosslinked resin particles is 10 to 500 nm, and the content of the crosslinked resin particles is The coating composition is 10 to 400 parts by mass with respect to 100 parts by mass of the binder resin.
[2] A coating film formed from the coating composition according to [1].
本発明の塗料組成物によれば、耐日焼け止め剤性試験後においても、外観が良好で、耐摩耗性に優れる塗膜を形成できる。
また、本発明の塗膜は、耐日焼け止め剤性試験後においても、外観が良好で、耐摩耗性に優れる。
According to the coating composition of the present invention, a coating film having a good appearance and excellent wear resistance can be formed even after the sunscreen resistance test.
In addition, the coating film of the present invention has a good appearance and excellent wear resistance even after the sunscreen resistance test.
以下、本発明について詳細に説明する。
なお、本発明において、「（メタ）アクリル酸」は、メタクリル酸およびアクリル酸の総称であり、「（メタ）アクリレート」とは、メタクリレートおよびアクリレートの総称である。
また、以下の明細書において、「塗膜」とは、本発明の塗料組成物より形成された塗膜のことであり、「耐日焼け止め剤性」とは、耐日焼け止め剤性試験後において、塗膜の外観と耐摩耗性のどちらにも優れることを意味する。すなわち、耐日焼け止め剤性に優れる塗膜とは、耐日焼け止め剤性試験後においても、外観が良好で、耐摩耗性に優れる塗膜を意味する。
ここで、「耐日焼け止め剤性試験」とは、例えば塗膜の表面上に日焼け止め剤を０．５ｇ／１００ｃｍ２の量で均一に塗布した後、５５℃で４時間放置することである。
Hereinafter, the present invention will be described in detail.
In the present invention, “(meth) acrylic acid” is a generic term for methacrylic acid and acrylic acid, and “(meth) acrylate” is a generic term for methacrylate and acrylate.
Further, in the following specification, “coating film” means a coating film formed from the coating composition of the present invention, and “sunscreen resistance” means after the sunscreen resistance test. This means that both the appearance and the abrasion resistance of the coating film are excellent. That is, the coating film excellent in sunscreen resistance means a coating film that has a good appearance and excellent wear resistance even after the sunscreen resistance test.
Here, the “sunscreen resistance test” means, for example, that a sunscreen is uniformly applied on the surface of the coating film in an amount of 0.5 g / 100 cm 2 and then left at 55 ° C. for 4 hours. .
［塗料組成物］
本発明の塗料組成物は、バインダー樹脂と、架橋樹脂粒子とを含有する。
[Coating composition]
The coating composition of the present invention contains a binder resin and crosslinked resin particles.
＜バインダー樹脂＞
バインダー樹脂としては、塗料に用いられるバインダー樹脂であれば特に制限されず、１液型であってもよいし、２液型であってもよい。ただし、２液型のバインダー樹脂は、使用する前に主剤と硬化剤とを混合する必要があり、手間がかかる。また、主剤と硬化剤とを混合してから塗料組成物として使用できるまでの使用可能時間（可使時間）が短い。また、可使時間内に使用できなかった塗料組成物は廃棄することとなる。よって、使用前に主剤と硬化剤とを混合する手間がなく、可使時間の制限がない点で、１液型のバインダー樹脂が好ましい。
<Binder resin>
The binder resin is not particularly limited as long as it is a binder resin used for a paint, and may be a one-pack type or a two-pack type. However, it is necessary to mix the main agent and the curing agent before using the two-component binder resin, which is troublesome. In addition, the usable time (potential time) from mixing the main agent and the curing agent to being able to be used as a coating composition is short. Moreover, the coating composition which could not be used within the pot life will be discarded. Therefore, a one-pack type binder resin is preferable in that there is no trouble of mixing the main agent and the curing agent before use, and there is no limitation on the usable time.
１液型のバインダー樹脂としては、例えばアクリル樹脂、ウレタン樹脂、オレフィン系樹脂、ポリ酢酸ビニル、シリコーン樹脂、ポリエステル樹脂、ポリアミド樹脂、フラン樹脂、エポキシ樹脂、キシレン樹脂、スチレン系共重合体などが挙げられる。これらバインダー樹脂は、１種単独で用いてもよく、２種以上を併用してもよい。
これらの中でも、透明性に優れた塗膜が得られる点で、アクリル樹脂が好ましい。アクリル樹脂は、アクリル樹脂以外のバインダー樹脂に比べて、後述する架橋樹脂粒子との屈折率差が小さいため、塗膜が濁るのを抑制できる。
Examples of the one-component binder resin include acrylic resin, urethane resin, olefin resin, polyvinyl acetate, silicone resin, polyester resin, polyamide resin, furan resin, epoxy resin, xylene resin, styrene copolymer, and the like. It is done. These binder resins may be used alone or in combination of two or more.
Among these, an acrylic resin is preferable in that a coating film excellent in transparency can be obtained. Since the acrylic resin has a smaller difference in refractive index from the crosslinked resin particles described later, compared to a binder resin other than the acrylic resin, the coating film can be prevented from becoming cloudy.
２液型のバインダー樹脂としては、アクリルポリオール、ポリエステルポリオール、アルキッド樹脂などの主剤と、イソシアネート化合物などの硬化剤とを含む２液型のウレタン樹脂などが挙げられる。 Examples of the two-component binder resin include a two-component urethane resin containing a main agent such as acrylic polyol, polyester polyol, and alkyd resin and a curing agent such as an isocyanate compound.
バインダー樹脂の質量平均分子量は、１００００〜１０００００が好ましく、４００００〜８００００がより好ましい。バインダー樹脂の質量平均分子量が１００００以上であれば、塗膜として十分な靱性が得られる。一方、バインダー樹脂の質量平均分子量が１０００００を超えると、塗料組成物の粘度が上昇し、塗料組成物の塗工性が悪くなる。その結果、塗工しやすくするために溶媒による大量の希釈が必要となる場合があり、塗膜に厚みをつけることが困難となることがある。 The mass average molecular weight of the binder resin is preferably 10,000 to 100,000, and more preferably 40,000 to 80,000. If the mass average molecular weight of the binder resin is 10,000 or more, sufficient toughness as a coating film can be obtained. On the other hand, when the mass average molecular weight of the binder resin exceeds 100,000, the viscosity of the coating composition increases, and the coating property of the coating composition deteriorates. As a result, a large amount of dilution with a solvent may be required to facilitate coating, and it may be difficult to thicken the coating film.
バインダー樹脂の質量平均分子量は、ゲルパーミエーションクロマトグラフ法で測定される値である。具体的には、移動相としてテトラヒドロフラン（ＴＨＦ）を用い、流速１．０ｍＬ／分の条件で、ゲルパーミエーションクロマトグラフにて測定し、ポリスチレン換算した値を質量平均分子量とする。 The mass average molecular weight of the binder resin is a value measured by gel permeation chromatography. Specifically, tetrahydrofuran (THF) is used as a mobile phase, and a gel permeation chromatograph is used under conditions of a flow rate of 1.0 mL / min.
バインダー樹脂のガラス転移温度は、６０〜１２０℃が好ましく、７０〜１１０℃がより好ましい。バインダー樹脂のガラス転移温度が６０℃以上であれば、高温環境下においても塗膜が軟化しにくく、耐日焼け止め剤性を良好に維持できる。一方、バインダー樹脂のガラス転移温度が１２０℃を超えると、塗料組成物の粘度が上昇し、塗料組成物の塗工性が悪くなる。その結果、塗工しやすくするために溶媒による大量の希釈が必要となる場合があり、塗膜に厚みをつけることが困難となることがある。 The glass transition temperature of the binder resin is preferably 60 to 120 ° C, more preferably 70 to 110 ° C. If the glass transition temperature of the binder resin is 60 ° C. or higher, the coating film is difficult to soften even in a high-temperature environment, and the sunscreen resistance can be maintained well. On the other hand, when the glass transition temperature of binder resin exceeds 120 degreeC, the viscosity of a coating composition will rise and the coating property of a coating composition will worsen. As a result, a large amount of dilution with a solvent may be required to facilitate coating, and it may be difficult to thicken the coating film.
バインダー樹脂のガラス転移温度は、バインダー樹脂を構成する単量体の種類やその配合量によって調整できる。また、バインダー樹脂のガラス転移温度は、下記式（ｉ）に示されるＦｏｘの式から求められる値である。
１／（ＴｇＡ＋２７３．１５）＝Σ［Ｗａ／（Ｔｇａ＋２７３．１５）］ ・・・（ｉ）
The glass transition temperature of the binder resin can be adjusted by the type of monomer constituting the binder resin and the blending amount thereof. The glass transition temperature of the binder resin is a value obtained from the Fox formula shown in the following formula (i).
1 / (Tg A +273.15) = Σ [W a / (Tg a +273.15)] (i)
式（ｉ）中、ＴｇＡはバインダー樹脂のガラス転移温度（℃）であり、Ｗａはバインダー樹脂を構成する単量体ａの質量分率であり、Ｔｇａは単量体ａの単独重合体（ホモポリマー）のガラス転移温度（℃）である。
なお、Ｔｇａはホモポリマーの特性値として広く知られており、例えば、「ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ、ＴＨＩＲＤ ＥＤＩＴＩＯＮ」に記載されている値や、メーカのカタログ値を用いればよい。
Wherein (i), Tg A is the glass transition temperature of the binder resin (° C.), W a is the mass fraction of the monomer a constituting the binder resin, homo- of Tg a monomeric a It is the glass transition temperature (° C.) of the coalescence (homopolymer).
