JP5656546B2 - Organic-inorganic composite fine particles, dispersion thereof, method for producing the dispersion, and coating composition - Google Patents
Organic-inorganic composite fine particles, dispersion thereof, method for producing the dispersion, and coating composition Download PDFInfo
- Publication number
- JP5656546B2 JP5656546B2 JP2010230461A JP2010230461A JP5656546B2 JP 5656546 B2 JP5656546 B2 JP 5656546B2 JP 2010230461 A JP2010230461 A JP 2010230461A JP 2010230461 A JP2010230461 A JP 2010230461A JP 5656546 B2 JP5656546 B2 JP 5656546B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- dispersion
- organic
- inorganic
- inorganic composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010419 fine particle Substances 0.000 title claims description 216
- 239000006185 dispersion Substances 0.000 title claims description 108
- 239000002131 composite material Substances 0.000 title claims description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 71
- 239000008199 coating composition Substances 0.000 title claims description 25
- 229920000642 polymer Polymers 0.000 claims description 121
- 239000000178 monomer Substances 0.000 claims description 102
- 239000002904 solvent Substances 0.000 claims description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000008119 colloidal silica Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000004922 lacquer Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 73
- 238000000034 method Methods 0.000 description 71
- -1 nitroxide compound Chemical class 0.000 description 64
- 238000010526 radical polymerization reaction Methods 0.000 description 59
- 238000006243 chemical reaction Methods 0.000 description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 239000011248 coating agent Substances 0.000 description 40
- 238000000576 coating method Methods 0.000 description 40
- 239000000203 mixture Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- 229910001873 dinitrogen Inorganic materials 0.000 description 24
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000007870 radical polymerization initiator Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000010992 reflux Methods 0.000 description 16
- 230000002441 reversible effect Effects 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 239000011368 organic material Substances 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000003776 cleavage reaction Methods 0.000 description 12
- 239000002612 dispersion medium Substances 0.000 description 12
- 229920000058 polyacrylate Polymers 0.000 description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 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 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 150000001723 carbon free-radicals Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010533 azeotropic distillation Methods 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- 238000006276 transfer reaction Methods 0.000 description 9
- 239000004342 Benzoyl peroxide Substances 0.000 description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 7
- 238000012711 chain transfer polymerization Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 5
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000010550 living polymerization reaction Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 3
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000012988 Dithioester Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000002320 enamel (paints) Substances 0.000 description 3
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000002497 iodine compounds Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- ZKECVHXIVHRIIA-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-1-yl)prop-2-enamide Chemical compound CC1(C)CCCC(C)(C)N1NC(=O)C=C ZKECVHXIVHRIIA-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000012989 trithiocarbonate Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- CYQGCJQJIOARKD-UHFFFAOYSA-N 4-carboxy-TEMPO Chemical group CC1(C)CC(C(O)=O)CC(C)(C)N1[O] CYQGCJQJIOARKD-UHFFFAOYSA-N 0.000 description 2
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- LAKYXBYUROTWBI-UHFFFAOYSA-N bis(benzylsulfanyl)methanethione Chemical compound C=1C=CC=CC=1CSC(=S)SCC1=CC=CC=C1 LAKYXBYUROTWBI-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- CKJMHSMEPSUICM-UHFFFAOYSA-N di-tert-butyl nitroxide Chemical class CC(C)(C)N([O])C(C)(C)C CKJMHSMEPSUICM-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 150000003498 tellurium compounds Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- AJOJTMNIQSTBAP-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-3-yl) prop-2-enoate Chemical compound CN1C(C)(C)CCC(OC(=O)C=C)C1(C)C AJOJTMNIQSTBAP-UHFFFAOYSA-N 0.000 description 1
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- GIIUJJXXMYYQQD-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)C=C GIIUJJXXMYYQQD-UHFFFAOYSA-N 0.000 description 1
- XMCLXVNPGNYTRE-VOTSOKGWSA-N (2,2,6,6-tetramethylpiperidin-4-yl) (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC1CC(C)(C)NC(C)(C)C1 XMCLXVNPGNYTRE-VOTSOKGWSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- PSZLOSABHFZLDK-VOTSOKGWSA-N (e)-n-(2,2,6,6-tetramethylpiperidin-4-yl)but-2-enamide Chemical compound C\C=C\C(=O)NC1CC(C)(C)NC(C)(C)C1 PSZLOSABHFZLDK-VOTSOKGWSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 1
- QEZSTBGQYFCJCW-UHFFFAOYSA-N 1-phenylethyl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(C)SC(=S)C1=CC=CC=C1 QEZSTBGQYFCJCW-UHFFFAOYSA-N 0.000 description 1
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- PYKCEDJHRUUDRK-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2-methylpropanenitrile Chemical compound CC(C)(C)N=NC(C)(C)C#N PYKCEDJHRUUDRK-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- CUGQQXKZSRAAEC-UHFFFAOYSA-N 2-[dimethoxy(methyl)silyl]ethyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCOC(=O)C=C CUGQQXKZSRAAEC-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- DDMXJSKEBBVELP-UHFFFAOYSA-N 2-ethyl-2-(2-methylpentan-2-ylperoxy)hexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)CCC DDMXJSKEBBVELP-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- KIFPIAKBYOIOCS-UHFFFAOYSA-N 2-methyl-2-(trioxidanyl)propane Chemical compound CC(C)(C)OOO KIFPIAKBYOIOCS-UHFFFAOYSA-N 0.000 description 1
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- KOBJYYDWSKDEGY-UHFFFAOYSA-N 2-phenylpropan-2-yl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(C)(C)SC(=S)C1=CC=CC=C1 KOBJYYDWSKDEGY-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PSLRXNFNXYNXEK-UHFFFAOYSA-N 2-triethoxysilylethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C=C PSLRXNFNXYNXEK-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-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
- 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
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- WSGDRFHJFJRSFY-UHFFFAOYSA-N 4-oxo-TEMPO Chemical compound CC1(C)CC(=O)CC(C)(C)N1[O] WSGDRFHJFJRSFY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007874 V-70 Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UBNGHBGXMXWFOS-UHFFFAOYSA-N [2-hydroxy-3-[3-hydroxy-4-(2-hydroxybenzoyl)phenoxy]propyl] 2-methylprop-2-enoate Chemical compound OC1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1O UBNGHBGXMXWFOS-UHFFFAOYSA-N 0.000 description 1
- QGZDXPBGRTUIQP-UHFFFAOYSA-N [2-hydroxy-3-[3-hydroxy-4-(2-hydroxybenzoyl)phenoxy]propyl] prop-2-enoate Chemical compound OC1=CC(OCC(COC(=O)C=C)O)=CC=C1C(=O)C1=CC=CC=C1O QGZDXPBGRTUIQP-UHFFFAOYSA-N 0.000 description 1
- OQLPQGIHIIPBCG-UHFFFAOYSA-N [2-phenyl-2-(2,2,6,6-tetramethylpiperidin-1-yl)oxyethyl] benzoate Chemical compound CC1(C)CCCC(C)(C)N1OC(C=1C=CC=CC=1)COC(=O)C1=CC=CC=C1 OQLPQGIHIIPBCG-UHFFFAOYSA-N 0.000 description 1
- FCRMARSNWJWNPW-UHFFFAOYSA-N [3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxypropyl] 2-methylprop-2-enoate Chemical compound OC1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 FCRMARSNWJWNPW-UHFFFAOYSA-N 0.000 description 1
- LUWALSGLYLSCKN-UHFFFAOYSA-N [3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxypropyl] prop-2-enoate Chemical compound OC1=CC(OCC(COC(=O)C=C)O)=CC=C1C(=O)C1=CC=CC=C1 LUWALSGLYLSCKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- ZCKPFAYILJKXAT-UHFFFAOYSA-N benzyl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(=S)SCC1=CC=CC=C1 ZCKPFAYILJKXAT-UHFFFAOYSA-N 0.000 description 1
- VDLOXZRCFJZRJH-UHFFFAOYSA-N benzyl ethanedithioate Chemical compound CC(=S)SCC1=CC=CC=C1 VDLOXZRCFJZRJH-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 description 1
- MMNIKCLHZKAPGA-UHFFFAOYSA-N bis(2-propan-2-ylphenyl)diazene Chemical compound CC(C)C1=CC=CC=C1N=NC1=CC=CC=C1C(C)C MMNIKCLHZKAPGA-UHFFFAOYSA-N 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-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
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- POSWICCRDBKBMH-UHFFFAOYSA-N dihydroisophorone Natural products CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GKCPCPKXFGQXGS-UHFFFAOYSA-N ditert-butyldiazene Chemical compound CC(C)(C)N=NC(C)(C)C GKCPCPKXFGQXGS-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PUSKHXMZPOMNTQ-UHFFFAOYSA-N ethyl 2,1,3-benzoselenadiazole-5-carboxylate Chemical group CCOC(=O)C1=CC=C2N=[Se]=NC2=C1 PUSKHXMZPOMNTQ-UHFFFAOYSA-N 0.000 description 1
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 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
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000015096 spirit Nutrition 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
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、有機無機複合微粒子、その分散体、及び上記分散体の製造方法、並びに上記複合微粒子又はその分散体を含む塗料組成物に関する。 The present invention relates to organic / inorganic composite fine particles, a dispersion thereof, a method for producing the dispersion, and a coating composition containing the composite fine particles or a dispersion thereof.
有機溶剤中に分散された、粒子径が２００ｎｍ以下の無機微粒子の分散体は、当該無機微粒子の１次粒子が不安定なため、他の化合物と混合すると、無機微粒子が凝集して沈降する場合がある。また上記分散体と樹脂溶液とを粒子が凝集しないように混合することができた場合においても、成型用途等のために有機溶剤を揮散させると、無機微粒子が凝集し、得られた成形物等の特性が低下することがあった。 A dispersion of inorganic fine particles dispersed in an organic solvent and having a particle size of 200 nm or less is unstable in primary particles of the inorganic fine particles, so that when mixed with other compounds, the inorganic fine particles aggregate and settle. There is. In addition, even when the dispersion and the resin solution can be mixed so that the particles do not aggregate, when the organic solvent is volatilized for the purpose of molding or the like, the inorganic fine particles are aggregated, and the obtained molded product or the like In some cases, the characteristics of the film deteriorated.
このような無機微粒子の凝集を防ぐために、無機微粒子をポリマーにより被覆した有機無機複合微粒子の分散体が検討されている。上記分散体は、塗膜、フィルム、熱可塑性樹脂、熱硬化性樹脂等の種々の有機系材料に適用されるために、無機微粒子を被覆するポリマーは種々の特性において幅広い設計が求められる。こうした要求に応えるために工業的に多くの種類が入手できる不飽和モノマーが利用され、その重合反応により得られたポリマーと無機微粒子との複合微粒子が検討されている。 In order to prevent such aggregation of inorganic fine particles, a dispersion of organic-inorganic composite fine particles in which inorganic fine particles are coated with a polymer has been studied. Since the dispersion is applied to various organic materials such as a coating film, a film, a thermoplastic resin, and a thermosetting resin, a polymer covering inorganic fine particles is required to have a wide design in various characteristics. In order to meet these requirements, industrially available unsaturated monomers are used, and composite fine particles of polymers and inorganic fine particles obtained by the polymerization reaction are being studied.
例えば、特許文献１には重合性不飽和基を有する顔料粒子と不飽和モノマーとをラジカル重合開始剤を用いて共重合することにより顔料粒子をポリマーで被覆する方法が開示されている。しかし、この方法で得られた有機無機複合微粒子の分散体を他の有機系材料と混合した場合、有機系材料の機械特性、光学特性等が低下することがあった。 For example, Patent Document 1 discloses a method of coating pigment particles with a polymer by copolymerizing pigment particles having a polymerizable unsaturated group and an unsaturated monomer using a radical polymerization initiator. However, when the dispersion of organic-inorganic composite fine particles obtained by this method is mixed with other organic materials, the mechanical properties, optical properties, etc. of the organic materials may deteriorate.
