JP2003238895A - Coating composition - Google Patents
Coating compositionInfo
- Publication number
- JP2003238895A JP2003238895A JP2002038137A JP2002038137A JP2003238895A JP 2003238895 A JP2003238895 A JP 2003238895A JP 2002038137 A JP2002038137 A JP 2002038137A JP 2002038137 A JP2002038137 A JP 2002038137A JP 2003238895 A JP2003238895 A JP 2003238895A
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- component
- parts
- coating composition
- weight
- 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.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 75
- -1 organosilane compound Chemical class 0.000 claims abstract description 41
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 20
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 6
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 115
- 239000007787 solid Substances 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003209 petroleum derivative Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 description 50
- 238000000576 coating method Methods 0.000 description 50
- 239000000178 monomer Substances 0.000 description 32
- 238000012360 testing method Methods 0.000 description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 17
- 239000003973 paint Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- 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 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000000049 pigment Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 239000011324 bead Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000013522 chelant Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000005595 acetylacetonate group Chemical group 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000001302 tertiary amino group Chemical group 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229930194542 Keto Natural products 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UVDDHYAAWVNATK-VGKOASNMSA-L (z)-4-[dibutyl-[(z)-4-oxopent-2-en-2-yl]oxystannyl]oxypent-3-en-2-one Chemical compound CC(=O)\C=C(C)/O[Sn](CCCC)(CCCC)O\C(C)=C/C(C)=O UVDDHYAAWVNATK-VGKOASNMSA-L 0.000 description 1
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- LAWHHRXCBUNWFI-UHFFFAOYSA-N 2-pentylpropanedioic acid Chemical compound CCCCCC(C(O)=O)C(O)=O LAWHHRXCBUNWFI-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SBHBXEGSFJXBTA-UHFFFAOYSA-N 3-methoxysilylpropyl prop-2-enoate Chemical compound CO[SiH2]CCCOC(=O)C=C SBHBXEGSFJXBTA-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- KJNZOAZUWTWQKR-UHFFFAOYSA-J 3-oxoheptanoate zirconium(4+) Chemical compound [Zr+4].CCCCC(=O)CC([O-])=O.CCCCC(=O)CC([O-])=O.CCCCC(=O)CC([O-])=O.CCCCC(=O)CC([O-])=O KJNZOAZUWTWQKR-UHFFFAOYSA-J 0.000 description 1
- ZBTZHBREPJUAJA-UHFFFAOYSA-J 3-oxohexanoate zirconium(4+) Chemical compound [Zr+4].[Zr+4].C(C)CC(CC(=O)[O-])=O.C(C)CC(CC(=O)[O-])=O.C(C)CC(CC(=O)[O-])=O.C(C)CC(CC(=O)[O-])=O ZBTZHBREPJUAJA-UHFFFAOYSA-J 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
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- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 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
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- UNKMHLWJZHLPPM-UHFFFAOYSA-N triethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CCO[Si](OCC)(OCC)COCC1CO1 UNKMHLWJZHLPPM-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- LFBULLRGNLZJAF-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](OC)(OC)COCC1CO1 LFBULLRGNLZJAF-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、塗料組成物に係
り、更に詳しくは、耐屈曲性及び耐クラック性に優れ
た、常温硬化が可能な2液型オルガノポリシロキサン系
塗料組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition, and more particularly to a room temperature curable two-pack type organopolysiloxane coating composition having excellent flex resistance and crack resistance.
【0002】[0002]
【従来の技術】従来より、耐候性及び耐汚染性に優れた
塗料組成物として、オルガノポリシロキサン系塗料が用
いられている。オルガノポリシロキサン系塗料のこれら
の性能は、三次元に形成されるシロキサン結合に起因す
るものであるが、その反面、塗膜の脆さ、基材への密着
不良という問題を有しており、また、塗膜の耐アルカリ
性に関しても充分な性能が得られていない。そこで、こ
れらの性能を向上させるため、アルキド樹脂、ポリエス
テル樹脂、アクリル樹脂、エポキシ樹脂等の有機樹脂を
塗料中に導入することが試みられてきた。2. Description of the Related Art Organopolysiloxane paints have hitherto been used as paint compositions having excellent weather resistance and stain resistance. These performances of the organopolysiloxane-based paint are due to siloxane bonds formed three-dimensionally, but on the other hand, they have problems of brittleness of the coating film and poor adhesion to the base material. Moreover, sufficient performance is not obtained with respect to alkali resistance of the coating film. Therefore, in order to improve these performances, it has been attempted to introduce an organic resin such as an alkyd resin, a polyester resin, an acrylic resin, or an epoxy resin into the paint.
【0003】例えば、特開2000−63612号公報
には、(A)エポキシ基との反応性官能基を有するアク
リル樹脂成分、有機金属化合物からなる硬化触媒成分及
び着色顔料を含有する有機質組成物と、(B)エポキシ
基を有するシラン化合物又はそのオリゴマー成分及びシ
リコーン樹脂成分を含有する無機質組成物とからなる、
2液型の塗料組成物が提案されている。そして、この2
液型塗料組成物を用いることで、耐候性及び旧塗膜に対
する付着性に優れた塗膜が得られることが開示されてい
る。また、この塗料組成物は、良好な貯蔵安定性を有し
ていることも記載されている。For example, JP-A-2000-63612 discloses (A) an organic composition containing an acrylic resin component having a functional group reactive with an epoxy group, a curing catalyst component made of an organometallic compound, and a color pigment. And (B) an silane compound having an epoxy group or an oligomer composition thereof and an inorganic composition containing a silicone resin component,
A two-pack type coating composition has been proposed. And this 2
It is disclosed that a coating film excellent in weather resistance and adhesion to an old coating film can be obtained by using a liquid coating composition. It is also described that this coating composition has good storage stability.
【0004】[0004]
【発明が解決しようとする課題】しかしながら、従来の
オルガノポリシロキサン系塗料では、塗膜にした際の耐
クラック性、耐屈曲性が充分ではないことが分かってき
た。特に、建築や土木構造物の分野においては、フレキ
シビリティーに富んだ部材が多く、優れた耐屈曲性、耐
クラック性を有する無機系の低汚染高耐候性塗料が強く
求められている。また、近年、戸建て住宅においても、
窯業系・金属系サイディング材を中心に10年、20年
といった長期に渡る塗膜性能の維持が求められている。However, it has been found that the conventional organopolysiloxane paints are not sufficient in crack resistance and flex resistance when formed into a coating film. In particular, in the field of construction and civil engineering structures, there are many highly flexible members, and there is a strong demand for an inorganic low-pollution high-weathering coating material having excellent bending resistance and crack resistance. In recent years, even in detached houses,
Mainly for ceramic and metal siding materials, it is required to maintain coating film performance for a long period such as 10 or 20 years.
【0005】そこで、得られる塗膜の耐屈曲・耐クラッ
ク性を改善するために、オルガノポリシロキサン系塗料
における有機樹脂の導入量を多くする検討がなされてい
る。有機樹脂を増量することで、確かに塗膜の耐屈曲性
・耐クラック性を改善することは可能であるが、一方、
オルガノポリシロキサン系塗料の特徴である耐候性能や
耐汚染性能が悪化することが分かった。Therefore, in order to improve the bending resistance and crack resistance of the resulting coating film, studies have been made to increase the amount of the organic resin introduced into the organopolysiloxane coating composition. By increasing the amount of organic resin, it is possible to improve the bending resistance and crack resistance of the coating film, but on the other hand,
It was found that the weather resistance and stain resistance, which are the characteristics of the organopolysiloxane coating, deteriorate.
【0006】このように、従来のオルガノポリシロキサ
ン系塗料においては、耐候性・耐汚染性と耐屈曲性・耐
クラック性との両立は達成されておらず、オルガノポリ
シロキサン系塗料本来の耐候性能を損なうことなく、耐
屈曲性及び耐クラック性にも優れたオルガノポリシロキ
サン系塗料組成物が望まれている。As described above, in the conventional organopolysiloxane-based paint, the weather resistance / contamination resistance and the flex resistance / crack resistance are not achieved at the same time. There is a demand for an organopolysiloxane-based coating composition which is excellent in flex resistance and crack resistance without impairing the resistance to cracking.
【0007】本発明は、かかる要望に基づきなされたも
のであって、その目的とするところは、優れた耐屈曲性
及び耐クラック性を有する2液常温硬化型のオルガノポ
リシロキサン系塗料組成物を提供することにある。The present invention has been made based on such a demand, and an object of the present invention is to provide a two-part room temperature curing type organopolysiloxane coating composition having excellent flex resistance and crack resistance. To provide.
【0008】[0008]
【課題を解決するための手段】すなわち、本発明は、
(a)Si含量が15重量%以上であるアルコキシ基含
有有機シラン化合物、(b)グリシジル基と反応し得る
官能基を有するアクリル系共重合体、(c)硬化触媒、
(d)グリシジル基含有オルガノシロキサン、及び
(e)エポキシ当量が100〜1500であり、重量平
均分子量が200以上、100,000以下である、S
i原子を含有しないグリシジル基含有化合物を含む、オ
ルガノポリシロキサン系塗料組成物である。That is, the present invention is
(A) an alkoxy group-containing organosilane compound having a Si content of 15% by weight or more, (b) an acrylic copolymer having a functional group capable of reacting with a glycidyl group, (c) a curing catalyst,
(D) a glycidyl group-containing organosiloxane, and (e) an epoxy equivalent of 100 to 1500 and a weight average molecular weight of 200 or more and 100,000 or less, S
An organopolysiloxane coating composition containing a glycidyl group-containing compound containing no i atom.
【0009】[0009]
【発明の実施の形態】本発明の2液常温硬化型のオルガ
ノポリシロキサン系塗料組成物は、上記した(a)〜
(e)成分を必須成分として含有するものであるが、使
用に際しては、第1液と第2液とからなる2液を混合し
て調製される。まず、本発明の塗料組成物に用いられる
各成分について以下に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The two-part room temperature curing type organopolysiloxane-based coating composition of the present invention has the above-mentioned (a) to (a).
Although it contains the component (e) as an essential component, it is prepared by mixing two liquids consisting of a first liquid and a second liquid in use. First, each component used in the coating composition of the present invention will be described below.
【0010】<(a)成分>(a)成分として用いるア
ルコキシ基含有有機シラン化合物は、塗料の耐候性能及
び耐汚染性能の点から、Si含量の下限が15重量%で
あり、好ましくは20重量%である。一方、Si含量の
上限については特に制限はないが、一般的に40重量
%、好ましくは35重量%である。<Component (a)> The alkoxy group-containing organosilane compound used as the component (a) has a lower limit of Si content of 15% by weight, preferably 20% by weight, from the viewpoint of weather resistance and stain resistance of the coating composition. %. On the other hand, the upper limit of the Si content is not particularly limited, but is generally 40% by weight, preferably 35% by weight.
【0011】ここで、(a)成分のSi含量は、道路公
団規格である熱分解方法より求めることができる。具体
的には、テフロン(登録商標)耐圧容器に約1gの
(a)成分(固形分)を精秤し、濃硫酸を2〜3ml加
える。次いで、150〜160℃に加熱して24時間放
置し、アルコキシ基含有有機シラン化合物を分解する。
得られた硫酸溶液を、予め質量(重量)を量った白金皿
に移し、ゆっくりと大気中で700〜800℃まで昇温
してアルコキシ基含有有機シラン化合物分を完全に分解
する。冷却後秤量し、残分から次式により、まず、シリ
カ(SiO2)量(重量%)を求める。
Here, the Si content of the component (a) can be determined by a thermal decomposition method which is a standard of the Highway Public Corporation. Specifically, about 1 g of component (a) (solid content) is precisely weighed in a Teflon (registered trademark) pressure resistant container, and 2-3 ml of concentrated sulfuric acid is added. Then, it is heated to 150 to 160 ° C. and left for 24 hours to decompose the alkoxy group-containing organosilane compound.
The obtained sulfuric acid solution is transferred to a platinum dish previously weighed (weight) and slowly heated to 700 to 800 ° C. in the atmosphere to completely decompose the alkoxy group-containing organosilane compound. After cooling, the weight is measured, and the amount of silica (SiO 2 ) (% by weight) is first determined from the residue by the following formula.