Tga is widely known as a homopolymer characteristic value. For example, a value described in “POLYMER HANDBOOK, THIRD EDITION” or a manufacturer's catalog value may be used.
＜架橋樹脂粒子＞
架橋樹脂粒子は、塗膜に耐日焼け止め剤性を付与する成分であり、共重合性単官能モノマーと、アクリル系多官能モノマーとを共重合した共重合体である。
<Crosslinked resin particles>
The crosslinked resin particles are a component that imparts sunscreen resistance to the coating film, and are a copolymer obtained by copolymerizing a copolymerizable monofunctional monomer and an acrylic polyfunctional monomer.
共重合性単官能モノマーとしては、アクリル系単官能モノマー、ビニル系モノマー、カルボキシ基含有モノマー、リン酸基含有モノマー、アミド基含有モノマーなどが挙げられる。 Examples of the copolymerizable monofunctional monomer include acrylic monofunctional monomers, vinyl monomers, carboxy group-containing monomers, phosphate group-containing monomers, amide group-containing monomers, and the like.
アクリル系単官能モノマーとしては、単官能（メタ）アクリレートが挙げられ、具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸へプチル、（メタ）アクリル酸オクチル等の（メタ）アクリル酸アルキルエステル；（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸２−（ｎ−プロポキシ）エチル、（メタ）アクリル酸２−（ｎ−ブトキシ）エチル、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸３−エトキシプロピル、（メタ）アクリル酸２−（ｎ−プロポキシ）プロピル、（メタ）アクリル酸２−（ｎ−ブトキシ）プロピル等の（メタ）アクリル酸アルコキシアルキルエステル；（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸イソボルニル等の脂環構造を有する（メタ）アクリル酸エステルなどが挙げられる。
ビニル系モノマーとしては、芳香族ビニルモノマー（例えばスチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン等）、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、アクリロニトリルなどが挙げられる。
カルボキシ基含有モノマーとしては、（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレートなどが挙げられる。
リン酸基含有モノマーとしては、２−アクリロイルオキシエチルアシッドホスフェート、２−メタクリロイルオキシエチルアシッドホスフェート、２−アクリロイルオキシプロピルアシッドホスフェート、２−メタクリロイルオキシプロピルアシッドホスフェートなどが挙げられる。
アミド基含有モノマーとしては、Ｎ−メチルアクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−メチロールアクリルアミドブチルエーテルなどが挙げられる。
これら共重合性単官能モノマーは、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the acrylic monofunctional monomer include monofunctional (meth) acrylates, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. (Meth) acrylic acid alkyl esters such as pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, ( (Meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (n-propoxy) ethyl, (meth) acrylic acid 2- (n-butoxy) ethyl, (meth) acrylic acid 3-methoxypropyl, (meth) 3-Ethoxypropyl acrylate, 2- (n-propoxy) propyl (meth) acrylate, 2- (n) (meth) acrylic acid (Meth) acrylic acid alkoxyalkyl esters such as butoxy) propyl; (meth) acrylic acid esters having an alicyclic structure such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate Etc.
As vinyl monomers, aromatic vinyl monomers (for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc.) , Vinyl acetate, vinyl propionate, vinyl chloride, acrylonitrile and the like.
Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, crotonic acid, and β-carboxyethyl acrylate.
Examples of the phosphoric acid group-containing monomer include 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate, and the like.
Examples of the amide group-containing monomer include N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide butyl ether and the like.
These copolymerizable monofunctional monomers may be used alone or in combination of two or more.
共重合性単官能モノマーとしては、上述した中でも、耐日焼け止め剤性がより向上する観点から、アクリル系単官能モノマーが特に好ましい。アクリル系単官能モノマーの割合は、共重合性単官能モノマー１００質量％中、９０質量％以上が好ましく、９５質量％以上がより好ましい。 Among the above-mentioned copolymerizable monofunctional monomers, acrylic monofunctional monomers are particularly preferable from the viewpoint of further improving sunscreen resistance. The proportion of the acrylic monofunctional monomer is preferably 90% by mass or more, and more preferably 95% by mass or more, in 100% by mass of the copolymerizable monofunctional monomer.
共重合性単官能モノマーとしては、該共重合性単官能モノマーを重合して得られる重合体のガラス転移温度が５０〜１３０℃となるモノマーを用いる。共重合性単官能モノマーを重合して得られる重合体のガラス転移温度が５０℃以上であれば、架橋樹脂粒子自体の日焼け止め剤に対する耐性が十分なものとなり、塗膜の耐日焼け止め剤性が向上する。ただし、共重合性単官能モノマーを重合して得られる重合体のガラス転移温度が高くなりすぎると、バインダー樹脂との相溶性が低下し、十分な耐日焼け止め剤性を発揮しにくくなる。共重合性単官能モノマーを重合して得られる重合体のガラス転移温度が１３０℃以下であれば、バインダー樹脂との相溶性を良好に維持できる。
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度は、７０〜１２０℃が好ましい。
なお、２種以上の共重合性単官能モノマーを用いる場合は、これら２種以上の共重合性単官能モノマーを重合して得られる重合体のガラス転移温度が５０〜１３０℃であり、７０〜１２０℃が好ましい。
As the copolymerizable monofunctional monomer, a monomer having a glass transition temperature of 50 to 130 ° C. of a polymer obtained by polymerizing the copolymerizable monofunctional monomer is used. If the glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer is 50 ° C. or higher, the crosslinked resin particles themselves have sufficient resistance to sunscreen, and the sunscreen resistance of the coating film Will improve. However, when the glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer is too high, the compatibility with the binder resin is lowered, and it becomes difficult to exhibit sufficient sunscreen resistance. If the glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer is 130 ° C. or lower, the compatibility with the binder resin can be maintained well.
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer is preferably 70 to 120 ° C.
In addition, when using 2 or more types of copolymerizable monofunctional monomers, the glass transition temperature of the polymer obtained by polymerizing these 2 or more types of copolymerizable monofunctional monomers is 50 to 130 ° C., and 70 to 120 ° C. is preferred.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度は、共重合性単官能モノマーの種類やその配合量によって調整できる。また、共重合性単官能モノマーを重合して得られる重合体のガラス転移温度は、下記式（ii）に示されるＦｏｘの式から求められる値である。
１／（ＴｇＢ＋２７３．１５）＝Σ［Ｗｂ／（Ｔｇｂ＋２７３．１５）］ ・・・（ii）
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer can be adjusted by the type of the copolymerizable monofunctional monomer and its blending amount. Further, the glass transition temperature of a polymer obtained by polymerizing a copolymerizable monofunctional monomer is a value obtained from the Fox formula shown in the following formula (ii).
1 / (Tg B +273.15) = Σ [W b / (Tg b +273.15)] (ii)
式（ｉ）中、ＴｇＢは共重合性単官能モノマーを重合して得られる重合体のガラス転移温度（℃）であり、Ｗｂは該重合体を構成する共重合性単官能モノマーｂの質量分率であり、Ｔｇｂは共重合性単官能モノマーｂの単独重合体（ホモポリマー）のガラス転移温度（℃）である。
なお、Ｔｇｂはホモポリマーの特性値として広く知られており、例えば、「ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ、ＴＨＩＲＤ ＥＤＩＴＩＯＮ」に記載されている値や、メーカのカタログ値を用いればよい。
In the formula (i), Tg B is a glass transition temperature (° C.) of a polymer obtained by polymerizing a copolymerizable monofunctional monomer, and W b is the copolymerizable monofunctional monomer b constituting the polymer. It is a mass fraction, and Tg b is a glass transition temperature (° C.) of a homopolymer of the copolymerizable monofunctional monomer b (homopolymer).
Incidentally, Tg b is widely known as a characteristic value of a homopolymer, for example, "POLYMER HANDBOOK-, and THIRD EDITION" and values that are described may be used to catalog value manufacturer.
アクリル系多官能モノマーは、架橋剤の役割を果たす。
アクリル系多官能モノマーとしては、分子中に２つ以上のラジカル重合性の二重結合を有する多官能（メタ）アクリレートが挙げられ、具体的には、トリメチロールプロパントリアクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、デカエチレングリコールジメタクリレート、ペンタデカエチレングリコールジメタクリレート、ペンタコンタヘプタエチレングリコールジメタクリレート、１，３−ブチレンジメタクリレート、アリルメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールテトラアクリレートなどが挙げられる。
これらアクリル多単官能モノマーは、１種単独で用いてもよく、２種以上を併用してもよい。
The acrylic polyfunctional monomer serves as a crosslinking agent.
Examples of the acrylic polyfunctional monomer include polyfunctional (meth) acrylates having two or more radically polymerizable double bonds in the molecule. Specifically, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, pentadecaethylene glycol dimethacrylate, pentacontaheptaethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol Examples include tetraacrylate.
These acrylic polymonofunctional monomers may be used alone or in combination of two or more.