上記の方法で得られた有機無機複合微粒子の分散体には無機微粒子に化学的に結合していないポリマーが多く含まれるので、そのポリマーが上記特性の低下の原因になったと考えられる。また、この方法においては有機無機複合微粒子の製造中に反応物がゲル化したり、生成した有機無機複合微粒子の分散体の粘度が高くなる場合があった。その原因は明らかではないが、無機微粒子上の重合性不飽和基が粒子間で共重合し、複数の無機微粒子が化学的に結合したためと推定される。 Since the dispersion of organic-inorganic composite fine particles obtained by the above method contains a large amount of polymer that is not chemically bonded to the inorganic fine particles, the polymer is considered to have caused the deterioration of the above characteristics. In this method, the reaction product may gel during the production of the organic / inorganic composite fine particles, or the viscosity of the produced dispersion of the organic / inorganic composite fine particles may increase. Although the cause is not clear, it is presumed that the polymerizable unsaturated groups on the inorganic fine particles are copolymerized between the particles, and a plurality of inorganic fine particles are chemically bonded.
近年、不飽和モノマーの重合技術としていくつか種類のリビングラジカル重合法が開発され、工業的な製造にも利用されるようになってきた。この重合法は不飽和モノマーが重合により消費された後でも生成したポリマーは重合活性な成長末端を有しているために新たにモノマーを追加すると再びリビングラジカル重合を開始するという特徴がある。このリビングラジカル重合の重合開始基を無機微粒子表面に化学的に結合させた無機微粒子上で、不飽和モノマーをリビングラジカル重合することによって、ポリマーで無機微粒子を被覆することが行われるようになってきた。 In recent years, several types of living radical polymerization methods have been developed as polymerization techniques for unsaturated monomers, and have been used for industrial production. This polymerization method is characterized in that the living radical polymerization is started again when a new monomer is added because the polymer produced after the unsaturated monomer is consumed by polymerization has a polymerization active growth terminal. It is becoming possible to coat inorganic fine particles with polymers by living radical polymerization of unsaturated monomers on inorganic fine particles in which the polymerization initiator group of this living radical polymerization is chemically bonded to the surface of the inorganic fine particles. It was.
例えば、特許文献２には、リビングラジカル重合法のひとつであるニトロキシド化合物系ラジカル重合法の開始基を、顔料粒子表面に導入し、これを用いて不飽和モノマーのリビングラジカル重合を行い、生成したポリマーにより顔料粒子を被覆した有機無機複合微粒子の分散体が開示されている。しかし、特許文献２の方法では、重合の進行に伴い、有機無機複合微粒子の分散体の粘度が高くなる場合があった。これは重合の進行に伴い複合微粒子が大きくなり粒子同士が接近してくると、隣合う微粒子上のポリマーの成長末端どうしが反応（停止反応）により化学的に結合した結果、粘度が高くなったものと推定される。 For example, in Patent Document 2, an initiator group of a nitroxide compound-based radical polymerization method, which is one of the living radical polymerization methods, is introduced into the pigment particle surface, and this is used to perform living radical polymerization of unsaturated monomers. Dispersions of organic-inorganic composite fine particles in which pigment particles are coated with a polymer are disclosed. However, in the method of Patent Document 2, the viscosity of the dispersion of organic-inorganic composite fine particles sometimes increases with the progress of polymerization. This is because when the composite fine particles become larger as the polymerization progresses and the particles approach each other, the growth ends of the polymers on adjacent fine particles are chemically bonded together by a reaction (stopping reaction), resulting in an increase in viscosity. Estimated.
また、特許文献３には、有機ハロゲン化合物を有する無機微粒子を用い、臭化銅の作用により上記有機ハロゲン化合物をリビングラジカル重合の開始基として利用する原子移動ラジカル重合を行って生成ポリマーで無機微粒子を被覆する方法が開示されている。しかし、特許文献３の方法においては、無機微粒子をポリマーが覆っていない状態で金属化合物等と混合する必要があり、製造工程中に凝集体が発生する場合があった。 Further, in Patent Document 3, inorganic fine particles having an organic halogen compound are used, and an inorganic fine particle is formed by performing atom transfer radical polymerization using the organic halogen compound as an initiation group for living radical polymerization by the action of copper bromide. A method of coating is disclosed. However, in the method of Patent Document 3, it is necessary to mix inorganic fine particles with a metal compound or the like in a state where the polymer is not covered, and aggregates may be generated during the manufacturing process.
従って、本発明は、他の有機材料と溶媒中で混合しても凝集することがなく、溶媒を揮散させた場合にも上記有機材料のマトリックス中に凝集することなく分散して、上記有機材料の光学特性、機械特性等の諸特性を低下させずに無機微粒子に起因する新しい特性、機能等を上記有機材料に付与することができる有機無機複合微粒子の分散体を提供することを目的とする。本発明はまた、粘度の増大、ゲル化等を生じさせずに上記有機無機複合微粒子の分散体を得ることができる、有機無機複合微粒子の分散体の製造方法を提供することを目的とする。 Therefore, the present invention does not agglomerate even when mixed with another organic material in a solvent, and even when the solvent is volatilized, the organic material is dispersed without agglomerating in the matrix of the organic material. An object of the present invention is to provide a dispersion of organic-inorganic composite fine particles capable of imparting new characteristics, functions, etc. resulting from inorganic fine particles to the organic material without degrading various properties such as optical properties and mechanical properties. . Another object of the present invention is to provide a method for producing a dispersion of organic-inorganic composite fine particles, which can obtain the dispersion of organic-inorganic composite fine particles without causing an increase in viscosity or gelation.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、リビングポリマー（ａ）と重合性不飽和基を有する無機微粒子（ｂ）とを、溶媒の存在下で反応させることにより製造された、又はリビングポリマー（ａ）と重合性不飽和基を有する無機微粒子（ｂ）と不飽和モノマー（ｃ）とを、溶媒の存在下で反応させることにより製造された、有機無機複合微粒子の分散体により、上記課題を解決できることを見出し、本発明を完成するに至った。すなわち、本発明は、以下の態様からなる。 As a result of intensive studies to achieve the above object, the inventors of the present invention produced a reaction between the living polymer (a) and inorganic fine particles (b) having a polymerizable unsaturated group in the presence of a solvent. Of the organic-inorganic composite fine particles produced by reacting the living polymer (a), the inorganic fine particles (b) having a polymerizable unsaturated group, and the unsaturated monomer (c) in the presence of a solvent. The present inventors have found that the above problems can be solved by using a dispersion, and have completed the present invention. That is, this invention consists of the following aspects.
［態様１］
リビングポリマー（ａ）と重合性不飽和基を有する無機微粒子（ｂ）とを、溶媒の存在下で反応させることにより製造された、又はリビングポリマー（ａ）と重合性不飽和基を有する無機微粒子（ｂ）と不飽和モノマー（ｃ）とを、溶媒の存在下で反応させることにより製造された、有機無機複合微粒子の分散体。
［態様２］
重合性不飽和基を有する無機微粒子（ｂ）が、重合性不飽和基を有するコロイダルシリカである、態様１に記載の有機無機複合微粒子の分散体。
[Aspect 1]
Inorganic fine particles produced by reacting living polymer (a) with inorganic fine particles (b) having a polymerizable unsaturated group in the presence of a solvent, or having living polymer (a) and a polymerizable unsaturated group A dispersion of organic-inorganic composite fine particles produced by reacting (b) and an unsaturated monomer (c) in the presence of a solvent.
[Aspect 2]
The dispersion of organic-inorganic composite fine particles according to aspect 1, wherein the inorganic fine particles (b) having a polymerizable unsaturated group are colloidal silica having a polymerizable unsaturated group.
［態様３］
態様１又は２に記載の有機無機複合微粒子の分散体から上記溶媒を除去することにより製造された、有機無機複合微粒子。
［態様４］
リビングポリマー（ａ）と重合性不飽和基を有する無機微粒子（ｂ）とを、溶媒の存在下で反応させる工程、又はリビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、さらに不飽和モノマー（ｃ）とを、溶媒の存在下で反応させる工程を含むことを特徴とする有機無機複合微粒子の分散体の製造方法。
［態様５］
態様１又は２に記載の有機無機複合微粒子の分散体、又は態様３に記載の有機無機複合微粒子を含む、焼付け硬化型、常温硬化型又はラッカー型塗料組成物。
[Aspect 3]
An organic-inorganic composite fine particle produced by removing the solvent from the dispersion of the organic-inorganic composite fine particle according to aspect 1 or 2.
[Aspect 4]
A step of reacting the living polymer (a) with inorganic fine particles (b) having a polymerizable unsaturated group in the presence of a solvent, or the living polymer (a) and inorganic fine particles (b) having a polymerizable unsaturated group And a step of reacting the unsaturated monomer (c) in the presence of a solvent, and a method for producing a dispersion of organic-inorganic composite fine particles.
[Aspect 5]
A baking curable, room temperature curable, or lacquer coating composition comprising the dispersion of organic-inorganic composite fine particles according to aspect 1 or 2, or the organic-inorganic composite fine particles according to aspect 3.
本発明の有機無機複合微粒子の分散体は、他の有機材料と溶媒中で混合しても凝集することがなく、溶媒を揮散させた場合にも上記有機材料のマトリックス中に凝集することなく分散して、上記有機材料の光学特性、機械特性等の諸特性を低下させずに無機微粒子に起因する新しい特性、機能等を上記有機材料に付与することができる。
本発明の有機無機複合微粒子の分散体の製造方法は、粘度の増大、ゲル化等を生じさせずに上記有機無機複合微粒子の分散体を得ることができる。
The dispersion of the organic-inorganic composite fine particles of the present invention does not aggregate even when mixed with other organic materials in a solvent, and is dispersed without aggregation in the matrix of the organic material even when the solvent is volatilized. Thus, new characteristics, functions, and the like resulting from the inorganic fine particles can be imparted to the organic material without degrading various characteristics such as optical characteristics and mechanical characteristics of the organic material.
The method for producing a dispersion of organic-inorganic composite fine particles of the present invention can obtain the dispersion of organic-inorganic composite fine particles without causing an increase in viscosity or gelation.
以下、本発明について詳細に説明する。
［リビングポリマー（ａ）］
本発明に用いられるリビングポリマー（ａ）は、公知のリビングラジカル重合法により得ることができる。リビングラジカル重合は近年盛んに研究が行われており、種々の方法が提案されている。これに対して「従来のラジカル重合」は、本明細書においてはリビングラジカル重合以外のラジカル重合を意味し、成型材料、塗料、接着剤等に使用する樹脂を製造するために工業的に広く行われている重合である。
Hereinafter, the present invention will be described in detail.
[Living polymer (a)]
The living polymer (a) used in the present invention can be obtained by a known living radical polymerization method. Living radical polymerization has been actively studied in recent years, and various methods have been proposed. In contrast, “conventional radical polymerization” means radical polymerization other than living radical polymerization in the present specification, and is widely used industrially to produce resins used for molding materials, paints, adhesives, and the like. Polymerization.
「従来のラジカル重合」の素反応は開始反応、生長反応、連鎖移動反応及び停止反応からなる（「高分子合成の化学」（第２版、著者：大津隆行、発行：（株）化学同人）の４７ページに記載）。生長反応において、生長ラジカル（重合体の生長末端が活性な炭素ラジカル種の状態にあるもの）に不飽和モノマーが連鎖的に付加して重合が進行し、連鎖移動反応又は停止反応により生長ラジカルの状態ではない重合体が生成する。
なお、本明細書において、リビングポリマー（ａ）を製造するための不飽和モノマーを、後述の不飽和モノマー（ｃ）と区別するために、不飽和モノマー（ａ−１）と称する場合がある。
Elementary reaction of “conventional radical polymerization” consists of initiation reaction, growth reaction, chain transfer reaction and termination reaction (“Chemistry of Polymer Synthesis” (2nd edition, author: Takayuki Otsu, published by Kagaku Dojin Co., Ltd.)) Page 47). In the growth reaction, an unsaturated monomer is added in a chain to the growth radical (in which the growth terminal of the polymer is in the state of an active carbon radical species), and the polymerization proceeds. A non-state polymer is produced.
