JP5864678B2 - paint - Google Patents
paint Download PDFInfo
- Publication number
- JP5864678B2 JP5864678B2 JP2014139585A JP2014139585A JP5864678B2 JP 5864678 B2 JP5864678 B2 JP 5864678B2 JP 2014139585 A JP2014139585 A JP 2014139585A JP 2014139585 A JP2014139585 A JP 2014139585A JP 5864678 B2 JP5864678 B2 JP 5864678B2
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin resin
- chlorinated polyolefin
- acrylic
- resin
- weight ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000003973 paint Substances 0.000 title claims description 64
- 229920005672 polyolefin resin Polymers 0.000 claims description 89
- 239000011248 coating agent Substances 0.000 claims description 80
- 238000000576 coating method Methods 0.000 claims description 80
- 239000003960 organic solvent Substances 0.000 claims description 68
- 229920005989 resin Polymers 0.000 claims description 65
- 239000011347 resin Substances 0.000 claims description 65
- 239000002245 particle Substances 0.000 claims description 64
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 38
- 239000010419 fine particle Substances 0.000 claims description 25
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 24
- 239000000194 fatty acid Substances 0.000 claims description 24
- 229930195729 fatty acid Natural products 0.000 claims description 24
- 150000004665 fatty acids Chemical class 0.000 claims description 24
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 19
- 229920000058 polyacrylate Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000002576 ketones Chemical class 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 230000009974 thixotropic effect Effects 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000010559 graft polymerization reaction Methods 0.000 claims description 4
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 36
- 239000000463 material Substances 0.000 description 28
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- 238000011156 evaluation Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 17
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 16
- 229920000098 polyolefin Polymers 0.000 description 16
- -1 polypropylene Polymers 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000000049 pigment Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000004606 Fillers/Extenders Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 210000002374 sebum Anatomy 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 5
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-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
- 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
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N isobutyl acetate Chemical compound CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NLAUYBDMLQNGCO-UHFFFAOYSA-N (2-methoxyphenyl) 2-methylprop-2-enoate Chemical compound COC1=CC=CC=C1OC(=O)C(C)=C NLAUYBDMLQNGCO-UHFFFAOYSA-N 0.000 description 1
- NCPCSICMICIMCE-UHFFFAOYSA-N (3-methoxyphenyl) 2-methylprop-2-enoate Chemical compound COC1=CC=CC(OC(=O)C(C)=C)=C1 NCPCSICMICIMCE-UHFFFAOYSA-N 0.000 description 1
- WIZMCLXMWBKNKH-UHFFFAOYSA-N (4-methoxyphenyl) 2-methylprop-2-enoate Chemical compound COC1=CC=C(OC(=O)C(C)=C)C=C1 WIZMCLXMWBKNKH-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241000238633 Odonata Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-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-COPLHBTASA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 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
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Description
本発明は、エステル系有機溶媒、ケトン系有機溶媒、アルコール系有機溶媒、および非芳香族炭化水素系有機溶媒のうちの１種以上から構成される有機溶媒を用いた塗料、言い換えると、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素を含有しない有機溶媒を用いた塗料に関するものである。 The present invention relates to a paint using an organic solvent composed of one or more of an ester organic solvent, a ketone organic solvent, an alcohol organic solvent, and a non-aromatic hydrocarbon organic solvent, in other words, toluene, The present invention relates to a coating material using an organic solvent not containing aromatic hydrocarbons such as xylene and ethylbenzene.
自動車部品などに使用されるポリプロピレン等のポリオレフィン基材には、意匠性の付与や表面保護の目的で塗料による塗装が行われている。この塗料には、前記樹脂基材との付着性を向上させるために、バインダーとして塩素化ポリオレフィン系樹脂が使用される。ここで、この塩素化ポリオレフィン系樹脂は、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素に良好な溶解性を示すことから、塗料には多量の芳香族炭化水素が含まれている。 Polyolefin substrates such as polypropylene used for automobile parts and the like are coated with a paint for the purpose of imparting design properties and protecting the surface. In this coating material, a chlorinated polyolefin resin is used as a binder in order to improve adhesion to the resin base material. Here, since the chlorinated polyolefin resin exhibits good solubility in aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, the paint contains a large amount of aromatic hydrocarbons.
しかし、近年、特定の有機溶媒の使用および排出については、世界的に規制が厳しくなる傾向にあり、日本も例外ではない。具体的には、日本では、トルエン、キシレン、エチルベンゼンを始めとした芳香族炭化水素等の有機溶媒が室内放出された際の濃度（室内濃度）の指針値が定められている。
上記事情を勘案し、当該指針値が示されている芳香族炭化水素の有機溶媒を含まない塗料の創出・開発が望まれている。
However, in recent years, the use and discharge of specific organic solvents have been stricter worldwide, and Japan is no exception. Specifically, in Japan, a guide value is set for the concentration (indoor concentration) when organic solvents such as aromatic hydrocarbons such as toluene, xylene, and ethylbenzene are released indoors.
In view of the above circumstances, it is desired to create and develop a paint that does not contain an aromatic hydrocarbon organic solvent for which the guideline value is shown.
なお、現在、塗料に関して、以下のような様々な技術が存在する。
例えば、特許文献１には、有機溶媒に、アクリル変性塩素化ポリプロピレン等を含むバインダー樹脂と、ウレタン樹脂粒子と、を含有させた塗料が開示されている。
また、特許文献２には、有機溶媒に、塩素化ポリオレフィンと、重合性不飽和二重結合を２つ以上有する単量体の重合体と、を含有させた塗料が開示されている。
また、特許文献３には、多孔質性の樹脂粒子と、アクリル系重合体変性塩素化ポリプロピレンを含む変性塩素化ポリプロピレン樹脂の水性エマルションを混合し、分散させた水性分散液を含有することを特徴とする水系塗料が開示されている。
Currently, there are various technologies related to paints as follows.
For example, Patent Document 1 discloses a paint in which an organic solvent contains a binder resin containing acrylic-modified chlorinated polypropylene and the like, and urethane resin particles.
Patent Document 2 discloses a paint in which an organic solvent contains a chlorinated polyolefin and a polymer of a monomer having two or more polymerizable unsaturated double bonds.
Patent Document 3 includes an aqueous dispersion in which porous resin particles and an aqueous emulsion of a modified chlorinated polypropylene resin containing an acrylic polymer-modified chlorinated polypropylene are mixed and dispersed. A water-based paint is disclosed.
しかしながら、特許文献１に開示された塗料は、基材に対する付着性および得られる塗膜の耐傷付き性の向上を課題とした技術であり、トルエン等の芳香族炭化水素の有機溶媒を含まないようにするという観点から創出された技術ではない。よって、特許文献１に開示された塗料に含まれる物質および当該物質の含有量は、当然、前記観点（トルエン等の芳香族炭化水素の有機溶媒を含まない）を考慮して決定されていない以上、特許文献１に開示された塗料は、この点に関して十分に対応することができない。これは、特許文献１に開示された塗料が、溶媒としてトルエンを用いていることからも明らかである（特許文献１の段落００３２、００４０参照）。 However, the paint disclosed in Patent Document 1 is a technique for improving adhesion to a substrate and scratch resistance of the resulting coating film, and does not include an organic solvent of an aromatic hydrocarbon such as toluene. It is not a technology created from the viewpoint of making it. Therefore, the substance contained in the paint disclosed in Patent Document 1 and the content of the substance are naturally not determined in consideration of the above viewpoint (not including an organic solvent of aromatic hydrocarbon such as toluene). The paint disclosed in Patent Document 1 cannot sufficiently cope with this point. This is clear from the fact that the paint disclosed in Patent Document 1 uses toluene as a solvent (see paragraphs 0032 and 0040 of Patent Document 1).
特許文献２に開示された塗料は、トルエン等の芳香族炭化水素以外の有機溶媒を用いてワニス化（＝顔料を加えず、樹脂を溶剤に溶解すること）しても安定性に問題はないが、顔料や粘度調整剤等を加えて一般的な塗料性状に調整した場合には、相分離や凝集物の発生が起こってしまい、塗装時の可使範囲が極端に狭くなってしまう。 The paint disclosed in Patent Document 2 has no problem in stability even if it is varnished using an organic solvent other than an aromatic hydrocarbon such as toluene (= adding a pigment and dissolving the resin in the solvent). However, when a pigment or a viscosity modifier is added to adjust to a general paint property, phase separation or agglomeration occurs, and the usable range at the time of coating becomes extremely narrow.
特許文献３に開示された塗料は、そもそも水系塗料であることから、有機溶媒を用いる塗料とは全く分野が異なる。この水系塗料は、水を溶媒として使用するものであることから、トルエン等の芳香族炭化水素の有機溶媒を含まないという点では好ましいが、管理条件（温度・湿度等）が非常に厳しいとともに、塗料の安定性が良くないことから取り扱いが難しく、その結果、塗装の作業性について、有機溶媒を用いる塗料と比較して劣ってしまう。 Since the paint disclosed in Patent Document 3 is originally a water-based paint, the field is completely different from a paint using an organic solvent. Since this water-based paint uses water as a solvent, it is preferable in that it does not contain an organic solvent for aromatic hydrocarbons such as toluene, but the management conditions (temperature, humidity, etc.) are very strict, Since the stability of the paint is not good, it is difficult to handle, and as a result, the workability of painting is inferior to that of a paint using an organic solvent.
そこで、本発明は、エステル系有機溶媒、ケトン系有機溶媒、アルコール系有機溶媒、および非芳香族炭化水素系有機溶媒のうちの１種以上から構成される有機溶媒を用いた塗料、言い換えると、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素を含有しない有機溶媒を用いた塗料であって、ポリオレフィン基材に塗膜として塗装した際、優れた付着性を有するとともに、耐傷付き性を向上させる塗料を提供することを課題とする。 Therefore, the present invention is a paint using an organic solvent composed of one or more of an ester organic solvent, a ketone organic solvent, an alcohol organic solvent, and a non-aromatic hydrocarbon organic solvent, in other words, A paint that uses an organic solvent that does not contain aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, and has excellent adhesion and improves scratch resistance when applied to a polyolefin substrate as a coating film It is an issue to provide.