共重合性単官能モノマーおよびアクリル系多官能モノマーの割合は、共重合性単官能モノマー：アクリル系多官能モノマーで表される質量比が９９．９：０．１〜０．１：９９．９となる量が好ましく、９９．０：１．０〜１．０：９９．０となる量がより好ましい。アクリル系多官能モノマーの割合が少なすぎると、架橋が不十分となり塗膜の耐摩耗性が低下する。一方、アクリル系多官能モノマーの割合が多すぎると、重合時に形成される架橋樹脂粒子が不安定となり、ブツとなって塗膜に現れる場合がある。 The ratio of the copolymerizable monofunctional monomer and the acrylic polyfunctional monomer is such that the mass ratio represented by the copolymerizable monofunctional monomer: acrylic polyfunctional monomer is 99.9: 0.1 to 0.1: 99.9. An amount of 99.0: 1.0 to 1.0: 99.0 is more preferable. When the ratio of the acrylic polyfunctional monomer is too small, crosslinking is insufficient and the wear resistance of the coating film is lowered. On the other hand, if the ratio of the acrylic polyfunctional monomer is too large, the crosslinked resin particles formed during polymerization become unstable and may appear as a scum on the coating film.
架橋樹脂粒子は、媒体として水を用いた乳化重合などにより得られる。具体的には、重合開始剤および乳化剤を用い、共重合性単官能モノマーとアクリル系多官能モノマーとを共重合することで得られる。 The crosslinked resin particles are obtained by emulsion polymerization using water as a medium. Specifically, it can be obtained by copolymerizing a copolymerizable monofunctional monomer and an acrylic polyfunctional monomer using a polymerization initiator and an emulsifier.
重合開始剤としては、例えばペルオキソ二硫酸カリウム、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸ナトリウム、過酸化水素等の無機過酸化物などが挙げられる。これら重合開始剤は、１種単独で用いてもよく、２種以上を併用してもよい。
重合開始剤の使用量は、共重合性単官能モノマーおよびアクリル系多官能モノマーの合計１００質量部に対して、０．０５〜３．０質量部が好ましく、０．２〜２．０質量部がより好ましい。重合開始剤の使用量が０．０５質量部以上であれば、未反応のモノマーの割合を減らすことができる。一方、重合開始剤の使用量が３．０質量部以下であれば、重合開始剤が分解した分解物が不純物として残るのを抑制できる。
Examples of the polymerization initiator include inorganic peroxides such as potassium peroxodisulfate, ammonium peroxodisulfate, sodium peroxodisulfate, and hydrogen peroxide. These polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator used is preferably 0.05 to 3.0 parts by mass, and 0.2 to 2.0 parts by mass with respect to a total of 100 parts by mass of the copolymerizable monofunctional monomer and acrylic polyfunctional monomer. Is more preferable. If the usage-amount of a polymerization initiator is 0.05 mass part or more, the ratio of the unreacted monomer can be reduced. On the other hand, if the usage-amount of a polymerization initiator is 3.0 mass parts or less, it can suppress that the decomposition product which the polymerization initiator decomposed | disassembled remains as an impurity.
乳化剤としては、アニオン系乳化剤、カチオン系乳化剤、ノニオン系乳化剤などが挙げられる。
アニオン系乳化剤としてはアニオン系界面活性剤が挙げられ、具体的には、オレイン酸ナトリウム、ステアリン酸ナトリウム等の高級脂肪酸塩類；ドデシルベンゼンスルホン酸ナトリウム、ドデシルジフェニルエーテルスルホン酸ジナトリウム等のアルキル（もしくはアリール）スルホン酸塩類；ラウリル硫酸ナトリウム、オレイル硫酸ナトリウム等のアルキル（もしくはアルケニル）硫酸エステル類；ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンオレイルエーテル硫酸アンモニウム、ポリオキシエチレンスチレン化フェニルエーテル硫酸アンモニウム等のポリオキシエチレンアルキル（もしくはアルケニル）エーテル硫酸塩類；ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類；モノオクチルスルホコハク酸ナトリウム、ジ−２−エチルへキシルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルスルホコハク酸ナトリウム等のアルキルスルホコハク酸エステル塩、またはこれらの誘導体類などが挙げられる。これらの中でも、重合時において架橋樹脂粒子が形成されやすく、また形成された架橋樹脂粒子が水中に安定に分散するという観点から、ドデシルジフェニルエーテルスルホン酸ジナトリウム、ポリオキシエチレンスチレン化フェニルエーテル硫酸アンモニウム、ジ−２−エチルへキシルスルホコハク酸ナトリウムが好ましい。
これらアニオン系乳化剤は、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the emulsifier include an anionic emulsifier, a cationic emulsifier, and a nonionic emulsifier.
Examples of anionic emulsifiers include anionic surfactants. Specifically, higher fatty acid salts such as sodium oleate and sodium stearate; alkyl (or aryl) such as sodium dodecylbenzenesulfonate and disodium dodecyldiphenylethersulfonate. ) Sulfonates; alkyl (or alkenyl) sulfates such as sodium lauryl sulfate and sodium oleyl sulfate; polyoxyethylene such as polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene oleyl ether ammonium sulfate, polyoxyethylene styrenated phenyl ether ammonium sulfate Ethylene alkyl (or alkenyl) ether sulfates; polyoxyethylene such as sodium polyoxyethylene nonylphenyl ether sulfate Alkyl aryl ether sulfates; alkyl sulfosuccinates such as sodium monooctylsulfosuccinate, sodium di-2-ethylhexylsulfosuccinate, sodium dioctylsulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate, and derivatives thereof Etc. Among these, from the viewpoint that the crosslinked resin particles are easily formed during polymerization and the formed crosslinked resin particles are stably dispersed in water, disodium dodecyl diphenyl ether sulfonate, polyoxyethylene styrenated phenyl ether ammonium sulfate, di- Sodium 2-ethylhexyl sulfosuccinate is preferred.
These anionic emulsifiers may be used alone or in combination of two or more.
カチオン系乳化剤としてはカチオン系界面活性剤が挙げられ、具体的には、ドデシルベンジルメチルアンモニウムクロライド等のアルキルベンジルメチルアンモニウム塩；ドデシルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライド等のアルキルトリメチルアンモニウム塩；ジデシルジメチルアンモニウムクロライド、ジステアリルジメチルンモニウムクロライド等のジアルキルジメチルアンモニウム塩；ドデシルベンジルジメチルアンモニウムクロライト等のアルキルベンジルジメチルアンモニウム塩；などの四級アンモニウム塩が挙げられる。これらの中でも、重合時において架橋樹脂粒子が形成されやすく、また形成された架橋樹脂粒子が水中に安定に分散するという観点から、ドデシルベンジルジメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド、ジデシルジメチルアンモニウムクロライドが好ましい。
これらカチオン系乳化剤は、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of cationic emulsifiers include cationic surfactants. Specifically, alkylbenzylmethylammonium salts such as dodecylbenzylmethylammonium chloride; alkyltrimethyls such as dodecyltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride. Quaternary ammonium salts such as ammonium salts; dialkyldimethylammonium salts such as didecyldimethylammonium chloride and distearyldimethylumonium chloride; alkylbenzyldimethylammonium salts such as dodecylbenzyldimethylammonium chlorite; Among these, dodecylbenzyldimethylammonium chloride, stearyltrimethylammonium chloride, didecyldimethylammonium chloride are used from the viewpoint that the crosslinked resin particles are easily formed during polymerization and the formed crosslinked resin particles are stably dispersed in water. preferable.
These cationic emulsifiers may be used alone or in combination of two or more.
ノニオン系乳化剤としてはノニオン系界面活性剤が挙げられ、具体的には、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンドデシルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンスチリルフェニルエーテル等のポリオキシアルキレンエーテル類；ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンステアレート等のポリオキシアルキレンエステル類；ポリオキシエチレンポリオキシプロピレンブロックまたはランダム共重合体、ポリエチレングリコール（メタ）アクリレート等のポリアルキレングリコールエステル類などが挙げられる。 Nonionic surfactants include nonionic surfactants. Specific examples include polyoxyethylene lauryl ether, polyoxyethylene dodecyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether. Polyoxyalkylene ethers such as polyoxyethylene styryl phenyl ether; polyoxyalkylene esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene stearate; polyoxyethylene polyoxypropylene block or random copolymer, polyethylene Examples include polyalkylene glycol esters such as glycol (meth) acrylate.
また、乳化剤としては、上述した以外にも、ビニル基などのラジカル重合性の二重結合を有する反応性乳化剤を用いてもよく、具体的には、ｐ−ビニルベンゼンスルホン酸ナトリウム、ｐ−ビニルベンゼンスルホン酸リチウム、ｐ−ビニルベンゼンスルホン酸メトキシド、ｐ−ビニルベンゼンスルホン酸エトキシドなどが挙げられる。なお、これら反応性乳化剤は、アニオン系乳化剤である。 Further, as the emulsifier, in addition to the above, a reactive emulsifier having a radical polymerizable double bond such as a vinyl group may be used, and specifically, sodium p-vinylbenzenesulfonate, p-vinyl. Examples include lithium benzenesulfonate, p-vinylbenzenesulfonate methoxide, and p-vinylbenzenesulfonate ethoxide. These reactive emulsifiers are anionic emulsifiers.