In addition, in this specification, in order to distinguish the unsaturated monomer for manufacturing a living polymer (a) from the below-mentioned unsaturated monomer (c), it may be called an unsaturated monomer (a-1).
上記重合体は、もはや生長ラジカルに戻ることはなく、重合を再開始することはできない（このような重合を再開始できない重合体を本明細書では「デッドポリマー」と表記することがある）。このような「従来のラジカル重合」に対してリビングラジカル重合は重合体の生長末端が安定な共有結合種（ドーマント種）から可逆的に活性な炭素ラジカル種を生成させることにより可能となる（このようなリビングラジカル重合により得られ、重合反応の活性を有する重合体を本明細書では「リビングポリマー」と表記する）。従って、リビングラジカル重合においては全ての不飽和モノマーが重合により消費された後に新たに不飽和モノマーを加えると、新たに別の重合体を生成することなく、既に生成していた重合体の成長末端がドーマント種から活性な炭素ラジカル種になって重合を再開始することが可能である。 The polymer no longer returns to the growing radical and cannot be reinitiated (a polymer that cannot reinitiate such polymerization may be referred to herein as a “dead polymer”). Living radical polymerization is possible by reversibly generating active carbon radical species from a covalently bonded species (dormant species) where the growth terminal of the polymer is stable. A polymer obtained by such living radical polymerization and having a polymerization reaction activity is referred to as “living polymer” in the present specification). Therefore, in living radical polymerization, if all unsaturated monomers are consumed by polymerization and newly added unsaturated monomers are added, the growth ends of the polymer that has already been formed can be produced without generating another polymer. Can be converted from dormant species to active carbon radical species to reinitiate polymerization.
本発明における、リビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）との反応は、このリビングラジカル重合の特性を利用したものである。即ち、リビングポリマー（ａ）の生長末端が、ドーマント種から炭素ラジカル種になったときに無機微粒子（ｂ）上の重合性不飽和基に付加するか、又は不飽和モノマー（ｃ）及び無機微粒子（ｂ）上の重合性不飽和基と共重合して本発明の有機無機複合微粒子の分散体を得ることが可能となる。このように、本発明は、リビングラジカル重合反応の機構を利用したものであるから、「従来のラジカル重合」のように新たに無機微粒子と化学的に結合していないデッドポリマーを生成することはほとんどなく、高い効率でリビングポリマーを無機微粒子上に化学的に結合して上記無機微粒子を被覆することが可能である。 In the present invention, the reaction between the living polymer (a), the inorganic fine particles (b) having a polymerizable unsaturated group, and the unsaturated monomer (c) as desired utilizes the characteristics of this living radical polymerization. . That is, the growth terminal of the living polymer (a) is added to the polymerizable unsaturated group on the inorganic fine particles (b) when the dormant species is changed to the carbon radical species, or the unsaturated monomer (c) and the inorganic fine particles are added. (B) It becomes possible to obtain a dispersion of the organic-inorganic composite fine particles of the present invention by copolymerizing with the above polymerizable unsaturated group. As described above, since the present invention utilizes the living radical polymerization reaction mechanism, it is not possible to newly generate a dead polymer that is not chemically bonded to inorganic fine particles as in “conventional radical polymerization”. It is possible to coat the inorganic fine particles by chemically bonding the living polymer onto the inorganic fine particles with little efficiency.
リビングポリマー（ａ）を得るためのリビングラジカル重合の方法としては、例えば、（１）ニトロキシド化合物系ラジカル重合法、（２）原子移動ラジカル重合法、（３）可逆的付加解裂型連鎖移動重合法、（４）有機テルル化合物系リビングラジカル重合法、（５）ヨウ素化合物系リビングラジカル重合法等を挙げることができる。これらのリビングラジカル重合の方法について以下に記載する。 Examples of the living radical polymerization method for obtaining the living polymer (a) include (1) nitroxide compound-based radical polymerization method, (2) atom transfer radical polymerization method, and (3) reversible addition-cleavage chain transfer weight. And (4) organic tellurium compound-based living radical polymerization method and (5) iodine compound-based living radical polymerization method. These living radical polymerization methods are described below.
［（１）ニトロキシド化合物系ラジカル重合法］
上記ニトロキシド化合物系ラジカル重合法は、ニトロキシド化合物等の安定ラジカル化合物を生長ラジカルの捕捉剤として用いて、生長末端が可逆的にドーマント種と炭素ラジカル種の状態になることができるように制御するリビングラジカル重合の方法であり、ＮＭＰ（Ｎｉｔｒｏｘｉｄｅ Ｍｅｄｉａｔｅｄ Ｌｉｖｉｎｇ Ｒａｄｉｃａｌ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ）と表現されることもある。上記ニトロキシド化合物系ラジカル重合法は、特開平６−１９９９１６号公報、特表２００５−５３４７１２号公報、マクロモレキュールズ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）、１９９４年、第２７巻、７２２８頁、等に記載の公知の方法を挙げることができる。
[(1) Nitroxide compound-based radical polymerization method]
The above nitroxide compound-based radical polymerization method uses a stable radical compound such as a nitroxide compound as a growth radical scavenger, and controls the living end to be reversibly converted into a dormant species and a carbon radical species. It is a method of radical polymerization, and may be expressed as NMP (Nitroxide Living Living Radical Polymerization). The nitroxide compound-based radical polymerization method is a known method described in JP-A-6-199916, JP-T 2005-534712, Macromolecules, 1994, Vol. 27, 7228, and the like. Can be mentioned.
［（２）原子移動ラジカル重合法］
上記原子移動ラジカル重合法は、ハロゲン原子を成長末端の炭素ラジカルに付加させ、この結合したハロゲン原子に金属錯体を作用させて成長末端の炭素ラジカルの可逆的な生成を可能とする方法であり、ＡＴＲＰ（Ａｔｏｍ Ｔｒａｎｓｆｅｒ Ｒａｄｉｃａｌ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ）と表現されることもある。上記原子移動ラジカル重合法は、ジャーナル・オブ・アメリカン・ケミカル・ソサエティ（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．）、１９９５年、第１１７巻、５６１４頁；マクロモレキュールズ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）、１９９５年、第２８巻、７９０１頁；サイエンス（Ｓｃｉｅｎｃｅ）、１９９６年、第２７２巻、８６６頁；又はマクロモレキュールズ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）、１９９５年、第２８巻、１７２１頁、等に記載の公知の方法を挙げることができる。
[(2) Atom transfer radical polymerization method]
The atom transfer radical polymerization method is a method that allows reversible generation of a growth end carbon radical by adding a halogen atom to a growth end carbon radical and allowing a metal complex to act on the bonded halogen atom, It may be expressed as ATRP (Atom Transfer Radical Polymerization). The atom transfer radical polymerization method is described in J. Am. Chem. Soc., 1995, 117, 5614; Macromolecules, 1995, No. 28, 7901; Science, 1996, 272, 866; or Macromolecules, 1995, 28, 1721, etc. Can do.
［（３）可逆的付加解裂型連鎖移動重合法］
上記可逆的付加解裂型連鎖移動重合法は、ジチオエステル化合物、トリチオカーボネート化合物等のチオカルボニルチオ化合物を、生長ラジカル（Ｘ）と付加解裂型連鎖移動反応させ、生長末端をドーマント種の状態とし、他の生長ラジカル（Ｙ）が上記生長末端に付加することにより生長ラジカル（Ｘ）が再生し、次いで、生長ラジカル（Ｙ）がドーマント種の状態になるようなリビングラジカル重合法であり、ＲＡＦＴ（Ｒｅｖｅｒｓｉｂｌｅ Ａｄｄｉｔｉｏｎ Ｆｒａｇｍｅｎｔａｔｉｏｎ Ｃｈａｉｎ Ｔｒａｎｓｆｅｒ Ｒａｄｉｃａｌ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ）と表現されることもある。上記可逆的付加解裂型連鎖移動重合法としては、例えば、国際公開第９８／５８９７４号、同第９８／０１４７８号、Ａｕｓｔ．Ｊ．Ｃｈｅｍ．，２００５年、５８巻、３７９頁〜４１０頁、Ｐｏｌｙｍｅｒ、２００７年、４８巻、１頁等に記載の公知の方法を挙げることができる。
[(3) Reversible addition-cleavage chain transfer polymerization method]
In the reversible addition-cleavage chain transfer polymerization method, a thiocarbonylthio compound such as a dithioester compound or a trithiocarbonate compound is subjected to an addition-cleavage-type chain transfer reaction with a growth radical (X), and the growth terminal is converted to a dormant species. It is a living radical polymerization method in which the growth radical (X) is regenerated by adding another growth radical (Y) to the above-mentioned growth terminal and then the growth radical (Y) is in the dormant species state. , RAFT (Reversible Addition Fragmentation Chain Transfer Radical Polymerization). Examples of the reversible addition-cleavage chain transfer polymerization method include, for example, International Publication Nos. 98/58974, 98/01478, and Aust. J. et al. Chem. 2005, 58, 379-410, Polymer, 2007, 48, 1 and the like.
また、特開平７−００２９５４号公報に開示されている２，４−ジフェニル−４−メチル−１−ペンテンを可逆的付加開裂型連鎖移動剤として用いたラジカル重合により得られる重合体、特公平６−２３２０９号公報、特公平７−３５４１１号公報等に開示されているコバルト錯体を用いた触媒的連鎖移動重合法（Ｃａｔａｌｙｔｉｃ Ｃｈａｉｎ Ｔｒａｎｓｆｅｒ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ）により得られる重合体又は特開２０００−８０２８８号公報に開示されている高温ラジカル重合により得られる重合体は、何れも生長末端に可逆的付加解裂連鎖移動反応することの可能な不飽和基を有しており、これらの重合体をリビングポリマー（ａ）として用いても良い。 Further, a polymer obtained by radical polymerization using 2,4-diphenyl-4-methyl-1-pentene as a reversible addition-cleavage chain transfer agent disclosed in JP-A-7-002954, No. 23209, Japanese Patent Publication No. 7-35411, etc., or a polymer obtained by catalytic chain transfer polymerization using a cobalt complex or disclosed in JP-A No. 2000-80288 Each of the polymers obtained by high temperature radical polymerization has an unsaturated group capable of reversible addition-fragmentation chain transfer reaction at the growing end, and these polymers are converted into living polymers (a). It may be used as
［（４）有機テルル系リビングラジカル重合法］
上記有機テルル系リビングラジカル重合法は、有機テルル化合物を用いたリビングラジカル重合法である。当該重合法として、国際公開第２００４／０１４９６２号、特開２００６−２９９２７８号公報、特開２００８−２４７９１９号公報等に記載の公知の方法を挙げることができる。
[(4) Organic tellurium-based living radical polymerization method]
The organic tellurium-based living radical polymerization method is a living radical polymerization method using an organic tellurium compound. Examples of the polymerization method include known methods described in International Publication No. 2004/014962, Japanese Patent Application Laid-Open No. 2006-299278, Japanese Patent Application Laid-Open No. 2008-247919, and the like.
［（５）ヨウ素化合物系リビングラジカル重合法］
ヨウ素化合物系リビングラジカル重合法は、ヨウ素原子を成長末端の炭素ラジカルに付加させ、この結合したヨウ素原子に触媒を作用させて成長末端の炭素ラジカルの可逆的な生成を可能とする方法である。当該重合法として、特開２００７−９２０１４号公報、Ｐｏｌｙｍｅｒ，２００８年，４９巻，２４号，５１７７頁等に記載された公知の方法を挙げることができる。
[(5) Iodine compound-based living radical polymerization method]
The iodine compound-based living radical polymerization method is a method that allows reversible generation of a carbon radical at the growth end by adding an iodine atom to the carbon radical at the growth end and causing a catalyst to act on the bonded iodine atom. Examples of the polymerization method include known methods described in JP 2007-92014 A, Polymer, 2008, 49, 24, 5177, and the like.
