JP5435009B2 - Paint composition - Google Patents
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- Publication number
- JP5435009B2 JP5435009B2 JP2011237108A JP2011237108A JP5435009B2 JP 5435009 B2 JP5435009 B2 JP 5435009B2 JP 2011237108 A JP2011237108 A JP 2011237108A JP 2011237108 A JP2011237108 A JP 2011237108A JP 5435009 B2 JP5435009 B2 JP 5435009B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- meth
- condensate
- addition reaction
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title description 12
- 239000003973 paint Substances 0.000 title description 9
- -1 silane compound Chemical class 0.000 claims description 64
- 150000001875 compounds Chemical class 0.000 claims description 62
- 238000007259 addition reaction Methods 0.000 claims description 40
- 239000008199 coating composition Substances 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 31
- 239000007795 chemical reaction product Substances 0.000 claims description 29
- 125000003277 amino group Chemical group 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 21
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 4
- 125000005595 acetylacetonate group Chemical group 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 3
- 239000005329 float glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 229910052718 tin Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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
- 239000007983 Tris buffer Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 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
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 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
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-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
- 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
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-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
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 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
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- AMUZLNGQQFNPTQ-UHFFFAOYSA-J 3-oxohexanoate zirconium(4+) Chemical compound [Zr+4].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O AMUZLNGQQFNPTQ-UHFFFAOYSA-J 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- JZYAVTAENNQGJB-UHFFFAOYSA-N 3-tripropoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C(C)=C JZYAVTAENNQGJB-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- VDTDBUWAIQVHCO-UHFFFAOYSA-N C(C)(=O)CC(=O)O.C(C)(=O)CC(=O)O.C(CC(=O)C)(=O)OCC Chemical compound C(C)(=O)CC(=O)O.C(C)(=O)CC(=O)O.C(CC(=O)C)(=O)OCC VDTDBUWAIQVHCO-UHFFFAOYSA-N 0.000 description 1
- XUDHTERFOUHVEQ-UHFFFAOYSA-N CC[Ti] Chemical compound CC[Ti] XUDHTERFOUHVEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- WBJGQYBOAOYTQD-UHFFFAOYSA-K aluminum 5-methyl-3-oxohexanoate Chemical compound [Al+3].C(C)(C)CC(CC(=O)[O-])=O.C(C)(C)CC(CC(=O)[O-])=O.C(C)(C)CC(CC(=O)[O-])=O WBJGQYBOAOYTQD-UHFFFAOYSA-K 0.000 description 1
- QVERTZDPVWSNIM-UHFFFAOYSA-K aluminum;3-oxoheptanoate Chemical compound [Al+3].CCCCC(=O)CC([O-])=O.CCCCC(=O)CC([O-])=O.CCCCC(=O)CC([O-])=O QVERTZDPVWSNIM-UHFFFAOYSA-K 0.000 description 1
- 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 1
- YABBMWRVNGAUNW-UHFFFAOYSA-K aluminum;3-oxooctanoate Chemical compound [Al+3].CCCCCC(=O)CC([O-])=O.CCCCCC(=O)CC([O-])=O.CCCCCC(=O)CC([O-])=O YABBMWRVNGAUNW-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HZXXNQUMSGYIKQ-JRYLAINFSA-N bis(6-methylheptyl) (Z)-but-2-enedioate dibutyltin Chemical compound CCCC[Sn]CCCC.CC(C)CCCCCOC(=O)\C=C/C(=O)OCCCCCC(C)C HZXXNQUMSGYIKQ-JRYLAINFSA-N 0.000 description 1
- RGCPMRIOBZXXBR-UHFFFAOYSA-N butan-1-olate;dibutyltin(2+) Chemical compound CCCCO[Sn](CCCC)(CCCC)OCCCC RGCPMRIOBZXXBR-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SVSRQMUJHHQAAX-UHFFFAOYSA-N dibenzyltin Chemical compound C=1C=CC=CC=1C[Sn]CC1=CC=CC=C1 SVSRQMUJHHQAAX-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- DRXHEPWCWBIQFJ-UHFFFAOYSA-N methyl(triphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C)OC1=CC=CC=C1 DRXHEPWCWBIQFJ-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- IIKJRDJBUFJZHS-UHFFFAOYSA-N methyl-tri(octan-2-yloxy)silane Chemical compound CCCCCCC(C)O[Si](C)(OC(C)CCCCCC)OC(C)CCCCCC IIKJRDJBUFJZHS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000006609 n-nonyloxy group Chemical group 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical group 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- IFJYVNTXUVQYOU-UHFFFAOYSA-J pentanoate zirconium(4+) Chemical compound [Zr+4].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O IFJYVNTXUVQYOU-UHFFFAOYSA-J 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 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
- 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
- 239000011342 resin composition Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 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
- UCSBCWBHZLSFGC-UHFFFAOYSA-N tributoxysilane Chemical compound CCCCO[SiH](OCCCC)OCCCC UCSBCWBHZLSFGC-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-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
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、塗料組成物に関する。 The present invention relates to a coating composition.
オルガノポリシロキサン系樹脂を主成分とした塗料は、耐候性や塗膜硬度に優れることから、建築や土木構造物の分野で汎用されている。
このオルガノポリシロキサン系塗料は、上記利点を有している反面、硬化速度が遅く、また得られた塗膜が耐クラック性に劣るという欠点も有している。
Paints mainly composed of organopolysiloxane resins are widely used in the fields of architecture and civil engineering structures because of their excellent weather resistance and coating film hardness.
This organopolysiloxane-based paint has the above-mentioned advantages, but also has a drawback that the curing rate is slow and the obtained coating film is inferior in crack resistance.
これらの欠点を改善すべく、従来、オルガノポリシロキサン系樹脂組成物中に、硬化触媒を添加したり、有機樹脂を加えたりする手法が試みられている（特許文献１〜３参照）。
しかし、硬化触媒を添加する手法では、硬化性は向上するものの耐クラック性に劣るという欠点は解消し得ない。
一方、有機樹脂を添加する手法では、硬化性や耐クラック性は改善するものの、オルガノポリシロキサン系樹脂塗膜本来の特徴である、塗膜硬度や耐候性が低下してしまう。
In order to improve these defects, conventionally, a method of adding a curing catalyst or adding an organic resin to an organopolysiloxane resin composition has been attempted (see Patent Documents 1 to 3).
However, the method of adding a curing catalyst cannot solve the disadvantage that the curability is improved but the crack resistance is inferior.
On the other hand, in the method of adding an organic resin, curability and crack resistance are improved, but the coating film hardness and weather resistance, which are inherent characteristics of the organopolysiloxane-based resin coating film, are lowered.
以上のような理由から、得られる塗膜の硬度や耐候性を保持しながら、塗料の硬化性を良好にし得、かつ、塗膜の耐クラック性を向上させ得る、オルガノポリシロキサン系塗料の開発が望まれているのが現状である。 For the reasons described above, development of organopolysiloxane paints that can improve the curability of the paint and improve the crack resistance of the paint film while maintaining the hardness and weather resistance of the resulting paint film This is the current situation.
本発明は、このような事情に鑑みてなされたものであり、常温硬化性に優れ、耐候性、硬度および耐クラック性に優れた塗膜を与え得る塗料組成物を提供することを目的とする。 This invention is made | formed in view of such a situation, and it aims at providing the coating composition which can give the coating film which was excellent in normal temperature curability, and was excellent in a weather resistance, hardness, and crack resistance. .
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、多官能（メタ）アクリルモノマー等のアクリレート成分と、アミノ基含有アルコキシシラン化合物等の活性水素含有アルコキシシラン化合物とを、アクリレート基／活性水素＝１／１〜１／２（モル比）で反応させて得られた付加反応物、所定の有機シラン化合物、エポキシ基含有化合物および硬化触媒を含む組成物が常温硬化性に優れるとともに、この組成物から得られた塗膜が、耐候性、硬度および耐クラック性に優れていることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventor obtained an acrylate component such as a polyfunctional (meth) acryl monomer and an active hydrogen-containing alkoxysilane compound such as an amino group-containing alkoxysilane compound. A composition containing an addition reaction product obtained by reacting with groups / active hydrogen = 1/1 to 1/2 (molar ratio), a predetermined organic silane compound, an epoxy group-containing compound and a curing catalyst is excellent in room temperature curability. In addition, the present inventors have found that the coating film obtained from this composition is excellent in weather resistance, hardness and crack resistance, and completed the present invention.