乳化剤の使用量は、共重合性単官能モノマーおよびアクリル系多官能モノマーの合計１００質量部に対して、０．０１〜２０質量部が好ましく、０．１〜０質量部がより好ましい。乳化剤の使用量が０．０１質量部以上であれば、安定して架橋樹脂粒子が形成されやすくなり、形成された架橋樹脂粒子の水中での分散性が良好となる。一方、乳化剤の使用量が２０質量部以下であれば、重合時に発泡が生じにくく、生産性よく架橋樹脂粒子を形成できる。 The use amount of the emulsifier is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 0 parts by mass with respect to 100 parts by mass in total of the copolymerizable monofunctional monomer and the acrylic polyfunctional monomer. If the usage-amount of an emulsifier is 0.01 mass part or more, it will become easy to form a crosslinked resin particle stably, and the dispersibility in water of the formed crosslinked resin particle will become favorable. On the other hand, if the amount of the emulsifier used is 20 parts by mass or less, foaming hardly occurs during polymerization, and the crosslinked resin particles can be formed with good productivity.
架橋樹脂粒子は、水中に分散した水性ラテックスの状態で得られる。この水性ラテックスをスプレードライ法などにより乾燥することで、粉体状の架橋樹脂粒子が得られる。
架橋樹脂粒子の平均粒子径は、１０〜５００ｎｍであり、３０〜３００ｎｍが好ましい。架橋樹脂粒子の５００ｎｍ以下であれば、耐日焼け止め剤性に優れた塗膜を形成できる。加えて、平滑性にも優れた塗膜を形成できる。なお、平均粒子径が１０ｎｍ未満の架橋樹脂粒子は製造が困難である。
ここで「平均粒子径」とは、体積基準のメジアン径のことであり、具体的にはレーザー回折式粒度分布測定装置を用いて測定した値である。
Crosslinked resin particles are obtained in the form of an aqueous latex dispersed in water. The aqueous latex is dried by a spray drying method or the like to obtain powdered crosslinked resin particles.
The average particle diameter of the crosslinked resin particles is 10 to 500 nm, and preferably 30 to 300 nm. If it is 500 nm or less of a crosslinked resin particle, the coating film excellent in the sunscreen-proof property can be formed. In addition, a coating film excellent in smoothness can be formed. In addition, it is difficult to produce crosslinked resin particles having an average particle diameter of less than 10 nm.
Here, the “average particle diameter” is a volume-based median diameter, and is specifically a value measured using a laser diffraction particle size distribution measuring apparatus.
架橋樹脂粒子は、球状であることが好ましい。架橋樹脂粒子が球状であれば、架橋樹脂粒子の比表面積が最小となりバインダー樹脂中により均一に分散されやすくなり、塗膜の耐日焼け止め剤性がより向上する。 The crosslinked resin particles are preferably spherical. If the cross-linked resin particles are spherical, the specific surface area of the cross-linked resin particles is minimized, and the cross-linked resin particles are more easily dispersed more uniformly in the binder resin, and the sunscreen resistance of the coating film is further improved.
架橋樹脂粒子の含有量は、バインダー樹脂の固形分１００質量部に対して１０〜４００質量部であり、３０〜３００質量部が好ましい。架橋樹脂粒子の含有量が１０質量部以上であれば、耐日焼け止め剤性に優れた塗膜を形成できる。一方、架橋樹脂粒子の含有量が４００質量部以下であれば、成膜性を維持できるので、均一な塗膜を形成できる。 Content of a crosslinked resin particle is 10-400 mass parts with respect to 100 mass parts of solid content of binder resin, and 30-300 mass parts is preferable. If content of a crosslinked resin particle is 10 mass parts or more, the coating film excellent in sunscreen-proof property can be formed. On the other hand, if the content of the crosslinked resin particles is 400 parts by mass or less, the film formability can be maintained, so that a uniform coating film can be formed.
＜他の成分＞
本発明の塗料組成物には、本発明の効果を損なわない範囲内であれば、添加剤や有機溶媒が含まれていてもよい。
添加剤としては、例えば顔料、充填剤、可塑剤、表面調整剤、分散剤、塗面調製剤、界面活性剤、光安定剤、酸化防止剤、増粘剤、揺変剤、帯電防止剤、紫外線吸収剤、光輝剤などが挙げられる。
<Other ingredients>
The coating composition of the present invention may contain additives and organic solvents as long as the effects of the present invention are not impaired.
Examples of additives include pigments, fillers, plasticizers, surface conditioners, dispersants, coating surface preparation agents, surfactants, light stabilizers, antioxidants, thickeners, thixotropic agents, antistatic agents, Examples include ultraviolet absorbers and brighteners.
有機溶媒としては、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、メチルイソアミルケトン、メチルイソブチルケトン、メチルイソプロピルケトン等のケトン系溶媒；酢酸エチル、酢酸−ｎ−プロピル、酢酸イソプロピル、酢酸−ｎ−ブチル、酢酸イソブチル、酢酸−ｓｅｃ−ブチル、アクリル酸−ｎ−ブチル、メタクリル酸メチル等のエステル系溶媒；エチレングリコールジエチルエーテル、２−エチル−１，３−ヘキサンジオール等のエーテル系溶媒；メタノール、エタノール、プロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブチルアルコール、ｔｅｒ−ブチルアルコール等のアルコール系溶媒；ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族系溶媒；トルエン、キシレン、ベンゼン等の芳香族系溶媒；エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル等のグリコール系溶媒などが挙げられる。これら有機溶媒は、１種単独で用いてもよく、２種以上を併用してもよい。
有機溶媒の含有量は、塗料組成物が所望の固形分濃度となる量であれば特に制限されない。塗料組成物の固形分濃度は、通常、２０〜４０質量％が好ましい。
Examples of organic solvents include ketone solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, methyl isoamyl ketone, methyl isobutyl ketone, and methyl isopropyl ketone; ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, acetic acid Ester solvents such as isobutyl, acetic acid-sec-butyl, acrylic acid-n-butyl, methyl methacrylate; ether solvents such as ethylene glycol diethyl ether and 2-ethyl-1,3-hexanediol; methanol, ethanol, propanol , N-butanol, isobutanol, sec-butyl alcohol, ter-butyl alcohol, and other alcohol solvents; hexane, heptane, octane, cyclohexane, and other aliphatic solvents; toluene, xylene, benzene, and other aromatic solvents Solvent, ethylene glycol monobutyl ether, and the like glycol-based solvents such as diethylene glycol monobutyl ether. These organic solvents may be used individually by 1 type, and may use 2 or more types together.
The content of the organic solvent is not particularly limited as long as the coating composition has a desired solid content concentration. The solid content concentration of the coating composition is usually preferably 20 to 40% by mass.
＜作用効果＞
上述したように、塗膜に日焼け止め剤が付着すると、塗膜が膨れ・膨潤などして外観が悪くなったり、塗膜の耐摩耗性が低下したりしやすくなる。
しかし、本発明の塗料組成物であれば、上述した架橋樹脂粒子を特定量含有するため、日焼け止め剤による塗膜の膨れ・膨潤を防ぎ、塗膜の外観の悪化や耐摩耗性の低下を抑制することができる。
<Effect>
As described above, when the sunscreen agent adheres to the coating film, the coating film swells and swells, resulting in a poor appearance or a decrease in the wear resistance of the coating film.
However, if the coating composition of the present invention contains a specific amount of the above-mentioned crosslinked resin particles, it prevents swelling and swelling of the coating film due to the sunscreen agent, and deteriorates the appearance and wear resistance of the coating film. Can be suppressed.
また、塗料組成物に含まれるバインダー樹脂が１液型であれば、使用前に主剤と硬化剤とを混合する手間がなく、可使時間の制限もない。
また、バインダー樹脂がアクリル樹脂であれば、架橋樹脂粒子との屈折率差が小さくなるので、濁りの少ない、透明な塗膜が得られやすい。特に、塗料組成物が顔料を含有する場合、透明な塗膜が得られれば、目的とする色合いを発現しやすくなる。また、塗料組成物が光輝剤を含有する場合、透明な塗膜が得られれば、光輝性が阻害されにくい。
Moreover, if the binder resin contained in the coating composition is a one-pack type, there is no need to mix the main agent and the curing agent before use, and there is no limitation on the usable time.
Further, when the binder resin is an acrylic resin, the difference in refractive index from the crosslinked resin particles is small, so that a transparent coating film with little turbidity can be easily obtained. In particular, when the coating composition contains a pigment, if a transparent coating film is obtained, it becomes easy to express the target color. Further, when the coating composition contains a brightening agent, if a transparent coating film is obtained, the glittering property is not easily inhibited.
「塗膜」
本発明の塗膜は、上述した本発明の塗料組成物より形成される。
塗膜は、例えば基材上に塗料組成物を塗布し、乾燥することで得られる。
"Coating"
The coating film of this invention is formed from the coating composition of this invention mentioned above.
The coating film can be obtained, for example, by applying a coating composition on a substrate and drying it.