上記リビングラジカル重合法によるリビングポリマー（ａ）の製造方法について、詳細に説明する。リビングラジカル重合は何れも反応容器内の気相を不活性ガスにより置換して撹拌しながら行うことが好ましい。不活性ガスとしては、例えば、窒素ガス、アルゴンガス等が挙げられる。反応温度及び反応時間は、選択したリビングラジカル重合の方法、リビングポリマー（ａ）の分子量、モノマーの種類等により適宜選択されうる。重合は、通常、常圧下で行われるが、加圧又は減圧下であってもよい。 A method for producing the living polymer (a) by the living radical polymerization method will be described in detail. In any case, the living radical polymerization is preferably carried out while substituting the gas phase in the reaction vessel with an inert gas and stirring. Examples of the inert gas include nitrogen gas and argon gas. The reaction temperature and reaction time can be appropriately selected depending on the selected living radical polymerization method, the molecular weight of the living polymer (a), the type of monomer, and the like. The polymerization is usually carried out under normal pressure, but may be under pressure or reduced pressure.
上記（１）〜（５）のリビングラジカル重合の方法の中で、本発明においては、重合反応に適用可能な不飽和モノマー（ａ−１）の種類が多い観点から、（１）ニトロキシド化合物系ラジカル重合法又は（３）可逆的付加解裂型連鎖移動重合法が好ましい。（１）及び（３）の重合方法について以下に説明する。 Among the above-mentioned living radical polymerization methods (1) to (5), in the present invention, from the viewpoint of many types of unsaturated monomers (a-1) applicable to the polymerization reaction, (1) nitroxide compound system A radical polymerization method or (3) a reversible addition-fragmentation chain transfer polymerization method is preferred. The polymerization methods (1) and (3) will be described below.
（１）ニトロキシド化合物系ラジカル重合法には、（１ａ）アミノエーテル化合物の存在下で重合を行う方法と、（１ｂ）安定ラジカルであるニトロキシド化合物とラジカル重合開始剤の存在下で重合を行う方法等がある。（１ａ）におけるアミノエーテル化合物は加熱により安定ラジカルであるニトロキシド化合物と重合開始ラジカルを発生することが可能な化合物である。 (1) Nitroxide compound-based radical polymerization includes (1a) polymerization in the presence of an amino ether compound and (1b) polymerization in the presence of a nitroxide compound that is a stable radical and a radical polymerization initiator. Etc. The amino ether compound in (1a) is a compound capable of generating a nitroxide compound that is a stable radical and a polymerization initiation radical by heating.
（１ａ）の方法において使用できるアミノエーテル化合物として、例えば、アルケマ社の商品名「ＢｌｏｃＢｕｉｌｄｅｒ ＭＡ」、ベンゾイルオキシ−２−［（２，２，６，６−テトラメチル−１−ピペリジニル）オキシ］−２−フェニルエチル（ＢＳ−ＴＥＭＰＯ）、２−ベンゾイルオキシ−１−フェニルエチル−ジ−ｔｅｒｔ−ブチル−ニトロキシド（ＢＳ−ＤＢＮ）を挙げることができる。ＢｌｏｃＢｕｉｌｄｅｒ ＭＡを用いたリビングラジカル重合は、モノマーとＢｌｏｃＢｕｉｌｄｅｒ ＭＡとを含む混合物を加熱することにより行うことができる。重合温度は、約６０〜約２００℃、好ましくは約８０〜約１６０℃、より好ましくは約９０〜約１２０℃であることができる。上記重合温度が約６０℃未満であると、重合速度が遅いために重合時間が長くなり製造効率が低下することがある。上記重合温度が約２００℃よりも高くなると、連鎖移動反応等により再開始反応を行うことのできない重合体が生成することがある。 As an amino ether compound that can be used in the method (1a), for example, trade name “BlocBuilder MA” of Arkema Co., Ltd., benzoyloxy-2-[(2,2,6,6-tetramethyl-1-piperidinyl) oxy] — Examples include 2-phenylethyl (BS-TEMPO) and 2-benzoyloxy-1-phenylethyl-di-tert-butyl-nitroxide (BS-DBN). Living radical polymerization using BlocBuilder MA can be performed by heating a mixture containing the monomer and Bloc Builder MA. The polymerization temperature can be about 60 to about 200 ° C, preferably about 80 to about 160 ° C, more preferably about 90 to about 120 ° C. When the polymerization temperature is less than about 60 ° C., the polymerization rate is slow, so that the polymerization time becomes long and the production efficiency may be lowered. When the said polymerization temperature becomes higher than about 200 degreeC, the polymer which cannot perform a restart reaction by chain transfer reaction etc. may produce | generate.
（１ｂ）の方法におけるニトロキシド化合物としては、特に限定されないが、例えば、ＴＥＭＰＯ（２，２，６，６−テトラメチルピペリジニル−１−オキシ）、ジ−ｔｅｒｔ−ブチル−ニトロキシド（ＤＢＮ）、４−カルボキシ−２，２，６，６−テトラメチルピペリジン１−オキシル（４−カルボキシＴＥＭＰＯ）、４−オキソ−ＴＥＭＰＯ、テトラメチル−イソインドリン−１−オキシル、テトラエチル−イソインドリン−１−オキシル、Ｎ−ｔｅｒｔ−ブチル−Ｎ−［１−ジエチルフォスフォノ−（２，２−ジメチルプロピル）］ニトロキシド（以下、ＤＥＰＮと略す）、２，２，５−トリメチル−４−フェニル−３−アザヘキサン−３−ニトロキシド（以下、ＴＩＰＮＯと略す）等が挙げられ、重合速度や分子量の制御の容易さから、ＤＥＰＮ及びＴＩＰＮＯを好適に使用することができる。 Although it does not specifically limit as a nitroxide compound in the method of (1b), For example, TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy), di-tert- butyl-nitroxide (DBN), 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-carboxy TEMPO), 4-oxo-TEMPO, tetramethyl-isoindoline-1-oxyl, tetraethyl-isoindoline-1-oxyl, N-tert-butyl-N- [1-diethylphosphono- (2,2-dimethylpropyl)] nitroxide (hereinafter abbreviated as DEPN), 2,2,5-trimethyl-4-phenyl-3-azahexane-3 -Is nitroxide (hereinafter abbreviated as TIPNO) and the like easy to control the polymerization rate and molecular weight? , It can be preferably used DEPN and TIPNO.
（１ｂ）の方法において、（１ａ）と同じ温度範囲で重合を行うことが好ましいが、マクロモレキュールズ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）、１９９４年、第２７巻、７２２８頁に記載されているように、重合反応を行うための予備反応としてニトロキシド化合物、ラジカル重合開始剤及びモノマーを含む混合物を、上記重合温度よりも低い温度で数時間撹拌することによりアミノエーテル化合物を生成させた後、反応温度を上げてリビングラジカル重合を行うことが好ましい。 In the method (1b), the polymerization is preferably carried out in the same temperature range as in (1a), but the polymerization reaction is carried out as described in Macromolecules, 1994, Vol. 27, page 7228. As a preliminary reaction for carrying out the reaction, a mixture containing a nitroxide compound, a radical polymerization initiator and a monomer is stirred at a temperature lower than the above polymerization temperature for several hours to produce an amino ether compound, and then the reaction temperature is raised to make a living It is preferable to perform radical polymerization.
（１ｂ）の方法におけるラジカル重合開始剤は、特に種類は制限されるものではなく、例えば、ベンゾイルパーオキサイド、パラメンタンハイドロパーオキサイド、クメンハイドロパーオキサイド、ラウロイルパーオキシド、シクロヘキサノンパーオキサイド、３，３，５−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、ｔｅｒｔ−ブチルパーオキシピバレート、１，１’−ビス（ｔｅｒｔ−ブチルパーオキシ）シクロヘキサン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルパーオキシ）バレレート、２，２’−ジ（ｔｅｒｔ−ブチルパーオキシ）ブタン、ｔｅｒｔ−ブチルヒドロキシパーオキシド、２，５−ジメチルヘキサン−２，５−ジハイドロパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキシド、ジ−ｎ−プロピルパーオキシジカーボネート、ｔｅｒｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、１，３−ビス（ｔｅｒｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、ジイソプロピルベンゼンパーオキサイド、ｔｅｒｔ−ブチルクミルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド、ビス（ｔｅｒｔ−ブチルシクロヘキシル）パーオキシジカーボネート、ｔｅｒｔ−ブチルパーオキシベンゾエート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、過酸化水素等の過酸化物系重合開始剤；１，１−アゾビス（シクロヘキサン−１−カルボニトリル）、アゾクメン、２，２’−アゾビス−（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−（４−メトキシ−２，４−ジメチルバレロニトリル、ジメチル２，２’−アゾビス（２−メチルプロピオネート）、２，２’−ジ（２−ヒドロキシエチル）アゾビスイソブチロニトリル、４，４’−アゾビス（４−シアノ吉草酸）、２−（ｔｅｒｔ−ブチルアゾ）−２−シアノプロパン、２，２’−アゾビス（２，４，４−トリメチルペンタン）、２，２’−アゾビス（２−メチルプロパン）、ジメチル２，２’−アゾビス（２−メチルプロピオネート）、２，２’−アゾビス−（Ｎ−ブチル−２−メチルプロピオンアミド）等のアゾ系重合開始剤、過硫酸カリウム、過硫酸ナトリウム等の過硫酸系開始剤、過酸化物と還元剤とからなるレドックス型開始剤等を挙げることができる。 The radical polymerization initiator in the method (1b) is not particularly limited, and examples thereof include benzoyl peroxide, paramentane hydroperoxide, cumene hydroperoxide, lauroyl peroxide, cyclohexanone peroxide, 3, 3 , 5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, tert-butyl peroxypivalate, 1,1′-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3 , 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2′-di (tert-butylperoxy) butane, tert-butylhydroxyperoxide, 2, -Dimethylhexane-2,5-dihydroperoxide, di-tert-butyl peroxide, di-n-propyl peroxydicarbonate, tert-hexylperoxy-2-ethylhexanoate, 1,3-bis ( tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butylcumyl peroxide, decanoyl peroxide, lauroyl Peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoyl) -Oxy) peroxide polymerization initiators such as hexane and hydrogen peroxide; 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile, dimethyl 2, 2′-azobis (2-methylpropionate), 2,2′-di (2-hydroxyethyl) azobisisobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), 2- (tert -Butylazo) -2-cyanopropane, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2,2'-azobis (2-methylpropionate), azo polymerization initiators such as 2,2′-azobis- (N-butyl-2-methylpropionamide), persulfate initiators such as potassium persulfate and sodium persulfate, Examples thereof include a redox type initiator composed of a peroxide and a reducing agent.
（１ｂ）の方法におけるニトロキシド化合物と上記ラジカル重合開始剤とのモル比は、前者／後者の比で約０．１〜約５．０であり、好ましくは約０．２〜約２．０の範囲である。上記モル比が約５．０を超える場合は、重合速度が低下して重合時間が長くなる場合がある。上記モル比が約０．１未満では生長末端にニトロキシド化合物が付加していないデッドポリマーが生成する場合がある。本発明の有機無機複合微粒子の分散体は、リビングポリマー（ａ）と重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）とを、溶媒の存在下で反応させることにより得られるので、リビングポリマー（ａ）を製造する際に、これらの反応を行うことができないデッドポリマーの生成ができるだけ少なくなるように、ニトロキシド化合物とラジカル重合開始剤とのモル比を、上記モル比の範囲内で調整することが好ましい。 The molar ratio of the nitroxide compound to the radical polymerization initiator in the method (1b) is about 0.1 to about 5.0, preferably about 0.2 to about 2.0, in the former / latter ratio. It is a range. When the molar ratio exceeds about 5.0, the polymerization rate may decrease and the polymerization time may become longer. When the molar ratio is less than about 0.1, a dead polymer in which a nitroxide compound is not added to the growing end may be generated. The dispersion of the organic-inorganic composite fine particles of the present invention reacts the living polymer (a), the inorganic fine particles (b) having a polymerizable unsaturated group, and the desired unsaturated monomer (c) in the presence of a solvent. Therefore, when producing the living polymer (a), the molar ratio of the nitroxide compound and the radical polymerization initiator is set to the above so that the production of a dead polymer that cannot perform these reactions is minimized. It is preferable to adjust within the range of molar ratio.