すなわち、本発明は、
１． 下記（Ａ）〜（Ｄ）成分を、（Ａ）成分１００質量部に対して、（Ｂ）成分３０〜２４０質量部、（Ｃ）成分１〜１００質量部、および（Ｄ）成分０．１〜５０質量部の割合で含むことを特徴とする塗料組成物、
（Ａ）ケイ素原子含量が１１質量％以上であり、ケイ素原子に直結する水酸基および／またはアルコキシ基を有する有機シラン化合物および／またはその縮合物
（Ｂ）多官能（メタ）アクリルモノマーと、アミノ基またはメルカプト基含有アルコキシシラン化合物および／またはその縮合物とを、（メタ）アクリレート基１ｍｏｌに対して活性水素を１〜２ｍｏｌの範囲で１，４−付加反応させて得られる付加反応物、並びに（ｉｉ）（メタ）アクリル基含有アルコキシシラン化合物および／またはその縮合物と、アミノ基またはメルカプト基含有アルコキシシラン化合物および／またはその縮合物とを、（メタ）アクリレート基１ｍｏｌに対して活性水素を１〜２ｍｏｌの範囲で１，４−付加反応させて得られる付加反応物から選ばれる少なくとも１種
（Ｃ）エポキシ基含有化合物
（Ｄ）硬化触媒
２． 前記（Ｂ）成分が、多官能（メタ）アクリルモノマーと、アミノ基含有アルコキシシラン化合物および／またはその縮合物とを、（メタ）アクリレート基１ｍｏｌに対して活性水素を１〜２ｍｏｌの範囲で１，４−付加反応させて得られる付加反応物、並びに（ｉｉ）（メタ）アクリレート基含有アルコキシシラン化合物および／またはその縮合物と、アミノ基含有アルコキシシラン化合物および／またはその縮合物とを、（メタ）アクリレート基１ｍｏｌに対して活性水素を１〜２ｍｏｌの範囲で１，４−付加反応させて得られる付加反応物から選ばれる少なくとも１種である１の塗料組成物、
３． 前記（Ｃ）成分が、水添ビスフェノールＡ型エポキシ樹脂である１または２の塗料組成物、
４． 前記（Ａ）成分が、下記式（１）で示される有機シラン化合物および／またはその縮合物である１〜３のいずれかの塗料組成物
を提供する。
That is, the present invention
1. The following components (A) to (D) are added to 100 parts by mass of ( A) component, 30 to 240 parts by mass of (B) component, 1 to 100 parts by mass of component (C), and 0.1 of component (D). A coating composition characterized by containing in a proportion of ˜50 parts by mass ,
(A) An organic silane compound having a silicon atom content of 11% by mass or more and having a hydroxyl group and / or alkoxy group directly bonded to a silicon atom and / or a condensate thereof (B) a polyfunctional (meth) acryl monomer, an amino group Alternatively, an addition reaction product obtained by subjecting a mercapto group-containing alkoxysilane compound and / or a condensate thereof to 1,4-addition reaction in a range of 1 to 2 mol of active hydrogen with respect to 1 mol of (meth) acrylate group, and ( ii) (meth) acryl group-containing alkoxysilane compound and / or condensate thereof, amino group or mercapto group-containing alkoxysilane compound and / or condensate thereof, 1 active hydrogen per mol of (meth) acrylate group small selected from addition reaction product obtained by 1,4-addition reaction in the range of ~2mol Kutomo one (C) an epoxy group-containing compound (D) curing catalyst 2. The component (B), a polyfunctional (meth) acrylic monomer, 1 an amino group-containing alkoxysilane compound and / or its condensate, the active hydrogen in the range of 1~2mol the (meth) acrylate groups 1mol , 4-Addition reaction product obtained by addition reaction, and (ii) (meth) acrylate group-containing alkoxysilane compound and / or condensate thereof, amino group-containing alkoxysilane compound and / or condensate thereof ( 1 coating composition which is at least one selected from addition reactants obtained by subjecting 1 to 2 mol of active hydrogen to 1,4-addition reaction to 1 mol of meth) acrylate groups,
3. The coating composition according to 1 or 2, wherein the component (C) is a hydrogenated bisphenol A type epoxy resin,
4). The coating composition according to any one of 1 to 3, wherein the component (A) is an organosilane compound represented by the following formula (1) and / or a condensate thereof:
I will provide a.
本発明の塗料組成物は、多官能（メタ）アクリルモノマー等のアクリレート成分と、アミノ基含有アルコキシシラン化合物等の活性水素含有アルコキシシラン化合物とを、アクリレート基／活性水素＝１／１〜１／２（モル比）で反応させて得られた付加反応物、所定の有機シラン化合物、エポキシ基含有化合物および硬化触媒を含んでいるから、常温硬化性に優れ、しかも、耐候性、常温硬化性、硬度および耐クラック性に優れた塗膜を与え得る。 The coating composition of the present invention comprises an acrylate component such as a polyfunctional (meth) acrylic monomer and an active hydrogen-containing alkoxysilane compound such as an amino group-containing alkoxysilane compound. Since it contains an addition reaction product obtained by reacting at 2 (molar ratio), a predetermined organic silane compound, an epoxy group-containing compound and a curing catalyst, it has excellent room temperature curability, and is weather resistant, room temperature curability, A coating film having excellent hardness and crack resistance can be provided.
以下、本発明についてさらに詳しく説明する。
本発明に係る塗料組成物は、下記（Ａ）〜（Ｄ）成分を含むものである。
（Ａ）ケイ素原子含量が１１質量％以上であり、ケイ素原子に直結する水酸基および／またはアルコキシ基を有する有機シラン化合物および／またはその縮合物
（Ｂ）多官能（メタ）アクリルモノマーと、アミノ基またはメルカプト基含有アルコキシシラン化合物および／またはその縮合物とを、（メタ）アクリレート基１ｍｏｌに対して活性水素を１〜２ｍｏｌの範囲で反応させて得られる付加反応物、並びに（ｉｉ）（メタ）アクリル基含有アルコキシシラン化合物および／またはその縮合物と、アミノ基またはメルカプト基含有アルコキシシラン化合物および／またはその縮合物とを、（メタ）アクリレート基１ｍｏｌに対して活性水素を１〜２ｍｏｌの範囲で反応させて得られる付加反応物から選ばれる少なくとも１種
（Ｃ）エポキシ基含有化合物
（Ｄ）硬化触媒
Hereinafter, the present invention will be described in more detail.
The coating composition according to the present invention includes the following components (A) to (D).
(A) An organic silane compound having a silicon atom content of 11% by mass or more and having a hydroxyl group and / or alkoxy group directly bonded to a silicon atom and / or a condensate thereof (B) a polyfunctional (meth) acryl monomer, an amino group Or an addition reaction product obtained by reacting a mercapto group-containing alkoxysilane compound and / or a condensate thereof with 1 to 2 mol of active hydrogen per 1 mol of (meth) acrylate group, and (ii) (meth) An acrylic group-containing alkoxysilane compound and / or a condensate thereof, and an amino group or mercapto group-containing alkoxysilane compound and / or a condensate thereof are used in a range of 1 to 2 mol of active hydrogen per mol of (meth) acrylate group. At least one (C) epoxide selected from addition products obtained by reaction Group-containing compound (D) a curing catalyst
以下、本発明の塗料組成物に含まれる各成分について説明する。
（Ａ）有機シラン化合物
本発明の塗料組成物では、ケイ素原子含量（以下、Ｓｉ含量という）が１１質量％以上であり、ケイ素原子に直結する水酸基および／またはアルコキシ基を有する有機シラン化合物および／またはその縮合物を用いる。
ここで、Ｓｉ含量が１１質量％未満であると、得られる塗膜の耐候性が不十分になる。好ましくは、１１．５質量％以上、より好ましくは１３質量％以上、より一層好ましくは１５質量％以上である。
また、その上限は、耐候性という点からは特に制限されるものではないが、Ｓｉ含量が多すぎると、得られる塗膜が割れ易くなる等の問題が生じる虞があるため、５０質量％程度が好ましく、４０質量％程度がより好ましく、３５質量％程度がより一層好ましい。
Hereinafter, each component contained in the coating composition of the present invention will be described.