【0012】そして、求められたシリカ(SiO2)量
(重量%)から、次式により、Si含量(重量%)を求
める。
Then, the Si content (% by weight) is calculated from the calculated amount of silica (SiO 2 ) (% by weight) by the following equation.
【0013】また、本発明においては、アルコキシ基含
有有機シラン化合物が、下記の一般式(1)、
(式中、R1は、水素原子又はアルキル基であり、R2、
R3及びR4は、それぞれ独立して、水素原子、OR1、
アルキル基又はアリール基である)を有するシラン化合
物またはその縮合物であることが好ましい。なお、縮合
物である場合、その縮合度としては2〜100の範囲が
一般的であり、相溶性の点からは、縮合度が2〜15で
ある液状のものが好ましい。また、本発明において、
(a)成分であるアルコキシ基含有有機シラン化合物
は、1種類のみとしてもよいし、2種以上を組み合わせ
て用いてもよい。In the present invention, the alkoxy group-containing organosilane compound has the following general formula (1): (In the formula, R 1 is a hydrogen atom or an alkyl group, and R 2 ,
R 3 and R 4 are each independently a hydrogen atom, OR 1 ,
It is preferably a silane compound having an alkyl group or an aryl group) or a condensate thereof. In the case of a condensate, the degree of condensation is generally in the range of 2 to 100, and from the viewpoint of compatibility, a liquid having a degree of condensation of 2 to 15 is preferable. In the present invention,
The alkoxy group-containing organosilane compound as the component (a) may be used alone or in combination of two or more.
【0014】本発明においては、(a)成分として、上
記一般式(1)中、R1がメチル基であり、R2、R3、
R4がそれぞれ独立にメチル基、フェニル基又はメトキ
シ基である化合物を用いることがより好ましい。In the present invention, as the component (a), in the general formula (1), R 1 is a methyl group, and R 2 , R 3 and
It is more preferable to use a compound in which each R 4 is independently a methyl group, a phenyl group or a methoxy group.
【0015】好ましいアルコキシ基含有有機シラン化合
物として、具体的には、DC3074、DC3037、
SR2402(以上、東レ・ダウコーニング・シリコー
ン(株)製品)、KR9218、KR500、KR40
0、X40−9225、KR−510、X40−922
7、X40−9247(以上、信越化学工業(株)製
品)などを例示することができる。Specific examples of preferable alkoxy group-containing organosilane compounds include DC3074, DC3037,
SR2402 (Toray Dow Corning Silicone Co., Ltd. product), KR9218, KR500, KR40
0, X40-9225, KR-510, X40-922
7, X40-9247 (above, Shin-Etsu Chemical Co., Ltd. product) etc. can be illustrated.
【0016】<(b)成分>(b)成分として用いるア
クリル系共重合体は、グリシジル基と反応し得る官能基
を有していることが必要である。かかる官能基として
は、カルボキシル基、第一級アミノ基、第二級アミノ
基、第三級アミノ基、メルカプト基、水酸基等を挙げる
ことができる。反応性の点から、アミノ基が好ましく、
特に、第三級アミノ基が好ましい。<Component (b)> The acrylic copolymer used as the component (b) is required to have a functional group capable of reacting with a glycidyl group. Examples of such a functional group include a carboxyl group, a primary amino group, a secondary amino group, a tertiary amino group, a mercapto group and a hydroxyl group. From the viewpoint of reactivity, an amino group is preferable,
Particularly, a tertiary amino group is preferable.
【0017】また、アクリル系共重合体は、重量平均分
子量(標準ポリスチレン換算)が3,000〜100,
000であることが好ましく、より好ましくは5,00
0〜50,000である。The acrylic copolymer has a weight average molecular weight (converted to standard polystyrene) of 3,000 to 100,
It is preferably 000, more preferably 5,000
It is 0 to 50,000.
【0018】なお、(b)成分におけるグリシジル基と
反応し得る官能基の量は、(d)及び(e)成分のグリ
シジル基1当量に対して、0.01〜2当量となるもの
が好ましく、より好ましくは0.1〜1.2当量であ
る。具体的には、アミン当量が300〜10000の範
囲にある第三級アミノ基を含有するアクリル系共重合体
が挙げられる。The amount of the functional group capable of reacting with the glycidyl group in the component (b) is preferably 0.01 to 2 equivalents relative to 1 equivalent of the glycidyl group in the components (d) and (e). , And more preferably 0.1 to 1.2 equivalents. Specifically, an acrylic copolymer containing a tertiary amino group having an amine equivalent in the range of 300 to 10,000 can be mentioned.
【0019】(b)成分を構成するモノマー組成は、グ
リシジル基と反応し得る官能基を有していれば、特に制
限はないが、(b)成分のTgが−10〜30℃になる
ようなモノマー組成とすることが好ましい。Tgが−1
0〜30℃の範囲にある(b)成分は、例えば、エチレ
ン性不飽和モノマー(b1)、及びこのモノマー(b
1)と共重合可能な、グリシジル基と反応し得る官能基
(好ましくは、アミノ基)含有エチレン性不飽和モノマ
ー(b2)を溶剤中においてラジカル重合開始剤を用い
て共重合することにより得ることができる。The monomer composition constituting the component (b) is not particularly limited as long as it has a functional group capable of reacting with the glycidyl group, but the Tg of the component (b) is -10 to 30 ° C. It is preferable to use a different monomer composition. Tg is -1
The component (b) in the range of 0 to 30 ° C. includes, for example, an ethylenically unsaturated monomer (b1), and this monomer (b1).
Obtained by copolymerizing a functional group (preferably amino group) -containing ethylenically unsaturated monomer (b2) copolymerizable with 1) with a radical polymerization initiator in a solvent. You can
【0020】ここで、エチレン性不飽和モノマー(b
1)としては、(メタ)アクリル酸、メチル(メタ)ア
クリレート、エチル(メタ)アクリレート、イソプロピ
ル(メタ)アクリレート、n−ブチル(メタ)アクリレ
ート、イソブチル(メタ)アクリレート、t−ブチル
(メタ)アクリレート、n−ヘキシル(メタ)アクリレ
ート、シクロヘキシル(メタ)アクリレート、2−エチ
ルヘキシル(メタ)アクリレート、ラウリル(メタ)ア
クリレート、ステアリル(メタ)アクリレートなどの
(メタ)アクリル酸のC1〜C24アルキルまたはシク
ロアルキルエステル、ヒドロキシプロピル(メタ)アク
リレートなどの(メタ)アクリル酸のC3〜C8のヒド
ロキシアルキルエステル、スチレン、ビニルトルエン、
α−メチルスチレン、N−ビニルピロリドン、ビニルピ
リジンなどの塩基性芳香族不飽和モノマー、エチレング
リコールジ(メタ)アクリレート等のアルキレングリコ
ールジ(メタ)アクリレート、酢酸ビニル、マレイン
酸、イタコン酸、クロトン酸などが挙げられる。なお、
上記したモノマー(b1)は、二種類以上組み合わせて
使用しても差しつかえない。Here, the ethylenically unsaturated monomer (b
1) includes (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate. , C-C24 alkyl or cycloalkyl esters of (meth) acrylic acid such as, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate. C3 to C8 hydroxyalkyl ester of (meth) acrylic acid such as hydroxypropyl (meth) acrylate, styrene, vinyltoluene,
Basic aromatic unsaturated monomers such as α-methylstyrene, N-vinylpyrrolidone and vinylpyridine, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, vinyl acetate, maleic acid, itaconic acid, crotonic acid And so on. In addition,
The above-mentioned monomers (b1) may be used in combination of two or more kinds.
【0021】また、エチレン性不飽和モノマー(b1)
として、水酸基含有エチレン性不飽和モノマーを用いる
ことも可能である。具体的には、2−ヒドロキシエチル
(メタ)アクリレート、ヒドロキシプロピル(メタ)ア
クリレート、4−ヒドロキシブチルアクリレート、ジエ
チレングリコール(メタ)アクリレート等のポリオキシ
アルキレングリコール(メタ)アクリレート(アルキレ
ン基の炭素数は2〜4であり、アルキレンオキシドの付
加モル数は1〜50である。)、カプロラクトン変性ヒ
ドロキシ(メタ)アクリレート(ダイセル化学(株)
製、商品名:プラクセルFM、FA)、N−メチロール
アクリルアミドなどが挙げられる。The ethylenically unsaturated monomer (b1)
As the above, it is also possible to use a hydroxyl group-containing ethylenically unsaturated monomer. Specifically, polyoxyalkylene glycol (meth) acrylates (wherein the alkylene group has 2 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, and diethylene glycol (meth) acrylate). 4 to 4, and the number of moles of alkylene oxide added is 1 to 50), and caprolactone-modified hydroxy (meth) acrylate (Daicel Chemical Co., Ltd.).
Manufactured, trade name: Praxel FM, FA), N-methylol acrylamide and the like.
【0022】グリシジル基と反応し得る官能基(好まし
くは、アミノ基)含有エチレン性不飽和モノマー(b
2)は、上記モノマー(b1)と共重合可能なモノマー
であり、具体的には、ジメチルアミノエチル(メタ)ア
クリレートなどのアミノ基含有(メタ)アクリル酸エス
テル、アクリルアミド、ジアセトンアクリルアミド、
N,N−ジメチルアミノプロピルアクリルアミド、N,
N−ジメチルアクリルアミド、アクリロイルモルホリ
ン、N−イソプロピルアクリルアミド、N,N−ジエチ
ルアクリルアミド、ジエチルアミノプロピルアクリルア
ミドなどのアミノ基含有(メタ)アクリルアミドなどが
挙げられる。これらの中でも、反応性の点から、ジメチ
ルアミノエチルメタクリレートが好ましい。なお、これ
らのモノマーも二種類以上組み合わせて使用することが
できる。An ethylenically unsaturated monomer (b) containing a functional group (preferably an amino group) capable of reacting with a glycidyl group.
2) is a monomer copolymerizable with the above-mentioned monomer (b1), and specifically, amino group-containing (meth) acrylic acid ester such as dimethylaminoethyl (meth) acrylate, acrylamide, diacetone acrylamide,
N, N-dimethylaminopropyl acrylamide, N,
Examples thereof include amino group-containing (meth) acrylamides such as N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide and diethylaminopropylacrylamide. Among these, dimethylaminoethyl methacrylate is preferable from the viewpoint of reactivity. In addition, these monomers can also be used in combination of 2 or more types.
【0023】重合に用いられる溶媒としては、溶液重合
が可能であり、使用するモノマー及び得られるポリマー
を溶解させることができるものであれば、特に制限はな
い。具体的には、トルエン、キシレン、メチルエチルケ
トン、酢酸エチル、アセトン、イソプロピルアルコー
ル、ミネラルスピリット等が挙げられる。また、これら
は二種類以上組み合わせて使用しても差しつかえない。The solvent used for the polymerization is not particularly limited as long as it can be solution polymerized and can dissolve the monomer used and the polymer obtained. Specific examples include toluene, xylene, methyl ethyl ketone, ethyl acetate, acetone, isopropyl alcohol, and mineral spirits. Also, it is acceptable to use two or more of these in combination.
【0024】なお、溶媒としてミネラルスピリット等の
石油炭化水素系溶剤を用いた場合には、モノマーとし
て、炭化数4〜8の側鎖アルキルを有するビニル系モノ
マー、特にn−ブチルメタクリレート、i−ブチルメタ
クリレート、t−ブチルメタクリレート又はシクロヘキ
シル(メタ)アクリレートを含むものが好ましい。When a petroleum hydrocarbon solvent such as mineral spirit is used as the solvent, the monomer is a vinyl monomer having a side chain alkyl having 4 to 8 carbon atoms, especially n-butyl methacrylate, i-butyl. Those containing methacrylate, t-butyl methacrylate or cyclohexyl (meth) acrylate are preferred.
【0025】重合開始剤に関しても、熱または還元性物
質などによってラジカル分解してモノマーへの付加重合
を起こさせるものであれば、特に制限はない。例えば、
アゾビスイソブチロニトリル、ベンゾイルパーオキシ
ド、t−ブチルパーベンゾエート、t−ブチルハイドロ
パーオキシド、ジ−t−ブチルパーオキシド、クメンハ
イドロパーオキシドなどを単独もしくは数種類を混合し
て使用することができる。また、樹脂の分子量の調節の
ため、オクチルメルカプタン、ドデシルメルカプタンな
どの連鎖移動剤を添加することも可能である。The polymerization initiator is not particularly limited as long as it is radically decomposed by heat or a reducing substance to cause addition polymerization to the monomer. For example,
Azobisisobutyronitrile, benzoyl peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and the like can be used alone or in combination of several kinds. . It is also possible to add a chain transfer agent such as octyl mercaptan or dodecyl mercaptan in order to control the molecular weight of the resin.