前記課題を解決するために、本発明に係る塗料は、エステル系有機溶媒、ケトン系有機溶媒、アルコール系有機溶媒、および非芳香族炭化水素系有機溶媒のうちの１種以上から構成される有機溶媒と、アクリル変性塩素化ポリオレフィン樹脂（Ａ）と、多孔質性の樹脂粒子（Ｂ）と、脂肪酸アミド（Ｃ）と、を含み、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）と前記脂肪酸アミド（Ｃ）との合計１００ｗｔ％に対して、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率は９３．４〜９７．５ｗｔ％、前記脂肪酸アミド（Ｃ）の重量比率は２．５〜６．６ｗｔ％であり、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）と、前記多孔質性の樹脂粒子（Ｂ）との合計１００ｗｔ％に対して、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率は、６２．５〜９１．０ｗｔ％、前記多孔質性の樹脂粒子（Ｂ）の重量比率は、９．０〜３７．５ｗｔ％であり、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）は、塩素化ポリオレフィン樹脂（ａ１）と、アクリル系重合体（ａ３）と、から構成されるとともに、当該アクリル系重合体（ａ３）は、前記塩素化ポリオレフィン樹脂（ａ１）にアクリル系単量体（ａ２）をグラフト重合して得られるグラフト重合鎖であり、前記塩素化ポリオレフィン樹脂（ａ１）と前記アクリル系重合体（ａ３）との合計１００ｗｔ％に対して、前記塩素化ポリオレフィン樹脂（ａ１）の重量比率は５．０〜１５．０ｗｔ％、前記アクリル系重合体（ａ３）の重量比率は８５．０〜９５．０ｗｔ％であり、前記多孔質性の樹脂粒子（Ｂ）は、アクリル系単量体および塩素化ポリオレフィン樹脂が重合した樹脂（ｂ１）から構成されるものであり、Ｂ型粘度計で測定したＴｈｉｘｏｔｒｏｐｉｃ Ｉｎｄｅｘ（ＴＩ値＝塗料温度２５℃で回転数６ｒｐｍにおける粘度／塗料温度２５℃で回転数６０ｒｐｍにおける粘度）が２．５〜５．０であることを特徴とする。 In order to solve the above-mentioned problems, the paint according to the present invention is an organic material composed of one or more of an ester organic solvent, a ketone organic solvent, an alcohol organic solvent, and a non-aromatic hydrocarbon organic solvent. A solvent, an acrylic-modified chlorinated polyolefin resin (A), porous resin particles (B), and a fatty acid amide (C), the acrylic-modified chlorinated polyolefin resin (A) and the fatty acid amide ( The weight ratio of the acrylic-modified chlorinated polyolefin resin (A) is 93.4 to 97.5 wt%, and the weight ratio of the fatty acid amide (C) is 2.5 to 6. 6 wt%, and the total amount of the acrylic modified chlorinated polyolefin resin (A) and the porous resin particles (B) is 100 wt%. The weight ratio of the fin resin (A) is 62.5 to 91.0 wt%, the weight ratio of the porous resin particles (B) is 9.0 to 37.5 wt%, and the acrylic modified chlorination The polyolefin resin (A) is composed of a chlorinated polyolefin resin (a1) and an acrylic polymer (a3), and the acrylic polymer (a3) is added to the chlorinated polyolefin resin (a1). A graft polymerization chain obtained by graft polymerization of an acrylic monomer (a2), and the chlorination is performed with respect to a total of 100 wt% of the chlorinated polyolefin resin (a1) and the acrylic polymer (a3). The weight ratio of the polyolefin resin (a1) is 5.0 to 15.0 wt%, and the weight ratio of the acrylic polymer (a3) is 85.0 to 95.0 wt%. Particles (B) are those composed of A acrylic monomers and chlorinated polyolefin resin is polymerized resin (b1), Thixotropic was measured by a B type viscometer Index (TI value = paint temperature 25 ° C. The viscosity at a rotational speed of 6 rpm / the viscosity at a coating temperature of 25 ° C. and a rotational speed of 60 rpm is 2.5 to 5.0.
本発明に係る塗料によれば、アクリル変性塩素化ポリオレフィン樹脂（Ａ）と、多孔質性の樹脂粒子（Ｂ）と、脂肪酸アミド（Ｃ）と、を含んでいることから、有機溶媒として、エステル系有機溶媒、ケトン系有機溶媒、アルコール系有機溶媒、および非芳香族炭化水素系有機溶媒のうちの１種以上から構成される有機溶媒を使用する場合であっても、言い換えると、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素を含有しない有機溶媒を使用する場合であっても、ポリオレフィン基材に塗膜として塗装した際、優れた付着性を有するとともに、耐傷付き性を向上させることができる。
そして、本発明に係る塗料は、多孔質性の樹脂粒子（Ｂ）を含んでいることから、塗膜を形成させた場合、艶消し効果を得ることができる。
また、この塗料によれば、塩素化ポリオレフィン樹脂（ａ１）と、アクリル系重合体（ａ３）と、の重量比率を所定範囲とすることにより、基材に対する付着性の向上を確実なものとしつつ、得られる塗膜の耐水付着性等の性能についても向上させることができる。
また、この塗料によれば、アクリル変性塩素化ポリオレフィン樹脂（Ａ）と多孔質性の樹脂粒子（Ｂ）との重量比率を所定範囲とすることにより、基材に対する付着性の向上を確実なものとしつつ、艶消し効果を十分に得ることができる。
また、この塗料によれば、アクリル変性塩素化ポリオレフィン樹脂（Ａ）と脂肪酸アミド（Ｃ）との重量比率を所定範囲とすることにより、塗料の揺変性の効果をより確実なものとすることができる。
また、この塗料によれば、ＴＩ値を所定範囲とすることにより、塗料の安定性（貯蔵安定性）を確実なものとするとともに、塗装作業性についても確保することができる。
According to the coating material of the present invention, since it contains the acrylic-modified chlorinated polyolefin resin (A), the porous resin particles (B), and the fatty acid amide (C), the organic solvent is an ester. Even when using an organic solvent composed of one or more of organic organic solvents, ketone organic solvents, alcohol organic solvents, and non-aromatic hydrocarbon organic solvents, in other words, toluene, xylene Even when using an organic solvent that does not contain an aromatic hydrocarbon such as ethylbenzene, when coated as a coating film on a polyolefin substrate, it has excellent adhesion and can improve scratch resistance. .
And since the coating material which concerns on this invention contains the porous resin particle (B), when a coating film is formed, the matte effect can be acquired.
Moreover, according to this coating material, by making the weight ratio of chlorinated polyolefin resin (a1) and acrylic polymer (a3) into a predetermined range, while ensuring the improvement of the adhesiveness with respect to a base material, The performance of the resulting coating film, such as water resistance adhesion, can also be improved.
Moreover, according to this coating material, the adhesiveness with respect to a base material is reliably improved by making the weight ratio of acrylic modified chlorinated polyolefin resin (A) and porous resin particles (B) into a predetermined range. In addition, the matte effect can be sufficiently obtained.
Moreover, according to this coating material, by making the weight ratio of the acrylic modified chlorinated polyolefin resin (A) and the fatty acid amide (C) within a predetermined range, the effect of the thixotropic property of the coating material can be further ensured. it can.
Further, according to this paint, by setting the TI value within a predetermined range, it is possible to ensure the stability (storage stability) of the paint and to ensure the coating workability.
また、本発明に係る塗料は、前記脂肪酸アミド（Ｃ）は、炭素数４〜１８の飽和脂肪酸アミド、炭素数４〜１８の不飽和脂肪酸アミドおよびこれらの誘導体のうちのそれぞれ単独、もしくは２種以上混合されたものであることが好ましい。 In the coating material according to the present invention, the fatty acid amide (C) is a saturated fatty acid amide having 4 to 18 carbon atoms, an unsaturated fatty acid amide having 4 to 18 carbon atoms, or a derivative thereof. A mixture of the above is preferable.
この塗料によれば、所定の脂肪酸アミド（Ｃ）を含有させることにより、塗料の揺変性の効果を確実なものとすることができる。 According to this paint, the thixotropic effect of the paint can be ensured by containing the predetermined fatty acid amide (C).
また、本発明に係る塗料は、ポリメチルシルセスキオキサン微粒子（Ｄ）をさらに含むとともに、前記ポリメチルシルセスキオキサン微粒子（Ｄ）の平均粒子径は、１．０〜５．０μｍであり、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）と前記ポリメチルシルセスキオキサン微粒子（Ｄ）との合計１００ｗｔ％に対して、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率は６６．０〜８３．０ｗｔ％、前記ポリメチルシルセスキオキサン微粒子（Ｄ）の重量比率は１７．０〜３４．０ｗｔ％であることが好ましい。 In addition, the coating material according to the present invention further includes polymethylsilsesquioxane fine particles (D), and the average particle size of the polymethylsilsesquioxane fine particles (D) is 1.0 to 5.0 μm. The weight ratio of the acrylic-modified chlorinated polyolefin resin (A) to the total of 100 wt% of the acrylic-modified chlorinated polyolefin resin (A) and the polymethylsilsesquioxane fine particles (D) is 66.0. 83.0 wt%, and the weight ratio of the polymethylsilsesquioxane fine particles (D) is preferably 17.0 to 34.0 wt%.
この塗料によれば、さらに、所定の平均粒径のポリメチルシルセスキオキサン微粒子（Ｄ）を所定量含有させることにより、ポリオレフィン基材に塗膜として塗装した際、外部滑性が向上することで、耐傷付き性が向上する。また、得られる塗膜の表面を手や爪で擦った後に残る爪および皮脂等の削りカスを少なくすることができ、摩擦跡が残り難く（視認し難く）なる。 Further, according to this paint, by containing a predetermined amount of polymethylsilsesquioxane fine particles (D) having a predetermined average particle diameter, the external lubricity is improved when the polyolefin base material is coated as a coating film. Thus, the scratch resistance is improved. Further, it is possible to reduce shavings such as nails and sebum remaining after rubbing the surface of the obtained coating film with a hand or nail, and it is difficult to leave a rubbing trace (hard to see).
本発明に係る塗料によれば、有機溶媒として、エステル系有機溶媒、ケトン系有機溶媒、アルコール系有機溶媒、および非芳香族炭化水素系有機溶媒のうちの１種以上から構成される有機溶媒を使用する場合であっても、言い換えると、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素を含有しない有機溶媒を使用する場合であっても、ポリオレフィン基材に塗膜として塗装した際、優れた付着性を有するとともに、耐傷付き性を向上させる塗料を提供することができる。 According to the paint of the present invention, an organic solvent composed of at least one of an ester organic solvent, a ketone organic solvent, an alcohol organic solvent, and a non-aromatic hydrocarbon organic solvent is used as the organic solvent. Even when used, in other words, even when using organic solvents that do not contain aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, excellent adhesion when coated as a coating on a polyolefin substrate It is possible to provide a coating material that has the properties of improving scratch resistance.
本発明に係る塗料は、エステル系有機溶媒、ケトン系有機溶媒、アルコール系有機溶媒、および非芳香族炭化水素系有機溶媒のうち１種以上から構成される有機溶媒と、アクリル変性塩素化ポリオレフィン樹脂（Ａ）と、多孔質性の樹脂粒子（Ｂ）と、脂肪酸アミド（Ｃ）と、を含むことを特徴とする。
また、本発明に係る塗料は、さらに、ポリメチルシルセスキオキサン微粒子（Ｄ）を含むことが好ましい。
The paint according to the present invention includes an organic solvent composed of at least one of an ester organic solvent, a ketone organic solvent, an alcohol organic solvent, and a non-aromatic hydrocarbon organic solvent, and an acrylic-modified chlorinated polyolefin resin. It contains (A), porous resin particles (B), and fatty acid amide (C).
Moreover, it is preferable that the coating material which concerns on this invention contains polymethylsilsesquioxane microparticles | fine-particles (D) further.