基材としては、金属基材、プラスチック基材などが挙げられる。
金属基材の材質としては、例えばアルミニウム、鉄、ニッケル、クロム、チタン、銅、銀、亜鉛、スズ、インジウム、マグネシウム、これらの酸化物、およびこれらの合金などが挙げられる。
一方、プラスチック基材の材質としては、例えばポリエステル（例えばポリエチレンテレフタレート、ポリブチレンテレフタレート等）、ポリオレフィン（例えば、ポリエチレン、ポリプロピレン等）、ポリカーボネート、アクリロニトリル−ブタジエン−スチレン共重合樹脂（ＡＢＳ）、アクリル樹脂、アクリロニトリル−スチレン共重合樹脂、アクリル−スチレン共重合樹脂、ポリ塩化ビニル樹脂などが挙げられる。
Examples of the substrate include a metal substrate and a plastic substrate.
Examples of the material of the metal substrate include aluminum, iron, nickel, chromium, titanium, copper, silver, zinc, tin, indium, magnesium, oxides thereof, and alloys thereof.
On the other hand, as a material of the plastic substrate, for example, polyester (for example, polyethylene terephthalate, polybutylene terephthalate, etc.), polyolefin (for example, polyethylene, polypropylene, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylic resin, Examples include acrylonitrile-styrene copolymer resin, acrylic-styrene copolymer resin, and polyvinyl chloride resin.
基材の形状については特に限定されず、フィルム状、立体状のいずれでもよい。
また、塗膜との密着性を高める観点から、塗膜が形成される基材表面は、コロナ放電処理やプラズマ処理など前処理が施されていてもよい。
The shape of the substrate is not particularly limited, and may be either a film shape or a three-dimensional shape.
Moreover, from the viewpoint of improving the adhesion with the coating film, the substrate surface on which the coating film is formed may be subjected to pretreatment such as corona discharge treatment or plasma treatment.
基材への塗料組成物の塗布方法については特に制限されず、公知の方法を採用できる。具体的には、スプレー塗装法、刷毛塗り法、ローラ塗装法、カーテンコート法、フローコート法、浸漬塗り法などにより、基材上に塗料組成物を塗布する。ついで、２５〜８０℃で乾燥することにより、基材上に塗料組成物からなる塗膜が形成された積層体が得られる。
塗膜の膜厚は、５〜５０μｍが好ましく、１０〜４０μｍがより好ましい。
The method for applying the coating composition to the substrate is not particularly limited, and a known method can be employed. Specifically, the coating composition is applied onto the substrate by spray coating, brush coating, roller coating, curtain coating, flow coating, dip coating, or the like. Subsequently, the laminated body by which the coating film which consists of a coating composition was formed on the base material by drying at 25-80 degreeC is obtained.
5-50 micrometers is preferable and, as for the film thickness of a coating film, 10-40 micrometers is more preferable.
基材上に塗膜が形成された積層体は、そのまま成形品（例えば自動車の内外装部品や、家電の筺体、模型、工芸品、雑貨等の各種成形品など）として、各種用途に用いることができる。 The laminate with the coating film formed on the base material is used as it is for various purposes as a molded product (for example, interior / exterior parts of automobiles, housings of home appliances, models, crafts, miscellaneous products, etc.). Can do.
＜作用効果＞
以上説明した本発明の塗膜は、本発明の塗料組成物より形成されるので、耐日焼け止め剤性に優れる。
<Effect>
Since the coating film of this invention demonstrated above is formed from the coating composition of this invention, it is excellent in sunscreen-proof property.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されるものではない。
なお、実施例２は参考例である。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
In addition, Example 2 is a reference example.
［実施例１］
＜架橋樹脂粒子の製造＞
フラスコに、共重合性単官能モノマーとしてメチルメタクリレート０．４５質量部と、アクリル系多官能モノマーとしてエチレングリコールジメタクリレート０．０５質量部と、純水３８０質量部と、重合開始剤としてペルオキソ二硫酸カリウム０．３質量部と、乳化剤としてアニオン系界面活性剤（ドデシルジフェニルエーテルスルホン酸ジナトリウム）０．４質量部とを仕込み、さらに窒素を供給して１０分間バブリングを行い、フラスコ内を脱気した。フラスコ内が７５℃になるよう加温し、７５℃に到達した時点でその温度を１０分間維持しながら、メチルメタクリレート８９．５５質量部と、エチレングリコールジメタクリレート９．９５質量部との混合物を１時間かけて滴下した。滴下終了後、フラスコ内の温度を７５℃に維持しながら２時間撹拌して乳化重合を行い、架橋樹脂粒子が水に分散した水性ラテックス（水分散体）を得た。
得られた水性ラテックスを、スプレードライ法により含水分量が２質量％以下になるまで乾燥し、粉体状の架橋樹脂粒子を得た。
[Example 1]
<Manufacture of crosslinked resin particles>
In a flask, 0.45 parts by mass of methyl methacrylate as a copolymerizable monofunctional monomer, 0.05 parts by mass of ethylene glycol dimethacrylate as an acrylic polyfunctional monomer, 380 parts by mass of pure water, and peroxodisulfuric acid as a polymerization initiator 0.3 parts by mass of potassium and 0.4 parts by mass of an anionic surfactant (disodium dodecyl diphenyl ether sulfonate) as an emulsifier were charged, and nitrogen was supplied to perform bubbling for 10 minutes to degas the flask. . The flask was heated to 75 ° C., and when the temperature reached 75 ° C., the temperature was maintained for 10 minutes, and a mixture of 89.55 parts by mass of methyl methacrylate and 9.95 parts by mass of ethylene glycol dimethacrylate was added. The solution was added dropwise over 1 hour. After completion of the dropping, emulsion polymerization was carried out by stirring for 2 hours while maintaining the temperature in the flask at 75 ° C. to obtain an aqueous latex (water dispersion) in which the crosslinked resin particles were dispersed in water.
The obtained aqueous latex was dried by a spray drying method until the water content became 2% by mass or less to obtain powdered crosslinked resin particles.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度を、上記式（ii）に示されるＦｏｘの式から求めたところ、１０５℃であった。なお、メチルメタクリレートの単独重合体（ホモポリマー）のガラス転移温度を１０５℃とした。結果を表１に示す。
また、水性ラテックス中の架橋樹脂粒子の平均粒子径を、レーザー回折式粒度分布測定装置を用いて測定したところ、１００ｎｍであった。結果を表１に示す。
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer was determined to be 105 ° C. from the Fox formula shown in the above formula (ii). The glass transition temperature of the homopolymer of methyl methacrylate was set to 105 ° C. The results are shown in Table 1.
Moreover, it was 100 nm when the average particle diameter of the crosslinked resin particle in aqueous latex was measured using the laser diffraction type particle size distribution measuring apparatus. The results are shown in Table 1.
＜塗料組成物の調製＞
バインダー樹脂としてアクリル樹脂（三菱レイヨン株式会社製、「ダイヤナールＢＲ−７７」、質量平均分子量６５０００、ガラス転移温度８０℃）１００質量部と、先に得られた架橋樹脂粒子５０質量部と、メチルイソブチルケトン３５０質量部とを混合し、均一になるまで撹拌して、固形分濃度３０質量％の塗料組成物を得た。
<Preparation of coating composition>
As binder resin, acrylic resin (Mitsubishi Rayon Co., Ltd., “Dyanal BR-77”, mass average molecular weight 65000, glass transition temperature 80 ° C.) 100 parts by mass, previously obtained crosslinked resin particles 50 parts by mass, methyl 350 parts by mass of isobutyl ketone was mixed and stirred until uniform to obtain a coating composition having a solid content concentration of 30% by mass.
＜塗膜の形成＞
ＡＢＳ板（５ｃｍ×１５ｃｍ）に、アプリケータを用いて乾燥膜厚が３０μｍになるように塗料組成物を塗布し、室温で１０分間養生した。その後、７０℃で３０分間焼付け乾燥を行い、さらに１日養生して、ＡＢＳ板上に塗膜が形成された積層体（試験片）を得た。
得られた試験片について、以下に示す条件にて耐日焼け止め剤性を評価した。結果を表１に示す。
<Formation of coating film>
The coating composition was applied to an ABS plate (5 cm × 15 cm) using an applicator so that the dry film thickness was 30 μm, and cured at room temperature for 10 minutes. Then, baking drying was performed for 30 minutes at 70 degreeC, and also it cured for 1 day, and obtained the laminated body (test piece) by which the coating film was formed on the ABS board.
About the obtained test piece, sunscreen resistance was evaluated on the conditions shown below. The results are shown in Table 1.
＜耐日焼け止め剤性の評価＞
（外観評価）
試験片の塗膜の表面上に、日焼け止め剤（株式会社資生堂製、「ＡＮＥＳＳＡパーフェクトＵＶサンスクリーンＡＡ」）を０．５ｇ／１００ｃｍ２の量で均一に塗布した。日焼け止め剤を塗布した試験片を強制対流のない電気炉内（炉内温度５５℃）で４時間放置した。その後、少量の中性洗剤を用いて塗膜の表面を十分に洗浄し、乾燥した。乾燥後の試験片の塗膜の表面状態を目視にて観察し、以下の評価基準にて評価した。
○：日焼け止め剤による跡が認められない。
△：日焼け止め剤による跡が認められるものの、膨れ・膨張といった劣化は認められない。
×：膨れ・膨張といった劣化が認められる。
<Evaluation of sunscreen resistance>
(Appearance evaluation)
On the surface of the coating film of the test piece, a sunscreen agent (manufactured by Shiseido Co., Ltd., “ANESSA Perfect UV Sunscreen AA”) was uniformly applied in an amount of 0.5 g / 100 cm 2 . The test piece coated with the sunscreen was left in an electric furnace without forced convection (furnace temperature 55 ° C.) for 4 hours. Thereafter, the surface of the coating film was sufficiently washed with a small amount of neutral detergent and dried. The surface condition of the coating film of the test piece after drying was visually observed and evaluated according to the following evaluation criteria.