【0026】(b)成分の具体的重合方法としては、溶
媒に、ラジカル重合開始剤の存在下、エチレン性不飽和
モノマー(b1)、及びグリシジル基と反応し得る官能
基(好ましくは、アミノ基)含有エチレン性不飽和モノ
マー(b2)の混合物を滴下するモノマー滴下法;溶
媒、ラジカル重合開始剤、並びにモノマー(b1)及び
(b2)からなる混合物のラジカル重合を行う一浴重合
法(モノマー等を一括装入して重合する方法)が挙げら
れる。安全性及び分子量の制御の点から、モノマー滴下
法が好ましい。The specific method for polymerizing the component (b) is as follows. A functional group (preferably an amino group) capable of reacting with the ethylenically unsaturated monomer (b1) and a glycidyl group in the presence of a radical polymerization initiator in a solvent. ) A monomer dropping method in which a mixture of the contained ethylenically unsaturated monomer (b2) is dropped; a one-bath polymerization method (monomer etc.) in which radical polymerization of a mixture of a solvent, a radical polymerization initiator, and the monomers (b1) and (b2) is performed. And a method of polymerizing the same. From the viewpoint of safety and control of molecular weight, the monomer dropping method is preferable.
【0027】本発明の(b)成分として、具体的には、
メタクリル酸メチル、アクリル酸n−ブチル、メタクリ
ル酸n−ブチル及びメタクリル酸ジメチルアミノエチル
から構成される共重合体、またはメタクリル酸シクロヘ
キシル、アクリル酸n−ブチル、メタクリル酸n−ブチ
ル及びメタクリル酸ジメチルアミノエチルから構成され
る共重合体等が挙げられる。As the component (b) of the present invention, specifically,
A copolymer composed of methyl methacrylate, n-butyl acrylate, n-butyl methacrylate and dimethylaminoethyl methacrylate, or cyclohexyl methacrylate, n-butyl acrylate, n-butyl methacrylate and dimethylamino methacrylate. Examples thereof include a copolymer composed of ethyl.
【0028】<(c)成分>(c)成分として用いる硬
化触媒は、有機金属化合物であることが好ましく、具体
的には、Ti、Al、Zr、Sn等の金属アルコキシド
化合物、金属キレート化合物、金属エステル化合物を用
いることができる。金属アルコキシド化合物としては、
例えば、アルミニウムトリメトキシド、アルミニウムト
リエトキシド、アルミニウムトリ−n−プロポキシド、
アルミニウムトリイソプロポキシド、アルミニウムトリ
−n−ブトキシド、アルミニウムトリイソブトキシド、
アルミニウムトリ−sec−ブトキシド、アルミニウムト
リ−tert−ブトキシド等のアルミニウムアルコキシド;
テトラメチルチタネート、テトラエチルチタネート、テ
トラ−n−プロピルチタネート、テトライソプロピルチ
タネート、テトラ−n−ブチルチタネート、テトライソ
ブチルチタネート、テトラ−tert−ブチルチタネート、
テトラ−n−ヘキシルチタネート、テトライソオクチル
チタネート、テトラ−n−ラウリルチタネート等のチタ
ニウムアルコキシド;テトラエチルジルコネート、テト
ラ−n−プロピルジルコネート、テトライソプロピルジ
ルコネート、テトラ−n−ブチルジルコネート、テトラ
−sec−ブチルジルコネート、テトラ−tert−ブチルジ
ルコネート、テトラ−n−ペンチルジルコネート、テト
ラ−tert−ペンチルジルコネート、テトラ−tert−ヘキ
シルジルコネート、テトラ−n−ヘプチルジルコネー
ト、テトラ−n−オクチルジルコネート、テトラ−n−ス
テアリルジルコネート等のジルコニウムアルコキシド;
ジブチルスズジブトキシド等が挙げられ、金属キレート
化合物としては、例えば、トリス(エチルアセトアセテ
ート)アルミニウム、トリス(n−プロピルアセトアセ
テート)アルミニウム、トリス(イソプロピルアセトア
セテート)アルミニウム、トリス(n−ブチルアセトア
セテート)アルミニウム、イソプロポキシビス(エチル
アセトアセテート)アルミニウム、トリス(アセチルア
セトナト)アルミニウム、トリス(プロポニルアセトナ
ト)アルミニウム、ジイソプロポキシプロピオニルアセ
トナトアルミニウム、アセチルアセトナト・ビス(プロ
ピオニルアセトナト)アルミニウム、モノエチルアセト
アセテート・ビス(アセチルアセトナト)アルミニウ
ム、アセチルアセトナトアルミニウム・ジ−sec−ブチ
レート、メチルアセトアセテ10−sec−ブチレート、
ジ(メチルアセトアセテート)アルミニウム・モノ−te
rt−ブチレート、ジイソプロポキシエチルアセトアセテ
ートアルミニウム、モノアセチルアセトナ・ビス(エチ
ルアセトアセテート)アルミニウム等のアルミニウムキ
レート化合物;ジイソプロポキシ・ビス(エチルアセト
アセテート)チタネート、ジイソプロポキシ・ビス(ア
セチルアセトナト)チタネート、ジ−n−ブトキシ・ビ
ス(アセチルアセトナト)チタネート等のチタニウムキ
レート化合物;テトラキス(アセチルアセトナト)ジル
コニウム、テトラキス(n−プロピルアセトアセテー
ト)ジルコニウム、テトラキス(エチルアセトアセテー
ト)ジルコニウム等のジルコニウムキレート化合物;ジ
ブチル錫ビス(アセチルアセトネート)等が挙げられ、
金属エステル化合物としては、例えば、ジブチル錫ジア
セテート、ジブチル錫ジ(2−エチルヘキシレート)、
ジベンジル錫ジ(2−エチルヘキシレート)、ジブチル
錫ジラウレート、ジブチル錫ジイソオクチルマレエート
等の錫エステル化合物等が挙げられる。これらの反応触
媒は1種又は2種以上を組み合わせて用いることが出来
る。<Component (c)> The curing catalyst used as the component (c) is preferably an organometallic compound, specifically, a metal alkoxide compound such as Ti, Al, Zr or Sn, a metal chelate compound, Metal ester compounds can be used. As the metal alkoxide compound,
For example, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide,
Aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide,
Aluminum alkoxides such as aluminum tri-sec-butoxide and aluminum tri-tert-butoxide;
Tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate,
Titanium alkoxides such as tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate; tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra- sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n- Zirconium alkoxides such as octyl zirconate and tetra-n-stearyl zirconate;
Examples thereof include dibutyltin dibutoxide, and examples of the metal chelate compound include tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, and tris (n-butylacetoacetate). Aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (proponylacetonato) aluminum, diisopropoxypropionylacetonato aluminum, acetylacetonato bis (propionylacetonato) aluminum, mono Ethyl acetoacetate bis (acetylacetonato) aluminum, acetylacetonato aluminum di-sec-butyrate, methylacetoacetate Te 10-sec- butyrate,
Di (methylacetoacetate) aluminum mono-te
Aluminum chelate compounds such as rt-butyrate, diisopropoxyethylacetoacetate aluminum, monoacetylacetona bis (ethylacetoacetate) aluminum; diisopropoxy bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetoacetate Titanium chelate compounds such as nato) titanate and di-n-butoxy bis (acetylacetonato) titanate; tetrakis (acetylacetonato) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium Zirconium chelate compound; dibutyltin bis (acetylacetonate) and the like,
Examples of the metal ester compound include dibutyltin diacetate, dibutyltin di (2-ethylhexylate),
Examples thereof include tin ester compounds such as dibenzyltin di (2-ethylhexylate), dibutyltin dilaurate and dibutyltin diisooctyl maleate. These reaction catalysts can be used alone or in combination of two or more.
【0029】また、硬化触媒によって塗料のポットライ
フや貯蔵安定性に問題が生じる場合には、ケト・エノー
ル型互変異性化合物を併用することが好ましい。ケト・
エノール型互変異性化合物としては、アセチルアセト
ン、アセト酢酸エチルエステル、マロン酸ジエステル、
ベンゾイルアセトン、ジベンジイルメタン、ダイアセト
ンアルコール、サリチル酸メチル等が挙げられる。When the curing catalyst causes problems in the pot life and storage stability of the coating material, it is preferable to use a keto / enol type tautomeric compound in combination. Keto
Examples of enol-type tautomeric compounds include acetylacetone, acetoacetic acid ethyl ester, malonic acid diester,
Examples thereof include benzoylacetone, dibendiylmethane, diacetone alcohol, methyl salicylate and the like.
【0030】<(d)成分>(d)成分として用いるグ
リシジル基含有オルガノシロキサンについては、特に制
限はなく、具体的には、グリシドキシメチルトリメトキ
シシラン、グリシドキシメチルトリエトキシシラン、β
−グリシドキシエチルトリメトキシシラン、β−グリシ
ドキシエチルトリエトキシシラン、γ−グリシドキシプ
ロピルトリメトキシシラン、γ−グリシドキシプロピル
トリエトキシシラン、γ−グリシドキシプロピル(メチ
ル)ジメトキシシラン、γ−グリシドキシプロピル(ジ
メチル)メトキシシラン、γ−グリシドキシプロピル
(エチル)ジメトキシシラン、(3,4−エポキシシク
ロヘキシル)メチルトリメトキシシラン、β−(3,4
−エポキシシクロヘキシル)エチルトリメトキシシラ
ン、γ−グリシドキシポリシロキサン等を挙げることが
できる。これらの中でも、相溶性及び反応性の点から、
γ−グリシドキシプロピルトリメトキシシランが好まし
い。<Component (d)> The glycidyl group-containing organosiloxane used as component (d) is not particularly limited, and specifically, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β
-Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl (methyl) dimethoxysilane , Γ-glycidoxypropyl (dimethyl) methoxysilane, γ-glycidoxypropyl (ethyl) dimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypolysiloxane and the like can be mentioned. Among these, from the viewpoint of compatibility and reactivity,
γ-glycidoxypropyltrimethoxysilane is preferred.
【0031】また、本発明においては、(d)成分とし
て、γ−(メタ)アクリロキシプロピルメトキシシラン
とグリシジル(メタ)アクリレートのようなグリシジル
基含有不飽和モノマーと、加水分解性シリル基含有不飽
和モノマーとの共重合体を用いることもできる。Further, in the present invention, as the component (d), γ- (meth) acryloxypropylmethoxysilane, a glycidyl group-containing unsaturated monomer such as glycidyl (meth) acrylate, and a hydrolyzable silyl group-containing unsaturated monomer. It is also possible to use a copolymer with a saturated monomer.
【0032】<(e)成分>(e)成分として用いるグ
リシジル基含有化合物は、エポキシ当量を100〜15
00とする必要があり、好ましくは150〜1000、
より好ましくは200〜500である。エポキシ当量が
上記範囲から外れる場合には、得られる塗料組成物の耐
屈曲性及び付着性が充分とはいえない。<Component (e)> The glycidyl group-containing compound used as component (e) has an epoxy equivalent of 100 to 15.
00, preferably 150-1000,
It is more preferably 200 to 500. If the epoxy equivalent is out of the above range, the resulting coating composition may not have sufficient flex resistance and adhesion.