≪本発明に係る塗料に含まれる物質≫
以下、本発明に係る塗料に含まれる物質（各構成物質）について詳細に説明する。
＜アクリル変性塩素化ポリオレフィン樹脂＞
本発明に係る塗料に用いるアクリル変性塩素化ポリオレフィン樹脂（Ａ）とは、塩素化ポリオレフィン樹脂（ａ１）と、アクリル系重合体（ａ３）と、から構成されるものである。そして、当該アクリル系重合体（ａ３）とは、塩素化ポリオレフィン樹脂（ａ１）にアクリル系単量体（ａ２）をグラフト重合して得られるグラフト重合鎖である。
≪Substances contained in paint according to the present invention≫
Hereinafter, the substance (each constituent substance) contained in the paint according to the present invention will be described in detail.
<Acrylic modified chlorinated polyolefin resin>
The acrylic-modified chlorinated polyolefin resin (A) used for the paint according to the present invention is composed of a chlorinated polyolefin resin (a1) and an acrylic polymer (a3). The acrylic polymer (a3) is a graft polymer chain obtained by graft polymerization of the acrylic monomer (a2) to the chlorinated polyolefin resin (a1).
アクリル変性塩素化ポリオレフィン樹脂（Ａ）の塩素化ポリオレフィン樹脂（ａ１）は、ポリオレフィン基材に対する付着性を向上させる。一方、アクリル変性塩素化ポリオレフィン樹脂（Ａ）のアクリル系重合体（ａ３）は、得られる塗膜の耐水付着性、耐油性、耐薬品性、耐光性等を向上させる。 The chlorinated polyolefin resin (a1) of the acrylic-modified chlorinated polyolefin resin (A) improves adhesion to the polyolefin substrate. On the other hand, the acrylic polymer (a3) of the acrylic-modified chlorinated polyolefin resin (A) improves water adhesion, oil resistance, chemical resistance, light resistance and the like of the obtained coating film.
塩素化ポリオレフィン樹脂（ａ１）のオレフィン重合体は、結晶性のものでも、非結晶性のものでもよいが、塩素化ポリオレフィン樹脂（ａ１）の塩素含有率は２０〜３５ｗｔ％（塩素化ポリオレフィン樹脂１００ｗｔ％中）が好ましい。塩素含有率が３５ｗｔ％を超えると、ポリオレフィン基材に対する付着性が低下し、２０ｗｔ％未満であると塗料安定性が低下するからである。 The olefin polymer of the chlorinated polyolefin resin (a1) may be crystalline or non-crystalline, but the chlorine content of the chlorinated polyolefin resin (a1) is 20 to 35 wt% (chlorinated polyolefin resin 100 wt%). %) Is preferred. This is because if the chlorine content exceeds 35 wt%, the adhesion to the polyolefin substrate decreases, and if it is less than 20 wt%, the coating stability decreases.
アクリル系重合体（ａ３）を構成するアクリル系単量体としては、例えば、メチルメタクリレート、エチルメタクリレート、ｉ−ブチルメタクリレート、ｎ−ブチルメタクリレート、ｔ−ブチルアクリレート、２−エチルヘキシルメタクリレート、ｎ−オクチルメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート、シクロヘキシルメタクリレート、イソボロニルメタクリレート、ｏ−メトキシフェニルメタクリレート、ｍ−メトキシフェニルメタクリレート、ｐ−メトキシフェニルメタクリレート等のアクリレート類、ヘキサンジオールジメタクリレート、ノナンジオールジメタクリレート、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等のジアクリレート類、およびアクリル酸、メタクリル酸等が挙げられ、これらはそれぞれ単独、もしくは２種類以上混合して使用することができる。 Examples of the acrylic monomer constituting the acrylic polymer (a3) include methyl methacrylate, ethyl methacrylate, i-butyl methacrylate, n-butyl methacrylate, t-butyl acrylate, 2-ethylhexyl methacrylate, and n-octyl methacrylate. Acrylates such as lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, o-methoxyphenyl methacrylate, m-methoxyphenyl methacrylate, p-methoxyphenyl methacrylate, hexanediol dimethacrylate, nonanediol dimethacrylate, ethylene glycol di Such as methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, etc. Acrylates, and acrylic acid, and methacrylic acid and the like, which can be used singly or in combination of two or more.
塩素化ポリオレフィン樹脂（ａ１）にアクリル系単量体（ａ２）をグラフト重合する場合には、重合開始剤として、一般的に使用されている開始剤、例えば、ベンゾイルパーオキサイド、メチルエチルケトンパーオキサイド、ジブチルパーオキサイド、アゾビスイソブチロニトリル等を使用することができる。 When the acrylic monomer (a2) is graft-polymerized to the chlorinated polyolefin resin (a1), generally used initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, dibutyl are used as the polymerization initiator. Peroxide, azobisisobutyronitrile, etc. can be used.
塩素化ポリオレフィン樹脂（ａ１）とアクリル系重合体（ａ３）との重量比率は、（ａ１）／（ａ３）＝５．０〜１５．０ｗｔ％／８５．０〜９５．０ｗｔ％（両者の合計を１００ｗｔ％とした場合）が好ましい。アクリル系重合体（ａ３）の重量比率が９５．０ｗｔ％を超えると、ポリオレフィン基材との付着性が低下し、８５．０ｗｔ％未満であると、得られる塗膜の耐薬品性、耐油性等の性能が低下するからである。 The weight ratio of the chlorinated polyolefin resin (a1) and the acrylic polymer (a3) is (a1) / (a3) = 5.0 to 15.0 wt% / 85.0 to 95.0 wt% (total of both) Is preferably 100 wt%). When the weight ratio of the acrylic polymer (a3) exceeds 95.0 wt%, the adhesion to the polyolefin substrate decreases, and when it is less than 85.0 wt%, the resulting coating film has chemical resistance and oil resistance. This is because the performance such as the above decreases.
なお、アクリル変性塩素化ポリオレフィン樹脂（Ａ）の塗料全体に対する重量比率については特に限定されないが、塗装作業性や塗料の安定性等を考慮し、１５〜４０ｗｔ％（塗料全体を１００ｗｔ％とした場合）であることが好ましい。 The weight ratio of the acrylic-modified chlorinated polyolefin resin (A) to the whole paint is not particularly limited, but 15 to 40 wt% (when the whole paint is 100 wt%) in consideration of the coating workability and the stability of the paint. ) Is preferable.
＜多孔質性の樹脂粒子＞
本発明に係る塗料に用いる多孔質性の樹脂粒子（Ｂ）とは、球状（または略球状）を呈するとともに、表面に多数の細孔を有する微粒子である。
そして、多孔質性の樹脂粒子（Ｂ）は、水溶性セルロース水溶液中において、アクリル系単量体および塩素化ポリオレフィン樹脂を分散剤の存在下で重合反応させた樹脂（ｂ１）から構成されるものであり、当該樹脂（ｂ１）を乾燥し、さらに必要に応じて所定の平均粒子径となるように粒子径調節処理（粉砕、分級等）を施すことにより得られる。
なお、分散剤については、従来公知のものを用いればよく、例えば、アニオン系界面活性剤等である。
<Porous resin particles>
The porous resin particles (B) used in the paint according to the present invention are fine particles having a spherical shape (or a substantially spherical shape) and a large number of pores on the surface.
The porous resin particles (B) are composed of a resin (b1) obtained by polymerizing an acrylic monomer and a chlorinated polyolefin resin in the presence of a dispersant in a water-soluble cellulose aqueous solution. The resin (b1) is dried, and further subjected to a particle size adjustment treatment (pulverization, classification, etc.) so as to obtain a predetermined average particle size as necessary.
In addition, about a dispersing agent, what is necessary is just to use a conventionally well-known thing, for example, an anionic surfactant etc.
多孔質性の樹脂粒子（Ｂ）を艶調整材料として塗料中に含有させ、塗膜を形成させた場合、大きな艶消し効果が得られる。詳細には、多孔質性の樹脂粒子（Ｂ）の表面形状が、通常の懸濁重合で得られる樹脂粒子の表面形状と比べて複雑であり（表面に設けられる細孔模様が複雑であり）、多孔質性の樹脂粒子（Ｂ）を含む塗料を用いて塗膜を形成した場合に、当該樹脂粒子（Ｂ）と同じ粒子径の非多孔質性粒子を同じ重量比率含んだ塗料を用いて塗膜を形成した場合に比べ、艶の低い外観となる。
加えて、多孔質性の樹脂粒子（Ｂ）を塗料に含有させた場合、塗料中に添加すべき珪酸マグネシウム（タルク）、珪酸カルシウム、珪酸アルミニウム、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム等の艶調整用体質顔料を減量しても、または無添加であっても、艶調整が可能となり、その結果、得られる塗膜の耐傷付き性を向上させることができる。これは塗膜中の艶調整用体質顔料の含有量が少ないほど、耐傷付き性が良好であるという従来の知見に基づくものである。
When the porous resin particles (B) are contained in the paint as a gloss adjusting material and a coating film is formed, a great matting effect is obtained. Specifically, the surface shape of the porous resin particles (B) is more complicated than the surface shape of the resin particles obtained by ordinary suspension polymerization (the pore pattern provided on the surface is complicated). When a coating film is formed using a paint containing porous resin particles (B), a paint containing the same weight ratio of non-porous particles having the same particle diameter as that of the resin particles (B) is used. Compared with the case where a coating film is formed, the appearance is less glossy.
In addition, when porous resin particles (B) are included in the paint, gloss adjustment of magnesium silicate (talc), calcium silicate, aluminum silicate, calcium carbonate, magnesium carbonate, barium sulfate, etc. to be added to the paint Even if the extender pigment is reduced or not added, the gloss can be adjusted, and as a result, the scratch resistance of the resulting coating film can be improved. This is based on the conventional knowledge that the smaller the content of the extender extender pigment in the coating film, the better the scratch resistance.
また、多孔質性の樹脂粒子（Ｂ）を艶調整材料として塗料中に含有させた場合、得られる塗膜の表面を手や爪で擦った後に残る爪および皮脂等の削りカスが、前記の艶調整用体質顔料や非多孔質性の樹脂粒子を艶調整材料として使用した場合に比べて少なくなり、摩擦跡が残り難く（視認し難く）なる。
これは前記のとおり、多孔質性の樹脂粒子（Ｂ）を含む塗膜の表面が、その樹脂粒子（Ｂ）の多孔質性を反映した細孔を呈する形状となるため、前記の艶調整用体質顔料や非多孔質性の樹脂粒子のみを艶調整材料として用い、同等な艶とした塗膜と比べ、多孔質性の樹脂粒子（Ｂ）の含有量を少なくすることができる。その結果、塗膜表面に形成されるミクロレベルの凸部（ラウンド）の存在割合を少なくできる。さらに、多孔質性の樹脂粒子（Ｂ）は粒状（または略粒状）を呈することから、当該凸部はなだらかなもの（球面状）となるため、爪や手の甲で塗膜表面を擦っても、爪や皮脂等が削られ難くなる。
Further, when the porous resin particles (B) are contained in the paint as a gloss adjusting material, the scraps such as nails and sebum remaining after rubbing the surface of the obtained coating film with hands or nails are the above-mentioned Compared with the use of gloss adjusting extender pigments and non-porous resin particles as the gloss adjusting material, the friction marks hardly remain (it is difficult to see).