(A) Organosilane compound In the coating composition of the present invention, the silicon atom content (hereinafter referred to as Si content) is 11% by mass or more, the organosilane compound having a hydroxyl group and / or an alkoxy group directly bonded to the silicon atom, and / or Or the condensate thereof is used.
Here, when the Si content is less than 11% by mass, the weather resistance of the obtained coating film becomes insufficient. Preferably, it is 11.5 mass% or more, More preferably, it is 13 mass% or more, More preferably, it is 15 mass% or more.
Further, the upper limit is not particularly limited from the viewpoint of weather resistance, but if the Si content is too large, there is a possibility that problems such as easy cracking of the resulting coating film occur, so about 50% by mass. Is preferable, about 40 mass% is more preferable, and about 35 mass% is still more preferable.
上記有機シラン化合物としては、特に限定されるものではなく、従来公知の有機シラン化合物から、上記Ｓｉ含量を満たすものを選択して用いればよいが、本発明では、特に式（１）で示される有機シラン化合物および／またはその縮合物が好適に用いられる。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、単独で用いても、２種類以上を組み合わせて用いてもよい。 The organic silane compound is not particularly limited and may be selected from conventionally known organic silane compounds that satisfy the Si content. In the present invention, the organic silane compound is particularly represented by the formula (1). Organosilane compounds and / or condensates thereof are preferably used. In addition, when it is a condensate, the range of 2-100 is common as the condensation degree, and the liquid thing whose condensation degree is 2-15 is preferable from a compatible point. Moreover, in this invention, the alkoxy group containing organosilane compound which is (A) component may be used independently, or may be used in combination of 2 or more types.
上記式中、Ｒ1は、水素原子またはアルキル基を表し、Ｒ2〜Ｒ4は、互いに独立して、アルキル基、アリール基、アルコキシ基またはアリールオキシ基を表す。
上記アルキル基の炭素数としては、特に限定されるものではないが、本発明においては、１〜１０、特に、１〜５が好ましい。また、その構造は、直鎖、分岐、環状のいずれでもよい。
アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、シクロプロピル基、ｎ−ブチル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基、シクロブチル基、ｎ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基等が挙げられる。
In said formula, R < 1 > represents a hydrogen atom or an alkyl group, R < 2 > -R < 4 > represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group mutually independently.
Although it does not specifically limit as carbon number of the said alkyl group, In this invention, 1-10, especially 1-5 are preferable. Further, the structure may be any of linear, branched and cyclic.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n -Pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
アリール基の炭素数としては、特に限定されるものではないが、本発明においては、６〜２０、特に、６〜１４が好ましい。
アリール基の具体例としては、フェニル基、α−ナフチル基、β−ナフチル基、ｏ−ビフェニリル基、ｍ−ビフェニリル基、ｐ−ビフェニリル基、１−アントリル基、２−アントリル基、９−アントリル基、１−フェナントリル基、２−フェナントリル基、３−フェナントリル基、４−フェナントリル基、９−フェナントリル基等が挙げられる。
Although it does not specifically limit as carbon number of an aryl group, In this invention, 6-20, especially 6-14 are preferable.
Specific examples of the aryl group include phenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, and 9-anthryl group. 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
アルコキシ基の炭素数としては、特に限定されるものではないが、本発明においては、１〜１０、特に、１〜５が好ましい。また、その構造は、直鎖、分岐、環状のいずれでもよい。
アルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｔ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基、ｎ−ヘプチルオキシ基、ｎ−オクチルオキシ基、ｎ−ノニルオキシ基、ｎ−デシルオキシ基等が挙げられる。
Although it does not specifically limit as carbon number of an alkoxy group, In this invention, 1-10, especially 1-5 are preferable. Further, the structure may be any of linear, branched and cyclic.
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy. Group, n-octyloxy group, n-nonyloxy group, n-decyloxy group and the like.
アリールオキシ基の炭素数としては、特に限定されるものではないが、本発明においては、６〜２０、特に、６〜１４が好ましい。
アリールオキシ基の具体例としては、フェノキシ基、α−ナフトキシ基、β−ナフトキシ基等が挙げられる。
Although it does not specifically limit as carbon number of an aryloxy group, In this invention, 6-20, especially 6-14 are preferable.
Specific examples of the aryloxy group include phenoxy group, α-naphthoxy group, β-naphthoxy group and the like.
有機シラン化合物の具体例としては、テトラメチルシリケート（テトラメトキシシラン）、テトラエチルシリケート（テトラエトキシシラン）等のテトラアルキルシリケート；メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン等のアルキルトリアルコキシシラン；フェニルトリメトキシシラン、フェニルトリエトキシシラン等のアリールトリアルコキシシラン、およびこれら各有機シラン化合物の縮合物等が挙げられる。
なお、縮合物は、例えば、上記有機シラン化合物の単一物または２種以上の混合物に、水を添加し、（部分）加水分解縮合させて得ることができる。
Specific examples of the organic silane compound include tetraalkyl silicate such as tetramethyl silicate (tetramethoxysilane) and tetraethyl silicate (tetraethoxysilane); alkyltrimethyl silane such as methyltrimethoxysilane, methyltriethoxysilane and methyltriisopropoxysilane. Examples include alkoxysilanes; aryltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane, and condensates of these organic silane compounds.
The condensate can be obtained, for example, by adding water and (partially) hydrolytic condensation to a single organic silane compound or a mixture of two or more.
また、本発明の有機シラン化合物としては、市販品を用いることもでき、その具体例としては、ＫＲ−５１０（Ｓｉ含量２０．５質量％、信越化学工業（株）製）、ＫＲ−２１３（Ｓｉ含量１７．７質量％、信越化学工業（株）製）、ＫＲ−２１７（Ｓｉ含量１１．６質量％、信越化学工業（株）製）、ＫＲ−５００（Ｓｉ含量２９．４質量％、信越化学工業（株）製）、ＫＣ−８９Ｓ（Ｓｉ含量２７．５質量％、信越化学工業（株）製）、Ｘ−４０−９２２５（Ｓｉ含量３１．３質量％、信越化学工業（株）製）、Ｘ−４０−９２４６（Ｓｉ含量３３．６質量％、信越化学工業（株）製）、Ｘ−４０−９２５０（Ｓｉ含量３４．１質量％、信越化学工業（株）製）、ＫＲ−４０１Ｎ（Ｓｉ含量２６．１質量％、信越化学工業（株）製）、Ｘ−４０−９２２７（Ｓｉ含量２７．５質量％、信越化学工業（株）製）、Ｘ−４０−９２４７（Ｓｉ含量２１．５質量％、信越化学工業（株）製）、ＫＲ−９２１８（Ｓｉ含量１８．７質量％、信越化学工業（株）製）、Ｘ−４０−２３０８（Ｓｉ含量２３．８質量％、信越化学工業（株）製）、Ｘ−４０−９２３８（Ｓｉ含量２１質量％、信越化学工業（株）製）などが挙げられる。 In addition, as the organosilane compound of the present invention, commercially available products can be used. Specific examples thereof include KR-510 (Si content 20.5% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), KR-213 ( Si content 17.7% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), KR-217 (Si content 11.6% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), KR-500 (Si content 29.4% by mass, Shin-Etsu Chemical Co., Ltd.), KC-89S (Si content 27.5% by mass, Shin-Etsu Chemical Co., Ltd.), X-40-9225 (Si content 31.3% by mass, Shin-Etsu Chemical Co., Ltd.) Manufactured), X-40-9246 (Si content 33.6% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), X-40-9250 (Si content 34.1% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), KR -401N (Si content 26.1% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), X 40-9227 (Si content 27.5% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), X-40-9247 (Si content 21.5% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), KR-9218 (Si content 18.7% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), X-40-2308 (Si content 23.8% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), X-40-9238 (Si content 21% by mass, Shin-Etsu Chemical Co., Ltd.).