【0033】ここで、エポキシ当量は、以下の方法によ
り求めることができる。まず、エポキシ化合物を0.2
〜1g程度精秤し、室温でメチルエチルケトン90ml
に溶解して試料溶液とする。これに氷酢酸を約10m
l、CTAB(臭化セチルトリメチルアンモニウム)を
1.0g、CV(クリスタルバイオレット)溶液(指示
薬)を10〜15滴加え、撹拌しながら0.1Nの過塩
素酸標準液で青緑色を呈するまで滴定する。終点は、青
緑色が1分持続する点とする。同様の方法で空試験を行
い、次式により、グリシジル基含有化合物のエポキシ等
量(WPE)を求める。
W : 試料の重量(g)
Vs : 0.1Nの過塩素酸標準液の使用量(滴下
量) ml数
Vb : 空試験の過塩素酸標準溶液の使用量(滴下
量) ml数
N : 過塩素酸液の規定度Here, the epoxy equivalent can be determined by the following method. First, the epoxy compound is 0.2
About 1g is precisely weighed and 90ml of methyl ethyl ketone at room temperature
Dissolve into a sample solution. About 10 m of glacial acetic acid
1, CTAB (cetyltrimethylammonium bromide) 1.0 g, CV (crystal violet) solution (indicator) 10 to 15 drops, and titrated with 0.1N perchloric acid standard solution until a blue-green color appears. To do. The end point is the point where blue-green color lasts for 1 minute. A blank test is conducted in the same manner, and the epoxy equivalent (WPE) of the glycidyl group-containing compound is calculated by the following formula. W: Weight of sample (g) Vs: Amount of 0.1N perchloric acid standard solution used (dripping amount) ml Vb: Amount of used perchloric acid standard solution in blank test (dripping amount) N number N: excess Normality of chloric acid solution
【0034】また、(e)成分のグリシジル基含有化合
物は、塗料組成物における他の成分(特に、(a)及び
(b)成分)との相溶性の点から、200以上、10
0,000以下の重量平均分子量を有していることが好
ましい。更に、得られる塗膜にフレキシビリティーを与
え耐屈曲性及び付着性を向上させるという点から、以下
の(i)〜(iii)に示すものを用いることが好まし
い。Further, the glycidyl group-containing compound as the component (e) is 200 or more and 10 or more from the viewpoint of compatibility with other components (particularly the components (a) and (b)) in the coating composition.
It preferably has a weight average molecular weight of 50,000 or less. Further, from the viewpoint of giving flexibility to the obtained coating film and improving bending resistance and adhesion, it is preferable to use the ones shown in the following (i) to (iii).
【0035】(i)ヒドロキシル基含有化合物をグリシ
ジルエーテル化した化合物
ここで、ヒドロキシ基含有化合物としては、(イ)メタ
ノール、エタノール、プロピルアルコール、高級アルコ
ール等の一価のアルコール類、エチレングリコール、プ
ロピレングリコール、ネオペンチルグリコール等のアル
キレングリコール、ポリエチレングリコール、ポリプロ
ピレングリコール、ポリテトラメチレンエーテルグリコ
ール等のポリアルキレングリコール、グリセリン、ソル
ビトール等の多価アルコール;(ロ)コハク酸、アジピ
ン酸、セバシン酸、アゼライン酸、テレフタル酸、イソ
フタル酸、オルソフタル酸、ヘキサヒドロテレフタル
酸、ヘキサヒドロイソフタル酸、ヘキサヒドロオルソフ
タル酸、ナフタレンジカルボン酸、1,4−シクロヘキ
サンジカルボン酸、トリメット酸等のポリカルボン酸、
酸エステル、又は酸無水物の1種以上と、エチレングリ
コール、1,2−プロパンジオール、1,3−プロパン
ジオール、1,2−ブタンジオール、1,3−ブタンジ
オール、1,4−ブタンジオール、1,5−ペンタンジ
オール、1,6−ヘキサンジオール、1,8−オクタン
ジオール、ネオペンチルグリコール、ジエチレングリコ
ール、ジプロピレングリコール、1,4−シクロヘキサ
ンジメタノール、トリメチロールプロパン、グリセリ
ン、ペンタエリスリトール等の低分子ポリオール類の1
種類以上との脱水縮合で得られるポリエステルポリオー
ル;(ハ)低分子ポリオール、低分子ポリアミン、低分
子アミノアルコールを開始剤として、ε−カプロラクト
ン、γ−バレロラクトン等の環状エステルモノマーの開
環重合で得られるラクトン系ポリエステルポリオール;
(ニ)低分子ポリオールと、ジエチレンカーボネート、
ジメチルカーボネート、ジエチルカーボネート、ジフェ
ニルカーボネート等との脱アルコール反応、脱フェノー
ル反応等で得られるポリカーボネートポリオール等が挙
げられる。(I) Compound obtained by converting a hydroxyl group-containing compound into a glycidyl ether Here, as the hydroxy group-containing compound, (a) monohydric alcohols such as methanol, ethanol, propyl alcohol and higher alcohols, ethylene glycol, propylene Glycol, alkylene glycol such as neopentyl glycol, polyethylene glycol, polypropylene glycol, polyalkylene glycol such as polytetramethylene ether glycol, polyhydric alcohol such as glycerin and sorbitol; (b) succinic acid, adipic acid, sebacic acid, azelaic acid , Terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, 1,4-sic Hexane dicarboxylic acid, polycarboxylic acids such as trimellitic acid,
One or more acid esters or acid anhydrides, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, etc. 1 of low molecular weight polyols
Polyester polyol obtained by dehydration condensation with more than one kind; (c) ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and γ-valerolactone using low molecular weight polyol, low molecular weight polyamine and low molecular weight amino alcohol as an initiator. The obtained lactone polyester polyol;
(D) Low molecular weight polyol, diethylene carbonate,
Examples thereof include polycarbonate polyols obtained by dealcoholation reaction with dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like, dephenolation reaction and the like.
【0036】具体的には、下記一般式で表せるような末
端にグリシジル基を有するエーテル化合物が挙げられ
る。
Specific examples thereof include ether compounds having a glycidyl group at the terminal as represented by the following general formula.
【0037】(ii)環状オキシラン型、グリシジルエ
ステル型、脂肪族不飽和化合物のエポキシ化型、多価カ
ルボン酸エステル型、ビスフェノールA型又はノボラッ
ク型の化合物
かかる化合物の例としては、下記の一般式で示されるよ
うなものが挙げられる。(Ii) Cyclic oxirane type, glycidyl ester type, epoxidized type of aliphatic unsaturated compound, polycarboxylic acid ester type, bisphenol A type or novolak type compound Examples of such compounds include the following general formulas. As shown in.
【0038】 [0038]
【0039】(iii)アクリル系重合体にグリシジル
基含有成分をグラフトした化合物
かかる化合物として具体的には、グリシジル基含有不飽
和モノマーと他のエチレン性不飽和モノマーの共重合体
が挙げられる。ここで、グリシジル基含有不飽和モノマ
ーとしては、グリシジル(メタ)アクリレート、β−メ
チルグリシジル(メタ)アクリレート、3,4−エポキ
シシクロヘキシルメチル(メタ)アクリレート、3,4
−エポキシシクロヘキシルプロピル(メタ)アクリレー
ト等が挙げられる。これらの中でも反応性の点からグリ
シジルメタクリレートが好ましい。また、耐屈曲性、耐
クラック性の点から、グリシジル基含有成分がグラフト
されたアクリル系重合体のTgが−50〜10℃の範囲
であり、エポキシ当量が500〜1500となるような
モノマー組成にすることが好ましい。例えば、グリシジ
ルメタクリレート、2−エチルヘキシルアクリレート、
n−ブチルメタクリレート及びn−ブチルアクリレート
から構成される共重合体を用いることができる。(Iii) A compound obtained by grafting a glycidyl group-containing component onto an acrylic polymer. Specific examples of such a compound include copolymers of a glycidyl group-containing unsaturated monomer and another ethylenically unsaturated monomer. Here, as the glycidyl group-containing unsaturated monomer, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4
-Epoxy cyclohexyl propyl (meth) acrylate etc. are mentioned. Among these, glycidyl methacrylate is preferable from the viewpoint of reactivity. Further, from the viewpoint of flex resistance and crack resistance, a monomer composition in which the Tg of the acrylic polymer grafted with the glycidyl group-containing component is in the range of -50 to 10 ° C and the epoxy equivalent is 500 to 1500. Is preferred. For example, glycidyl methacrylate, 2-ethylhexyl acrylate,
A copolymer composed of n-butyl methacrylate and n-butyl acrylate can be used.
【0040】<(f)成分>本発明の塗料組成物は、上
記した必須成分である(a)〜(e)成分に加えて、
(f)成分として、着色顔料、体質顔料及び有機溶剤を
適宜含んでいてもよい。<Component (f)> The coating composition of the present invention comprises, in addition to the above-mentioned essential components (a) to (e),
As the component (f), a color pigment, an extender pigment and an organic solvent may be appropriately contained.
【0041】着色顔料としては、酸化チタン、酸化亜
鉛、カーボンブラック、酸化第二鉄(ベンガラ)、黄
鉛、黄色酸化鉄、オーカー、群青、コバルトグリーン等
の無機系顔料、アゾ系、ナフトール系、ピラゾロン系、
アントラキノン系、ペリレン系、キナクリドン系、ジス
アゾ系、イソインドリノン系、ベンゾイミダゾール系、
フタロシアニン系、キノフタロン系等の有機顔料が挙げ
られる。The color pigments include inorganic pigments such as titanium oxide, zinc oxide, carbon black, ferric oxide (red iron oxide), yellow lead, yellow iron oxide, ocher, ultramarine blue, cobalt green, azo pigments, naphthol pigments, Pyrazolone,
Anthraquinone type, perylene type, quinacridone type, disazo type, isoindolinone type, benzimidazole type,
Examples include organic pigments such as phthalocyanine type and quinophthalone type.
【0042】体質顔料としては、重質炭酸カルシウム、
クレー、カオリン、タルク、沈降性硫酸バリウム、炭酸
バリウム、ホワイトカーボン、珪藻土等が挙げられる。Extending pigments include heavy calcium carbonate,
Examples thereof include clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon and diatomaceous earth.
【0043】有機溶剤としては、例えば、トルエン、キ
シレン、エチルベンゼン等の芳香族系溶剤、酢酸エチ
ル、酢酸ブチル、プロピレングリコールメチルエーテル
アセテート、プロピレングリコールメチルエーテルプロ
ピオネート等のエステル系溶剤、アセトン、メチルエチ
ルケトン、メチルイソブチルケトン、シクロヘキサノン
等のケトン系溶剤、ジエチレングリコールジメチルエー
テル、ジエチレングリコールジエチルエーテル、ジプロ
ピレングリコールジメチルエーテル等のエーテル系溶
剤、シクロヘキサン、メチルシクロヘキサン、エチルシ
クロヘキサン等の脂環式炭化水素系溶剤、メチルアルコ
ール、エチルアルコール、プロピルアルコール、ブチル
アルコール等のアルコール系溶剤、ミネラルスピリット
等の石油炭化水素系溶剤等が使用できる。これらの中で
も、特に、ミネラルスピリット等の石油炭化水素系溶剤
は、旧塗膜や基材を侵しにくく、また、低臭であるため
作業環境の改善に大きく役立つため、非常に好ましい。Examples of the organic solvent include aromatic solvents such as toluene, xylene and ethylbenzene, ester solvents such as ethyl acetate, butyl acetate, propylene glycol methyl ether acetate and propylene glycol methyl ether propionate, acetone and methyl ethyl ketone. , Methyl isobutyl ketone, ketone solvents such as cyclohexanone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, methyl alcohol, ethyl Alcohol-based solvents such as alcohol, propyl alcohol and butyl alcohol, petroleum hydrocarbon-based solvents such as mineral spirits Etc. can be used. Among these, petroleum hydrocarbon solvents such as mineral spirit are particularly preferable because they do not easily attack the old coating film and the base material and have a low odor, which greatly contributes to the improvement of the working environment.
【0044】更に、本発明の塗料組成物には、本発明の
目的を損なわない範囲で、可塑剤、防腐剤、防かび剤、
防藻剤、消泡剤、レベリング剤、顔料分散剤、沈降防止
剤、たれ防止剤、艶消し剤、紫外線吸収剤、光触媒酸化
チタン等の塗料用添加剤を適宜配合することができる。Further, the coating composition of the present invention contains a plasticizer, an antiseptic agent, an antifungal agent, within a range not impairing the object of the present invention.
Additives for paints such as an anti-algae agent, an antifoaming agent, a leveling agent, a pigment dispersant, an anti-settling agent, an anti-sagging agent, a matting agent, an ultraviolet absorber and a titanium oxide photocatalyst can be appropriately added.
【0045】続いて、本発明の塗料組成物中における、
各成分の配合量について説明する。Subsequently, in the coating composition of the present invention,
The blending amount of each component will be described.