As described above, the surface of the coating film containing the porous resin particles (B) has a shape reflecting pores reflecting the porous property of the resin particles (B). Only the extender pigment and the non-porous resin particles are used as the gloss adjusting material, and the content of the porous resin particles (B) can be reduced as compared with the equivalent glossy coating film. As a result, it is possible to reduce the proportion of micro-level convex portions (rounds) formed on the coating film surface. Furthermore, since the porous resin particles (B) are granular (or substantially granular), the convex portions are gentle (spherical), so even if the surface of the coating film is rubbed with a nail or the back of the hand, Nails and sebum are less likely to be removed.
多孔質性の樹脂粒子（Ｂ）の平均粒子径は、好ましくは３〜１２μｍ、さらに好ましくは５〜１０μｍである。樹脂粒子（Ｂ）の平均粒子径が３μｍ未満であると、十分な艶消し効果を得ることができず、樹脂粒子（Ｂ）の平均粒子径が１２μｍを超えると、塗膜表面に形成されるミクロレベルの凸部（ラウンド）が大きくなり、爪および皮脂等の削り跡が残り易くなる。また、多孔質性の樹脂粒子（Ｂ）の有する細孔の幅は、好ましくは０．５μｍ以上である。多孔質性の樹脂粒子（Ｂ）の細孔の幅が０．５μｍ未満であると、得られる艶消し効果は、珪酸マグネシウム（タルク）、珪酸カルシウム、珪酸アルミニウム、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム等の艶調整用体質顔料や非多孔質性樹脂粒子を用いた場合とあまり変わらなくなるからである。 The average particle diameter of the porous resin particles (B) is preferably 3 to 12 μm, more preferably 5 to 10 μm. When the average particle diameter of the resin particles (B) is less than 3 μm, a sufficient matting effect cannot be obtained, and when the average particle diameter of the resin particles (B) exceeds 12 μm, it is formed on the coating film surface. Micro-level convex portions (rounds) become large, and scratches such as nails and sebum are likely to remain. The width of the pores of the porous resin particles (B) is preferably 0.5 μm or more. When the pore width of the porous resin particles (B) is less than 0.5 μm, the resulting matte effect is magnesium silicate (talc), calcium silicate, aluminum silicate, calcium carbonate, magnesium carbonate, barium sulfate. This is because it is not much different from the case of using an extender pigment for gloss adjustment or the like and non-porous resin particles.
アクリル変性塩素化ポリオレフィン樹脂（Ａ）と、多孔質性の樹脂粒子（Ｂ）との重量比率は、（Ａ）／（Ｂ）＝６２．５〜９１．０ｗｔ％／９．０〜３７．５ｗｔ％（両者の合計は１００ｗｔ％）が好ましい。アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率が９１．０ｗｔ％を超えると、十分な艶消し効果を得ることができないとともに、傷付き性等の性能の低下を引き起こすからである。一方、アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率が６２．５ｗｔ％未満であると、ポリオレフィン基材との付着性が低下するからである。 The weight ratio of the acrylic modified chlorinated polyolefin resin (A) and the porous resin particles (B) is (A) / (B) = 62.5-91.0 wt% / 9.0-37.5 wt. % (The total of both is 100 wt%). This is because if the weight ratio of the acrylic-modified chlorinated polyolefin resin (A) exceeds 91.0 wt%, a sufficient matting effect cannot be obtained, and performance such as scratching is reduced. On the other hand, when the weight ratio of the acrylic-modified chlorinated polyolefin resin (A) is less than 62.5 wt%, the adhesion to the polyolefin substrate is lowered.
＜脂肪酸アミド＞
本発明に係る塗料に用いる脂肪酸アミド（Ｃ）とは、脂肪酸と低級アミンから形成されるアミド化合物であり、好ましくは、炭素数４〜１８の飽和脂肪酸アミド、炭素数４〜１８の不飽和脂肪酸アミドおよびこれらの誘導体のうちのそれぞれ単独、もしくは２種以上混合されたものである。
詳細には、脂肪酸アミド（Ｃ）は、脂肪酸として、酪酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸等の炭素数４〜１８の飽和脂肪酸、不飽和脂肪酸およびこれらの誘導体のうち、それぞれ単独、もしくは２種類以上混合されたものを用いた脂肪酸アミドである。
<Fatty acid amide>
The fatty acid amide (C) used in the coating material according to the present invention is an amide compound formed from a fatty acid and a lower amine, preferably a saturated fatty acid amide having 4 to 18 carbon atoms and an unsaturated fatty acid having 4 to 18 carbon atoms. Each of amides and their derivatives is used alone or in combination of two or more.
Specifically, fatty acid amide (C) is a fatty acid having 4 to 18 carbon atoms such as butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and the like. Among saturated fatty acids, unsaturated fatty acids, and derivatives thereof, each is a fatty acid amide using one or a mixture of two or more.
脂肪酸アミド（Ｃ）は、塗料溶液に安定に膨潤・分散させることにより、塗料中に網目状の構造が形成され、これにより構造粘性が発現し塗料溶液に揺変性を付与することができる。この作用により、本発明に係る塗料は低温および高温の環境に放置しても、塗料液内で相分離および凝集物の発生が起こり難くなる。 The fatty acid amide (C) can swell and disperse stably in the coating solution, thereby forming a network structure in the coating material, thereby developing structural viscosity and imparting thixotropic properties to the coating solution. Due to this action, the coating according to the present invention is less likely to cause phase separation and aggregation in the coating liquid even when left in a low and high temperature environment.
アクリル変性塩素化ポリオレフィン樹脂（Ａ）と、脂肪酸アミド（Ｃ）との重量比率は、（Ａ）／（Ｃ）＝９３．４〜９７．５ｗｔ％／２．５〜６．６ｗｔ％（両者の合計は１００ｗｔ％）が好ましい。アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率が９７．５ｗｔ％を超えると、塗料溶液が十分な揺変効果を得ることができず、９３．４ｗｔ％未満であると、ポリオレフィン基材との付着性の低下や、得られる塗膜の耐水付着性、耐油性、耐傷付き性等の性能の低下を引き起こすからである。 The weight ratio of the acrylic-modified chlorinated polyolefin resin (A) and the fatty acid amide (C) is (A) / (C) = 93.4-97.5 wt% / 2.5-6.6 wt% (both The total is preferably 100 wt%). When the weight ratio of the acrylic-modified chlorinated polyolefin resin (A) exceeds 97.5 wt%, the coating solution cannot obtain a sufficient thixotropic effect, and when it is less than 93.4 wt%, This is because the adhesiveness is lowered and the resulting coating film is deteriorated in water resistance, oil resistance, scratch resistance, and other performances.
なお、現在、エステル系有機溶媒、ケトン系有機溶媒、非芳香族炭化水素系有機溶媒に塩素化ポリオレフィン樹脂を溶解させ、さらにアクリル樹脂をバインダーとして配合するといった検討もなされているが、それぞれのＳＰ値（溶解パラメーター）の差が小さくないため、塗料の安定的な保存が困難である。一方、本発明は、上記のとおり塗料溶液に揺変性を付与することにより、塗料の安定性（貯蔵安定性）を向上させることができることから、このような従来技術に対しても優位性を確保することができる。 Currently, studies have been made to dissolve a chlorinated polyolefin resin in an ester organic solvent, a ketone organic solvent, or a non-aromatic hydrocarbon organic solvent, and further blend an acrylic resin as a binder. Since the difference in value (solubility parameter) is not small, it is difficult to stably store the paint. On the other hand, the present invention can improve the stability (storage stability) of the paint by imparting thixotropy to the paint solution as described above. can do.
（ＴＩ値）
脂肪酸アミド（Ｃ）を含有することにより塗料溶液の揺変性が発現するが、得られる揺変効果をより確実なものとするために、Ｂ型粘度計（Ｂｒｏｏｋｆｉｅｌｄ粘度計）で求めた塗料のＴｈｉｘｏｔｒｏｐｉｃ Ｉｎｄｅｘ（ＴＩ値＝塗料温度２５℃で回転数６ｒｐｍにおける粘度／塗料温度２５℃で回転数６０ｒｐｍにおける粘度）は２．５〜５．０であることが好ましい。ＴＩ値が２．５未満であると、塗料溶液が相分離しないための十分な揺変効果を得ることができず、ＴＩ値が５．０を超えると、塗装作業性および得られる塗膜の外観が低下するからである。
(TI value)
Although the thixotropic property of the coating solution is manifested by containing the fatty acid amide (C), the thixotropic property of the coating obtained with a B-type viscometer (Brookfield viscometer) is obtained in order to ensure the obtained thixotropic effect. The Index (TI value = viscosity at a coating temperature of 25 ° C. and a viscosity at a rotation speed of 6 rpm / viscosity at a coating temperature of 25 ° C. and a viscosity at a rotation speed of 60 rpm) is preferably 2.5 to 5.0. When the TI value is less than 2.5, a sufficient thixotropic effect for preventing the phase separation of the coating solution cannot be obtained. When the TI value exceeds 5.0, the coating workability and the obtained coating film This is because the appearance deteriorates.
＜ポリメチルシルセスキオキサン微粒子＞
本発明に係る塗料に用いるポリメチルシルセスキオキサン微粒子（Ｄ）とは、球状（または略球状）を呈する微粒子である。なお、ポリメチルシルセスキオキサン微粒子（Ｄ）は、本発明に係る塗料の必須の物質ではないが、後述するような効果を発揮するため、塗料に含有させるのが好ましい。
<Polymethylsilsesquioxane fine particles>
The polymethylsilsesquioxane fine particles (D) used in the coating material according to the present invention are fine particles exhibiting a spherical shape (or a substantially spherical shape). The polymethylsilsesquioxane fine particles (D) are not an essential substance of the paint according to the present invention, but are preferably contained in the paint in order to exhibit the effects described below.
ポリメチルシルセスキオキサン微粒子（Ｄ）は、塗料中に含有させた場合、得られる塗膜表面の耐久性を向上させることができる。これは、ポリメチルシルセスキオキサン粒子（Ｄ）が優れた耐溶剤性、撥水性を有することから、塗膜表面が汚染されにくく、さらに形状が球状の微粒子であることから、塗膜表面に配置した場合、外部滑性が向上し塗膜の耐傷付き性が向上するためである。
また、ポリメチルシルセスキオキサン微粒子（Ｄ）は、得られる塗膜の外部滑性を向上させることにより、塗膜の表面を手や爪で擦った後に残る爪および皮脂等の削りカスを極めて少なくすることができ、さらに摩擦跡が非常に残り難く（視認し難く）なる。
When the polymethylsilsesquioxane fine particles (D) are contained in the paint, the durability of the resulting coating film surface can be improved. This is because the polymethylsilsesquioxane particles (D) have excellent solvent resistance and water repellency, so that the coating surface is hardly contaminated, and the shape is spherical fine particles. This is because when arranged, the external lubricity is improved and the scratch resistance of the coating film is improved.
In addition, the polymethylsilsesquioxane fine particles (D) improve the external lubricity of the obtained coating film, thereby greatly reducing scraps such as nails and sebum remaining after the surface of the coating film is rubbed with hands or nails. In addition, the frictional traces are hardly left (it is difficult to see).