○: No trace due to sunscreen.
Δ: Traces due to sunscreen agent are observed, but deterioration such as swelling and swelling is not observed.
X: Deterioration such as swelling and swelling is observed.
（耐摩耗性）
外観評価と同様にして、試験片の塗膜の表面上に日焼け止め剤を塗布し、電気炉内で放置した後、塗膜の表面を洗浄し、乾燥した。
乾燥後の試験片を学振型摩擦堅牢度試験台に固定した。試験片の塗膜の表面に、５枚重ねのガーゼを摩擦子として載置した。該摩擦子を４９ｋＰａの荷重および１００ｍｍのストロークで、塗膜上を２００往復させ、摩擦試験を行った。摩擦試験後の試験片の塗膜の表面状態を目視にて観察し、以下の評価基準にて評価した。
○：塗膜が摩滅していない。
△：塗膜が摩滅しているが、素地（ＡＢＳ板）は露出していない。
×：塗膜が摩滅し、素地（ＡＢＳ板）が露出している。
(Abrasion resistance)
In the same manner as the appearance evaluation, a sunscreen agent was applied on the surface of the coating film of the test piece and left in an electric furnace, and then the surface of the coating film was washed and dried.
The test piece after drying was fixed to a Gakushin type friction fastness test stand. A five-layered gauze was placed as a friction element on the surface of the coating film of the test piece. The friction piece was reciprocated 200 times on the coating film with a load of 49 kPa and a stroke of 100 mm, and a friction test was performed. The surface state of the coating film of the test piece after the friction test was visually observed and evaluated according to the following evaluation criteria.
○: The coating film is not worn.
(Triangle | delta): Although a coating film is worn out, a base material (ABS board) is not exposed.
X: The coating film was worn away and the substrate (ABS plate) was exposed.
［実施例２〜５］
実施例１と同様にして架橋樹脂粒子を製造した。
架橋樹脂粒子の配合量を表１に示すように変更した以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表１に示す。
なお、塗料組成物の固形分濃度が３０質量％となるように、メチルイソブチルケトンの配合量を調節した。
[Examples 2 to 5]
Crosslinked resin particles were produced in the same manner as in Example 1.
Except having changed the compounding quantity of the crosslinked resin particle as shown in Table 1, the coating composition was prepared like Example 1, the coating film was formed, and sunscreen-proof property was evaluated. The results are shown in Table 1.
The blending amount of methyl isobutyl ketone was adjusted so that the solid content concentration of the coating composition was 30% by mass.
［実施例６〜９］
架橋樹脂粒子の平均粒子径が表１、２に示す値となるように、乳化重合時の撹拌速度を変更した以外は、実施例１と同様にして架橋樹脂粒子を製造した。
得られた架橋樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表１、２に示す。
[Examples 6 to 9]
Crosslinked resin particles were produced in the same manner as in Example 1 except that the stirring speed at the time of emulsion polymerization was changed so that the average particle diameter of the crosslinked resin particles became the values shown in Tables 1 and 2.
A coating composition was prepared in the same manner as in Example 1 except that the obtained crosslinked resin particles were used, a coating film was formed, and sunscreen resistance was evaluated. The results are shown in Tables 1 and 2.
［実施例１０］
共重合性単官能モノマーとしてメチルメタクリレート０．４５質量部に代えて、メチルメタクリレート０．１８質量部とｎ−ブチルメタクリレート０．２７質量部とを用いた以外は、実施例１と同様にして共重合性単官能モノマー、アクリル系多官能モノマー、純水、重合開始剤、乳化剤をフラスコに仕込み、さらに窒素を供給して１０分間バブリングを行い、フラスコ内を脱気した。ついで、メチルメタクリレート３５．８２質量部と、ｎ−ブチルメタクリレート５３．７３質量部と、エチレングリコールジメタクリレート９．９５質量部との混合物を１時間かけて滴下した以外は、実施例１と同様にして水性ラテックス、および粉体状の架橋樹脂粒子を得た。
[Example 10]
In the same manner as in Example 1, except that 0.18 parts by mass of methyl methacrylate and 0.27 parts by mass of n-butyl methacrylate were used as the copolymerizable monofunctional monomer instead of 0.45 parts by mass of methyl methacrylate. A polymerizable monofunctional monomer, an acrylic polyfunctional monomer, pure water, a polymerization initiator, and an emulsifier were charged into the flask, and nitrogen was supplied to perform bubbling for 10 minutes to degas the inside of the flask. Then, the same procedure as in Example 1 was conducted except that a mixture of 35.82 parts by mass of methyl methacrylate, 53.73 parts by mass of n-butyl methacrylate, and 9.95 parts by mass of ethylene glycol dimethacrylate was added dropwise over 1 hour. Aqueous latex and powdered crosslinked resin particles were obtained.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度、水性ラテックス中の架橋樹脂粒子の平均粒子径を実施例１と同様にして求めた。結果を表２に示す。なお、ｎ−ブチルメタクリレートの単独重合体（ホモポリマー）のガラス転移温度を２０℃とした。
また、得られた架橋樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表２に示す。
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer and the average particle size of the crosslinked resin particles in the aqueous latex were determined in the same manner as in Example 1. The results are shown in Table 2. The glass transition temperature of the homopolymer of n-butyl methacrylate was 20 ° C.
Moreover, except having used the obtained crosslinked resin particle, the coating composition was prepared like Example 1, the coating film was formed, and sunscreen-proof property was evaluated. The results are shown in Table 2.
［実施例１１］
共重合性単官能モノマーとしてメチルメタクリレート０．４５質量部に代えて、メチルメタクリレート０．２９質量部とｎ−ブチルメタクリレート０．１６質量部とを用いた以外は、実施例１と同様にして共重合性単官能モノマー、アクリル系多官能モノマー、純水、重合開始剤、乳化剤をフラスコに仕込み、さらに窒素を供給して１０分間バブリングを行い、フラスコ内を脱気した。ついで、メチルメタクリレート５８．２１質量部と、ｎ−ブチルメタクリレート３１．３４質量部と、エチレングリコールジメタクリレート９．９５質量部との混合物を１時間かけて滴下した以外は、実施例１と同様にして水性ラテックス、および粉体状の架橋樹脂粒子を得た。
[Example 11]
In the same manner as in Example 1, except that instead of 0.45 parts by mass of methyl methacrylate as a copolymerizable monofunctional monomer, 0.29 parts by mass of methyl methacrylate and 0.16 parts by mass of n-butyl methacrylate were used. A polymerizable monofunctional monomer, an acrylic polyfunctional monomer, pure water, a polymerization initiator, and an emulsifier were charged into the flask, and nitrogen was supplied to perform bubbling for 10 minutes to degas the inside of the flask. Then, the same procedure as in Example 1 was conducted except that a mixture of 58.21 parts by mass of methyl methacrylate, 31.34 parts by mass of n-butyl methacrylate, and 9.95 parts by mass of ethylene glycol dimethacrylate was added dropwise over 1 hour. Aqueous latex and powdered crosslinked resin particles were obtained.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度、水性ラテックス中の架橋樹脂粒子の平均粒子径を実施例１と同様にして求めた。結果を表２に示す。
また、得られた架橋樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表２に示す。
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer and the average particle size of the crosslinked resin particles in the aqueous latex were determined in the same manner as in Example 1. The results are shown in Table 2.
Moreover, except having used the obtained crosslinked resin particle, the coating composition was prepared like Example 1, the coating film was formed, and sunscreen-proof property was evaluated. The results are shown in Table 2.
［実施例１２］
共重合性単官能モノマーとしてメチルメタクリレート（ＭＭＡ）０．４５質量部に代えて、メチルメタクリレート０．２９質量部とイソボルニルメタクリレート０．１６質量部とを用いた以外は、実施例１と同様にして共重合性単官能モノマー、アクリル系多官能モノマー、純水、重合開始剤、乳化剤をフラスコに仕込み、さらに窒素を供給して１０分間バブリングを行い、フラスコ内を脱気した。ついで、メチルメタクリレート５８．２１質量部と、イソボルニルメタクリレート３１．３４質量部と、エチレングリコールジメタクリレート９．９５質量部との混合物を１時間かけて滴下した以外は、実施例１と同様にして水性ラテックス、および粉体状の架橋樹脂粒子を得た。
[Example 12]
The same as Example 1 except that instead of 0.45 parts by mass of methyl methacrylate (MMA) as a copolymerizable monofunctional monomer, 0.29 parts by mass of methyl methacrylate and 0.16 parts by mass of isobornyl methacrylate were used. Then, a copolymerizable monofunctional monomer, an acrylic polyfunctional monomer, pure water, a polymerization initiator, and an emulsifier were charged into the flask, and nitrogen was supplied for bubbling for 10 minutes to degas the inside of the flask. Subsequently, the same procedure as in Example 1 was conducted except that a mixture of 58.21 parts by mass of methyl methacrylate, 31.34 parts by mass of isobornyl methacrylate, and 9.95 parts by mass of ethylene glycol dimethacrylate was added dropwise over 1 hour. Aqueous latex and powdered crosslinked resin particles were obtained.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度、水性ラテックス中の架橋樹脂粒子の平均粒子径を実施例１と同様にして求めた。結果を表２に示す。なお、イソボルニルメタクリレートの単独重合体（ホモポリマー）のガラス転移温度を１５５℃とした。
また、得られた架橋樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表２に示す。
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer and the average particle size of the crosslinked resin particles in the aqueous latex were determined in the same manner as in Example 1. The results are shown in Table 2. The glass transition temperature of the homopolymer of isobornyl methacrylate was 155 ° C.