（３）可逆的付加解裂型連鎖移動重合法において用いられうる、可逆的付加解裂型連鎖移動反応が可能な化合物であるジチオエステル化合物は、例えば、国際公開第９８／０１４７８号に記載の方法により得ることが可能である。上記ジチオエステル化合物の具体的として、１−フェニルエチルジチオベンゾエート（１−ｐｈｅｎｙｌｅｔｈｙｌ ｄｉｔｈｉｏｂｅｎｚｏａｔｅ）、ジチオ安息香酸ベンジル、ジチオ安息香酸クミル、ジチオ酢酸ベンジル等を挙げることができる。また、上記可逆的付加解裂型連鎖移動重合法に用いられうるトリチオカーボネート化合物としては、例えば、特開昭５３−１０５４５０号公報に記載の方法により得られるものを挙げることができる。上記トリチオカーボネート化合物の具体例としては、ジベンジルトリチオカーボネート等を挙げることができる。他の可逆的付加解裂型連鎖移動反応が可能な化合物である、２，４−ジフェニル−４−メチル−１−ペンテンは、市販品をそのまま使用することができる。 (3) A dithioester compound that can be used in a reversible addition-cleavage type chain transfer polymerization method and is capable of a reversible addition-cleavage type chain transfer reaction is described in, for example, WO 98/01478. It can be obtained by a method. Specific examples of the dithioester compound include 1-phenylethyl dithiobenzoate, benzyl dithiobenzoate, cumyl dithiobenzoate, and benzyl dithioacetate. Examples of the trithiocarbonate compound that can be used in the reversible addition-cleavage chain transfer polymerization method include those obtained by the method described in JP-A-53-105450. Specific examples of the trithiocarbonate compound include dibenzyltrithiocarbonate. A commercially available product can be used as it is for 2,4-diphenyl-4-methyl-1-pentene, which is a compound capable of other reversible addition-cleavage type chain transfer reactions.
（３）可逆的付加解裂型連鎖移動重合は、可逆的付加解裂型連鎖移動反応可能な化合物又は重合体、及びラジカル重合開始剤の存在下において行うことができる。上記ラジカル重合開始剤としては、例えば、上述の（１）ニトロキシド化合物系ラジカル重合法における（１ｂ）の方法で用いることの可能なラジカル重合開始剤が挙げられる。 (3) Reversible addition-fragmentation chain transfer polymerization can be performed in the presence of a compound or polymer capable of reversible addition-cleavage chain transfer reaction and a radical polymerization initiator. As said radical polymerization initiator, the radical polymerization initiator which can be used by the method of (1b) in the above-mentioned (1) nitroxide compound type | system | group radical polymerization method is mentioned, for example.
上述のチオカルボニルチオ化合物及び２，４−ジフェニル−４−メチル−１−ペンテンの使用量は、ラジカル重合開始剤１質量部あたり、好ましくは約０．０５〜約１００質量部、更に好ましくは約０．１〜約５０質量部である。上記使用量が、約０．０５質量部よりも少ないと、リビングポリマーに対するデッドポリマーの生成比率が高くなる場合がある。上記使用量が、約１００質量部よりも多いと、チオカルボニルチオ化合物及び２，４−ジフェニル−４−メチル−１−ペンテンが、未反応のまま残る場合がある。また、ラジカル重合開始剤の使用量は、不飽和モノマー（ａ−１）１００質量部あたり、好ましくは約０．０１〜約２０質量部であり、さらに好ましくは約０．１〜約１０質量部である。 The amount of the thiocarbonylthio compound and 2,4-diphenyl-4-methyl-1-pentene used is preferably about 0.05 to about 100 parts by mass, more preferably about about 100 parts by mass per 1 part by mass of the radical polymerization initiator. 0.1 to about 50 parts by mass. If the amount used is less than about 0.05 part by mass, the production ratio of dead polymer to living polymer may be increased. When the amount used is more than about 100 parts by mass, the thiocarbonylthio compound and 2,4-diphenyl-4-methyl-1-pentene may remain unreacted. The amount of the radical polymerization initiator used is preferably about 0.01 to about 20 parts by mass, more preferably about 0.1 to about 10 parts by mass, per 100 parts by mass of the unsaturated monomer (a-1). It is.
上記リビングラジカル重合の際の重合温度に特に制限はないが、約０〜約２５０℃、好ましくは約３０〜約２００℃、更に好ましくは、約６０〜約１８０℃であることができる。約０℃未満の重合温度では重合速度が遅いために重合時間が長くなり製造効率が低下する場合がある。約２５０℃よりも高い重合温度では、生長末端をドーマント種にするためのチオカルボニルチオ化合物由来の基が熱分解したり、可逆的付加解裂型連鎖移動反応以外の連鎖移動反応や停止反応が起こったりすることによりデッドポリマーが生成する場合がある。 Although there is no restriction | limiting in particular in the polymerization temperature in the case of the said living radical polymerization, About 0-about 250 degreeC, Preferably it is about 30-about 200 degreeC, More preferably, it can be about 60-about 180 degreeC. When the polymerization temperature is less than about 0 ° C., the polymerization rate is slow, so that the polymerization time becomes long and the production efficiency may decrease. At a polymerization temperature higher than about 250 ° C., a group derived from a thiocarbonylthio compound for converting the growing end into a dormant species is thermally decomposed, or chain transfer reaction or termination reaction other than reversible addition-cleavage type chain transfer reaction occurs. In some cases, a dead polymer may be generated.
リビングポリマー（ａ）を得るために用いることのできる不飽和モノマー（ａ−１）は、リビングラジカル重合することが可能なものであれば、特に種類は制限されるものではなく、例えば、以下のものを挙げることができる。 The unsaturated monomer (a-1) that can be used to obtain the living polymer (a) is not particularly limited as long as it can be subjected to living radical polymerization. Things can be mentioned.
（ｉ）アルキル又はシクロアルキル（メタ）アクリレート：例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（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、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、トリデシル（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、イソステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、ｔｅｒｔ−ブチルシクロヘキシル（メタ）アクリレート、シクロドデシル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート等。 (I) alkyl or cycloalkyl (meth) acrylate: for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) ) Acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate.
（ii）イソボルニル基を有する不飽和モノマー：例えば、イソボルニル（メタ）アクリレート等。
（iii）アダマンチル基を有する不飽和モノマー：例えば、アダマンチル（メタ）アクリレート等。
（iv）トリシクロデセニル基を有する不飽和モノマー：例えば、トリシクロデセニル（メタ）アクリレート等。
(Ii) Unsaturated monomer having an isobornyl group: for example, isobornyl (meth) acrylate.
(Iii) Unsaturated monomer having an adamantyl group: for example, adamantyl (meth) acrylate and the like.
(Iv) Unsaturated monomer having a tricyclodecenyl group: for example, tricyclodecenyl (meth) acrylate.
（ｖ）芳香環含有不飽和モノマー：例えば、ベンジル（メタ）アクリレート、スチレン、α−メチルスチレン、ビニルトルエン等。
（vi）アルコキシシリル基を有する不飽和モノマー：例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、γ−（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリエトキシシラン等。
(V) Aromatic ring-containing unsaturated monomer: For example, benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene and the like.
(Vi) Unsaturated monomer having an alkoxysilyl group: for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) Acryloyloxypropyltriethoxysilane and the like.
（vii）フッ素化アルキル基を有する不飽和モノマー：例えば、パーフルオロブチルエチル（メタ）アクリレート、パーフルオロオクチルエチル（メタ）アクリレート等のパーフルオロアルキル（メタ）アクリレート；フルオロオレフィン等。
（viii）マレイミド基等の光重合性官能基を有する不飽和モノマー。
（ix）ビニル化合物：例えば、Ｎ−ビニル−２−ピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニル等。
(Vii) Unsaturated monomer having a fluorinated alkyl group: for example, perfluoroalkyl (meth) acrylate such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; fluoroolefin and the like.
(Viii) An unsaturated monomer having a photopolymerizable functional group such as a maleimide group.
(Ix) Vinyl compound: For example, N-vinyl-2-pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate and the like.
（ｘ）リン酸基含有不飽和モノマー：例えば、２−アクリロイルオキシエチルアシッドホスフェート、２−メタクリロイルオキシエチルアシッドホスフェート、２−アクリロイルオキシプロピルアシッドホスフェート、２−メタクリロイルオキシプロピルアシッドホスフェート等。
（xi）水酸基含有不飽和モノマー：例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−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（メタ）アクリレート等の（メタ）アクリル酸と炭素数２〜８の２価アルコールとのモノエステル化物；上記（メタ）アクリル酸と炭素数２〜８の２価アルコールとのモノエステル化物のε−カプロラクトン変性体；Ｎ−ヒドロキシメチル（メタ）アクリルアミド；アリルアルコール；分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等。
(X) Phosphoric acid group-containing unsaturated monomer: for example, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate, and the like.
(Xi) Hydroxyl group-containing unsaturated monomer: For example, (meta) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. ) Monoesterified product of acrylic acid and C2-8 dihydric alcohol; ε-caprolactone modified product of monoesterified product of (meth) acrylic acid and C2-8 dihydric alcohol; N-hydroxy Methyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end.
（xii）カルボキシル基含有不飽和モノマー：例えば、（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレート等。
（xiii）含窒素不飽和モノマー：例えば、（メタ）アクリロニトリル、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、メチレンビス（メタ）アクリルアミド、エチレンビス（メタ）アクリルアミド、２−（メタクリロイルオキシ）エチルトリメチルアンモニウムクロライド、グリシジル（メタ）アクリレートとアミン類との付加物等。
(Xii) Carboxyl group-containing unsaturated monomer: For example, (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and the like.
(Xiii) Nitrogen-containing unsaturated monomer: For example, (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylamino Propyl (meth) acrylamide, methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 2- (methacryloyloxy) ethyltrimethylammonium chloride, adducts of glycidyl (meth) acrylate and amines.
（xiv）重合性不飽和基を１分子中に少なくとも２個有する不飽和モノマー：例えば、アリル（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート等。
（xv）エポキシ基含有不飽和モノマー：例えば、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エチル（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、アリルグリシジルエーテル、４−（グリシジルオキシ）ブチル（メタ）アクリレート等。
(Xiv) Unsaturated monomer having at least two polymerizable unsaturated groups in one molecule: for example, allyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc.
(Xv) Epoxy group-containing unsaturated monomer: for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether, 4- (glycidyloxy) butyl (meth) acrylate, and the like.
（xvi）分子末端がアルコキシ基であるポリオキシエチレン鎖を有する（メタ）アクリレート。
（xvii）スルホン酸基を有する不飽和モノマー：例えば、２−アクリルアミド−２−メチルプロパンスルホン酸、２−スルホエチル（メタ）アクリレート、アリルスルホン酸、４−スチレンスルホン酸等；これらスルホン酸のナトリウム塩及びアンモニウム塩等。
(Xvi) (meth) acrylate having a polyoxyethylene chain whose molecular end is an alkoxy group.
(Xvii) unsaturated monomers having a sulfonic acid group: for example, 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc .; sodium salts of these sulfonic acids And ammonium salts.