ポリメチルシルセスキオキサン微粒子（Ｄ）の平均粒子径は、好ましくは１〜５μｍ、さらに好ましくは１〜３μｍである。ポリメチルシルセスキオキサン微粒子（Ｄ）の平均粒子径が１μｍ未満であると、十分な滑性を得ることができず、ポリメチルシルセスキオキサン微粒子（Ｄ）の平均粒子径が５μｍより大きいと、塗膜表面のミクロレベルの平滑性がなくなり、爪および皮脂等の削りカス（摩擦跡）が残り易くなる。 The average particle diameter of the polymethylsilsesquioxane fine particles (D) is preferably 1 to 5 μm, more preferably 1 to 3 μm. When the average particle diameter of the polymethylsilsesquioxane fine particles (D) is less than 1 μm, sufficient lubricity cannot be obtained, and the average particle diameter of the polymethylsilsesquioxane fine particles (D) is larger than 5 μm. Then, the smoothness on the surface of the coating film is lost, and shavings (friction marks) such as nails and sebum easily remain.
アクリル変性塩素化ポリオレフィン樹脂（Ａ）とポリメチルシルセスキオキサン微粒子（Ｄ）の重量比率は、（Ａ）／（Ｄ）＝６６．０〜８３．０ｗｔ％／１７．０〜３４．０ｗｔ％（両者の合計は１００ｗｔ％）が好ましい。アクリル変性塩素化ポリオレフィン樹脂（Ａ）の比率が８３．０ｗｔ％を超えると、十分な滑性を得ることができないため、得られる塗膜の表面に摩擦跡が残り易くなり、６６．０ｗｔ％未満であると、ポリオレフィン基材との付着性が低下する。 The weight ratio of the acrylic modified chlorinated polyolefin resin (A) and the polymethylsilsesquioxane fine particles (D) is (A) / (D) = 66.0-83.0 wt% / 17.0-34.0 wt%. (The total of both is 100 wt%). When the ratio of the acrylic-modified chlorinated polyolefin resin (A) exceeds 83.0 wt%, sufficient lubricity cannot be obtained, and therefore, a friction mark tends to remain on the surface of the obtained coating film, and is less than 66.0 wt%. When it is, adhesiveness with a polyolefin base material falls.
＜有機溶媒＞
本発明に係る塗料に用いる有機溶媒とは、エステル系有機溶媒、ケトン系有機溶媒、アルコール系有機溶媒、および非芳香族炭化水素系有機溶媒のうちの１種以上から構成される有機溶媒、言い換えると、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素を含有しない有機溶媒である。
詳細には、本発明に係る塗料に用いる有機溶媒とは、エチルアセテート、ｎ−プロピルアセテート、ｎ−ブチルアセテート、ｉ−ブチルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル系有機溶媒、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン等のケトン系有機溶媒、エタノール、ｉ−プロパノール、ｎ−ブタノール、ｉ−ブタノール等のアルコール系有機溶媒、メチルシクロヘキサン、ジメチルシクロヘキサン、エチルシクロヘキサン等の非芳香族炭化水素系有機溶媒からそれぞれ単独、もしくは２種類以上混合されたものである。
<Organic solvent>
The organic solvent used in the paint according to the present invention is an organic solvent composed of one or more of an ester organic solvent, a ketone organic solvent, an alcohol organic solvent, and a non-aromatic hydrocarbon organic solvent, in other words. And organic solvents that do not contain aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.
Specifically, the organic solvent used in the paint according to the present invention is an ester organic solvent such as ethyl acetate, n-propyl acetate, n-butyl acetate, i-butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl. Ketone organic solvents such as ketone, diisobutyl ketone and cyclohexanone, alcohol organic solvents such as ethanol, i-propanol, n-butanol and i-butanol, non-aromatic hydrocarbon organic such as methylcyclohexane, dimethylcyclohexane and ethylcyclohexane Each of these solvents is used alone or in combination of two or more.
＜塗料の塗装対象＞
本発明に係る塗料の塗装対象は、難付着性のプラスチック基材であり、特にポリプロピレン等のポリオレフィン樹脂を主成分とするポリオレフィン基材である。
ここで、難付着性のプラスチック基材としては、例えば自動車、電化製品、携帯端末機器等の分野で使用されるプラスチック基材が挙げられ、具体的には、自動車の内装用ポリオレフィン樹脂部品等が挙げられるが、これらに限定されるものではない。
<Coating object>
The coating object of the paint according to the present invention is a hardly adherent plastic substrate, and in particular, a polyolefin substrate mainly composed of a polyolefin resin such as polypropylene.
Here, examples of the hard-to-adhere plastic base material include plastic base materials used in the fields of automobiles, electrical appliances, portable terminal devices, and the like, specifically, polyolefin resin parts for automobile interiors, etc. Although it is mentioned, it is not limited to these.
≪本発明に係る塗料の製造方法≫
本発明に係る塗料の製造方法を説明する。
まず、塩素化ポリオレフィン樹脂（ａ１）にアクリル系単量体（ａ２）を重合反応させてアクリル変性塩素化ポリオレフィン樹脂（Ａ）を作製する。この重合反応における塩素化ポリオレフィン樹脂（ａ１）溶液へのアクリル系単量体（ａ２）の導入（滴下または注入）の際の好ましい反応温度は、５０〜１００℃であり、好ましい導入（滴下または注入）時間は３〜６時間である。
≪Method for producing paint according to the present invention≫
A method for producing a paint according to the present invention will be described.
First, the acrylic monomer (a2) is polymerized with the chlorinated polyolefin resin (a1) to produce an acrylic-modified chlorinated polyolefin resin (A). The preferable reaction temperature at the time of introduction (dropping or injection) of the acrylic monomer (a2) into the chlorinated polyolefin resin (a1) solution in this polymerization reaction is 50 to 100 ° C., and preferable introduction (dropping or injection). ) Time is 3-6 hours.
次に、水溶性セルロース水溶液中、分散剤の存在下で、アクリル系単量体及び塩素化ポリオレフィン樹脂を重合反応して樹脂（ｂ１）を作製する。この重合反応において、アクリル系単量体及び塩素化ポリオレフィン樹脂の好ましい配合重量比率は、アクリル系単量体／塩素化ポリオレフィン樹脂＝９／１〜１／９であり、分散剤の好ましい配合重量比率は、水溶液１００ｗｔ％に対して０．１〜３０ｗｔ％である。また、この重合反応における好ましい反応温度は５０〜７０℃、好ましい反応時間は２〜５時間である。
なお、この重合反応において好ましく用いられる分散媒体としては、上記水溶性セルロース水溶液であるが、これに水溶性であるポリビニルアルコール、ポリビニルピロリドンを添加してもよい。
その後、重合反応混合物である樹脂（ｂ１）を乾燥し、さらに必要に応じて粉砕・分級等の粒子径調節の処理をすることで多孔質性の樹脂粒子（Ｂ）を作製する。
Next, an acrylic monomer and a chlorinated polyolefin resin are polymerized in a water-soluble cellulose aqueous solution in the presence of a dispersant to produce a resin (b1). In this polymerization reaction, the preferred blending weight ratio of the acrylic monomer and the chlorinated polyolefin resin is acrylic monomer / chlorinated polyolefin resin = 9/1 to 1/9, and the preferred blending weight ratio of the dispersant. Is 0.1 to 30 wt% with respect to 100 wt% of the aqueous solution. Moreover, the preferable reaction temperature in this polymerization reaction is 50-70 degreeC, and preferable reaction time is 2 to 5 hours.
The dispersion medium preferably used in this polymerization reaction is the water-soluble cellulose aqueous solution described above, and water-soluble polyvinyl alcohol and polyvinyl pyrrolidone may be added thereto.
Thereafter, the resin (b1), which is a polymerization reaction mixture, is dried, and further, particle size adjustment processing such as pulverization and classification is performed as necessary to produce porous resin particles (B).
そして、アクリル変性塩素化ポリオレフィン樹脂（Ａ）を前記有機溶媒に安定的に溶解させたアクリル変性塩素化ポリオレフィン樹脂溶液（ワニス）に、前記方法で作製した多孔質性の樹脂粒子（Ｂ）と、脂肪酸アミド（Ｃ）と、ポリメチルシルセスキオキサン微粒子（Ｄ）と、を混合・分散させる。
なお、この混合・分散工程における混合・分散の時間は好ましくは０．５〜１時間である。
このようにして製造された塗料は、ポリオレフィン基材に塗装され、比較的短時間（５〜１５分）、低温度（５０〜６０℃）の強制乾燥条件で乾燥されることにより塗膜として形成されることとなる。
And, in the acrylic modified chlorinated polyolefin resin solution (varnish) in which the acrylic modified chlorinated polyolefin resin (A) is stably dissolved in the organic solvent, the porous resin particles (B) prepared by the above method, The fatty acid amide (C) and the polymethylsilsesquioxane fine particles (D) are mixed and dispersed.
The mixing / dispersing time in this mixing / dispersing step is preferably 0.5 to 1 hour.
The coating material thus produced is applied to a polyolefin substrate and formed as a coating film by drying under forced drying conditions at a relatively short time (5 to 15 minutes) and low temperature (50 to 60 ° C.). Will be.
本発明に係る塗料には、必要に応じて、アクリル樹脂、ポリウレタン樹脂、塩素化ポリオレフィン樹脂、テルペン系樹脂等の副樹脂、前述した芳香族炭化水素を含有しない有機溶媒、公知の体質顔料、着色顔料、金属顔料、マイカ粉顔料、染料、光安定剤、紫外線吸収剤、表面調整剤、消泡剤等を加えることができる。 The paint according to the present invention includes, if necessary, an auxiliary resin such as an acrylic resin, a polyurethane resin, a chlorinated polyolefin resin, a terpene resin, an organic solvent not containing the aromatic hydrocarbon, a known extender pigment, a coloring Pigments, metal pigments, mica powder pigments, dyes, light stabilizers, ultraviolet absorbers, surface conditioners, antifoaming agents, and the like can be added.
以下に実施例を挙げて本発明を具体的に説明するが、これにより本発明を限定するものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereby.
［使用するアクリル変性塩素化ポリオレフィン樹脂の製造方法］
まず、使用するアクリル変性塩素化ポリオレフィン樹脂Ａ１〜Ａ４の製造方法について、それぞれ説明する。
（アクリル変性塩素化ポリオレフィン樹脂Ａ１）
滴下ロート、温度計、窒素導入管、冷却管、撹拌装置を備えた２リットルの丸底四つ口フラスコに、塩素化ポリプロピレン樹脂（東洋紡社製、ハードレンＤＸ−５２３Ｐ、塩素含有量２３ｗｔ％、Ｍｗ１００，０００）を４０ｇ、メチルシクロヘキサンを８０ｇ、メチルエチルケトンを８０ｇ仕込んだ後、撹拌を行いながらフラスコ内の温度を６０℃に保ち塩素化ポリオレフィン樹脂を溶解した。そして、フラスコ内の温度を８０℃に上昇しこれを保ちながら、メチルメタクリレート２５２ｇ、シクロヘキシルメタクリレート１８ｇ、ｔ−ブチルアクリレート６８．４ｇ、１，６−ヘキサンジオールジメタクリレート１８ｇ、メタクリル酸３．６ｇ、ベンゾイルパーオキサイド１０ｇからなる単量体混合物を４時間にわたり滴下し、さらに温度を９０℃に上げて３時間撹拌を続けた後、メチルシクロヘキサン１００ｇ、メチルエチルケトン４９０ｇを加え攪拌を行い、冷却してアクリル変性塩素化ポリオレフィン樹脂（Ａ１）溶液（固形分：３４．８ｗｔ％、アクリル変性塩素化ポリオレフィン樹脂中の塩素化ポリオレフィン樹脂の固形分重量比率：１０ｗｔ％）を得た。
[Method for producing acrylic-modified chlorinated polyolefin resin to be used]
First, the manufacturing method of acrylic modified chlorinated polyolefin resin A1-A4 to be used is each demonstrated.