（Ｂ）付加反応物
また、本発明の塗料組成物では、多官能（メタ）アクリルモノマーと、アミノ基またはメルカプト基含有アルコキシシラン化合物および／またはその縮合物とを反応させて得られる付加反応物、並びに（ｉｉ）（メタ）アクリル基含有アルコキシシラン化合物および／またはその縮合物と、アミノ基またはメルカプト基含有アルコキシシラン化合物および／またはその縮合物とを反応させて得られる付加反応物から選ばれる少なくとも１種を用いる。
(B) Addition reaction product In the coating composition of the present invention, an addition reaction product obtained by reacting a polyfunctional (meth) acrylic monomer with an amino group or mercapto group-containing alkoxysilane compound and / or a condensate thereof. And (ii) (meth) acryl group-containing alkoxysilane compound and / or its condensate, and an addition reaction product obtained by reacting an amino group or mercapto group-containing alkoxysilane compound and / or its condensate. At least one kind is used.
上記多官能（メタ）アクリルモノマーとしては、（メタ）アクリル基を２個以上有するものであれば特に限定されるものではなく、例えば、ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、エトキシル化ビスフェノールジアクリレート等のジ（メタ）アクリレート化合物；トリメチロールプロパントリメタクリレート（ＴＭＰＴＡ）、エトキシル化トリメチロールプロパントリアクリレート（ＥＴＭＰＴＡ）等のトリ（メタ）アクリレート化合物；ペンタエリスリトールテトラアクリレート、エトキシル化ペンタエリスリトールテトラアクリレート、ジ（トリメチロールプロパン）テトラアクリレート（ＤＴＭＰＴＡ）等のテトラ（メタ）アクリレート化合物；ジペンタエリスリトールペンタアクリレート（ＤＰＡＡ）等のペンタ（メタ）アクリレート化合物；ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）等のヘキサ（メタ）アクリレート化合物などが挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。 The polyfunctional (meth) acrylic monomer is not particularly limited as long as it has two or more (meth) acrylic groups. For example, hexanediol diacrylate, neopentyl glycol diacrylate, ethoxylated bisphenol di Di (meth) acrylate compounds such as acrylate; tri (meth) acrylate compounds such as trimethylolpropane trimethacrylate (TMPTA) and ethoxylated trimethylolpropane triacrylate (ETMPTA); pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, Tetra (meth) acrylate compounds such as di (trimethylolpropane) tetraacrylate (DTMPTA); dipentaerythritol pentaacrylate (DP A) such penta (meth) acrylate; dipentaerythritol hexaacrylate (DPHA) hexa such (meth) acrylate compounds such as the like. These may be used singly or may be used in combination of two or more.
アミノ基含有アルコキシシランの具体例としては、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルメチルジエトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン等が挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。
メルカプト基含有アルコキシシラン化合物の具体例としては、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリエトキシシラン等が挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。
Specific examples of the amino group-containing alkoxysilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3. -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane etc. are mentioned, These may be used independently or may be used in combination of 2 or more types.
Specific examples of the mercapto group-containing alkoxysilane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like. A combination of the above may also be used.
上記アルコキシシラン化合物の縮合物としては、例えば、上記アルコキシシラン化合物に水を添加し、（部分）加水分解させて縮合させて得られた化合物や、上記アルコキシシラン化合物と、その他のアルコキシシラン化合物との混合物に水を添加し、（部分）加水分解させて縮合させて得られた化合物が挙げられる。
その他のアルコキシシラン化合物を用いる場合、アミノ基またはメルカプト基含有アルコキシシラン化合物とその他のアルコキシシラン化合物との混合比率は任意であるが、１／１〜１／２（モル比）が好ましい。
なお、これらの部分加水分解縮合物は、市販品を用いてもよく、例えば、３−メルカプトプロピルトリメトキシシランとテトラエチルシリケートとの部分加水分解縮合物であるＸ４１−１８０５（信越化学工業（株）製）等を用いることができる。
As the condensate of the alkoxysilane compound, for example, a compound obtained by adding water to the alkoxysilane compound and hydrolyzing and condensing the alkoxysilane compound, the alkoxysilane compound, and other alkoxysilane compounds The compound obtained by adding water to this mixture, hydrolyzing and condensing (partially) is exemplified.
When other alkoxysilane compounds are used, the mixing ratio of the amino group or mercapto group-containing alkoxysilane compound and the other alkoxysilane compound is arbitrary, but is preferably 1/1 to 1/2 (molar ratio).
As these partial hydrolysis condensates, commercially available products may be used. For example, X41-1805 (Shin-Etsu Chemical Co., Ltd.), which is a partial hydrolysis condensate of 3-mercaptopropyltrimethoxysilane and tetraethyl silicate. Etc.) can be used.
なお、その他のアルコキシシラン化合物としても、特に限定されるものではなく、例えば、テトラメチルシリケート（テトラメトキシシラン）、テトラエチルシリケート（テトラエトキシシラン）、テトラ−ｎ−プロピルシリケート（テトラｎ−プロポキシシシラン）、テトライソプロピルシリケート（テトラｉ−プロポキシシシラン）、テトラ−ｎ−ブチルシリケート（テトラｎ−ブトキシシラン）、テトライソブチルシリケート（テトラｉ−ブトキシシラン）、テトラ−ｔ−ブチルシリケート（テトラｔ−ブトキシシラン）等のテトラアルキルシリケート；メチルトリメトキシシラン、メチルトリエトキシシラン、オクタデシルトリエトキシシラン、メチルトリ−ｓｅｃ−オクチルオキシシラン、メチルトリイソプロポキシシラン、メチルトリブトキシシラン等のアルキルトリアルコキシシラン；フェニルトリメトキシシラン、フェニルトリエトキシシラン等のアリールトリアルコキシシラン；メチルトリフェノキシシラン等のアルキルトリアリールオキシシラン；３−グリシドキシプロピルトリメトキシシランなどのグリシドキシトリアルコキシシラン等が挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。 The other alkoxysilane compounds are not particularly limited, and examples thereof include tetramethyl silicate (tetramethoxysilane), tetraethyl silicate (tetraethoxysilane), and tetra-n-propyl silicate (tetran-propoxysilane). ), Tetraisopropyl silicate (tetra i-propoxy silane), tetra-n-butyl silicate (tetra n-butoxy silane), tetraisobutyl silicate (tetra i-butoxy silane), tetra-t-butyl silicate (tetra t-butoxy) Silane), etc .; methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-sec-octyloxysilane, methyltriisopropoxysilane, methyl Alkyltrialkoxysilanes such as tributoxysilane; aryltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; alkyltriaryloxysilanes such as methyltriphenoxysilane; glycides such as 3-glycidoxypropyltrimethoxysilane Examples include doxytrialkoxysilane, which may be used alone or in combination of two or more.
上記多官能（メタ）アクリルモノマーとアミノ基またはメルカプト基含有アルコキシシラン化合物との付加反応物は、これらをマイケル付加反応等の従来公知のα，β−不飽和カルボニル化合物へのアミノ基またはメルカプト基の１，４−付加反応を用いて製造することができる。
また、多官能（メタ）アクリルモノマーとメルカプト基含有アルコキシシラン化合物との付加反応は、塗料の研究，Ｎｏ．１３８，ｐｐ．２−７，２００２年に記載の方法等を採用してもよい。
The addition reaction product of the polyfunctional (meth) acrylic monomer and an amino group or mercapto group-containing alkoxysilane compound is an amino group or mercapto group to a conventionally known α, β-unsaturated carbonyl compound such as a Michael addition reaction. The 1,4-addition reaction of
The addition reaction between a polyfunctional (meth) acrylic monomer and a mercapto group-containing alkoxysilane compound is described in Paint Research, No. 138, pp. The method described in 2-7, 2002 may be adopted.