【0046】まず、必須成分である(b)成分、(c)
成分及び(d)成分は、(a)成分100重量部に対し
て、それぞれ、30〜130重量部(固形分)、0.1
〜30重量部、1〜50重量部であることが好ましい。
ここで、(b)成分の量が少なくなると塗膜の耐アルカ
リ性が不充分となり、多すぎると塗膜の耐候性が低下す
る。また、(d)成分の量が少ないと塗膜の付着性が悪
化し、一方、多量に用いると塗膜のフレキシビリティー
が低下し耐屈曲性等に悪影響を及ぼす。なお、(c)成
分の量が0.1重量部より少ない場合には、硬化触媒と
して充分に機能することができず、また、30重量部よ
り多く用いても塗膜性能の向上はなく、経済的観点から
も好ましくない。耐候性、耐汚染性、耐屈曲性、耐クラ
ック性及び耐アルカリ性のバランスという点からは、
(b)成分、(c)成分及び(d)成分の配合量を、
(a)成分100重量部に対して、それぞれ50〜10
0重量部(固形分)、5〜15重量部、5〜30重量部
とすることが特に好ましい。First, the essential components (b) and (c)
The component and the component (d) are 30 to 130 parts by weight (solid content) and 0.1 to 100 parts by weight of the component (a), respectively.
-30 parts by weight, preferably 1-50 parts by weight.
Here, if the amount of the component (b) is small, the alkali resistance of the coating film is insufficient, and if it is too large, the weather resistance of the coating film is deteriorated. Further, if the amount of the component (d) is small, the adhesion of the coating film is deteriorated, while if used in a large amount, the flexibility of the coating film is reduced and the flex resistance is adversely affected. When the amount of the component (c) is less than 0.1 parts by weight, it cannot function sufficiently as a curing catalyst, and even when it is used in an amount of more than 30 parts by weight, the coating film performance is not improved. It is not preferable from an economic point of view. From the viewpoint of the balance of weather resistance, stain resistance, flex resistance, crack resistance and alkali resistance,
The blending amounts of the component (b), the component (c) and the component (d) are
50 to 10 parts by weight per 100 parts by weight of component (a).
It is particularly preferable that the amount is 0 parts by weight (solid content), 5 to 15 parts by weight, and 5 to 30 parts by weight.
【0047】同じく必須成分である(e)成分について
は、その分子量により好ましい配合量が異なってくる。
すなわち、(e)成分の重量平均分子量が200以上、
5000未満の場合には、(a)成分100重量部に対
して5〜30重量部(固形分)であることが好ましい。
一方、(e)成分の重量平均分子量が5000以上、1
00,000以下の場合には、(a)成分100重量部
に対して10〜60重量部(固形分)であることが好ま
しく、より好ましくは25〜45重量部(固形分)であ
る。(e)成分の配合量が少ないと塗膜のフレキシビリ
ティーが低下する傾向があり、また、多くなると塗膜の
耐汚染性が悪化する場合がある。Similarly, regarding the component (e) which is an essential component, the preferable blending amount varies depending on the molecular weight.
That is, the weight average molecular weight of the component (e) is 200 or more,
When it is less than 5,000, it is preferably 5 to 30 parts by weight (solid content) with respect to 100 parts by weight of the component (a).
On the other hand, the weight average molecular weight of the component (e) is 5,000 or more, 1
When it is at most 0,000, it is preferably 10 to 60 parts by weight (solid content), and more preferably 25 to 45 parts by weight (solid content) with respect to 100 parts by weight of the component (a). If the amount of component (e) is small, the flexibility of the coating film tends to decrease, and if it is large, the stain resistance of the coating film may deteriorate.
【0048】次に、任意成分である(f)成分について
であるが、これらの成分は、各種用途等に応じ、本発明
の目的を損なわない範囲で配合すればよい。なお、有機
溶剤の量は、塗料固形分100重量部に対して20〜2
00重量部とすることが好ましい。Next, regarding the optional component (f), these components may be blended in a range that does not impair the object of the present invention depending on various applications. The amount of the organic solvent is 20 to 2 with respect to 100 parts by weight of the coating solid content.
It is preferably set to 00 parts by weight.
【0049】上記したように、本発明の塗料組成物は第
1液と第2液とからなり、使用に際して、かかる2液を
混合する。本発明の塗料組成物においては、貯蔵安定性
の点から、(b)成分と(d)及び(e)成分とが使用
直前に混合されるように、第1液及び第2液を調製する
ことが望ましい。すなわち、本発明の2液型塗料組成物
に含まれる各成分は、以下のように調製されていること
が好ましい。また、任意成分である(f)成分は、第1
液若しくは第2液のいずれかに、または、第1液及び第
2液の両方に存在させることが可能である。As described above, the coating composition of the present invention comprises the first liquid and the second liquid, and the two liquids are mixed at the time of use. In the coating composition of the present invention, the first liquid and the second liquid are prepared from the viewpoint of storage stability so that the component (b) and the components (d) and (e) are mixed immediately before use. Is desirable. That is, each component contained in the two-pack type coating composition of the present invention is preferably prepared as follows. The component (f), which is an optional component, is
It can be present in either the liquid or the second liquid, or in both the first and second liquids.
【0050】 (a)成分:第1液及び/又は第2液に存在、 (b)成分:第1液に存在、 (c)成分:第1液及び/又は第2液に存在、 (d)成分:第2液に存在、 (e)成分:第2液に存在。[0050] (A) component: present in the first liquid and / or the second liquid, (B) component: present in the first liquid, (C) component: present in the first liquid and / or the second liquid, (D) component: present in the second liquid, Component (e): Present in the second liquid.
【0051】本発明の2液型塗料組成物においては、塗
料の貯蔵安定性を良好にし、また、塗料の使用環境や使
用用途に柔軟に対応させるという点から、(a)〜
(e)成分を以下のように調製することが、特に好まし
い。In the two-pack type coating composition of the present invention, from the viewpoint of improving the storage stability of the coating and flexibly responding to the use environment and use of the coating,
It is particularly preferable to prepare the component (e) as follows.
【0052】
(a)成分:第1液及び第2液に存在、
(b)成分:第1液に存在、
(c)成分:第1液に存在、
(d)成分:第2液に存在、
(e)成分:第2液に存在。
なお、(f)成分として、第1液に着色顔料及び有機溶
剤を、第2液に有機溶剤を存在させることがより好まし
い。(A) component: present in the first and second liquids, (b) component: present in the first liquid, (c) component: present in the first liquid, (d) component: present in the second liquid , (E) component: present in the second liquid. As the component (f), it is more preferable that the first liquid contains a color pigment and an organic solvent, and the second liquid contains an organic solvent.
【0053】
(a)成分:第2液に存在、
(b)成分:第1液に存在、
(c)成分:第1液に存在、
(d)成分:第2液に存在、
(e)成分:第2液に存在。
なお、(f)成分として、(1)第1液に着色顔料及び
有機溶剤を、第2液に有機溶剤を存在させるか、又は、
(2)第1液に有機溶剤を、第2液に着色顔料及び有機
溶剤を存在させることがより好ましい。(A) component: present in second liquid, (b) component: present in first liquid, (c) component: present in first liquid, (d) component: present in second liquid, (e) Ingredient: Present in the second liquid. As the component (f), (1) a color pigment and an organic solvent are present in the first liquid, and an organic solvent is present in the second liquid, or
(2) It is more preferable that the first liquid contains an organic solvent, and the second liquid contains a color pigment and an organic solvent.
【0054】
(a)成分:第1液に存在、
(b)成分:第1液に存在、
(c)成分:第1液に存在、
(d)成分:第2液に存在、
(e)成分:第2液に存在。
なお、(f)成分として、第1液に着色顔料及び有機溶
剤を、第2液に有機溶剤を存在させることがより好まし
い。(A) component: present in first liquid, (b) component: present in first liquid, (c) component: present in first liquid, (d) component: present in second liquid, (e) Ingredient: Present in the second liquid. As the component (f), it is more preferable that the first liquid contains a color pigment and an organic solvent, and the second liquid contains an organic solvent.
【0055】
(a)成分:第1液に存在、
(b)成分:第2液に存在、
(c)成分:第1液に存在、
(d)成分:第1液に存在、
(e)成分:第1液に存在。
なお、(f)成分として、第1液に着色顔料及び有機溶
剤を、第2液に有機溶剤を存在させることがより好まし
い。(A) component: present in first liquid, (b) component: present in second liquid, (c) component: present in first liquid, (d) component: present in first liquid, (e) Ingredient: Present in the first liquid. As the component (f), it is more preferable that the first liquid contains a color pigment and an organic solvent, and the second liquid contains an organic solvent.
【0056】本発明の塗料組成物の製造方法について
は、特に制限はなく、使用の際に第1液と第2液とを混
合・攪拌すればよい。なお、第1液と第2液との混合割
合についても特に制限はない。また、塗料としての可使
時間は3〜8時間とすることが好ましい。The method for producing the coating composition of the present invention is not particularly limited, and the first liquid and the second liquid may be mixed and stirred at the time of use. The mixing ratio of the first liquid and the second liquid is not particularly limited. The pot life of the paint is preferably 3 to 8 hours.
【0057】本発明の塗料組成物は、常温硬化、低汚染
高耐候性であることから、機械、船舶、車両、航空機、
土木、建築、重防食、インキ、その他一般工業分野にお
いて好適に用いられる。特に、本発明の塗料組成物を用
いると、優れた耐屈曲性及び耐クラック性に優れた塗膜
を得ることが可能となるため、フレキシビリティーに富
んだ部材が多い建築及び土木構造物用の素材に対して好
適である。また、本発明の塗料組成物は、10〜20年
といった長期に渡る塗膜性能の維持が求められている戸
建て住宅の窯業系や金属系サイディング材に対しても好
適に用いることができる。Since the coating composition of the present invention is cured at room temperature and has low pollution and weather resistance, it can be used in machines, ships, vehicles, aircraft,
It is preferably used in civil engineering, construction, heavy corrosion protection, ink, and other general industrial fields. In particular, when the coating composition of the present invention is used, it is possible to obtain a coating film having excellent flex resistance and crack resistance, and therefore for many construction and civil engineering structures that have many flexible members. Suitable for the above materials. Further, the coating composition of the present invention can be suitably used for a ceramic siding material and a metal siding material of a detached house, which is required to maintain the coating performance for a long period of 10 to 20 years.
【0058】[0058]
【発明の効果】以上のように、本発明の塗料組成物にお
いては、(a)成分〜(e)成分という特定の5成分を
組み合わせることにより、オルガノポリシロキサン系塗
料本来の耐候性及び耐汚染性を損なうことなく、耐屈曲
性及び耐クラック性にも優れたオルガノポリシロキサン
系塗料組成物を得ることができる。また、(a)成分〜
(e)成分の配合量を特定の量とすることにより、耐候
性、耐汚染性、耐屈曲性、耐クラック性及び耐アルカリ
性の全てにおいて優れた性能を有する塗料組成物を得る
ことが可能となる。As described above, in the coating composition of the present invention, by combining the five specific components (a) to (e), the weather resistance and stain resistance of the original organopolysiloxane coating are improved. It is possible to obtain an organopolysiloxane-based coating composition excellent in bending resistance and crack resistance without impairing the properties. In addition, the component (a)
By adjusting the compounding amount of the component (e) to a specific amount, it is possible to obtain a coating composition having excellent performance in all of weather resistance, stain resistance, flex resistance, crack resistance and alkali resistance. Become.
【0059】更に、本発明の塗料組成物に(f)成分と
して石油炭化水素系溶剤を配合した場合、旧塗膜や基材
を侵しにくい塗料となるため、旧塗膜や基材の塗り替え
を容易に行うことが可能となる。また、石油炭化水素系
溶剤が配合された塗料は、低臭であるため作業環境を大
幅に改善することも可能となる。Furthermore, when a petroleum hydrocarbon solvent is added as the component (f) to the coating composition of the present invention, the coating composition does not easily attack the old coating film or the base material. It can be easily performed. In addition, since the paint containing a petroleum hydrocarbon solvent has a low odor, it is possible to greatly improve the working environment.