（xviii）紫外線吸収性官能基を有する不飽和モノマー：例えば、２−ヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２−ヒドロキシ−４−（３−アクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２，２’−ジヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２，２’−ジヒドロキシ−４−（３−アクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２−（２’−ヒドロキシ−５’−メタクリロイルオキシエチルフェニル）−２Ｈ−ベンゾトリアゾール等。 (Xviii) Unsaturated monomer having a UV-absorbing functional group: for example, 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxy Propoxy) benzophenone, 2,2′-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and the like.
（xix）光安定性不飽和モノマー：例えば、４−（メタ）アクリロイルオキシ−１，２，２，６，６−ペンタメチルピペリジン、４−（メタ）アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルアミノ−２，２，６，６−テトラメチルピペリジン、１−クロトノイル−４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン等。 (Xix) photostable unsaturated monomer: for example, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6- Tetramethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6 -Tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6- Tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-te La-methylpiperidine and the like.
（xx）カルボニル基を有する不飽和モノマー：例えば、アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、約４〜約７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等。
（xxi）酸無水物基を有する不飽和モノマー：例えば、無水マレイン酸、無水イタコン酸、無水シトラコン酸等。
不飽和モノマー（ａ−１）は、１種又は２種以上を組合せて使用することができる。
(Xx) Unsaturated monomer having a carbonyl group: for example, acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, vinyl alkyl ketone having about 4 to about 7 carbon atoms (for example, vinyl Methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like.
(Xxi) An unsaturated monomer having an acid anhydride group: for example, maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
An unsaturated monomer (a-1) can be used 1 type or in combination of 2 or more types.
なお、本明細書において、「（メタ）アクリレート」は、アクリレート又はメタクリレートを意味し、「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を意味する。また、「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味し、（メタ）アクリルアミド」は、「アクリルアミド又はメタクリルアミド」を意味する。 In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid. In addition, “(meth) acryloyl” means acryloyl or methacryloyl, and (meth) acrylamide ”means“ acrylamide or methacrylamide ”.
上述のリビングラジカル重合は、無溶媒で行ってもよく、又は溶媒中で行ってもよい。上記溶媒としては、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族化合物、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロヘプタン、ミネラルスピリット等の炭化水素系溶媒、酢酸エチル、酢酸ｎ−ブチル、酢酸イソブチル、メチルセロソルブアセテート、ブチルカルビトールアセテート、エチレングリコールモノメ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、３−エトキシプロピオン酸エチル等のエステル系溶媒、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン等のケトン系溶媒、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、イソブタノール、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のアルコール系溶媒、ｎ−ブチルエーテル、ジオキサン、エチレングリコールジメチルエーテル等のエーテル系溶媒、ジメチルスルホキシド、ジメチルホルムアミド、Ｎ−メチルピロリドン又は水等、あるいはこれらの組み合わせを挙げることができる。 The living radical polymerization described above may be performed without a solvent or may be performed in a solvent. Examples of the solvent include aromatic compounds such as benzene, toluene, xylene, and ethylbenzene, hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, and mineral spirits, ethyl acetate, n-butyl acetate, Ester solvents such as isobutyl acetate, methyl cellosolve acetate, butyl carbitol acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, ethyl 3-ethoxypropionate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone , Methanol, ethanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol, ethylene Alcohol solvents such as glycol monomethyl ether and ethylene glycol monoethyl ether, ether solvents such as n-butyl ether, dioxane, and ethylene glycol dimethyl ether, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, water, etc., or combinations thereof be able to.
リビングラジカル重合により得られるリビングポリマー（ａ）の数平均分子量は、約５００〜約５００，０００、さらに約１，０００〜約３０，０００の範囲にあることが好ましい。本発明の有機無機複合微粒子の分散体が取り扱い安い粘度になるためである。 The number average molecular weight of the living polymer (a) obtained by living radical polymerization is preferably in the range of about 500 to about 500,000, more preferably about 1,000 to about 30,000. This is because the dispersion of the organic-inorganic composite fine particles of the present invention has a low handling viscosity.
なお、本明細書において、数平均分子量及び重量平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用いて測定した保持時間（保持容量）を、同一条件で測定した分子量既知の標準ポリスチレンの保持時間（保持容量）によりポリスチレンの分子量に換算して求めた値である。具体的には、ゲルパーミエーションクロマトグラフ装置として、「ＨＬＣ８１２０ＧＰＣ」（商品名、東ソー社製）を使用し、カラムとして、「ＴＳＫｇｅｌ Ｇ−４０００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ−３０００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ−２５００ＨＸＬ」及び「ＴＳＫｇｅｌ Ｇ−２０００ＨＸＬ」（商品名、いずれも東ソー社製）の４本を使用し、検出器として、示差屈折率計を使用し、移動相：テトラヒドロフラン、測定温度：４０℃、流速：１ｍＬ／ｍｉｎの条件下で測定することができる。 In this specification, the number average molecular weight and the weight average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC) and the retention time of a standard polystyrene with a known molecular weight measured under the same conditions. (Retention capacity) is a value obtained by converting to the molecular weight of polystyrene. Specifically, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” are used as columns. ”And“ TSKgel G-2000HXL ”(trade names, all manufactured by Tosoh Corporation), a differential refractometer is used as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: It can be measured under the condition of 1 mL / min.
リビングポリマー（ａ）を得るためのリビングラジカル重合において、不飽和モノマー（ａ−１）の重合率は約１００％であっても、又は約１００％未満であってもよい。重合率が約１００％未満の場合においても、リビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）との反応を、リビングポリマー（ａ）を得るためのリビングラジカル重合における不飽和モノマー（ａ−１）のうち、未反応のもの（以下、「未反応の不飽和モノマー（ａ−１）」と称する場合がある）の存在下で行うことができる。 In the living radical polymerization for obtaining the living polymer (a), the polymerization rate of the unsaturated monomer (a-1) may be about 100% or less than about 100%. Even in the case where the polymerization rate is less than about 100%, the reaction of the living polymer (a), the inorganic fine particles (b) having a polymerizable unsaturated group, and the unsaturated monomer (c) as desired is converted into a living polymer (a In the presence of an unreacted monomer (a-1) in the living radical polymerization (hereinafter sometimes referred to as “unreacted unsaturated monomer (a-1)”). It can be carried out.
リビングポリマー（ａ）を得るためのリビングラジカル重合における不飽和モノマー（ａ−１）の重合率は、約３０％以上、好ましくは約５０％以上、さらに好ましくは約８０％以上であることができる。重合率が約３０％未満であると、後述するリビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）との反応における反応時間が長くなり、製造効率が低下する場合がある。また、未反応の不飽和モノマー（ａ−１）、重合に使用した溶媒等は、減圧下で除去したり、リビングポリマー（ａ）が溶解しない溶剤を用いて沈殿処理したりすることによりリビングポリマー（ａ）を単離してから、重合性不飽和基を有する無機微粒子（ｂ）との反応に用いてもよい。 The polymerization rate of the unsaturated monomer (a-1) in the living radical polymerization for obtaining the living polymer (a) can be about 30% or more, preferably about 50% or more, more preferably about 80% or more. . When the polymerization rate is less than about 30%, the reaction time in the reaction of the living polymer (a) described later, the inorganic fine particles (b) having a polymerizable unsaturated group, and the unsaturated monomer (c) as desired is long. Thus, the production efficiency may be reduced. In addition, the unreacted unsaturated monomer (a-1), the solvent used for the polymerization, etc. are removed under reduced pressure, or the living polymer (a) is precipitated using a solvent that does not dissolve the living polymer (a). After isolating (a), it may be used for the reaction with inorganic fine particles (b) having a polymerizable unsaturated group.
［重合性不飽和基を有する無機微粒子（ｂ）］
重合性不飽和基を有する無機微粒子（ｂ）は、無機微粒子と加水分解性シリル基を有するモノマーとを反応させることにより得られる。上記無機微粒子は、後述する加水分解性シリル基を有するモノマーとの反応により共有結合を形成して重合性不飽和基による表面修飾が可能な無機微粒子であれば何れでも使用することができる。このような無機微粒子としては、例えば、シリカ微粒子、酸化亜鉛微粒子、酸化チタン微粒子、酸化ジルコニウム微粒子、酸化アルミニウム微粒子、酸化錫微粒子、又はこれらを主成分とする複合酸化物微粒子が挙げられる。これらの中でも、シリカ微粒子、特に、水酸基及び／又はアルコキシ基を粒子表面に有し、分散媒に分散されたシリカ微粒子であるコロイダルシリカが好ましい。
[Inorganic fine particles having a polymerizable unsaturated group (b)]
The inorganic fine particles (b) having a polymerizable unsaturated group can be obtained by reacting inorganic fine particles with a monomer having a hydrolyzable silyl group. As the inorganic fine particles, any inorganic fine particles can be used as long as they form a covalent bond by reaction with a monomer having a hydrolyzable silyl group described later and can be surface-modified with a polymerizable unsaturated group. Examples of such inorganic fine particles include silica fine particles, zinc oxide fine particles, titanium oxide fine particles, zirconium oxide fine particles, aluminum oxide fine particles, tin oxide fine particles, and composite oxide fine particles containing these as main components. Among these, silica fine particles, particularly colloidal silica which is silica fine particles having a hydroxyl group and / or an alkoxy group on the particle surface and dispersed in a dispersion medium is preferable.
上記分散媒としては、例えば、水；メタノール、エタノール、イソプロパノール、ｎ−プロパノール、イソブタノール、ｎ−ブタノール等のアルコール系溶剤；エチレングリコール等の多価アルコール系溶剤；エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル等の多価アルコール誘導体；メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール等のケトン系溶剤等が挙げられる。上記分散媒としては、炭素数３以下の低級アルコール系溶剤が好ましい。重合性不飽和基を有する無機微粒子（ｂ）の製造における溶剤除去工程で除去しやすいからである。 Examples of the dispersion medium include water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol Examples thereof include polyhydric alcohol derivatives such as monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol. As the dispersion medium, a lower alcohol solvent having 3 or less carbon atoms is preferable. This is because it is easy to remove in the solvent removal step in the production of the inorganic fine particles (b) having a polymerizable unsaturated group.
コロイダルシリカとしては、例えば、メタノールシリカゾル、ＩＰＡ−ＳＴ、ＭＥＫ−ＳＴ、ＮＢＡ−ＳＴ、ＸＢＡ−ＳＴ、ＤＭＡＣ−ＳＴ、ＰＧＭ−ＳＴ、ＳＴ−ＵＰ、ＳＴ−ＯＵＰ、ＳＴ−２０、ＳＴ−４０、ＳＴ−Ｃ、ＳＴ−Ｎ、ＳＴ−Ｏ、ＳＴ−５０、ＳＴ−ＯＬ（いずれも日産化学工業社製）等が挙げられる。 Examples of colloidal silica include methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, PGM-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL (all manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.
コロイダルシリカの平均一次粒子径は、約１〜約２００ｎｍが好ましく、約５〜約８０ｎｍがより好ましい。平均一次粒子径が約１ｎｍ未満であると、本発明の有機無機複合微粒子の分散体を他の有機材料と混合して使用した場合に、上記材料の、機械特性等の改良効果が小さくなるときがある。平均一次粒子径が約２００ｎｍ以上であると、上記材料の透明性が損なわれる場合がある。
本明細書において、「平均一次粒子径」は、動的光散乱法によって測定される体積基準粒度分布のメジアン径（ｄ５０）を意味し、例えば、日機装社製のナノトラック粒度分布測定装置を用いて測定することができる。
The average primary particle size of the colloidal silica is preferably about 1 to about 200 nm, more preferably about 5 to about 80 nm. When the average primary particle size is less than about 1 nm, when the dispersion of organic-inorganic composite fine particles of the present invention is used in combination with other organic materials, the effect of improving the above-described materials, such as mechanical properties, is reduced. There is. When the average primary particle diameter is about 200 nm or more, the transparency of the material may be impaired.
In this specification, the “average primary particle diameter” means a median diameter (d50) of a volume-based particle size distribution measured by a dynamic light scattering method. For example, a nanotrack particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd. is used. Can be measured.