本発明では、上記付加反応時のアミノ基またはメルカプト基含有アルコキシシラン化合物の使用量として、多官能（メタ）アクリルモノマーの不飽和二重結合が残存しない割合、具体的には、多官能（メタ）アクリレートモノマーの（メタ）アクリレート基１ｍｏｌに対してアミノ基またはメルカプト基含有アルコキシシラン化合物の活性水素を１〜２ｍｏｌの範囲で用いる。 In the present invention, the amount of the amino group or mercapto group-containing alkoxysilane compound used in the addition reaction is the ratio at which the unsaturated double bond of the polyfunctional (meth) acrylic monomer does not remain, specifically, the polyfunctional (meta ) The active hydrogen of the amino group or mercapto group-containing alkoxysilane compound is used in the range of 1 to 2 mol with respect to 1 mol of the (meth) acrylate group of the acrylate monomer.
（メタ）アクリレート基１ｍｏｌに対し、アミノ基またはメルカプト基含有アルコキシシラン化合物の活性水素を１ｍｏｌ未満で用いると、不飽和二重結合が残存し、塗料組成物の常温硬化性が低下するとともに、常温硬化させて得られた塗膜の硬度が低下する。
一方、活性水素を２ｍｏｌ超で用いると、この場合も塗料組成物の常温硬化性が低下するとともに、塗膜の硬度および耐候性が低下する。
塗料組成物の常温硬化性をより高めるとともに、得られる塗膜の硬度や耐候性をより高めることを考慮すると、（メタ）アクリレート基１ｍｏｌに対し、アミノ基またはメルカプト基含有アルコキシシラン化合物の活性水素を１ｍｏｌ以上２ｍｏｌ未満で用いることが好ましく、（メタ）アクリレート基／活性水素＝１／１〜１／１．８（モル比）が好ましく、１／１〜１／１．５（モル比）がより一層好ましい。
When the active hydrogen of the amino group or mercapto group-containing alkoxysilane compound is used in an amount of less than 1 mol with respect to 1 mol of the (meth) acrylate group, the unsaturated double bond remains, and the room temperature curability of the coating composition is lowered. The hardness of the coating film obtained by curing decreases.
On the other hand, when the active hydrogen is used in excess of 2 mol, the room temperature curability of the coating composition is lowered, and the hardness and weather resistance of the coating film are also lowered.
In consideration of further improving the room temperature curability of the coating composition and further increasing the hardness and weather resistance of the resulting coating film, the active hydrogen of the amino group or mercapto group-containing alkoxysilane compound with respect to 1 mol of the (meth) acrylate group Is preferably used at 1 mol or more and less than 2 mol, (meth) acrylate group / active hydrogen = 1/1 to 1 / 1.8 (molar ratio) is preferable, and 1/1 to 1 / 1.5 (molar ratio) is Even more preferred.
一方、（メタ）アクリレート基含有アルコキシシラン化合物としては、公知の化合物から適宜選択して用いればよい。
その具体例としては、例えば、３−メタクリロキシプロピルメチルジエトキシシラン、３−アクリロキシプロピルメチルジメトキシシラン等の（メタ）アクリロキシジアルコキシシラン；３−アクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−メタクリロキシプロピルトリプロポキシシラン等の（メタ）アクリロキシトリアルコキシシランなどが挙げられる。
また、これらの縮合物としては、上記と同様の手法にて（部分）加水分解縮合させたものが挙げられる。
なお、（メタ）アクリレート基含有アルコキシシラン化合物の縮合物としては、市販品を用いることもでき、その具体例としては、ＫＲ−５１３、Ｘ−４０−２６５５Ａ（いずれも信越化学工業（株）製）などが挙げられる。
On the other hand, the (meth) acrylate group-containing alkoxysilane compound may be appropriately selected from known compounds.
Specific examples thereof include, for example, (meth) acryloxy dialkoxysilanes such as 3-methacryloxypropylmethyldiethoxysilane and 3-acryloxypropylmethyldimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxy Examples include (meth) acryloxytrialkoxysilane such as propyltriethoxysilane and 3-methacryloxypropyltripropoxysilane.
Moreover, as these condensates, the thing which carried out the (partial) hydrolysis condensation by the method similar to the above is mentioned.
In addition, as a condensate of a (meth) acrylate group containing alkoxysilane compound, a commercial item can also be used, As the specific example, KR-513, X-40-2655A (all are Shin-Etsu Chemical Co., Ltd. product). ) And the like.
この（メタ）アクリレート基含有アルコキシシラン化合物を用いる場合も、多官能（メタ）アクリルモノマーの場合と同様の理由から、アミノ基またはメルカプト基含有アルコキシシラン化合物との反応において、（メタ）アクリレート基／活性水素＝１／１〜１／２（モル比）で反応を行う必要がある。
この場合も、塗料組成物の常温硬化性をより高めるとともに、得られる塗膜の硬度や耐候性をより高めることを考慮すると、（メタ）アクリレート基１ｍｏｌに対し、アミノ基またはメルカプト基含有アルコキシシラン化合物の活性水素を１ｍｏｌ以上２ｍｏｌ未満で用いることが好ましく、（メタ）アクリレート基／活性水素＝１／１〜１／１．８（モル比）が好ましく、１／１〜１／１．５（モル比）がより一層好ましい。
Even when this (meth) acrylate group-containing alkoxysilane compound is used, for the same reason as in the case of the polyfunctional (meth) acrylic monomer, in the reaction with the amino group or mercapto group-containing alkoxysilane compound, the (meth) acrylate group / It is necessary to carry out the reaction at active hydrogen = 1/1 to 1/2 (molar ratio).
Also in this case, in consideration of further increasing the room temperature curability of the coating composition and further increasing the hardness and weather resistance of the resulting coating film, an amino group or mercapto group-containing alkoxysilane with respect to 1 mol of (meth) acrylate group. The active hydrogen of the compound is preferably used in an amount of 1 mol or more and less than 2 mol, preferably (meth) acrylate group / active hydrogen = 1/1 to 1 / 1.8 (molar ratio), 1/1 to 1 / 1.5 ( (Molar ratio) is even more preferable.
本発明の組成物において、上記（Ａ）成分と（Ｂ）成分との配合割合は、塗布性等の通常の塗料に要求される性質が実用上問題ない範囲であれば任意であるが、本発明においては、（Ａ）成分１００質量部に対して、（Ｂ）成分３０〜２４０質量部程度が好ましく、５０〜２００質量部程度がより好ましく、５０〜１５０質量部程度がより一層好ましい。
In the composition of the present invention, the blending ratio of the component (A) and the component (B) is arbitrary as long as the properties required for ordinary paints such as coating properties are practically acceptable. in the present invention, with respect to 100 parts by weight of (A), (B) component 30 to 240 parts by weight approximately, more preferably 50 to 200 parts by mass, and still more preferably, 50 to 150 parts by weight.
（Ｃ）エポキシ基含有化合物
エポキシ基含有化合物としては特に限定されるものではないが、その分子中にエポキシ基を少なくとも２個以上有する化合物が好ましい。
その具体例としては、ビスフェノールＡ、ビスフェノールＦ、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン等のポリフェノール化合物のグリシジルエーテル系エポキシ樹脂；上記ポリフェノール化合物の水添化物のグリシジルエーテル系エポキシ樹脂；カテコール、レゾルシン、ヒドロキノン、フロログルシン等の多価フェノール化合物のグリシジルエーテル系エポキシ樹脂；エチレングリコール、グリセリン、ペンタエリスリトール、ポリオキシアルキレングリコール等の多価アルコール化合物のグリシジルエーテル系エポキシ樹脂；ノボラック型エポキシ樹脂；ビニルシクロヘキセンジオキシド、ジシクロペンタジエンジオキシド等の脂環族系エポキシ樹脂；フタル酸、イソフタル酸、テレフタル酸、ヘキサヒドロフタル酸、コハク酸等のポリカルボン酸のポリグリシジルエステル系エポキシ樹脂；４，４′−ジアミノジフェニルメタン、ｐ−アミノフェノール、ｍ−アミノフェノール、１，３−ビス（アミノメチル）シクロヘキサン等のアミン類のポリグリシジルアミン系エポキシ樹脂；メチルエピクロ型エポキシ樹脂等が挙げられ、これらは単独で用いても、２種類以上混合して用いてもよい。
これらの中でも、水添ビスフェノールＡ型エポキシ樹脂が好適である。
(C) Epoxy group-containing compound The epoxy group-containing compound is not particularly limited, but a compound having at least two epoxy groups in the molecule is preferable.