(Acrylic modified chlorinated polyolefin resin A1)
To a 2 liter round bottom four-necked flask equipped with a dropping funnel, thermometer, nitrogen introduction tube, cooling tube, and stirring device, chlorinated polypropylene resin (manufactured by Toyobo Co., Ltd., Hardren DX-523P, chlorine content 23 wt%, Mw 100) , 000), 80 g of methylcyclohexane, and 80 g of methyl ethyl ketone, and the temperature inside the flask was kept at 60 ° C. while stirring to dissolve the chlorinated polyolefin resin. And while raising the temperature in the flask to 80 ° C. and keeping it, 252 g of methyl methacrylate, 18 g of cyclohexyl methacrylate, 68.4 g of t-butyl acrylate, 18 g of 1,6-hexanediol dimethacrylate, 3.6 g of methacrylic acid, benzoyl A monomer mixture consisting of 10 g of peroxide was added dropwise over 4 hours, and the temperature was further raised to 90 ° C. and stirring was continued for 3 hours. Then, 100 g of methylcyclohexane and 490 g of methyl ethyl ketone were added, and the mixture was cooled and cooled with acrylic modified chlorine. Polyolefin resin (A1) solution (solid content: 34.8 wt%, solid content weight ratio of chlorinated polyolefin resin in acrylic-modified chlorinated polyolefin resin: 10 wt%) was obtained.
（アクリル変性塩素化ポリオレフィン樹脂Ａ２）
滴下ロート、温度計、窒素導入管、冷却管、撹拌装置を備えた２リットルの丸底四つ口フラスコに、塩素化ポリプロピレン樹脂（東洋紡社製、ハードレンＤＸ−５２３Ｐ、塩素含有量２３ｗｔ％、Ｍｗ１００，０００）を３１ｇ、メチルシクロヘキサンを１３５ｇ、メチルエチルケトンを１３５ｇ仕込んだ後、撹拌を行いながらフラスコ内の温度を６０℃に保ち塩素化ポリオレフィン樹脂を溶解した。そして、フラスコ内の温度を８０℃に上昇しこれを保ちながら、メチルメタクリレート１４７ｇ、シクロヘキシルメタクリレート１１ｇ、ｔ−ブチルアクリレート３９．９ｇ、１，６−ヘキサンジオールジメタクリレート１０ｇ、メタクリル酸２．１ｇ、ベンゾイルパーオキサイド６．７ｇからなる単量体混合物を４時間にわたり滴下し、さらに温度を９０℃に上げて３時間撹拌を続けた後、メチルシクロヘキサン３５ｇ、メチルエチルケトン１０４．７ｇを加え攪拌を行い、冷却してアクリル変性塩素化ポリオレフィン樹脂（Ａ２）溶液（固形分：３４．８ｗｔ％、アクリル変性塩素化ポリオレフィン樹脂中の塩素化ポリオレフィン樹脂の固形分重量比率：１５ｗｔ％）を得た。
(Acrylic modified chlorinated polyolefin resin A2)
To a 2 liter round bottom four-necked flask equipped with a dropping funnel, thermometer, nitrogen introduction tube, cooling tube, and stirring device, chlorinated polypropylene resin (manufactured by Toyobo Co., Ltd., Hardren DX-523P, chlorine content 23 wt%, Mw 100) , 1,000), 135 g of methylcyclohexane, and 135 g of methyl ethyl ketone were charged, and the temperature in the flask was kept at 60 ° C. while stirring to dissolve the chlorinated polyolefin resin. And while raising the temperature in a flask to 80 degreeC and keeping this, 147 g of methyl methacrylate, 11 g of cyclohexyl methacrylate, 39.9 g of t-butyl acrylate, 10 g of 1, 6-hexanediol dimethacrylate, 2.1 g of methacrylic acid, benzoyl A monomer mixture consisting of 6.7 g of peroxide was added dropwise over 4 hours, and the temperature was further raised to 90 ° C. and stirring was continued for 3 hours. Then, 35 g of methylcyclohexane and 104.7 g of methyl ethyl ketone were added and the mixture was stirred and cooled. Thus, an acrylic-modified chlorinated polyolefin resin (A2) solution (solid content: 34.8 wt%, solid content weight ratio of chlorinated polyolefin resin in the acrylic-modified chlorinated polyolefin resin: 15 wt%) was obtained.
（アクリル変性塩素化ポリオレフィン樹脂Ａ３）
滴下ロート、温度計、窒素導入管、冷却管、撹拌装置を備えた２リットルの丸底四つ口フラスコに、塩素化ポリプロピレン樹脂（東洋紡社製、ハードレンＤＸ−５２３Ｐ、塩素含有量２３ｗｔ％、Ｍｗ１００，０００）を１５．８ｇ、メチルシクロヘキサンを９０ｇ、メチルエチルケトンを９０ｇ仕込んだ後、撹拌を行いながらフラスコ内の温度を６０℃に保ち塩素化ポリオレフィン樹脂を溶解した。そして、フラスコ内の温度を８０℃に上昇しこれを保ちながら、メチルメタクリレート２６６ｇ、シクロヘキシルメタクリレート１９ｇ、ｔ−ブチルアクリレート７２．２ｇ、１，６−ヘキサンジオールジメタクリレート１９ｇ、メタクリル酸３．８ｇ、ベンゾイルパーオキサイド１１ｇからなる単量体混合物を４時間にわたり滴下し、さらに温度を９０℃に上げて３時間撹拌を続けた後、メチルシクロヘキサン９０ｇ、メチルエチルケトン４６８ｇを加え攪拌を行い、冷却してアクリル変性塩素化ポリオレフィン樹脂（Ａ３）溶液（固形分：３４．８ｗｔ％、アクリル変性塩素化ポリオレフィン樹脂中の塩素化ポリオレフィン樹脂の固形分重量比率：４ｗｔ％）を得た。
(Acrylic modified chlorinated polyolefin resin A3)
To a 2 liter round bottom four-necked flask equipped with a dropping funnel, thermometer, nitrogen introduction tube, cooling tube, and stirring device, chlorinated polypropylene resin (manufactured by Toyobo Co., Ltd., Hardren DX-523P, chlorine content 23 wt%, Mw 100) ) Was charged with 15.8 g, methylcyclohexane 90 g and methyl ethyl ketone 90 g, and the temperature inside the flask was kept at 60 ° C. while stirring to dissolve the chlorinated polyolefin resin. And while raising the temperature in the flask to 80 ° C. and keeping it, 266 g of methyl methacrylate, 19 g of cyclohexyl methacrylate, 72.2 g of t-butyl acrylate, 19 g of 1,6-hexanediol dimethacrylate, 3.8 g of methacrylic acid, benzoyl A monomer mixture consisting of 11 g of peroxide was added dropwise over 4 hours, and the temperature was further raised to 90 ° C. and stirring was continued for 3 hours. Then, 90 g of methylcyclohexane and 468 g of methyl ethyl ketone were added, and the mixture was cooled and cooled. Polyolefin resin (A3) solution (solid content: 34.8 wt%, solid content weight ratio of chlorinated polyolefin resin in acrylic-modified chlorinated polyolefin resin: 4 wt%) was obtained.
（アクリル変性塩素化ポリオレフィン樹脂Ａ４）
滴下ロート、温度計、窒素導入管、冷却管、撹拌装置を備えた２リットルの丸底四つ口フラスコに、塩素化ポリプロピレン樹脂（東洋紡社製、ハードレンＤＸ−５２３Ｐ、塩素含有量２３ｗｔ％、Ｍｗ１００，０００）を５２．５ｇ、メチルシクロヘキサンを１３５ｇ、メチルエチルケトンを１３５ｇ仕込んだ後、撹拌を行いながらフラスコ内の温度を６０℃に保ち塩素化ポリオレフィン樹脂を溶解した。そして、フラスコ内の温度を８０℃に上昇しこれを保ちながら、メチルメタクリレート１４７ｇ、シクロヘキシルメタクリレート１１ｇ、ｔ−ブチルアクリレート３９．９ｇ、１，６−ヘキサンジオールジメタクリレート１０ｇ、メタクリル酸２．１ｇ、ベンゾイルパーオキサイド６ｇからなる単量体混合物を４時間にわたり滴下し、さらに温度を９０℃に上げて３時間撹拌を続けた後、メチルエチルケトン１８４．２ｇを加え攪拌を行い、冷却してアクリル変性塩素化ポリオレフィン樹脂（Ａ４）溶液（固形分：３４．８ｗｔ％、アクリル変性塩素化ポリオレフィン樹脂中の塩素化ポリオレフィン樹脂の固形分重量比率：２０ｗｔ％）を得た。
(Acrylic modified chlorinated polyolefin resin A4)
To a 2 liter round bottom four-necked flask equipped with a dropping funnel, thermometer, nitrogen introduction tube, cooling tube, and stirring device, chlorinated polypropylene resin (manufactured by Toyobo Co., Ltd., Hardren DX-523P, chlorine content 23 wt%, Mw 100) 5,000), 135 g of methylcyclohexane and 135 g of methyl ethyl ketone were charged, and the temperature in the flask was kept at 60 ° C. while stirring to dissolve the chlorinated polyolefin resin. And while raising the temperature in a flask to 80 degreeC and keeping this, 147 g of methyl methacrylate, 11 g of cyclohexyl methacrylate, 39.9 g of t-butyl acrylate, 10 g of 1, 6-hexanediol dimethacrylate, 2.1 g of methacrylic acid, benzoyl A monomer mixture consisting of 6 g of peroxide was added dropwise over 4 hours, and the temperature was further raised to 90 ° C. and stirring was continued for 3 hours. Then, 184.2 g of methyl ethyl ketone was added, and the mixture was cooled and cooled to an acrylic-modified chlorinated polyolefin. A resin (A4) solution (solid content: 34.8 wt%, solid content weight ratio of chlorinated polyolefin resin in acrylic-modified chlorinated polyolefin resin: 20 wt%) was obtained.