Moreover, except having used the obtained crosslinked resin particle, the coating composition was prepared like Example 1, the coating film was formed, and sunscreen-proof property was evaluated. The results are shown in Table 2.
［実施例１３］
共重合性単官能モノマーとしてメチルメタクリレート０．４５質量部に代えて、メチルメタクリレート０．２３質量部とイソボルニルメタクリレート０．２３質量部とを用いた以外は、実施例１と同様にして共重合性単官能モノマー、アクリル系多官能モノマー、純水、重合開始剤、乳化剤をフラスコに仕込み、さらに窒素を供給して１０分間バブリングを行い、フラスコ内を脱気した。ついで、メチルメタクリレート４４．７７質量部と、イソボルニルメタクリレート４４．７７質量部と、エチレングリコールジメタクリレート９．９５質量部との混合物を１時間かけて滴下した以外は、実施例１と同様にして水性ラテックス、および粉体状の架橋樹脂粒子を得た。
[Example 13]
In the same manner as in Example 1, except that 0.23 parts by mass of methyl methacrylate and 0.23 parts by mass of isobornyl methacrylate were used as the copolymerizable monofunctional monomer instead of 0.45 parts by mass of methyl methacrylate. A polymerizable monofunctional monomer, an acrylic polyfunctional monomer, pure water, a polymerization initiator, and an emulsifier were charged into the flask, and nitrogen was supplied to perform bubbling for 10 minutes to degas the inside of the flask. Then, the same procedure as in Example 1 was conducted except that a mixture of 44.77 parts by mass of methyl methacrylate, 44.77 parts by mass of isobornyl methacrylate, and 9.95 parts by mass of ethylene glycol dimethacrylate was added dropwise over 1 hour. Aqueous latex and powdered crosslinked resin particles were obtained.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度、水性ラテックス中の架橋樹脂粒子の平均粒子径を実施例１と同様にして求めた。結果を表２に示す。
また、得られた架橋樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表２に示す。
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer and the average particle size of the crosslinked resin particles in the aqueous latex were determined in the same manner as in Example 1. The results are shown in Table 2.
Moreover, except having used the obtained crosslinked resin particle, the coating composition was prepared like Example 1, the coating film was formed, and sunscreen-proof property was evaluated. The results are shown in Table 2.
［比較例１］
バインダー樹脂としてアクリル樹脂（三菱レイヨン株式会社製、「ダイヤナールＢＲ−７７」、質量平均分子量６５０００、ガラス転移温度８０℃）１００質量部と、メチルイソブチルケトン２３３質量部とを混合し、均一になるまで撹拌して、固形分濃度３０質量％の塗料組成物を得た。
得られた塗料組成物を用いた以外は、実施例１と同様にして塗膜を形成し、耐日焼け止め剤性を評価した。結果を表３に示す。
[Comparative Example 1]
As a binder resin, 100 parts by mass of acrylic resin (Mitsubishi Rayon Co., Ltd., “Dianar BR-77”, mass average molecular weight 65000, glass transition temperature 80 ° C.) and 233 parts by mass of methyl isobutyl ketone are mixed to be uniform. To obtain a coating composition having a solid content concentration of 30% by mass.
A coating film was formed in the same manner as in Example 1 except that the obtained coating composition was used, and the sunscreen resistance was evaluated. The results are shown in Table 3.
［比較例２］
実施例１と同様にして架橋樹脂粒子を製造した。
バインダー樹脂としてアクリル樹脂（三菱レイヨン株式会社製、「ダイヤナールＢＲ−７７」、質量平均分子量６５０００、ガラス転移温度８０℃）１００質量部と、架橋樹脂粒子５００質量部と、メチルイソブチルケトン１４００質量部とを混合し、均一になるまで撹拌して、固形分濃度３０質量％の塗料組成物を得た。
得られた塗料組成物を用い、実施例１と同様にして塗膜を形成しようとしたが、成膜性に劣り、均一な塗膜を形成できなかった。よって、耐日焼け止め剤性の評価には値せずとし、耐日焼け止め剤性の評価は行わなかった。
[Comparative Example 2]
Crosslinked resin particles were produced in the same manner as in Example 1.
As binder resin, 100 parts by mass of acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., “Dianar BR-77”, mass average molecular weight 65000, glass transition temperature 80 ° C.), 500 parts by mass of crosslinked resin particles, and 1400 parts by mass of methyl isobutyl ketone Were mixed until they became uniform to obtain a coating composition having a solid content concentration of 30% by mass.
An attempt was made to form a coating film using the obtained coating composition in the same manner as in Example 1, but the film-forming property was inferior, and a uniform coating film could not be formed. Therefore, it was not worthy of the evaluation of sunscreen resistance, and sunscreen resistance was not evaluated.
［比較例３］
架橋樹脂粒子の平均粒子径が５ｎｍとなるように、乳化重合時の撹拌速度を変更した以外は、実施例１と同様にして架橋樹脂粒子を製造しようとしたが、平均粒子径が５ｎｍ架橋樹脂粒子は得られなかった。
[Comparative Example 3]
An attempt was made to produce crosslinked resin particles in the same manner as in Example 1 except that the stirring speed during the emulsion polymerization was changed so that the average particle diameter of the crosslinked resin particles was 5 nm, but the average particle diameter was 5 nm. Particles were not obtained.
［比較例４］
架橋樹脂粒子の平均粒子径が７００ｎｍとなるように、乳化重合時の撹拌速度を変更した以外は、実施例１と同様にして架橋樹脂粒子を製造した。
得られた架橋樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表３に示す。
[Comparative Example 4]
Crosslinked resin particles were produced in the same manner as in Example 1 except that the stirring speed during emulsion polymerization was changed so that the average particle diameter of the crosslinked resin particles was 700 nm.
A coating composition was prepared in the same manner as in Example 1 except that the obtained crosslinked resin particles were used, a coating film was formed, and sunscreen resistance was evaluated. The results are shown in Table 3.
［比較例５］
共重合性単官能モノマーとしてメチルメタクリレート０．４５質量部に代えて、メチルメタクリレート０．０７質量部とｎ−ブチルメタクリレート０．３８質量部とを用いた以外は、実施例１と同様にして共重合性単官能モノマー、アクリル系多官能モノマー、純水、重合開始剤、乳化剤をフラスコに仕込み、さらに窒素を供給して１０分間バブリングを行い、フラスコ内を脱気した。ついで、メチルメタクリレート１３．４３質量部と、ｎ−ブチルメタクリレート７６．１２質量部と、エチレングリコールジメタクリレート９．９５質量部との混合物を１時間かけて滴下した以外は、実施例１と同様にして水性ラテックス、および粉体状の架橋樹脂粒子を得た。
[Comparative Example 5]
In the same manner as in Example 1, except that 0.07 parts by mass of methyl methacrylate and 0.38 parts by mass of n-butyl methacrylate were used as the copolymerizable monofunctional monomer instead of 0.45 parts by mass of methyl methacrylate. A polymerizable monofunctional monomer, an acrylic polyfunctional monomer, pure water, a polymerization initiator, and an emulsifier were charged into the flask, and nitrogen was supplied to perform bubbling for 10 minutes to degas the inside of the flask. Subsequently, the same procedure as in Example 1 was performed except that a mixture of 13.43 parts by mass of methyl methacrylate, 76.12 parts by mass of n-butyl methacrylate, and 9.95 parts by mass of ethylene glycol dimethacrylate was added dropwise over 1 hour. Aqueous latex and powdered crosslinked resin particles were obtained.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度、水性ラテックス中の架橋樹脂粒子の平均粒子径を実施例１と同様にして求めた。結果を表３に示す。
また、得られた架橋樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表３に示す。
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer and the average particle size of the crosslinked resin particles in the aqueous latex were determined in the same manner as in Example 1. The results are shown in Table 3.
Moreover, except having used the obtained crosslinked resin particle, the coating composition was prepared like Example 1, the coating film was formed, and sunscreen-proof property was evaluated. The results are shown in Table 3.