Specific examples thereof include glycidyl ether type epoxy resins of polyphenol compounds such as bisphenol A, bisphenol F, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane; glycidyl ether type of hydrogenated products of the above polyphenol compounds. Epoxy resin; glycidyl ether type epoxy resin of polyhydric phenol compound such as catechol, resorcin, hydroquinone, phloroglucin; glycidyl ether type epoxy resin of polyhydric alcohol compound such as ethylene glycol, glycerin, pentaerythritol, polyoxyalkylene glycol; novolac type Epoxy resins; Alicyclic epoxy resins such as vinylcyclohexene dioxide and dicyclopentadiene dioxide; phthalic acid, isophthalic acid, terephthalic acid, hexahydrophenol Polyglycidyl ester epoxy resins of polycarboxylic acids such as phosphoric acid and succinic acid; amines such as 4,4'-diaminodiphenylmethane, p-aminophenol, m-aminophenol, 1,3-bis (aminomethyl) cyclohexane Polyglycidylamine epoxy resin; methyl epichloro epoxy resin, and the like. These may be used alone or in combination of two or more.
Among these, hydrogenated bisphenol A type epoxy resin is preferable.
エポキシ基含有化合物の配合量は、上記（Ａ）成分１００質量部に対して、１〜１００質量部程度が好ましく、５〜８０質量部程度がより好ましく、１０〜６０質量部程度がより一層好ましい。 As for the compounding quantity of an epoxy-group containing compound, about 1-100 mass parts is preferable with respect to 100 mass parts of said (A) component, About 5-80 mass parts is more preferable, About 10-60 mass parts is still more preferable. .
（Ｄ）硬化触媒
硬化触媒としては、オルガノシロキサン系塗料において一般的に用いられるものであれば、特に限定されるものではないが、有機金属化合物であることが好ましい。
その具体例としては、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等が挙げられる。
金属アルコキシド化合物の具体例としては、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る。
(D) Curing catalyst Although it will not specifically limit if it is generally used in an organosiloxane type coating material as a curing catalyst, It is preferable that it is an organometallic compound.
Specific examples thereof include metal alkoxide compounds such as Ti, Al, Zr, and Sn, metal chelate compounds, metal ester compounds, and the like.
Specific examples of the metal alkoxide compound include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec- Aluminum alkoxide such as butoxide, aluminum tri-tert-butoxide; tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetra Titanium alkoxides such as n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate; Ethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra Zirconium alkoxides such as -tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate; and dibutyltin dibutoxide .
金属キレート化合物の具体例としては、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（プロピオニルアセトナト）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ートアルミニウム・ジ−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−ｔｅｒｔ−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ト・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）等が挙げられる。 Specific examples of the metal chelate compound include tris (ethyl acetoacetate) aluminum, tris (n-propyl acetoacetate) aluminum, tris (isopropyl acetoacetate) aluminum, tris (n-butyl acetoacetate) aluminum, isopropoxybis (ethyl) Acetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, diisopropoxypropionylacetonatoaluminum, acetylacetonato bis (propionylacetonato) aluminum, monoethyl acetoacetate bis (acetylacetate) Nato) aluminum, acetylacetonatoaluminum di-sec-butyrate, methyl acetoacetate aluminum di-se -Aluminum chelate compounds such as butyrate, di (methyl acetoacetate) aluminum mono-tert-butyrate, diisopropoxyethyl acetoacetate aluminum, monoacetylacetonato bis (ethyl acetoacetate) aluminum; diisopropoxy bis (ethyl Titanium chelate compounds such as acetoacetate) titanate, diisopropoxy bis (acetylacetonato) titanate, di-n-butoxy bis (acetylacetonato) titanate; tetrakis (acetylacetonato) zirconium, tetrakis (n-propylacetate) Zirconium chelate compounds such as acetate) zirconium and tetrakis (ethylacetoacetate) zirconium; and dibutyltin bis (acetylacetonate) That.
金属エステル化合物の具体例としては、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。
これら錫エステル化合物としては、市販品を用いることもでき、例えば、ネオスタンＵ−１００、Ｕ−１３０、Ｕ−２００、Ｕ−２２０Ｈ、Ｕ−３０３、Ｕ−７００、Ｕ−８１０、Ｕ−８２０、Ｕ−８３０（以上、日東化成（株）製）等を好適に用いることができる。
以上で例示した各硬化触媒は単独で用いても、２種以上を組み合わせて用いてもよい。
Specific examples of the metal ester compound include dibutyltin diacetate, dibutyltin di (2-ethylhexylate), dibenzyltin di (2-ethylhexylate), dibutyltin dilaurate, and dibutyltin diisooctyl maleate. And tin ester compounds.
As these tin ester compounds, commercially available products can also be used. For example, Neostan U-100, U-130, U-200, U-220H, U-303, U-700, U-810, U-820, U-830 (made by Nitto Kasei Co., Ltd.) etc. can be used suitably.
Each curing catalyst illustrated above may be used independently, or may be used in combination of 2 or more type.
硬化触媒の配合量は、有効量であれば任意であり、使用する触媒の種類によっても変動するものであるため一概には規定できないが、上記（Ａ）成分１００質量部に対して、０．１〜５０質量部程度が好ましく、１〜５０質量部程度がより好ましく、１〜２０質量部程度がより一層好ましい。 The blending amount of the curing catalyst is arbitrary as long as it is an effective amount, and since it varies depending on the type of catalyst used, it cannot be defined unconditionally. About 1-50 mass parts is preferable, About 1-50 mass parts is more preferable, About 1-20 mass parts is still more preferable.
なお、本発明の塗料組成物には、本発明の効果を損なわない限りにおいて、消泡剤、増粘剤、沈降防止剤、紫外線吸収剤、光安定剤、触媒等の各種添加剤を組成物中に、０．１〜３０質量％配合してもよいが、後に実施例を挙げて示すように、本発明の塗料組成物では、紫外線吸収剤や光安定剤を配合しなくとも、得られた塗膜は十分な耐候性を発揮する。 The coating composition of the present invention contains various additives such as an antifoaming agent, a thickener, an anti-settling agent, an ultraviolet absorber, a light stabilizer, and a catalyst as long as the effects of the present invention are not impaired. In the coating composition of the present invention, it can be obtained without blending an ultraviolet absorber or a light stabilizer, as shown in the examples below. The coated film exhibits sufficient weather resistance.
本発明の塗料組成物は、上記各成分を任意の順序で適宜配向して調製することができ、その調製の際には溶剤を用いてもよい。
溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素溶剤；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；酢酸エチル、酢酸ｎ−ブチル、酢酸ｎ−アミル等のエステル溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン溶剤；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溶剤；ミネラルスピリット等の石油系炭化水素溶剤；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート等のグリコールエーテルエステル類溶剤などが挙げられる。これらの溶剤は、単独で用いても、２種以上混合して用いてもよい。
溶剤の使用量には特に制限はないが、組成物中の総固形分量が１０〜７０質量％程度となる量が好ましい。
The coating composition of the present invention can be prepared by properly orienting the above components in any order, and a solvent may be used in the preparation.
Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; ester solvents such as ethyl acetate, n-butyl acetate, and n-amyl acetate. Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane; petroleum hydrocarbon solvents such as mineral spirits; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol Monoethyl ether acetate, and the like glycol ether esters solvent such as diethylene glycol monobutyl ether acetate. These solvents may be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in the usage-amount of a solvent, The quantity from which the total solid content in a composition will be about 10-70 mass% is preferable.
以上説明した塗料組成物の使用法としては、例えば、基材表面に直接本発明の組成物を塗布し、これを常温にて乾燥する手法が挙げられる。
この場合、本発明の組成物の塗布法は特に限定されるものではなく、刷毛塗り、ローラ塗りなどの公知の手法から適宜選択すればよい。また、塗布量、塗膜の厚み、乾燥時間などは、基材の材質や被覆品の用途などに応じて適宜なものとすればよい。
本発明の組成物を適用する基材としては、金属基材、プラスチック基材、ガラス基材等任意であるが、本発明の塗料組成物から得られた塗膜は、耐候性に優れていることから、特に、外壁、窓ガラス、ヘッドランプカバー等の外装材用途に、好適に用いることができる。
Examples of the method of using the coating composition described above include a method in which the composition of the present invention is directly applied to the surface of a substrate and dried at room temperature.