【0060】[0060]
【実施例】以下、本発明についてより詳細に説明する
が、本発明はこれらの例に限定される訳ではない。ま
ず、実施例及び比較例で用いられる塗料組成物の物性評
価法について説明する。なお、以下において、「部」及
び「%」とあるのは、特に断りのない限り、それぞれ
「重量部」及び「重量%」を意味する。The present invention will be described in more detail below, but the present invention is not limited to these examples. First, the methods for evaluating the physical properties of coating compositions used in Examples and Comparative Examples will be described. In the following, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.
【0061】<耐屈曲性>耐屈曲性の評価は、JIS
K5400 8.1の方法に準拠し、心棒の直径が10
mmのものを使用した。また、試験片としては、150
×50×0.3mmの鋼板に、乾燥塗膜厚が50μmに
なるように塗料組成物をスプレーで塗布し、23℃,5
0%RHの条件下で4日間養生後、さらに80℃で3日
間の強制乾燥を行ったものを使用した。評価は、目視に
より塗膜の屈曲部を観察し、試験片の割れ、剥がれのな
いものを「○」とし、それ以外を「×」とした。<Bending Resistance> The bending resistance is evaluated according to JIS.
According to the method of K5400 8.1, the diameter of the mandrel is 10
The thing of mm was used. Also, as a test piece, 150
The coating composition was spray coated onto a steel plate of × 50 × 0.3 mm so that the dry coating film thickness would be 50 μm, and the temperature was maintained at 23 ° C. for 5 minutes.
After being aged for 4 days under the condition of 0% RH, it was subjected to forced drying at 80 ° C. for 3 days. In the evaluation, the bent portion of the coating film was visually observed, and the test piece without cracking or peeling was rated as "O", and the others were rated as "X".
【0062】<耐クラック性>耐クラック性は、JIS
K5400 9.4(耐湿潤冷熱繰返し性試験)に準
じ、20℃の水に18時間浸水し、その後−20℃の冷
凍庫で3時間、更に50℃で3時間加温した。この繰り
返しを10サイクル行い、試験終了後の塗膜の状態を目
視にて観察し、塗膜における割れ、膨れ及び白化の程度
を以下の3段階で評価した。なお、試験片は、70×7
0×6mmのフレキシブルボードに乾燥塗膜厚が50μ
mになるように塗料組成物をスプレーで塗装し、23
℃,50%RHの条件下で4日間養生後、さらに80℃
で3日間の強制乾燥を行うことにより作製した。
○:塗膜に変化が見られない。
△:塗膜の一部に割れ、膨れが認められる。
×:塗膜に著しい割れ、膨れが認められる。<Crack resistance> The crack resistance is JIS
According to K5400 9.4 (wet cold / heat repeatability test), water was immersed in water at 20 ° C for 18 hours, and then heated in a freezer at -20 ° C for 3 hours and further at 50 ° C for 3 hours. This cycle was repeated 10 times, the state of the coating film after the test was visually observed, and the degree of cracking, swelling and whitening in the coating film was evaluated according to the following 3 grades. The test piece is 70 × 7.
Dry coating thickness is 50μ on 0x6mm flexible board
spray paint composition to reach m.
After curing for 4 days at ℃ and 50% RH, 80 ℃
It was prepared by carrying out forced drying for 3 days. ◯: No change is seen in the coating film. Δ: Cracks and swelling are observed in part of the coating film. X: Significant cracks and swelling are observed in the coating film.
【0063】<促進耐候性>促進耐候性試験は、超促進
耐候試験機(岩崎電気(株)製アイスーパーUVテスタ
ー)を用いて行った。また、試験片は、50×50×4
mmのフレキシブルボードに乾燥塗膜厚が50μmにな
るように塗料組成物をスプレーで塗装し、23℃,50
%RHの条件下で7日間乾燥を行うことにより作製し
た。試験条件としては、波長295〜450nm、紫外
線照射度100mW/cm2、ブラックパネル温度63
℃,50%RH、1サイクルを照射4時間、結露4時間
とし、125サイクル(1000時間)試験した。試験
終了後、塗膜の初期60度鏡面光沢値に対する光沢保持
率を求め、以下の3段階で評価した。
○:光沢保持率 70%以上
△:光沢保持率 50%以上 70%未満
×:光沢保持率 50%未満<Accelerated weather resistance> The accelerated weather resistance test was carried out using a super accelerated weather resistance tester (Isuper UV tester manufactured by Iwasaki Electric Co., Ltd.). Moreover, the test piece is 50 × 50 × 4.
mm of flexible board is spray coated with the coating composition so that the dry coating thickness is 50 μm, and the temperature is 50 ° C. at 23 ° C.
It was prepared by performing drying for 7 days under the condition of% RH. The test conditions include a wavelength of 295 to 450 nm, an ultraviolet irradiation degree of 100 mW / cm 2 , and a black panel temperature of 63.
C., 50% RH, 1 cycle was 4 hours for irradiation and 4 hours for condensation, and 125 cycles (1000 hours) were tested. After the test was completed, the gloss retention rate with respect to the initial 60-degree specular gloss value of the coating film was obtained and evaluated in the following three grades. ◯: Gloss retention rate 70% or more B: Gloss retention rate 50% or more and less than 70% ×: Gloss retention rate less than 50%
【0064】<耐アルカリ性>耐アルカリ性試験は、J
IS K5400 8.21に準じ、水酸化ナトリウム
を脱イオン水で5W/V%に調整した液に、試験片を2
3℃の条件下で7日間浸せきさせた。浸せき後、試験片
を流水で静かに洗い、2時間乾燥させて、塗膜の膨れ、
割れ、剥がれ、つやの変化を目視によって観察し、3段
階で評価した。なお、試験片としては、150×70×
4mmのフレキシブルボードに乾燥塗膜厚が50μmに
なるようにスプレーで塗装し、23℃,50%RHの条
件下で14日間乾燥したものを用いた。
○:現状試験片と比べて大きな変化が見られない。
△:現状試験片と比べてやや艶引けがある。
×:現状試験片と比べて著しい艶引け、割れ、剥がれが
ある。<Alkali resistance> For the alkali resistance test, see J.
According to IS K5400 8.21, sodium hydroxide was adjusted to 5 W / V% with deionized water, and two test pieces were used.
It was dipped for 7 days under the condition of 3 ° C. After the immersion, the test piece was gently washed with running water and dried for 2 hours to swell the coating film.
Cracking, peeling, and change in gloss were visually observed and evaluated in three levels. In addition, as a test piece, 150 × 70 ×
A 4 mm flexible board was spray-coated so that the dry coating film thickness was 50 μm, and dried for 14 days at 23 ° C. and 50% RH. ◯: No significant change compared with the current test piece. Δ: There is a slight luster compared to the current test piece. X: Significant luster, cracking, and peeling are present as compared with the current test piece.
【0065】<付着性>付着性試験は、JIS K54
00 8.5.2碁盤目テープ法に準じ、隙間間隔2m
mのカッターガイドを用いて、碁盤目状(25マス;縦
5分割×横5分割)に切り傷をつけ、この碁盤目の上に
セロハン粘着テープをはり、テープの一端を持って塗面
に直角方向に瞬間的に引き剥がし、塗膜の剥がれの面積
を測定することで行った。なお、試験片としては、15
0×70×4mmのフレキシブルボードに乾燥塗膜厚が
50μmになるように塗料組成物をスプレーで塗装し、
23℃,50%RHの条件下で14日間乾燥したものを
用いた。塗膜の全面積に対する塗膜の剥がれの面積か
ら、付着性を以下の通り評価した。
○:塗膜の剥がれの面積が全面積の5%未満の場合
△:塗膜の剥がれの面積が全面積の5%以上、35%未
満の場合
×:塗膜の剥がれの面積が全面積の35%以上の場合<Adhesion> The adhesion test is conducted according to JIS K54.
00 8.5.2 According to the cross-cut tape method, the gap distance is 2m
Using a cutter guide of m, make a cut in a grid pattern (25 squares; vertical 5 divisions × horizontal 5 divisions), stick cellophane adhesive tape on this grid and hold one end of the tape at a right angle to the coated surface. The film was peeled off instantaneously in the direction, and the peeled area of the coating film was measured. In addition, as a test piece, 15
A paint composition is sprayed onto a 0 × 70 × 4 mm flexible board so that the dry coating film thickness is 50 μm.
The one dried for 14 days under the conditions of 23 ° C. and 50% RH was used. From the peeled area of the coating film to the total area of the coating film, the adhesion was evaluated as follows. ◯: When the peeled area of the coating film is less than 5% of the total area Δ: When the peeled area of the coating film is 5% or more and less than 35% of the total area ×: When the peeled area of the coating film is of the total area If more than 35%
【0066】<強制汚染>150×70×0.8mmの
アルミ板に乾燥塗膜厚が50μmになるように塗料組成
物をスプレーで塗装し、23℃,50%RHの条件下で
14日間乾燥し、試験片を作製した。得られた試験片
に、カーボン懸濁水(デグサ・ヒュルス社製カーボンブ
ラック Color Black FW200 5部と
脱イオン水95部にガラスビーズを加えペイントシェー
カーで2時間分散した分散液)をエアスプレーで、隠ぺ
いするまで塗布し、直ちに60℃で1時間乾燥させた。
乾燥後、室温まで放冷し、試験片の表面を流水下にてガ
ーゼを使用して、汚れ物質が落ちなくなるまで洗浄し
た。洗浄後、室温で3時間乾燥し、汚れの程度を色差計
にて測定して、試験前後における塗膜の明度差(ΔL
*)を求め、以下の3段階で評価した。なお、明度差が
小さいものほど、耐汚染性に優れた塗料であることを示
している。
明度差(ΔL*)=[試験後の塗膜明度(L*1)−試
験前の塗膜明度(L*0)]
○:明度差 −5以上
△:明度差 −10以上 −5未満
×:明度差 −10未満<Forced Contamination> The coating composition was sprayed onto a 150 × 70 × 0.8 mm aluminum plate so that the dry coating film thickness was 50 μm, and dried under conditions of 23 ° C. and 50% RH for 14 days. Then, a test piece was prepared. Hidden carbon suspension water (dispersion liquid in which 5 parts of carbon black Color Black FW200 manufactured by Degussa Hurus and 95 parts of deionized water and glass beads were added and dispersed for 2 hours with a paint shaker) was air-sprayed on the obtained test piece. And was immediately dried at 60 ° C. for 1 hour.
After drying, the sample was allowed to cool to room temperature, and the surface of the test piece was washed under running water using gauze until the dirt substance could not be removed. After washing, it was dried at room temperature for 3 hours, and the degree of stain was measured with a color difference meter, and the difference in lightness of the coating film before and after the test (ΔL
*) Was obtained and evaluated in the following three stages. The smaller the difference in brightness, the better the stain resistance. Brightness difference (ΔL *) = [Coating film brightness after test (L * 1) -Coating film brightness before test (L * 0)] ○: Brightness difference −5 or more Δ: Brightness difference −10 or more and less than −5 × : Brightness difference less than -10
【0067】<総合評価>上に示した塗料組成物の性能
測定の結果に基づき、塗料組成物の総合評価を以下に示
す基準で行った。
○:全てが○の評価であり、塗料組成物として非常に好
適に使用できるレベル。
△:△の評価があり、塗料組成物として使用できるレベ
ルであるが、その用途が限られる場合がある。
×:×の評価があり、塗料組成物として使用が困難なレ
ベル。<Comprehensive Evaluation> Based on the results of the performance measurement of the coating composition shown above, the comprehensive evaluation of the coating composition was performed according to the following criteria. ◯: All are evaluated as ◯, which is a level that can be used very suitably as a coating composition. Δ: There is an evaluation of Δ, which is a level that can be used as a coating composition, but its use may be limited. X: There is an evaluation of x, which is a level that is difficult to use as a coating composition.