次に、多孔質性の樹脂粒子Ｂ１の製造方法について説明する。
［多孔質性の樹脂粒子Ｂ１の製造方法］
滴下ロート、温度計、窒素導入管、冷却管、撹拌装置を備えた１リットルの丸底四つ口フラスコに、水溶性セルロース（信越化学製、メトローズ６０ＳＨ５０）２．５％水溶液８００ｇとアニオン系分散剤（日本乳化剤製、ニューコール７０７ＳＦ）０．２ｇ仕込んだ後、フラスコ内を窒素ガスで置換した。強く撹拌を行いながら、イソブチルメタクリレート７５ｇ、エチレングリコールジメタクリレート３０ｇ、塩素化ポリオレフィン樹脂（東洋化成製、ハードレンＢ−１３）２５ｇ（固形分：３０ｗｔ％）、過酸化物溶液（化薬アクゾ製、トリゴノックス２３−Ｃ７０）３ｇからなるアクリルモノマー、ポリオレフィン系ポリマー、過酸化物の混合物を３０分かけて滴下した。滴下終了後フラスコ内を強力に撹拌しながら温度を６０℃に上げて６時間温度を一定に保った後、冷却してフラスコ内容物を取り出し、十分に水洗を行った。得られた粒子を乾燥し粉砕を行った後、さらに分級して平均粒子径８μｍの樹脂粒子（Ｂ１）を得た。
Next, the manufacturing method of porous resin particle B1 is demonstrated.
[Method for Producing Porous Resin Particle B1]
In a 1 liter round bottom four-necked flask equipped with a dropping funnel, thermometer, nitrogen inlet tube, condenser tube, and stirring device, 800 g of 2.5% aqueous solution of water-soluble cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose 60SH50) and anionic dispersion After charging 0.2 g of an agent (Nippon Emulsifier, New Coal 707SF), the inside of the flask was replaced with nitrogen gas. While stirring vigorously, 75 g of isobutyl methacrylate, 30 g of ethylene glycol dimethacrylate, 25 g of chlorinated polyolefin resin (manufactured by Toyo Kasei, Hardren B-13) (solid content: 30 wt%), peroxide solution (manufactured by Kayaku Akzo, Trigonox) 23-C70) A mixture of 3 g of acrylic monomer, polyolefin polymer and peroxide was added dropwise over 30 minutes. After completion of dropping, the temperature in the flask was raised to 60 ° C. with vigorous stirring, and the temperature was kept constant for 6 hours. Then, the flask was cooled and the contents of the flask were taken out and washed thoroughly with water. The obtained particles were dried and pulverized, and further classified to obtain resin particles (B1) having an average particle diameter of 8 μm.
次に、試験体１〜１７（塗料）の製造方法について説明する。
［試験体の製造方法］
前記製造方法で得られたアクリル変性ポリオレフィン樹脂溶液１４４ｇ（不揮発分：５０ｇ、種類は表１を参照）と、多孔質性の樹脂粒子（種類および使用量は表１を参照）と、ポリメチルシルセスキオキサン微粒子（ガンツ化成社製、ＳＩ−０２０：使用量は表１を参照）と、表面調整剤（ビックケミー社製、ＢＹＫ−３７５）１ｇと、を攪拌機を用いて混合し、これにメチルシクロヘキサン１０ｇ、ｎ−ブチルアセテート２０ｇ、脂肪酸アミド（伊藤製油社製、ＴＳ−８２３［固形分２０ｗ％］：使用量は表１を参照）と、をホモディスパー（攪拌条件５，０００ｒｐｍ×３０分）を用いて別容器で作成したペーストを攪拌しながら加えた。さらに、塗装後の塗膜光沢が６０°反射においてグロス値１．５になるまで体質顔料（エボニック社製、ＴＳ−１００）を加えて攪拌を行い、さらにＢ型粘度計で求めたＴＩ値（塗料温度２５℃で回転数６ｒｐｍにおける粘度／塗料温度２５℃で回転数６０ｒｐｍにおける粘度）が表２、３、４に示す値になるまでｎ−ブチルアセテートを加えて攪拌を行い塗料を得た。
なお、表１中の「非多孔性」とは、非多孔性の樹脂粒子（ガンツ化成社製、ガンツパールＧＭ−０８０１）のことである。また、表１中の「−」の記載は、該当物質の使用量が０ｇであることを示す。そして、表１中の使用量とは、溶媒を含まない量である。
Next, the manufacturing method of the test bodies 1-17 (paint) is demonstrated.
[Method for producing specimen]
144 g of the acrylic modified polyolefin resin solution obtained by the above production method (nonvolatile content: 50 g, see Table 1 for types), porous resin particles (see Table 1 for types and amounts used), polymethylsil Sesquioxane fine particles (manufactured by Ganz Kasei Co., Ltd., SI-020: see Table 1 for the amount used) and 1 g of a surface conditioner (BYK-375, manufactured by BYK-Chemie Co., Ltd.) were mixed using a stirrer. Cyclohexane 10 g, n-butyl acetate 20 g, fatty acid amide (manufactured by Ito Oil Co., Ltd., TS-823 [solid content 20 w%]: see Table 1 for amount used), and homodispers (stirring conditions 5,000 rpm × 30 minutes) The paste prepared in a separate container was added with stirring. Further, an extender pigment (TS-100, manufactured by Evonik Co., Ltd.) was added and stirred until the gloss of the coated film after coating was 60 ° reflection and a gloss value of 1.5, and the TI value obtained with a B-type viscometer ( N-Butyl acetate was added and stirred until the viscosity at a coating temperature of 25 ° C. and a viscosity at a rotational speed of 6 rpm / the viscosity at a coating temperature of 25 ° C. and a viscosity at a rotational speed of 60 rpm were as shown in Tables 2, 3 and 4.
“Nonporous” in Table 1 refers to nonporous resin particles (manufactured by Ganz Kasei Co., Ltd., Ganzpearl GM-0801). Moreover, description of "-" in Table 1 shows that the usage-amount of an applicable substance is 0g. And the usage-amount in Table 1 is the quantity which does not contain a solvent.
［評価用試験板の作製］
前記製造方法により得られた試験体１〜１７（塗料）を、希釈溶剤（オリジン電気社製、エコネットシンナー＃９５０５）でＢ型粘度計の測定値で２０ｍＰａ・ｓ（６０ｒｐｍ、２５℃）になるように希釈調整し、表面未処理ポリプロピレン系樹脂素材（新神戸電機製、ＰＰ−Ｎ−ＡＮ）に乾燥膜厚２０μｍになるようにスプレー塗装を行った。スプレー終了後、恒温槽により６０℃で５分間強制乾燥を行った後、２５℃、５５％ＲＨの条件に４８時間放置したものを評価用試験板とし、下記項目の試験を行った。
[Preparation of test plate for evaluation]
Specimens 1 to 17 (paints) obtained by the above production method were adjusted to 20 mPa · s (60 rpm, 25 ° C.) as measured by a B-type viscometer using a diluent solvent (Econnet Thinner # 9505, manufactured by Origin Electric Co., Ltd.). Dilution adjustment was performed, and spray coating was performed on the untreated polypropylene resin material (manufactured by Shin-Kobe Electric Machinery Co., Ltd., PP-N-AN) to a dry film thickness of 20 μm. After completion of spraying, forced drying was performed at 60 ° C. for 5 minutes in a thermostatic bath, and the samples were left for 48 hours under conditions of 25 ° C. and 55% RH as test plates for evaluation, and the following items were tested.
［試験項目と試験方法］
（付着性試験）
前記の評価用試験板の表面を、１ｍｍ×１ｍｍ×１００個の碁盤目状にカットし、セロハンテープ剥離試験後の残存碁盤目数から評価を行った。評価基準は、１００個の碁盤目が残存している場合を極めて良好（○）、７６〜９９個の碁盤目が残存している場合を良好（△）、残存碁盤目数が７５個以下の場合を不良（×）と評価した。
[Test items and test methods]
(Adhesion test)
The surface of the test plate for evaluation was cut into 1 mm × 1 mm × 100 grids, and evaluation was performed from the number of grids remaining after the cellophane tape peeling test. The evaluation criteria are very good (◯) when 100 grids remain, good (△) when 76 to 99 grids remain, and the number of remaining grids is 75 or less. The case was evaluated as bad (x).
（耐水付着性試験）
前記の評価用試験板を５０℃温水中に４８時間浸漬後、その表面を１ｍｍ×１ｍｍ×１００個の碁盤目状にカットし、セロハンテープ剥離試験後の残存碁盤目数から評価を行った。なお、評価基準は付着性試験と同様である。
(Water adhesion test)
The test plate for evaluation was immersed in warm water at 50 ° C. for 48 hours, and then the surface was cut into 1 mm × 1 mm × 100 grids, and evaluation was performed from the number of grids remaining after the cellophane tape peeling test. The evaluation criteria are the same as in the adhesion test.
（耐油性試験）
前記の評価用試験板の表面（塗膜上）にエンジンオイルを０．２ｍｌ滴下し、８０℃×３時間放置した後に拭き取り、塗膜の外観を調べた。評価基準は、塗膜膨潤およびエンジンオイル跡がない場合を極めて良好（○）、エンジンオイル跡はあるが、塗膜膨潤がない場合を良好（△）、塗膜膨潤があるとともに、エンジンオイル跡もある場合を不良（×）と評価した。
(Oil resistance test)
0.2 ml of engine oil was dropped on the surface of the test plate for evaluation (on the coating film), left to stand at 80 ° C. for 3 hours, and then wiped off to examine the appearance of the coating film. The evaluation criteria are very good (◯) when there is no coating film swelling and no engine oil trace, good (△) when there is an engine oil trace, but no coating film swelling, and there is coating film swelling and engine oil trace. In some cases, it was evaluated as bad (×).
（耐傷付き性試験）
前記の評価用試験板の表面（塗膜上）に１平方センチメートルあたり１００ｇの荷重をかけた１００〜１５０μｍのガラスビーズを敷き、１０ｃｍ／秒の速度で塗膜上（１０ｃｍ）を５往復した後の光沢保持率を測定して評価した。評価基準は、光沢保持率が１００〜１１０％の場合を極めて良好（○）、光沢保持率が１１０％を超えて１２０％未満の場合を良好（△）、光沢保持率が１２０％以上の場合を不良（×）と評価した。
(Scratch resistance test)
The surface of the test plate for evaluation (on the coating film) was laid with 100 to 150 μm glass beads applied with a load of 100 g per square centimeter, and after 5 reciprocations on the coating film (10 cm) at a speed of 10 cm / second. The gloss retention was measured and evaluated. Evaluation criteria are very good when the gloss retention is 100 to 110% (◯), good when the gloss retention exceeds 110% and less than 120% (Δ), and when the gloss retention is 120% or more. Was evaluated as defective (x).
（耐跡残り性試験）
前記の評価用試験板（Ｎｏ．７、８、１６、１７）の表面（塗膜上）に１平方センチメートルあたり５０ｇの荷重をかけた消しゴム（トンボ鉛筆社製、ＳＡＮＤ ＥＲＡＳＥＲ ５１２Ｎ）で１０ｃｍ／秒の速度で塗膜上（１０ｃｍ）を５往復した後の消しゴムのカスの跡残りの程度により評価した。評価基準は、目視により塗膜表面を確認した際に、跡残りのない場合を極めて良好（○）、線状の跡残りのある場合（面状の跡残りはない）を良好（△）、面状の跡残りのある場合を不良（×）と評価した。
(Remaining trace resistance test)
An eraser (SAND ERASER 512N, manufactured by Dragonfly Pencil Co., Ltd.) having a load of 50 g per square centimeter on the surface (on the coating film) of the test plate for evaluation (No. 7, 8, 16, 17) was 10 cm / second. Evaluation was made based on the extent of traces of eraser residue after 5 reciprocations on the coating film (10 cm) at a speed. The evaluation criteria are very good (◯) when there is no trace when visually checking the coating film surface, and good (△) when there is a linear trace (no planar trace), The case where a planar trace remained was evaluated as defective (x).