In this case, the coating method of the composition of the present invention is not particularly limited, and may be appropriately selected from known methods such as brush coating and roller coating. Moreover, what is necessary is just to make an application quantity, the thickness of a coating film, drying time, etc. suitable according to the material of a base material, the use of a coated article, etc.
As a substrate to which the composition of the present invention is applied, a metal substrate, a plastic substrate, a glass substrate and the like are arbitrary, but the coating film obtained from the coating composition of the present invention is excellent in weather resistance. Therefore, it can be suitably used for exterior materials such as outer walls, window glass, and headlamp covers.
以下、合成例、実施例および比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、実施例における粘度は、芝浦システム（株）のビスメトロン ＶＧ−Ａを用いて測定した。また、以下において、「部」は「質量部」を意味し、「％」は「質量％」を意味する。 Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the viscosity in an Example was measured using the Bismetron VG-A of Shibaura System Co., Ltd. In the following, “part” means “part by mass”, and “%” means “mass%”.
［合成例１］アクリルモノマーとアミノ基含有アルコキシシランの付加反応物Ａの合成
撹拌機、温度計および還流冷却器を備えた反応容器に、トリメチロールプロパンアクリレート（ＴＭＰＴＡ）２９６．０部、３−アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＥ−９０３）３３２．１部を仕込み、５０℃で１２時間反応を行い、固形分１００％、粘度１５００ｍＰａ・ｓ（２５℃、以下同様）の付加反応物Ａを得た。
[Synthesis Example 1] Synthesis of addition reaction product A of acrylic monomer and amino group-containing alkoxysilane A reaction vessel equipped with a stirrer, thermometer and reflux condenser was charged with 296.0 parts of trimethylolpropane acrylate (TMPTA), 3- Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) 332.1 parts was charged, reacted at 50 ° C. for 12 hours, solid content 100%, viscosity 1500 mPa · s (25 ° C., the same applies hereinafter) Of addition reaction product A was obtained.
［合成例２］アクリルモノマーとアミノ基含有アルコキシシランの付加反応物Ｂの合成
撹拌機、温度計および還流冷却器を備えた反応容器に、トリメチロールプロパンアクリレート（ＴＭＰＴＡ）２９６．０部、３−アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＥ−９０３）４９８．２部を仕込み、５０℃で１２時間反応を行い、固形分１００％、粘度３００ｍＰａ・ｓの付加反応物Ｂを得た。
Synthesis Example 2 Synthesis of Addition Reaction Product B of Acrylic Monomer and Amino Group-Containing Alkoxysilane In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 296.0 parts of trimethylolpropane acrylate (TMPTA), 3- 498.2 parts of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) was charged and reacted at 50 ° C. for 12 hours to obtain an addition reaction product B having a solid content of 100% and a viscosity of 300 mPa · s. It was.
［合成例３］アクリルモノマーとアミノ基含有アルコキシシランの付加反応物Ｃの合成
撹拌機、温度計および還流冷却器を備えた反応容器に、トリメチロールプロパンアクリレート（ＴＭＰＴＡ）２９６．０部、３−アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＥ−９０３）６６４．２部を仕込み、５０℃で１２時間反応を行い、固形分１００％、粘度９０ｍＰａ・ｓの付加反応物Ｃを得た。
Synthesis Example 3 Synthesis of Addition Reaction Product C of Acrylic Monomer and Amino Group-Containing Alkoxysilane In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 296.0 parts of trimethylolpropane acrylate (TMPTA), 3- 664.2 parts of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) is charged and reacted at 50 ° C. for 12 hours to obtain an addition reaction product C having a solid content of 100% and a viscosity of 90 mPa · s. It was.
［合成例４］アクリルモノマーとアミノ基含有アルコキシシランの付加反応物Ｄの合成
撹拌機、温度計および還流冷却器を備えた反応容器に、ジトリメチロールプロパンアクリレート（ＤＴＭＰＴＡ）４６６．０部、３−アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＥ−９０３）６６４．２部を仕込み、５０℃で１２時間反応を行い、固形分１００％、粘度１２９０ｍＰａ・ｓの付加反応物Ｄを得た。
[Synthesis Example 4] Synthesis of addition reaction product D of acrylic monomer and amino group-containing alkoxysilane In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 466.0 parts of ditrimethylolpropane acrylate (DTMPTA), 3- 664.2 parts of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) is charged and reacted at 50 ° C. for 12 hours to obtain an addition reaction product D having a solid content of 100% and a viscosity of 1290 mPa · s. It was.
［合成例５］アクリルモノマーとアミノ基含有アルコキシシランの付加反応物Ｅの合成
撹拌機、温度計および還流冷却器を備えた反応容器に、ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）５７８．０部、３−アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＥ−９０３）８３０．３部を仕込み、５０℃で１２時間反応を行い、固形分１００％、粘度３９０００ｍＰａ・ｓの付加反応物Ｅを得た。
[Synthesis Example 5] Synthesis of addition reaction product E of acrylic monomer and amino group-containing alkoxysilane 578.0 parts of dipentaerythritol hexaacrylate (DPHA) was added to a reaction vessel equipped with a stirrer, thermometer and reflux condenser. -830.3 parts of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) was charged and reacted at 50 ° C for 12 hours to give an addition reaction product E having a solid content of 100% and a viscosity of 39000 mPa · s. Obtained.
［合成例６］アクリルモノマーとアミノ基含有アルコキシシランの付加反応物Ｆの合成
撹拌機、温度計および還流冷却器を備えた反応容器に、トリメチロールプロパンアクリレート（ＴＭＰＴＡ）２９６．０部、３−アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＥ−９０３）９９．６部を仕込み、５０℃で１２時間反応を行い、固形分１００％、粘度１６００ｍＰａ・ｓの付加反応物Ｆを得た。
[Synthesis Example 6] Synthesis of Addition Reaction Product F of Acrylic Monomer and Amino Group-Containing Alkoxysilane In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 296.0 parts of trimethylolpropane acrylate (TMPTA), 3- 99.6 parts of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) is charged and reacted at 50 ° C. for 12 hours to obtain an addition reaction product F having a solid content of 100% and a viscosity of 1600 mPa · s. It was.
［合成例７］アクリルモノマーとアミノ基含有アルコキシシランの付加反応物Ｇの合成
撹拌機、温度計および還流冷却器を備えた反応容器に、トリメチロールプロパンアクリレート（ＴＭＰＴＡ）２９６．０部、３−アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＥ−９０３）８３０．３部を仕込み、５０℃で１２時間反応を行い、固形分１００％、粘度５０ｍＰａ・ｓの付加反応物Ｇを得た。
[Synthesis Example 7] Synthesis of addition reaction product G of acrylic monomer and amino group-containing alkoxysilane In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 296.0 parts of trimethylolpropane acrylate (TMPTA), 3- 830.3 parts of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) is charged and reacted at 50 ° C. for 12 hours to obtain an addition reaction product G having a solid content of 100% and a viscosity of 50 mPa · s. It was.
［合成例８］アクリレート基含有アルコキシシランとアミノ基含有アルコキシシランの付加反応物Ｈの合成
撹拌機、温度計、還留冷却器を備えた反応容器に、３−アクリロキシプロピルトリメトキシシラン２３４．３部、３−アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＥ−９０３）１６６．１部を仕込み、５０℃で１２時間反応を行い、固形分１００％、粘度２０ｍＰａ・ｓの付加反応物Ｈを得た。
Synthesis Example 8 Synthesis of Addition Reaction Product H of Acrylate Group-Containing Alkoxysilane and Amino Group-Containing Alkoxysilane In a reaction vessel equipped with a stirrer, thermometer, and reflux condenser, 3-acryloxypropyltrimethoxysilane 234. 3 parts, 166.1 parts of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) are charged and reacted at 50 ° C. for 12 hours to add 100% solids and a viscosity of 20 mPa · s. Reactant H was obtained.