【0068】次に、塗料組成物に配合する成分について
説明する。
<(a)成分>
(a−1) メチルフェニル系アルコキシシランオリゴ
マー(商品名:DC3074、東レ・ダウコーニング・
シリコーン社製、有効成分100%、Si原子約25%
含有)
(a−2) メチル系アルコキシシランオリゴマー(S
R2402、東レ・ダウコーニング・シリコーン社製、
有効成分100%,Si原子約30%含有)Next, the components to be added to the coating composition will be described. <Component (a)> (a-1) Methylphenyl-based alkoxysilane oligomer (trade name: DC3074, Toray Dow Corning
Made by Silicone, active ingredient 100%, Si atom about 25%
(A-2) Methyl-based alkoxysilane oligomer (S
R2402, manufactured by Toray Dow Corning Silicone,
(100% active ingredient, about 30% Si atom)
【0069】<(b)成分>
(b−1) 攪拌装置、温度計、冷却管および窒素ガス
導入管、滴下装置を備えた反応器に、トルエン400部
を仕込み、撹拌しながら110℃まで昇温した。そこ
に、メチルメタクリレート200部、n−ブチルアクリ
レート130部、n−ブチルメタクリレート120部、
ジメチルアミノエチルメタクリレート部50部、アゾビ
スイソブチロニトリル5部、トルエン10部からなる混
合物を、3時間かけて滴下した。滴下終了後、同温度で
1時間反応させた。さらに、アゾビスイソブチロニトリ
ル2.5部、トルエン90部からなる混合物を1時間か
けて滴下した。滴下終了後、同温度で3時間反応させ、
不揮発分(固形分)50%、粘度1000mPa・s
(25℃)、重量平均分子量20000、アミン当量3
100の、透明な第3級アミン含有アクリル樹脂溶液
(b−1)を得た。<Component (b)> (b-1) 400 parts of toluene was charged into a reactor equipped with a stirrer, a thermometer, a cooling pipe, a nitrogen gas introducing pipe, and a dropping device, and the temperature was raised to 110 ° C. with stirring. Warmed. 200 parts of methyl methacrylate, 130 parts of n-butyl acrylate, 120 parts of n-butyl methacrylate,
A mixture of 50 parts of dimethylaminoethyl methacrylate, 5 parts of azobisisobutyronitrile and 10 parts of toluene was added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Furthermore, a mixture of 2.5 parts of azobisisobutyronitrile and 90 parts of toluene was added dropwise over 1 hour. After completion of the dropping, react at the same temperature for 3 hours,
Nonvolatile content (solid content) 50%, viscosity 1000 mPa · s
(25 ° C), weight average molecular weight 20000, amine equivalent 3
100 transparent acrylic resin solutions containing a tertiary amine (b-1) were obtained.
【0070】(b−2) 攪拌装置、温度計、冷却管お
よび窒素ガス導入管、滴下装置を備えた反応器に、石油
炭化水素系溶剤(商品名:LAWS、シェルジャパン株
式会社製)300部、及び石油炭化水素系溶剤(商品
名:HAWS、シェルジャパン株式会社製)100部を
仕込み、撹拌しながら110℃まで昇温した。そこに、
n−ブチルアクリレート50部、n−ブチルメタクリレ
ート200部、シクロヘキシルメタクリレート部200
部、ジメチルアミノエチルメタクリレート50部、アゾ
ビスイソブチロニトリル5部、LAWS10部からなる
混合物を、3時間かけて滴下した。滴下終了後、同温度
で1時間反応させた。さらに、アゾビスイソブチロニト
リル2.5部、LAWS 90部からなる混合物を1時
間かけて滴下した。滴下終了後、同温度で3時間反応さ
せ、不揮発分(固形分)50%、粘度1000mPa・
s(25℃)、重量平均分子量15000、アミン価当
量3100の、透明な第3級アミノ基含有アクリル樹脂
溶液(b−2)を得た。(B-2) 300 parts of petroleum hydrocarbon solvent (trade name: LAWS, manufactured by Shell Japan Co., Ltd.) in a reactor equipped with a stirrer, a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a dropping device. , And petroleum hydrocarbon solvent (trade name: HAWS, manufactured by Shell Japan Co., Ltd.) were charged, and the temperature was raised to 110 ° C. with stirring. there,
50 parts of n-butyl acrylate, 200 parts of n-butyl methacrylate, 200 parts of cyclohexyl methacrylate
Part, 50 parts of dimethylaminoethyl methacrylate, 5 parts of azobisisobutyronitrile, and 10 parts of LAWS were added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Furthermore, a mixture of 2.5 parts of azobisisobutyronitrile and 90 parts of LAWS was added dropwise over 1 hour. After completion of the dropping, the mixture is reacted at the same temperature for 3 hours to give a nonvolatile content (solid content) of 50% and a viscosity of 1000 mPa.
A transparent tertiary amino group-containing acrylic resin solution (b-2) having s (25 ° C.), a weight average molecular weight of 15,000 and an amine value equivalent of 3100 was obtained.
【0071】<(c)成分>
(c−1) アルキルアセトアセテートアルミニウムジ
イソプロピレート(商品名:アルミキレートM、川研フ
ァインケミカル社製)<Component (c)> (c-1) Alkyl acetoacetate aluminum diisopropylate (trade name: aluminum chelate M, manufactured by Kawaken Fine Chemical Co., Ltd.)
【0072】<(d)成分>
(d−1) γ−グリシドキシプロピルトリメトキシシ
ラン(商品名:SH6040、東レ・ダウコーニング・
シリコーン社製)<Component (d)> (d-1) γ-glycidoxypropyltrimethoxysilane (trade name: SH6040, Toray Dow Corning
(Made by Silicone)
【0073】<(e)成分>
(e−1) ポリプロピレングリコールジグリシジルエ
ーテル(商品名:エポライト400P、共栄社化学製、
エポキシ当量315)
(e−2) ポリエチレングリコールジグリシジルエー
テル(商品名:エポライト400E、共栄社化学製、エ
ポキシ当量290)
(e−3) 攪拌装置、温度計、冷却管および窒素ガス
導入管、滴下装置を備えた反応器に、トルエン400部
を仕込み、撹拌しながら110℃まで昇温した。そこ
に、メチルメタクリレート70部、n−ブチルアクリレ
ート130部、n−ブチルメタクリレート150部、グ
リシジルメタクリレート70部、2酸2−エチルヘキシ
ルアクリレート80部、アゾビスイソブチロニトリル5
部、トルエン10部からなる混合物を、3時間かけて滴
下した。滴下終了後、同温度で1時間反応させた。さら
に、アゾビスイソブチロニトリル2.5部、トルエン9
0部からなる混合物を1時間かけて滴下した。滴下終了
後、同温度で3時間反応させ、不揮発分(固形分)50
%、粘度1000mPa・s(25℃)、重量平均分子
量20000、エポキシ当量1000の、透明なグリシ
ジル含有アクリル樹脂溶液(e−3)を得た。<Component (e)> (e-1) Polypropylene glycol diglycidyl ether (trade name: Epolite 400P, manufactured by Kyoeisha Chemical Co., Ltd.,
Epoxy equivalent 315) (e-2) Polyethylene glycol diglycidyl ether (trade name: Epolite 400E, manufactured by Kyoeisha Chemical Co., Ltd., epoxy equivalent 290) (e-3) Stirrer, thermometer, cooling pipe and nitrogen gas introduction pipe, dropping device 400 parts of toluene was charged into a reactor equipped with and heated to 110 ° C. with stirring. 70 parts of methyl methacrylate, 130 parts of n-butyl acrylate, 150 parts of n-butyl methacrylate, 70 parts of glycidyl methacrylate, 80 parts of 2-ethyl 2-hexyl acrylate, and azobisisobutyronitrile 5
And 10 parts of toluene were added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Furthermore, 2.5 parts of azobisisobutyronitrile and 9 parts of toluene
A mixture of 0 parts was added dropwise over 1 hour. After the completion of the dropping, the reaction is carried out at the same temperature for 3 hours, and the nonvolatile content (solid content)
%, A viscosity of 1000 mPa · s (25 ° C.), a weight average molecular weight of 20,000, and an epoxy equivalent of 1000, to obtain a transparent glycidyl-containing acrylic resin solution (e-3).
【0074】<(f)成分>
(f−1) 酢酸ブチル
(f−2) 石油炭化水素系溶剤(商品名:LAWS、
シェルジャパン株式会社)
(f−3) 酸化チタン(商品名:TIPAQUE C
R−90、石原産業製)<Component (f)> (f-1) Butyl acetate (f-2) Petroleum hydrocarbon solvent (trade name: LAWS,
Shell Japan Co., Ltd. (f-3) Titanium oxide (trade name: TIPAQUE C
R-90, made by Ishihara Sangyo)
【0075】<塗料組成物の配合><Blending of coating composition>
【例1】塗料配合例1
〈第1液〉
(a−1)18部、(b−1)30部、(f−1)24
部、(f−3)25部、及びガラスビーズ100部を混
合容器に仕込み、ペイントシェーカーで1時間分散を行
った。分散終了後、ガラスビーズの除去を行い、(c−
1)3部を添加して、撹拌機で3分間混合した。得られ
た第1液は、固形分60%、粘度300mPa・s(2
5℃)であった。[Example 1] Coating composition example 1 <First liquid> (a-1) 18 parts, (b-1) 30 parts, (f-1) 24
Parts, (f-3) 25 parts, and glass beads 100 parts were placed in a mixing container and dispersed for 1 hour with a paint shaker. After the dispersion is completed, the glass beads are removed, and (c-
1) 3 parts were added and mixed with a stirrer for 3 minutes. The obtained first liquid has a solid content of 60% and a viscosity of 300 mPa · s (2
5 ° C.).
【0076】〈第2液〉
(e−1)10部、(a−2)30部、(d−1)15
部、及び(f−1)45部を混合容器に仕込み、撹拌機
で3分間撹拌した。得られた第2液は、固形分55%、
粘度10mPa・s(25℃)であった。<Second liquid> (e-1) 10 parts, (a-2) 30 parts, (d-1) 15
Parts and (f-1) 45 parts were charged into a mixing vessel and stirred with a stirrer for 3 minutes. The obtained second liquid has a solid content of 55%,
The viscosity was 10 mPa · s (25 ° C).
【0077】上記第1液及び第2液を、第1液/第2液
=5/1の重量比で混合、攪拌し、塗料組成物を得た。
得られた塗料組成物について、上記した方法で物性評価
を行った。結果を表1に示す。The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 5/1 to obtain a coating composition.
Physical properties of the obtained coating composition were evaluated by the methods described above. The results are shown in Table 1.
【0078】[0078]
【例2〜17】各成分の組成、及び第1液と第2液の重
量比を表1に従い変更した以外は、例1と同様にして塗
料組成物を作製し、得られた塗料組成物について、上記
した方法で物性評価を行った。結果を表1に示す。Examples 2 to 17 A coating composition was prepared in the same manner as in Example 1 except that the composition of each component and the weight ratio of the first liquid and the second liquid were changed according to Table 1. For, the physical properties were evaluated by the methods described above. The results are shown in Table 1.
【0079】[0079]
【表1】 [Table 1]
【0080】塗料配合例2
〈第1液〉
(a−1)30部、(a−2)10部、(f−3)4
1.7部、(d−1)5部、(e−1)3.3部、(f
−1)10部、及びガラスビーズ100部を混合容器に
仕込み、ペイントシェーカーで1時間分散を行った。分
散終了後、ガラスビーズの除去を行った。得られた第1
液は、固形分90%、粘度500mPa・s(25℃)
であった。 Coating Composition Example 2 <First Liquid> 30 parts of (a-1), 10 parts of (a-2), (f-3) 4
1.7 parts, (d-1) 5 parts, (e-1) 3.3 parts, (f
-1) 10 parts and 100 parts of glass beads were placed in a mixing container and dispersed for 1 hour with a paint shaker. After the dispersion was completed, the glass beads were removed. First obtained
The liquid has a solid content of 90% and a viscosity of 500 mPa · s (25 ° C)
Met.
【0081】〈第2液〉
(b−1)50部、(c−1)5部、及び(f−1)4
5部を混合容器に仕込み、撹拌機で3分間撹拌を行っ
た。得られた第2液は固形分30%、粘度100mPa
・s(25℃)であった。<Second Liquid> (b-1) 50 parts, (c-1) 5 parts, and (f-1) 4
5 parts were placed in a mixing vessel and stirred with a stirrer for 3 minutes. The obtained second liquid has a solid content of 30% and a viscosity of 100 mPas.
-It was s (25 degreeC).
【0082】上記第1液及び第2液を、第1液/第2液
=1/1の重量比で混合、攪拌し、塗料組成物を得た。
得られた塗料組成物について、上記した方法で物性評価
を行ったところ、例1の塗料組成物と同等の物性が確認
された。The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 1/1 to obtain a coating composition.