（安定性試験）
前記の試験体（塗料）を約１００ｍｌ、ガラス瓶に移し密閉した後、４０℃雰囲気の条件に７日間放置したものを評価用塗料とし、相分離および沈殿物が発生していないか確認を行った。評価基準は、相分離、沈殿物ともにない場合を極めて良好（○）、相分離はあるが沈殿物はない場合を良好（△）、相分離、沈殿物ともにある場合を不良（×）と評価した。
各試験結果を表２、３、４および図１に示す。
(Stability test)
About 100 ml of the above-mentioned test body (paint) was transferred to a glass bottle and sealed, and then allowed to stand for 7 days in an atmosphere of 40 ° C. was used as an evaluation paint, and it was confirmed whether phase separation or precipitation had occurred. . Evaluation criteria are very good (○) when there is neither phase separation nor precipitate, good (△) when there is phase separation but no precipitate, and poor (×) when both phase separation and precipitate are present. did.
The test results are shown in Tables 2, 3, 4 and FIG.
試験体１〜１１、１４、１５については、アクリル変性塩素化ポリオレフィン樹脂（Ａ）と、多孔質性の樹脂粒子（Ｂ）と、脂肪酸アミド（Ｃ）と、を含むことから、付着性、耐傷付き性のいずれについても、極めて良好（○）または良好（△）という評価となった。
一方、試験体１２については、多孔質性の樹脂粒子（Ｂ）を含有せず、試験体１３については、非多孔性の樹脂粒子を含有していたことから、耐傷付き性が不良（×）という結果となった。
About the test bodies 1-11,14,15, since it contains acrylic modified chlorinated polyolefin resin (A), porous resin particle (B), and fatty acid amide (C), it is adhesive and scratch-resistant. All of the sticking properties were evaluated as extremely good (◯) or good (Δ).
On the other hand, since the test body 12 did not contain porous resin particles (B) and the test body 13 contained non-porous resin particles, the scratch resistance was poor (x). It became the result.
なお、試験体１〜１１、１４、１５のなかでも、試験体１〜８については、（Ａ）中の（ａ１）（ａ３）の重量比率、（Ｂ）の重量比率、（Ｃ）の重量比率、ＴＩ値について、本発明の規定する範囲内であったため、付着性、耐傷付き性だけでなく、耐水付着性、耐油性、安定性の全ての試験で、極めて良好（○）という結果となった。
また、その中でも、試験体７、８については、さらに、ポリメチルシルセスキオキサン微粒子（Ｄ）を本発明の規定する範囲内で含有していたため、前記試験だけでなく跡残り性についても、極めて良好（○）という結果となった。
In addition, among the test bodies 1-11, 14, and 15, about the test bodies 1-8, the weight ratio of (a1) (a3) in (A), the weight ratio of (B), the weight of (C). Since the ratio and TI value were within the ranges specified by the present invention, not only adhesion and scratch resistance, but also all the tests for water adhesion, oil resistance and stability were extremely good (◯). became.
Among them, for the test bodies 7 and 8, since the polymethylsilsesquioxane fine particles (D) were contained within the range defined by the present invention, not only the test but also traceability, The result was very good (◯).
試験体９については、（Ａ）中の（ａ１）の重量比率が本発明の規定する下限値未満であったことから、付着性が良好（△）という評価にとどまるとともに、耐水付着性が不良（×）という結果となった。
試験体１０については、（Ａ）中の（ａ１）の重量比率が本発明の規定する上限値を超えていたことから、耐油性が良好（△）という評価にとどまるという結果となった。
For the test specimen 9, the weight ratio of (a1) in (A) was less than the lower limit specified by the present invention, so that the evaluation of good adhesion (Δ) remained and the water adhesion resistance was poor. The result was (×).
With respect to the test body 10, since the weight ratio of (a1) in (A) exceeded the upper limit defined by the present invention, the result was that the oil resistance was only evaluated as good (Δ).
試験体１１〜１３については、（Ｂ）の重量比率が本発明の規定する下限値未満であった（含有しなかった）または上限値を超えていたことから、前記試験のうち１つ以上について、良好（△）という評価にとどまる、または、不良（×）という結果となった。 About the test bodies 11-13, since the weight ratio of (B) was less than the lower limit prescribed | regulated by this invention (it did not contain) or exceeded the upper limit, about one or more of the said tests The evaluation was only good (Δ), or was poor (×).
試験体１４については、（Ｃ）の重量比率が本発明の規定する下限値未満であるとともに、ＴＩ値が本発明の規定する下限値未満であったため、安定性が不良（×）という結果となった。この結果は、図１からも明らかである。
試験体１５については、（Ｃ）の重量比率が本発明の規定する上限値を超えていたことから、耐水付着性、耐油性、および耐傷付き性が良好（△）という評価にとどまるという結果となった。
For the test specimen 14, the weight ratio of (C) was less than the lower limit defined by the present invention, and the TI value was less than the lower limit defined by the present invention. became. This result is also apparent from FIG.
As for the test body 15, since the weight ratio of (C) exceeded the upper limit defined by the present invention, the result was that the evaluation of the water adhesion resistance, the oil resistance, and the scratch resistance was good (Δ). became.
試験体１６については、（Ｄ）の重量比率が本発明の規定する上限値を超えていたことから、付着性および耐水付着性が不良（×）という結果となった。
試験体１７については、（Ｄ）の重量比率が本発明の規定する下限値未満であったことから、跡残り性が良好（△）という評価にとどまるという結果となった。
About the test body 16, since the weight ratio of (D) exceeded the upper limit prescribed | regulated by this invention, it resulted in that adhesiveness and water-resistant adhesiveness were unsatisfactory (x).
With respect to the test body 17, since the weight ratio of (D) was less than the lower limit defined by the present invention, the result was that the traceability was only evaluated as good (Δ).
Claims (3)
前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）と前記脂肪酸アミド（Ｃ）との合計１００ｗｔ％に対して、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率は９３．４〜９７．５ｗｔ％、前記脂肪酸アミド（Ｃ）の重量比率は２．５〜６．６ｗｔ％であり、
前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）と、前記多孔質性の樹脂粒子（Ｂ）との合計１００ｗｔ％に対して、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率は、６２．５〜９１．０ｗｔ％、前記多孔質性の樹脂粒子（Ｂ）の重量比率は、９．０〜３７．５ｗｔ％であり、
前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）は、塩素化ポリオレフィン樹脂（ａ１）と、アクリル系重合体（ａ３）と、から構成されるとともに、当該アクリル系重合体（ａ３）は、前記塩素化ポリオレフィン樹脂（ａ１）にアクリル系単量体（ａ２）をグラフト重合して得られるグラフト重合鎖であり、
前記塩素化ポリオレフィン樹脂（ａ１）と前記アクリル系重合体（ａ３）との合計１００ｗｔ％に対して、前記塩素化ポリオレフィン樹脂（ａ１）の重量比率は５．０〜１５．０ｗｔ％、前記アクリル系重合体（ａ３）の重量比率は８５．０〜９５．０ｗｔ％であり、
前記多孔質性の樹脂粒子（Ｂ）は、アクリル系単量体および塩素化ポリオレフィン樹脂が重合した樹脂（ｂ１）から構成されるものであり、
Ｂ型粘度計で測定したＴｈｉｘｏｔｒｏｐｉｃ Ｉｎｄｅｘ（ＴＩ値＝塗料温度２５℃で回転数６ｒｐｍにおける粘度／塗料温度２５℃で回転数６０ｒｐｍにおける粘度）が２．５〜５．０であることを特徴とする塗料。 An organic solvent composed of at least one of an ester-based organic solvent, a ketone-based organic solvent, an alcohol-based organic solvent, and a non-aromatic hydrocarbon-based organic solvent; an acrylic-modified chlorinated polyolefin resin (A); Quality resin particles (B) and fatty acid amide (C),
The total weight of the acrylic modified chlorinated polyolefin resin (A) and the fatty acid amide (C) is 100 wt%, and the weight ratio of the acrylic modified chlorinated polyolefin resin (A) is 93.4 to 97.5 wt%, The weight ratio of the fatty acid amide (C) is 2.5 to 6.6 wt%,
The total weight of the acrylic modified chlorinated polyolefin resin (A) and the porous resin particles (B) is 100 wt%, and the weight ratio of the acrylic modified chlorinated polyolefin resin (A) is 62.5 to 91.0 wt%, the weight ratio of the porous resin particles (B) is 9.0 to 37.5 wt%,
The acrylic-modified chlorinated polyolefin resin (A) is composed of a chlorinated polyolefin resin (a1) and an acrylic polymer (a3), and the acrylic polymer (a3) is composed of the chlorinated polyolefin resin (a3). A graft polymer chain obtained by graft polymerization of the acrylic monomer (a2) to the resin (a1),
The total weight of the chlorinated polyolefin resin (a1) and the acrylic polymer (a3) is 100 wt%, and the weight ratio of the chlorinated polyolefin resin (a1) is 5.0 to 15.0 wt%. The weight ratio of the polymer (a3) is 85.0 to 95.0 wt%,
The porous resin particle (B) is intended to be composed of A acrylic monomers and chlorinated polyolefin resin is polymerized resin (b1),
Thixotropic index (TI value = viscosity at a coating temperature of 25 ° C. at a rotation speed of 6 rpm / viscosity temperature at a coating temperature of 25 ° C. and a viscosity at a rotation speed of 60 rpm) measured by a B-type viscometer is 2.5 to 5.0 paint.
前記ポリメチルシルセスキオキサン微粒子（Ｄ）の平均粒子径は、１．０〜５．０μmであり、
前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）と前記ポリメチルシルセスキオキサン微粒子（Ｄ）との合計１００ｗｔ％に対して、前記アクリル変性塩素化ポリオレフィン樹脂（Ａ）の重量比率は６６．０〜８３．０ｗｔ％、前記ポリメチルシルセスキオキサン微粒子（Ｄ）の重量比率は１７．０〜３４．０ｗｔ％であることを特徴とする請求項１または請求項２に記載の塗料。 Further comprising polymethylsilsesquioxane fine particles (D),
The polymethylsilsesquioxane fine particles (D) have an average particle size of 1.0 to 5.0 μm,
The weight ratio of the acrylic modified chlorinated polyolefin resin (A) is 66.0 to 83 with respect to 100 wt% in total of the acrylic modified chlorinated polyolefin resin (A) and the polymethylsilsesquioxane fine particles (D). The paint according to claim 1 or 2, wherein the weight ratio of the polymethylsilsesquioxane fine particles (D) is 17.0 to 34.0 wt%.
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