加水分解性シリル基を有するモノマーとしては、例えば、３−（メタ）アクリロイルオキシプロピルトリメトキシシラン、３−（メタ）アクリロイルオキシプロピルトリエトキシシラン、２−（メタ）アクリロイルオキシエチルトリメトキシシラン、２−（メタ）アクリロイルオキシエチルトリエトキシシラン、３−（メタ）アクリロイルオキシプロピルメチルジメトキシシラン、２−（メタ）アクリロイルオキシエチルメチルジメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン、アリルトリエトキシシラン、各種シランカップリング剤と不飽和化合物との反応により得られる加水分解性シリル基を有するモノマー等、又はその加水分解物を挙げることができる。 Examples of the monomer having a hydrolyzable silyl group include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 2 -(Meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 2- (meth) acryloyloxyethylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, Examples include allyltriethoxysilane, a monomer having a hydrolyzable silyl group obtained by a reaction between various silane coupling agents and an unsaturated compound, or a hydrolyzate thereof.
シリカ微粒子と加水分解性シリル基を有するモノマーとを反応させる方法としては、特に限定されない。例えば、［ｉ］水を含む有機溶剤の存在下にシリカ微粒子と加水分解性シリル基を有するモノマーとを混合し、加水分解縮合を行う方法、［ｉｉ］水を含む有機溶剤の存在下で加水分解性シリル基を有するモノマーを加水分解した後に得られる加水分解物とシリカ微粒子とを縮合させる方法が挙げられる。
ここで、これら製造方法において使用する水は、原材料に含まれる水、例えば、コロイダルシリカの分散媒である水であってもよい。
The method for reacting the silica fine particles with the monomer having a hydrolyzable silyl group is not particularly limited. For example, [i] a method in which silica fine particles and a monomer having a hydrolyzable silyl group are mixed in the presence of an organic solvent containing water and hydrolytic condensation is performed, and [ii] water is added in the presence of an organic solvent containing water. The method of condensing the hydrolyzate obtained after hydrolyzing the monomer which has a decomposable silyl group, and silica fine particles is mentioned.
Here, the water used in these production methods may be water contained in the raw material, for example, water that is a dispersion medium of colloidal silica.
重合性不飽和基を有する無機微粒子（ｂ）を製造する方法についてより具体的に説明する。重合性不飽和基を有する無機微粒子（ｂ）は、例えば、コロイダルシリカと、加水分解性シリル基を有するモノマーと、所望による低級アルコールとの存在下で、コロイダルシリカの分散媒、及び低級アルコール（加水分解性シリル基を有するモノマーを加水分解して生じた低級アルコールを含む。）を常圧又は減圧下で低級アルコールよりも高沸点の溶剤とともに共沸留出させ、分散媒を上記高沸点の溶剤に置換しながら、又は置換した後に加熱下で脱水縮合反応させることにより製造することができる。 The method for producing the inorganic fine particles (b) having a polymerizable unsaturated group will be described more specifically. The inorganic fine particles (b) having a polymerizable unsaturated group include, for example, colloidal silica, a monomer having a hydrolyzable silyl group, and optionally a lower alcohol, a colloidal silica dispersion medium, and a lower alcohol ( A lower alcohol produced by hydrolyzing a monomer having a hydrolyzable silyl group.) Is azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure. It can manufacture by making it dehydrate-condensation reaction under heating, after substituting with a solvent.
この製造方法においては、シリカ微粒子であるコロイダルシリカと、加水分解性シリル基を有するモノマーと、所望による低級アルコールとの混合物に必要により加水分解触媒を加え、常温又は加熱下で攪拌する等の常法によって、加水分解性シリル基を有するモノマーの加水分解を行う。続いて、コロイダルシリカの分散媒、及び低級アルコールを常圧又は減圧下で低級アルコールよりも高沸点の溶剤とともに共沸留出させ、分散媒を上記高沸点溶剤に置換した後、約６０〜約１５０℃、好ましくは約８０〜約１３０℃の温度で、通常不揮発分濃度を約５〜約５０質量％の範囲に保ちながら、約０．５〜約１０時間攪拌下で反応させる。反応後には、縮合反応又は加水分解で生ずる水及び低級アルコールを、低級アルコールよりも高沸点の溶剤とともに共沸留去することが好ましい。 In this production method, if necessary, a hydrolysis catalyst is added to a mixture of colloidal silica, which is fine silica particles, a monomer having a hydrolyzable silyl group, and a desired lower alcohol, and the mixture is stirred at room temperature or under heating. According to the method, a monomer having a hydrolyzable silyl group is hydrolyzed. Subsequently, the dispersion medium of colloidal silica and the lower alcohol are azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure, and the dispersion medium is replaced with the above-mentioned high boiling point solvent. The reaction is carried out at a temperature of 150 ° C., preferably about 80 to about 130 ° C., with stirring for about 0.5 to about 10 hours, usually while maintaining the nonvolatile content concentration in the range of about 5 to about 50 mass%. After the reaction, it is preferable to azeotropically distill water and lower alcohol generated by condensation reaction or hydrolysis together with a solvent having a boiling point higher than that of the lower alcohol.
上記反応に用いられる溶媒としては、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン、シクロヘキサン等の炭化水素類；トリクロルエチレン、テトラクロルエチレン等のハロゲン化炭化水素類；１，４−ジオキサン、ジブチルエーテル等のエーテル類；メチルイソブチルケトン等のケトン類；酢酸ｎ−ブチル、酢酸イソブチル、酢酸エチル、プロピオン酸エチル等のエステル類；エチレングリコールモノブチルエーテル等の多価アルコール誘導体等が挙げられる。 Examples of the solvent used in the above reaction include hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cyclohexane; halogenated hydrocarbons such as trichloroethylene and tetrachloroethylene; 1,4-dioxane, dibutyl ether, and the like. Ethers; ketones such as methyl isobutyl ketone; esters such as n-butyl acetate, isobutyl acetate, ethyl acetate and ethyl propionate; polyhydric alcohol derivatives such as ethylene glycol monobutyl ether;
反応中の不揮発分濃度は約５〜約５０質量％の範囲が好ましい。不揮発分濃度が約５質量％未満、すなわち溶媒が約９５質量％を超えると、シリカ微粒子と加水分解性シリル基を有するモノマーとの反応時間が長くなり製造効率が低下する場合がある。一方、不揮発分濃度が約５０質量％を超えると、生成物がゲル化する恐れがある。 The non-volatile content concentration during the reaction is preferably in the range of about 5 to about 50% by mass. When the non-volatile content concentration is less than about 5% by mass, that is, the solvent exceeds about 95% by mass, the reaction time between the silica fine particles and the monomer having a hydrolyzable silyl group becomes long, and the production efficiency may decrease. On the other hand, when the non-volatile content concentration exceeds about 50% by mass, the product may be gelled.
これらの製造方法によりシリカ微粒子表面のケイ素原子と、加水分解性シリル基を有するモノマーのケイ素原子が酸素原子を介して結合することにより、シリカ微粒子と加水分解性シリル基を有するモノマーとが化学的に結合した重合性不飽和基を有する無機微粒子（ｂ）が得られる。 By these production methods, the silicon atom on the surface of the silica fine particle and the silicon atom of the monomer having a hydrolyzable silyl group are bonded via an oxygen atom, whereby the silica fine particle and the monomer having a hydrolyzable silyl group are chemically synthesized. Inorganic fine particles (b) having a polymerizable unsaturated group bonded to are obtained.
重合性不飽和基を有する無機微粒子（ｂ）を得る際の加水分解性シリル基を有するモノマーの配合割合は、シリカ微粒子１００質量部に対して、好ましくは約０．２質量部〜約９５質量部であり、より好ましくは約０．５質量部〜約９０質量部、そしてさらに好ましくは約１．０質量部〜約８０質量部である。加水分解性シリル基を有するモノマーの割合が約０．２質量部未満であると、生成する有機無機複合微粒子が、分散媒中で安定性に劣る場合がある。加水分解性シリル基を有するモノマーの割合が約９５質量部よりも多いと、無機微粒子（ｂ）との反応において加水分解性シリル基を有するモノマーが未反応のまま残存する場合がある。 The blending ratio of the monomer having a hydrolyzable silyl group in obtaining the inorganic fine particles (b) having a polymerizable unsaturated group is preferably about 0.2 parts by mass to about 95 parts by mass with respect to 100 parts by mass of the silica fine particles. More preferably from about 0.5 parts by weight to about 90 parts by weight, and even more preferably from about 1.0 parts by weight to about 80 parts by weight. When the proportion of the monomer having a hydrolyzable silyl group is less than about 0.2 parts by mass, the produced organic-inorganic composite fine particles may be inferior in stability in the dispersion medium. If the proportion of the monomer having a hydrolyzable silyl group is more than about 95 parts by mass, the monomer having a hydrolyzable silyl group may remain unreacted in the reaction with the inorganic fine particles (b).
［不飽和モノマー（ｃ）］
本発明の有機無機複合微粒子の分散体はまた、リビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、不飽和モノマー（ｃ）とを、溶媒の存在下で反応させることによっても得られる。
[Unsaturated monomer (c)]
The organic-inorganic composite fine particle dispersion of the present invention also reacts the living polymer (a), the inorganic fine particles (b) having a polymerizable unsaturated group, and the unsaturated monomer (c) in the presence of a solvent. Can also be obtained.
不飽和モノマー（ｃ）は、リビングポリマー（ａ）を製造するための不飽和モノマー（ａ−１）、又はその組み合わせであることができる。また、リビングポリマー（ａ）の製造における不飽和モノマー（ａ−１）の重合率が約１００％未満の場合であって、リビングポリマー（ａ）から未反応の不飽和モノマー（ａ−１）が持ち込まれるときには、未反応の不飽和モノマー（ａ−１）は、不飽和モノマー（ｃ）に含まれる。不飽和モノマー（ｃ）の使用量は、リビングポリマー（ａ）１００質量部に対して約２３０質量部以下、好ましくは約１００質量部以下であることができる。不飽和モノマー（ｃ）が約２３０質量部よりも多いと、反応時間が長くなり製造効率が低下する場合がある。 The unsaturated monomer (c) can be the unsaturated monomer (a-1) for producing the living polymer (a), or a combination thereof. Moreover, it is a case where the polymerization rate of the unsaturated monomer (a-1) in manufacture of a living polymer (a) is less than about 100%, Comprising: Unreacted unsaturated monomer (a-1) is from a living polymer (a). When brought in, the unreacted unsaturated monomer (a-1) is included in the unsaturated monomer (c). The amount of the unsaturated monomer (c) used can be about 230 parts by mass or less, preferably about 100 parts by mass or less, with respect to 100 parts by mass of the living polymer (a). When there are more unsaturated monomers (c) than about 230 mass parts, reaction time may become long and manufacturing efficiency may fall.
［有機無機複合微粒子の分散体］
本発明の有機無機複合微粒子の分散体は、リビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）とを、溶媒の存在下で反応させることにより得られる。
[Dispersion of organic-inorganic composite fine particles]
The dispersion of organic-inorganic composite fine particles of the present invention comprises a reaction between a living polymer (a), inorganic fine particles (b) having a polymerizable unsaturated group, and an unsaturated monomer (c) as desired in the presence of a solvent. Is obtained.
上記反応は、リビングポリマー（ａ）を得るために用いられたリビングラジカル重合法に応じて、リビングポリマー（ａ）に、適宜、触媒、ラジカル重合開始剤等を添加して、実施することができる。（１）ニトロキシド化合物系ラジカル重合法により得られたリビングポリマー（ａ）を用いる場合には、リビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）との混合物を加熱することにより有機無機複合微粒子の分散体を得ることができる。 The above reaction can be carried out by appropriately adding a catalyst, a radical polymerization initiator and the like to the living polymer (a) according to the living radical polymerization method used to obtain the living polymer (a). . (1) When the living polymer (a) obtained by the nitroxide compound-based radical polymerization method is used, the living polymer (a), inorganic fine particles (b) having a polymerizable unsaturated group, and an optional unsaturated monomer A dispersion of organic-inorganic composite fine particles can be obtained by heating the mixture with (c).