When the physical properties of the obtained coating composition were evaluated by the methods described above, the same physical properties as those of the coating composition of Example 1 were confirmed.
【0083】塗料配合例3
〈第1液〉
(b−1)37.5部、(f−3)31.2部、(f−
1)27.5部、及びガラスビーズ100部を混合容器
に仕込み、ペイントシェーカーで1時間分散を行った。
分散終了後、ガラスビーズの除去を行い、(c−1)
3.8部を添加して、撹拌機で3分間混合した。得られ
た第1液は、固形分54%、粘度500mPa・s(2
5℃)であった。 Coating composition example 3 <First liquid> (b-1) 37.5 parts, (f-3) 31.2 parts, (f-
1) 27.5 parts and 100 parts of glass beads were placed in a mixing container and dispersed for 1 hour with a paint shaker.
After the dispersion is completed, the glass beads are removed, and (c-1)
3.8 parts were added and mixed with a stirrer for 3 minutes. The obtained first liquid has a solid content of 54% and a viscosity of 500 mPa · s (2
5 ° C.).
【0084】〈第2液〉
(a−1)45部、(a−2)15部、(d−1)7.
5部、(e−1)5部、及び(f−1)27.5部を混
合容器に仕込み、撹拌機で3分間撹拌を行った。得られ
た第2液は、固形分72.5%、粘度50mPa・s
(25℃)であった。<Second liquid> (a-1) 45 parts, (a-2) 15 parts, (d-1) 7.
5 parts, 5 parts of (e-1), and 27.5 parts of (f-1) were charged into a mixing vessel, and stirred for 3 minutes with a stirrer. The obtained second liquid has a solid content of 72.5% and a viscosity of 50 mPa · s.
(25 ° C).
【0085】上記第1液及び第2液を、第1液/第2液
=2/1の重量比で混合、攪拌し、塗料組成物を得た。
得られた塗料組成物について、上記した方法で物性評価
を行ったところ、例1の塗料組成物と同等の物性が確認
された。The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 2/1 to obtain a coating composition.
When the physical properties of the obtained coating composition were evaluated by the methods described above, the same physical properties as those of the coating composition of Example 1 were confirmed.
【0086】塗料配合例4
〈第1液〉
(a−1)18部、(a−2)6部、(b−1)30
部、(f−1)18部、(f−3)25部、及びガラス
ビーズ100部を混合容器に仕込み、ペイントシェーカ
ーで1時間分散を行った。分散終了後、ガラスビーズの
除去を行い、(c−1)3部を添加して、撹拌機で3分
間混合した。得られた第1液は、固形分67%、粘度3
00mPa・s(25℃)であった。 Coating Composition Example 4 <First Liquid> 18 parts of (a-1), 6 parts of (a-2), 30 of (b-1)
Parts, 18 parts of (f-1), 25 parts of (f-3), and 100 parts of glass beads were charged in a mixing container, and dispersed for 1 hour with a paint shaker. After the dispersion was completed, the glass beads were removed, 3 parts of (c-1) was added, and mixed for 3 minutes with a stirrer. The obtained first liquid has a solid content of 67% and a viscosity of 3
It was 00 mPa · s (25 ° C.).
【0087】〈第2液〉
(e−1)10部、(d−1)15部、及び(f−1)
75部を混合容器に仕込み、撹拌機で3分間撹拌を行っ
た。得られた第2液は、固形分25%、粘度10mPa
・s(25℃)であった。<Second liquid> (e-1) 10 parts, (d-1) 15 parts, and (f-1)
75 parts were charged into a mixing vessel and stirred with a stirrer for 3 minutes. The obtained second liquid has a solid content of 25% and a viscosity of 10 mPas.
-It was s (25 degreeC).
【0088】上記第1液及び第2液を、第1液/第2液
=5/1の重量比で混合、攪拌し、塗料組成物を得た。
得られた塗料組成物について、上記した方法で物性評価
を行ったところ、例1の塗料組成物と同等の物性が確認
された。The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 5/1 to obtain a coating composition.
When the physical properties of the obtained coating composition were evaluated by the methods described above, the same physical properties as those of the coating composition of Example 1 were confirmed.
【0089】塗料配合例5
〈第1液〉
(a−1)22.5部、(a−2)7.5部、(f−
3)31.2部、(d−1)3.8部、(e−1)2.
5部、(f−1)28.7部、及びガラスビーズ100
部を混合容器に仕込み、ペイントシェーカーで1時間分
散を行った。分散終了後、ガラスビーズの除去を行い、
(c−1)3.8部を添加して、撹拌機で3分間混合し
た。得られた第1液は、固形分71%、粘度500mP
a・s(25℃)であった。 Coating Composition Example 5 <First Liquid> (a-1) 22.5 parts, (a-2) 7.5 parts, (f-
3) 31.2 parts, (d-1) 3.8 parts, (e-1) 2.
5 parts, (f-1) 28.7 parts, and glass beads 100
Parts were placed in a mixing container and dispersed for 1 hour with a paint shaker. After dispersion, remove the glass beads,
(C-1) 3.8 parts was added and mixed with a stirrer for 3 minutes. The obtained first liquid has a solid content of 71% and a viscosity of 500 mP.
It was a * s (25 degreeC).
【0090】〈第2液〉
(b−1)75部、(f−1)25部を混合容器に仕込
み、撹拌機で3分間撹拌を行った。得られた第2液は固
形分38%、粘度100mPa・s(25℃)であっ
た。<Second Liquid> 75 parts of (b-1) and 25 parts of (f-1) were placed in a mixing vessel and stirred for 3 minutes with a stirrer. The obtained second liquid had a solid content of 38% and a viscosity of 100 mPa · s (25 ° C.).
【0091】上記第1液及び第2液を、第1液/第2液
=2/1の重量比で混合、攪拌し、塗料組成物を得た。
得られた塗料組成物について、上記した方法で物性評価
を行ったところ、例1の塗料組成物と同等の物性が確認
された。The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 2/1 to obtain a coating composition.
When the physical properties of the obtained coating composition were evaluated by the methods described above, the same physical properties as those of the coating composition of Example 1 were confirmed.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 百鳥 洋 埼玉県北葛飾郡鷲宮町大字上内478 わし 宮団地1−1−102 (72)発明者 野村 和義 埼玉県加須市睦町1−11−12 (72)発明者 今井 健太郎 埼玉県久喜市古久喜901−8 エトワール 久喜305 (72)発明者 平間 信行 埼玉県加須市花崎北3−2−6 (72)発明者 厚地 幹人 茨城県高萩市下手綱1505−1−B201 (72)発明者 乾 国昭 茨城県高萩市春日町2−24−202 (72)発明者 高市 恭規 神奈川県茅ヶ崎市香川8−4−4−404 Fターム(参考) 4J038 BA202 CG141 CG142 CH201 CH202 DB002 DB032 DB262 DL031 DL032 DL052 GA03 GA06 GA09 GA13 JA23 JA69 JC32 JC34 JC38 JC39 KA04 KA06 MA14 NA11 PA18 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hiroshi Momori Saitama Prefecture Kita-Katsushika-gun Washimiya-cho Ookami 478 I Miya housing complex 1-1-102 (72) Inventor Kazuyoshi Nomura 1-11-12 Mutsumicho, Kazo City, Saitama Prefecture (72) Inventor Kentaro Imai 901-8 Kokuki, Kuki-shi, Saitama Etoile Kuki 305 (72) Nobuyuki Hirama, Inventor 3-2-6 Hanasakikita, Kazo City, Saitama Prefecture (72) Inventor Atsushi Miki 1505-1-B201 Shimoteguna, Takahagi City, Ibaraki Prefecture (72) Inventor Kuniaki Inui 2-24-202 Kasuga Town, Takahagi City, Ibaraki Prefecture (72) Inventor Kyoki Takaichi 8-4--4-404 Kagawa, Chigasaki City, Kanagawa Prefecture F-term (reference) 4J038 BA202 CG141 CG142 CH201 CH202 DB002 DB032 DB262 DL031 DL032 DL052 GA03 GA06 GA09 GA13 JA23 JA69 JC32 JC34 JC38 JC39 KA04 KA06 MA14 NA11 PA18
Claims (7)
アルコキシ基含有有機シラン化合物、(b)グリシジル
基と反応し得る官能基を有するアクリル系共重合体、
(c)硬化触媒、(d)グリシジル基含有オルガノシロ
キサン、及び(e)エポキシ当量が100〜1500で
あり、重量平均分子量が200以上、100,000以
下である、Si原子を含有しないグリシジル基含有化合
物を含む、オルガノポリシロキサン系塗料組成物。1. An (a) alkoxy group-containing organosilane compound having a Si content of 15% by weight or more, (b) an acrylic copolymer having a functional group capable of reacting with a glycidyl group,
(C) Curing catalyst, (d) Glycidyl group-containing organosiloxane, and (e) Epoxy equivalent of 100 to 1500, weight average molecular weight of 200 or more and 100,000 or less, Si atom-free glycidyl group-containing An organopolysiloxane-based coating composition containing a compound.
上、5000未満であり、(b)成分、(c)成分、
(d)成分及び(e)成分の量が、(a)成分100重
量部に対して、それぞれ、30〜130重量部(固形
分)、0.1〜30重量部、1〜50重量部及び5〜3
0重量部(固形分)である、請求項1記載の塗料組成
物。2. The weight average molecular weight of the component (e) is 200 or more and less than 5,000, and the component (b), the component (c),
The amounts of the component (d) and the component (e) are 30 to 130 parts by weight (solid content), 0.1 to 30 parts by weight, 1 to 50 parts by weight, and 100 parts by weight of the component (a), respectively. 5-3
The coating composition according to claim 1, which is 0 part by weight (solid content).
0以上、100,000以下であり、(b)成分、
(c)成分、(d)成分及び(e)成分の量が、(a)
成分100重量部に対して、それぞれ、30〜130重
量部(固形分)、0.1〜30重量部、1〜50重量部
及び10〜60重量部(固形分)である、請求項1記載
の塗料組成物。3. The weight average molecular weight of component (e) is 5,000.
0 or more and 100,000 or less, the component (b),
The amounts of the components (c), (d) and (e) are (a)
The amount is 30 to 130 parts by weight (solid content), 0.1 to 30 parts by weight, 1 to 50 parts by weight, and 10 to 60 parts by weight (solid content) with respect to 100 parts by weight of the component, respectively. Coating composition.
の塗料組成物。4. The coating composition according to claim 1, further comprising an organic solvent.
請求項4記載の塗料組成物。5. The organic solvent is a petroleum hydrocarbon solvent,
The coating composition according to claim 4.
なる2液型の塗料組成物であり、(a)成分が第1液及
び/又は第2液に存在し、(b)成分が第1液に存在
し、(c)成分が第1液及び/又は第2液に存在し、
(d)及び(e)成分が第2液に存在する、請求項1記
載の塗料組成物。6. The coating composition is a two-pack type coating composition comprising a first liquid and a second liquid, wherein the component (a) is present in the first liquid and / or the second liquid, and (b). The component is present in the first liquid, the component (c) is present in the first liquid and / or the second liquid,
The coating composition according to claim 1, wherein the components (d) and (e) are present in the second liquid.
なる2液型の塗料組成物であり、(a)成分が第1液及
び/又は第2液に存在し、(b)成分が第1液に存在
し、(c)成分が第1液及び/又は第2液に存在し、
(d)及び(e)成分が第2液に存在し、有機溶剤が第
1液及び/又は第2液に存在する、請求項4記載の塗料
組成物。7. The coating composition is a two-pack type coating composition comprising a first liquid and a second liquid, wherein the component (a) is present in the first liquid and / or the second liquid, and (b). The component is present in the first liquid, the component (c) is present in the first liquid and / or the second liquid,
The coating composition according to claim 4, wherein the components (d) and (e) are present in the second liquid and the organic solvent is present in the first liquid and / or the second liquid.
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JP7220336B1 (en) * | 2022-09-29 | 2023-02-09 | 日本ペイント株式会社 | Paint resin composition, paint and coating film |
WO2023068380A1 (en) * | 2022-09-29 | 2023-04-27 | 日本ペイント株式会社 | Resin composition for paint, paint, and coating |
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