［実施例１］
アルコキシ基含有有機シラン化合物（信越化学工業（株）製、ＫＲ−５１０）１００．０部、合成例１で得られた付加反応物Ａ１００．０部、エポキシ基含有化合物（（株）ＡＤＥＫＡ製、水添ビスフェノールＡ型エポキシ樹脂、アデカレジンＥＰ−４０８０Ｅ）４０部、硬化触媒（日東化成（株）製、ネオスタンＵ−３０３）１２部を撹拌・混合し、塗料組成物を調製した。
[Example 1]
100.0 parts of alkoxy group-containing organic silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., KR-510), addition reaction product A100.0 parts obtained in Synthesis Example 1, epoxy group-containing compound (manufactured by ADEKA Corporation) 40 parts of hydrogenated bisphenol A type epoxy resin, Adeka Resin EP-4080E) and 12 parts of a curing catalyst (manufactured by Nitto Kasei Co., Ltd., Neostan U-303) were stirred and mixed to prepare a coating composition.
［実施例２〜８，比較例１〜９］
下記表１の組成に変更した以外は、実施例１と同様にして塗料組成物を調製した。
[Examples 2-8, Comparative Examples 1-9]
A coating composition was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1 below.
上記各実施例および比較例で調製した塗料組成物について、以下の評価を行った。その結果を表２に併せて示す。
（１）表面乾燥時間
各実施例および比較例で調製した塗料組成物を、フロートガラス上にＮｏ．１２のバーコーターで塗布し、ＪＩＳ Ｋ ５６００−３−２：１９９９に基づいて、表面乾燥までの時間を評価した。
（２）鉛筆硬度
各実施例および比較例で調製した塗料組成物を、フロートガラス上にＮｏ．１２のバーコーターで塗布した後、２３℃にて２週間養生し、塗膜を硬化させた。硬化させた塗膜をＪＩＳ Ｋ ５６００−５−４：１９９９に基づいて、塑性変形するまでの鉛筆硬度を評価した。
（３）促進耐候性
各実施例および比較例で調製した塗料組成物を、フロートガラス上にＮｏ．１２のバーコーターで塗布した後、２３℃にて２週間養生し、塗膜を硬化させた。硬化させた塗膜を促進耐候性試験機（岩崎電気（株）製、アイスーパーＵＶテスター）にて１０００ｈｒ暴露し、外観を目視にて以下の基準により評価した。
○：異常なし
△：若干の白化、クラックが認められる
×：白化、クラックが認められる
The following evaluation was performed about the coating composition prepared by each said Example and comparative example. The results are also shown in Table 2.
(1) Surface drying time The coating composition prepared in each of the examples and comparative examples was subjected to No. 1 on the float glass. It applied with 12 bar coaters, and time to surface drying was evaluated based on JIS K 5600-3-2: 1999.
(2) Pencil hardness The coating composition prepared in each of the examples and comparative examples was placed on a float glass with No. After coating with a 12 bar coater, the coating was cured at 23 ° C. for 2 weeks to cure the coating. The pencil hardness until plastic deformation of the cured coating film was evaluated based on JIS K 5600-5-4: 1999.
(3) Accelerated weather resistance The coating compositions prepared in each of the examples and comparative examples were placed on a float glass with No. After coating with a 12 bar coater, the coating was cured at 23 ° C. for 2 weeks to cure the coating. The cured coating film was exposed for 1000 hours with an accelerated weathering tester (Iwasaki Electric Co., Ltd., iSuper UV Tester), and the appearance was visually evaluated according to the following criteria.
○: No abnormality △: Some whitening and cracks are observed ×: Whitening and cracks are observed
表２に示されるように、実施例１〜８で調製した塗料組成物は表面乾燥時間が短く、また、得られた塗膜は硬度および耐候性に優れていることがわかる。
これに対し、比較例１で調製した塗料組成物は、（Ｃ）成分を含まないため、耐候性に劣ることがわかる。
比較例２で調製した塗料組成物は、（Ｂ）成分製造時のアクリレート基／活性水素＝１／０．３であり、不飽和二重結合が残存しているため、表面乾燥時間が著しく長い上に、塗膜の硬度および耐候性にも劣ることがわかる。
比較例３で調製した塗料組成物は、（Ｂ）成分製造時のアクリレート基／活性水素＝１／２．５であるため、表面乾燥時間が長い上に、塗膜の硬度および耐候性にも劣ることがわかる。
比較例４〜９で調製した塗料組成物は、（Ａ）成分のＳｉ含量が１１質量％未満であるため、得られた塗膜の耐候性に劣ることがわかる。
As shown in Table 2, it can be seen that the coating compositions prepared in Examples 1 to 8 have a short surface drying time, and the obtained coating films are excellent in hardness and weather resistance.
On the other hand, since the coating composition prepared in Comparative Example 1 does not contain the component (C), it is understood that the weather resistance is inferior.
The coating composition prepared in Comparative Example 2 has an acrylate group / active hydrogen at the time of production of component (B) = 1 / 0.3, and since the unsaturated double bond remains, the surface drying time is extremely long. Furthermore, it turns out that the hardness and weather resistance of a coating film are also inferior.
Since the coating composition prepared in Comparative Example 3 has an acrylate group / active hydrogen at the time of production of component (B) = 1 / 2.5, the surface drying time is long and the hardness and weather resistance of the coating film are also long. You can see that it is inferior.
It can be seen that the coating compositions prepared in Comparative Examples 4 to 9 are inferior in weather resistance of the obtained coating films because the Si content of the component (A) is less than 11% by mass.
Claims (4)
（Ａ）ケイ素原子含量が１１質量％以上であり、ケイ素原子に直結する水酸基および／またはアルコキシ基を有する有機シラン化合物および／またはその縮合物
（Ｂ）多官能（メタ）アクリルモノマーと、アミノ基またはメルカプト基含有アルコキシシラン化合物および／またはその縮合物とを、（メタ）アクリレート基１ｍｏｌに対して活性水素を１〜２ｍｏｌの範囲で１，４−付加反応させて得られる付加反応物、並びに（ｉｉ）（メタ）アクリル基含有アルコキシシラン化合物および／またはその縮合物と、アミノ基またはメルカプト基含有アルコキシシラン化合物および／またはその縮合物とを、（メタ）アクリレート基１ｍｏｌに対して活性水素を１〜２ｍｏｌの範囲で１，４−付加反応させて得られる付加反応物から選ばれる少なくとも１種
（Ｃ）エポキシ基含有化合物
（Ｄ）硬化触媒 The following components (A) to (D) are added to 100 parts by mass of ( A) component, 30 to 240 parts by mass of (B) component, 1 to 100 parts by mass of component (C), and 0.1 of component (D). The coating composition characterized by including in the ratio of -50 mass parts .
(A) An organic silane compound having a silicon atom content of 11% by mass or more and having a hydroxyl group and / or alkoxy group directly bonded to a silicon atom and / or a condensate thereof (B) a polyfunctional (meth) acryl monomer, an amino group Alternatively, an addition reaction product obtained by subjecting a mercapto group-containing alkoxysilane compound and / or a condensate thereof to 1,4-addition reaction in a range of 1 to 2 mol of active hydrogen with respect to 1 mol of (meth) acrylate group, and ( ii) (meth) acryl group-containing alkoxysilane compound and / or condensate thereof, amino group or mercapto group-containing alkoxysilane compound and / or condensate thereof, 1 active hydrogen per mol of (meth) acrylate group small selected from addition reaction product obtained by 1,4-addition reaction in the range of ~2mol Kutomo one (C) an epoxy group-containing compound (D) a curing catalyst
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| CA2141516A1 (en) * | 1994-06-13 | 1995-12-14 | John D. Blizzard | Radiation-curable oligomer-based coating composition |
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| JP2003201444A (en) * | 2001-10-09 | 2003-07-18 | Mitsubishi Chemicals Corp | Active energy ray-curable antistatic coating composition |
| JP4906219B2 (en) * | 2002-02-15 | 2012-03-28 | 亜細亜工業株式会社 | Paint composition |
| JP2004043689A (en) * | 2002-07-15 | 2004-02-12 | Nippon Arc Co Ltd | Amorphous polyolefin resin article covered with modified surface layer and production method used for the same |
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