［比較例６］
共重合性単官能モノマーとしてメチルメタクリレート０．４５質量部に代えて、メチルメタクリレート０．０５質量部とイソボルニルメタクリレート０．４質量部とを用いた以外は、実施例１と同様にして共重合性単官能モノマー、アクリル系多官能モノマー、純水、重合開始剤、乳化剤をフラスコに仕込み、さらに窒素を供給して１０分間バブリングを行い、フラスコ内を脱気した。ついで、メチルメタクリレート８．９５質量部と、イソボルニルメタクリレート８０．６質量部と、エチレングリコールジメタクリレート９．９５質量部との混合物を１時間かけて滴下した以外は、実施例１と同様にして水性ラテックス、および粉体状の架橋樹脂粒子を得た。
[Comparative Example 6]
Copolymerization was performed in the same manner as in Example 1 except that 0.05 mass part of methyl methacrylate and 0.4 mass part of isobornyl methacrylate were used in place of 0.45 mass part of methyl methacrylate as a copolymerizable monofunctional monomer. A polymerizable monofunctional monomer, an acrylic polyfunctional monomer, pure water, a polymerization initiator, and an emulsifier were charged into the flask, and nitrogen was supplied to perform bubbling for 10 minutes to degas the inside of the flask. Then, the same procedure as in Example 1 was conducted except that a mixture of 8.95 parts by mass of methyl methacrylate, 80.6 parts by mass of isobornyl methacrylate, and 9.95 parts by mass of ethylene glycol dimethacrylate was added dropwise over 1 hour. Aqueous latex and powdered crosslinked resin particles were obtained.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度、水性ラテックス中の架橋樹脂粒子の平均粒子径を実施例１と同様にして求めた。結果を表３に示す。
また、得られた架橋樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表３に示す。
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer and the average particle size of the crosslinked resin particles in the aqueous latex were determined in the same manner as in Example 1. The results are shown in Table 3.
Moreover, except having used the obtained crosslinked resin particle, the coating composition was prepared like Example 1, the coating film was formed, and sunscreen-proof property was evaluated. The results are shown in Table 3.
［比較例７］
アクリル系多官能モノマーを用いなかった以外は、実施例１と同様にして粉体状の非架橋の樹脂粒子を製造した。
[Comparative Example 7]
Powdered non-crosslinked resin particles were produced in the same manner as in Example 1 except that the acrylic polyfunctional monomer was not used.
共重合性単官能モノマーを重合して得られる重合体のガラス転移温度、水性ラテックス中の非架橋の樹脂粒子の平均粒子径を実施例１と同様にして求めた。結果を表３に示す。
また、得られた非架橋の樹脂粒子を用いた以外は、実施例１と同様にして塗料組成物を調製し、塗膜を形成し、耐日焼け止め剤性を評価した。結果を表３に示す。
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer and the average particle size of the non-crosslinked resin particles in the aqueous latex were determined in the same manner as in Example 1. The results are shown in Table 3.
Further, a coating composition was prepared in the same manner as in Example 1 except that the obtained non-crosslinked resin particles were used, a coating film was formed, and sunscreen resistance was evaluated. The results are shown in Table 3.
［比較例８］
バインダー樹脂としてアクリル樹脂（三菱レイヨン株式会社製、「ダイヤナールＢＲ−７７」、質量平均分子量６５０００、ガラス転移温度８０℃）１００質量部と、ニトロセルロース（稲畑産業株式会社製、「ＤＨＸ５−１０」）１００質量部と、セルロースアセテートブチレート（イーストマンケミカル社製、「ＣＡＢ−３８１−２０」）１００質量部と、メチルイソブチルケトン７００質量部とを混合し、均一になるまで撹拌して、固形分濃度３０質量％の塗料組成物を得た。
得られた塗料組成物を用いた以外は、実施例１と同様にして塗膜を形成し、耐日焼け止め剤性を評価した。結果を表３に示す。
[Comparative Example 8]
As binder resin, acrylic resin (Mitsubishi Rayon Co., Ltd., “Dianar BR-77”, mass average molecular weight 65000, glass transition temperature 80 ° C.) 100 parts by mass, nitrocellulose (Inabata Sangyo Co., Ltd., “DHX5-10”) ) 100 parts by weight, 100 parts by weight of cellulose acetate butyrate (manufactured by Eastman Chemical Co., “CAB-381-20”) and 700 parts by weight of methyl isobutyl ketone are mixed and stirred until uniform. A coating composition having a partial concentration of 30% by mass was obtained.
A coating film was formed in the same manner as in Example 1 except that the obtained coating composition was used, and the sunscreen resistance was evaluated. The results are shown in Table 3.
表１〜３中の「ガラス転移温度」は、共重合性単官能モノマーを重合して得られる重合体のガラス転移温度である。
また、表１〜３中の略号は下記化合物を示す。なお、各単量体のカッコ内のＴｇは、ホモポリマーのＴｇである。
「ＭＭＡ」：メチルメタクリレート（Ｔｇ：１０５℃）、
「ｎ−ＢＭＡ」：ｎ−ブチルメタクリレート（Ｔｇ：２０℃）、
「ＩＢＸＭＡ」：イソボルニルメタクリレート（Ｔｇ：１５５℃）、
「ＥＧＤＭＡ」：エチレングリコールジメタクリレート。
“Glass transition temperature” in Tables 1 to 3 is a glass transition temperature of a polymer obtained by polymerizing a copolymerizable monofunctional monomer.
Moreover, the symbol in Tables 1-3 shows the following compound. In addition, Tg in parentheses of each monomer is Tg of a homopolymer.
“MMA”: methyl methacrylate (Tg: 105 ° C.),
“N-BMA”: n-butyl methacrylate (Tg: 20 ° C.),
“IBXMA”: isobornyl methacrylate (Tg: 155 ° C.),
“EGDMA”: ethylene glycol dimethacrylate.
表１〜３から明らかなように、各実施例で得られた塗料組成物は、耐日焼け止め剤性に優れた塗膜を形成できた。
一方、架橋樹脂粒子を含有しない比較例１の塗料組成物より得られた塗膜は、耐日焼け止め剤性に劣っていた。
架橋樹脂粒子の平均粒子径が７００ｎｍである比較例４の塗料組成物より得られた塗膜は、耐日焼け止め剤性に劣っていた。
架橋樹脂粒子のガラス転移温度が３０℃である比較例５の塗料組成物より得られた塗膜、および架橋樹脂粒子のガラス転移温度が１５０℃である比較例６の塗料組成物より得られた塗膜は、耐日焼け止め剤性に劣っていた。
非架橋の樹脂粒子を含有する比較例７の塗料組成物より得られた塗膜は、耐日焼け止め剤性に劣っていた。
架橋樹脂粒子の代わりにセルロース誘導体を含有する比較例８の塗料組成物より得られた塗膜は、耐日焼け止め剤性に劣っていた。
As is apparent from Tables 1 to 3, the coating compositions obtained in each Example were able to form a coating film having excellent sunscreen resistance.
On the other hand, the coating film obtained from the coating composition of Comparative Example 1 containing no crosslinked resin particles was inferior in sunscreen resistance.
The coating film obtained from the coating composition of Comparative Example 4 in which the average particle diameter of the crosslinked resin particles was 700 nm was inferior in sunscreen resistance.
The coating film obtained from the coating composition of Comparative Example 5 in which the glass transition temperature of the crosslinked resin particles was 30 ° C. and the coating composition of Comparative Example 6 in which the glass transition temperature of the crosslinked resin particles was 150 ° C. The coating film was inferior in sunscreen resistance.
The coating film obtained from the coating composition of Comparative Example 7 containing non-crosslinked resin particles was inferior in sunscreen resistance.
The coating film obtained from the coating composition of Comparative Example 8 containing a cellulose derivative instead of the crosslinked resin particles was inferior in sunscreen resistance.
なお、上述したように、架橋樹脂粒子の配合量が５００質量部である比較例２の塗料組成物は造膜性に劣っていたため、耐日焼け止め剤性の評価には値せずとし、耐日焼け止め剤性の評価は行わなかった。
平均粒子径が５ｎｍの架橋樹脂粒子は製造できなかったため、比較例３は耐日焼け止め剤性の評価ができなかった。
As described above, since the coating composition of Comparative Example 2 in which the blended amount of the crosslinked resin particles was 500 parts by mass was inferior in film-forming property, it was not worthy of evaluation of sunscreen resistance, Sunscreen properties were not evaluated.
Since crosslinked resin particles having an average particle diameter of 5 nm could not be produced, Comparative Example 3 was unable to evaluate sunscreen resistance.
Claims (2)
前記バインダー樹脂がアクリル樹脂であり、
前記架橋樹脂粒子が、共重合性単官能モノマーとアクリル系多官能モノマーとを共重合した共重合体であり、
前記共重合性単官能モノマーを重合して得られる重合体のガラス転移温度が５０〜１３０℃であり、
前記架橋樹脂粒子の平均粒子径が１０〜５００ｎｍであり、
前記架橋樹脂粒子の含有量が、前記バインダー樹脂１００質量部に対して３０〜４００質量部である、塗料組成物。 A coating composition containing a binder resin and crosslinked resin particles (excluding those having a refractive index of 1.45 or less),
The binder resin is an acrylic resin;
The crosslinked resin particles are a copolymer obtained by copolymerizing a copolymerizable monofunctional monomer and an acrylic polyfunctional monomer,
The glass transition temperature of the polymer obtained by polymerizing the copolymerizable monofunctional monomer is 50 to 130 ° C.,
The crosslinked resin particles have an average particle size of 10 to 500 nm,
The content of the crosslinked resin particles is 30 to 400 parts by weight with respect to the binder resin 100 parts by weight of the coating composition.
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