（３）可逆的付加解裂型連鎖移動重合法により得られたリビングポリマー（ａ）を用いる場合には、上記混合物にラジカル重合開始剤を添加して加熱することにより、有機無機複合微粒子の分散体を得ることができる。上記ラジカル重合開始剤は、上記（１ｂ）の方法において記載したものを使用することができ、その使用量はリビングポリマー（ａ）１００質量部に対して約０．０５〜約２０質量部、好ましくは約０．１〜約１０質量部であることができる。上記ラジカル重合開始剤が約０．０５質量部未満であると、重合性不飽和基を有する無機微粒子（ｂ）と反応しない未反応のリビングポリマー（ａ）の割合が多くなる場合がある。上記ラジカル重合開始剤が約２０質量部よりも多いと、ラジカル重合開始剤由来の開始ラジカル種が、リビングポリマー（ａ）の生長末端に付加して無機微粒子（ｂ）と反応できないデッドポリマーの生成割合が多くなる場合がある。 (3) When the living polymer (a) obtained by the reversible addition-cleavage type chain transfer polymerization method is used, the dispersion of the organic-inorganic composite fine particles is dispersed by adding a radical polymerization initiator to the above mixture and heating. You can get a body. As the radical polymerization initiator, those described in the above method (1b) can be used, and the amount used is about 0.05 to about 20 parts by weight, preferably 100 parts by weight of the living polymer (a). Can be from about 0.1 to about 10 parts by weight. When the radical polymerization initiator is less than about 0.05 part by mass, the proportion of the unreacted living polymer (a) that does not react with the inorganic fine particles (b) having a polymerizable unsaturated group may increase. When the amount of the radical polymerization initiator is more than about 20 parts by mass, a dead polymer that cannot be reacted with the inorganic fine particles (b) by adding the starting radical species derived from the radical polymerization initiator to the growing terminal of the living polymer (a) The ratio may increase.
リビングポリマー（ａ）と所望による不飽和モノマー（ｃ）の合計質量と、重合性不飽和基を有する無機微粒子（ｂ）との質量比は、約５：９５〜約９５：５、好ましくは約２０：８０〜約８０：２０であることができる。上記質量比が約５：９５よりも小さいと、得られる有機無機複合微粒子の分散体の貯蔵安定性が劣る場合がある。上記質量比が約９５：５よりも大きいと、本発明の有機無機複合微粒子の分散体を他の有機材料と混合して使用した場合に、上記有機材料の機械特性等の改良効果が小さくなることがある。 The mass ratio of the living polymer (a) and the optionally unsaturated monomer (c) to the inorganic fine particles (b) having a polymerizable unsaturated group is about 5:95 to about 95: 5, preferably about 20:80 to about 80:20. If the mass ratio is less than about 5:95, the storage stability of the resulting dispersion of organic-inorganic composite fine particles may be inferior. When the mass ratio is greater than about 95: 5, when the dispersion of organic-inorganic composite fine particles of the present invention is used by mixing with other organic materials, the effect of improving the mechanical properties and the like of the organic materials is reduced. Sometimes.
リビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）との反応は、溶媒中で行なうことができる。リビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）との合計質量濃度は、約１０質量％〜約９０質量％、好ましくは約２０質量％〜約７０質量％であることができる。上記合計質量濃度が約１０質量％未満であると、反応時間が長くなり製造効率が低下する場合がある。上記合計質量濃度が約９０質量％よりも高いと、反応系の粘度が高くなり攪拌が困難になる場合がある。溶媒はリビングポリマー（ａ）の製造において使用した溶剤、重合性不飽和基を有する無機微粒子（ｂ）の分散媒として使用した溶剤等を使用することができる。 The reaction of the living polymer (a), the inorganic fine particles (b) having a polymerizable unsaturated group, and the optionally unsaturated monomer (c) can be performed in a solvent. The total mass concentration of the living polymer (a), the inorganic fine particles (b) having a polymerizable unsaturated group, and the optionally unsaturated monomer (c) is about 10% by mass to about 90% by mass, preferably about 20%. It can be from mass% to about 70 mass%. When the total mass concentration is less than about 10 mass%, the reaction time may be long and the production efficiency may be reduced. When the total mass concentration is higher than about 90% by mass, the viscosity of the reaction system becomes high and stirring may be difficult. As the solvent, the solvent used in the production of the living polymer (a), the solvent used as a dispersion medium for the inorganic fine particles (b) having a polymerizable unsaturated group, and the like can be used.
リビングポリマー（ａ）の生長末端と、重合性不飽和基を有する無機微粒子（ｂ）の重合性不飽和基との反応、又はリビングポリマー（ａ）の生長末端と、重合性不飽和基を有する無機微粒子（ｂ）の重合性不飽和基と、不飽和モノマー（ｃ）の重合性不飽和基との反応は、リビングラジカル重合と同様に反応容器内の気相を不活性ガスにより置換して撹拌しながら行うことが好ましい。反応温度と反応時間は、リビングポリマー（ａ）の製造におけるリビングラジカル重合の方法、不飽和モノマー（ｃ）の種類等により適宜選択することができるが、反応温度は約０〜約２５０℃の範囲内であるのが好ましく、反応時間は１〜７２時間の範囲内であるのが好ましい。反応は、通常、常圧下で行われるが、加圧又は減圧下で行うことができる。 Reaction between the growing terminal of the living polymer (a) and the polymerizable unsaturated group of the inorganic fine particle (b) having a polymerizable unsaturated group, or the growing terminal of the living polymer (a) and the polymerizable unsaturated group The reaction between the polymerizable unsaturated group of the inorganic fine particles (b) and the polymerizable unsaturated group of the unsaturated monomer (c) is performed by replacing the gas phase in the reaction vessel with an inert gas in the same manner as in the living radical polymerization. It is preferable to carry out with stirring. The reaction temperature and reaction time can be appropriately selected depending on the method of living radical polymerization in the production of the living polymer (a), the type of unsaturated monomer (c), etc., but the reaction temperature is in the range of about 0 to about 250 ° C. The reaction time is preferably in the range of 1 to 72 hours. The reaction is usually performed under normal pressure, but can be performed under pressure or reduced pressure.
上記反応における、不飽和モノマー（ｃ）の重合率は、約９０％以上、好ましくは約９５％以上であることができる。不飽和モノマー（ｃ）の重合率が約９０％未満だと、得られる有機無機複合微粒子の分散体の使用時に未反応の不飽和モノマー（ｃ）に起因する臭気が問題になる場合がある。未反応のモノマーは、反応時間を延長して消費させてもよく、又は未反応モノマーが少量の場合には、ラジカル重合開始剤を添加して重合反応により消費させてもよい。また、得られた有機無機複合微粒子の分散体は、所望により、溶媒が水等の他の溶媒に置換されてもよい。 The polymerization rate of the unsaturated monomer (c) in the above reaction can be about 90% or more, preferably about 95% or more. If the polymerization rate of the unsaturated monomer (c) is less than about 90%, the odor caused by the unreacted unsaturated monomer (c) may be a problem when the resulting dispersion of organic-inorganic composite fine particles is used. The unreacted monomer may be consumed by extending the reaction time, or when the amount of unreacted monomer is small, a radical polymerization initiator may be added and consumed by the polymerization reaction. In addition, in the obtained dispersion of organic-inorganic composite fine particles, the solvent may be replaced with another solvent such as water, if desired.
［塗料組成物］
本発明の塗料組成物は、上述の有機無機複合微粒子の分散体、又は有機無機複合微粒子を含む。上記塗料組成物は、有機無機複合微粒子の分散体、又は有機無機複合微粒子以外に、樹脂（ｄ）、硬化剤（ｆ）、顔料等を含んでいてもよく、そして１液型又は２液型以上の塗料組成物であることができる。また、上記塗料組成物は、クリヤー塗料又はエナメル塗料であることができる。さらに、上記塗料組成物は、焼付け硬化型、例えば、１液型の焼き付け硬化型塗料組成物若しくは２液型の焼き付け硬化型塗料組成物、又は常温硬化型、例えば、１液型の常温硬化型塗料組成物若しくは２液型の常温硬化型塗料組成物であることができ、又は非硬化型のラッカー型、例えば、１液型のラッカー型塗料組成物であることができる。
[Coating composition]
The coating composition of the present invention contains the above-mentioned dispersion of organic-inorganic composite fine particles or organic-inorganic composite fine particles. The coating composition may contain a resin (d), a curing agent (f), a pigment, and the like in addition to the dispersion of organic-inorganic composite fine particles or the organic-inorganic composite fine particles, and one-component type or two-component type It can be the above coating composition. The coating composition may be a clear coating or an enamel coating. Further, the coating composition may be a bake curable type, for example, a one-component bake curable coating composition or a two-component bake curable coating composition, or a room temperature curable type, for example, a one-component room temperature curable type. It can be a coating composition or a two-component room temperature curable coating composition, or it can be a non-curable lacquer type, for example, a one-component lacquer type coating composition.
上記塗料組成物に含まれうる樹脂（ｄ）としては、例えば、アクリル、ポリスチレン、アルキド、エポキシ樹脂、ポリエステル、ポリオレフィン、ポリカーボネート、ポリエチレンカーボネート等、又はこれらの組み合わせが挙げられる。有機無機複合微粒子と樹脂（ｄ）との固形分の質量比は、約０．１：９９．９〜約１００：０の範囲内が好ましく、約０．５：９９．５〜約１００：０の範囲内がより好ましい。上記質量比が約０．１：９９．９よりも小さいと、有機無機複合微粒子による塗膜の物性の改良効果が小さくなる場合がある。 Examples of the resin (d) that can be included in the coating composition include acrylic, polystyrene, alkyd, epoxy resin, polyester, polyolefin, polycarbonate, polyethylene carbonate, and combinations thereof. The mass ratio of the solid content of the organic-inorganic composite fine particles and the resin (d) is preferably in the range of about 0.1: 99.9 to about 100: 0, and about 0.5: 99.5 to about 100: 0. The range of is more preferable. If the mass ratio is less than about 0.1: 99.9, the effect of improving the physical properties of the coating film by the organic / inorganic composite fine particles may be reduced.
上記塗料組成物に含まれうる硬化剤（ｆ）としては、例えば、ポリイソシアネート、ブロックポリイソシアネート、アミノ樹脂、エポキシ樹脂、フェノール樹脂、カルボジイミド基含有化合物、オキサゾリン化合物等、又はこれらの組み合わせを挙げることができる。
上記塗料組成物がエナメル塗料である場合には、上記塗料組成物は、顔料として、塗料分野で既知の着色顔料、光輝性顔料、体質顔料、防錆顔料等を含むことができる。
Examples of the curing agent (f) that can be included in the coating composition include polyisocyanate, block polyisocyanate, amino resin, epoxy resin, phenol resin, carbodiimide group-containing compound, oxazoline compound, and combinations thereof. Can do.
When the coating composition is an enamel coating, the coating composition may contain a color pigment, a luster pigment, an extender pigment, a rust preventive pigment, and the like known in the paint field as a pigment.
本発明の塗料組成物はまた、所望により、有機溶剤、水、硬化触媒、紫外線吸収剤、表面調整剤、流動性調整剤、顔料分散剤等を含むことができる。
上記塗料組成物の用途は、特に限定されるものではなく、上記塗料組成物は、建築用、自動車外板用、自動車部品用、建材用、一般工業用等に用いられうる。
The coating composition of the present invention can also optionally contain an organic solvent, water, a curing catalyst, an ultraviolet absorber, a surface conditioner, a fluidity conditioner, a pigment dispersant and the like.
The use of the coating composition is not particularly limited, and the coating composition can be used for construction, automotive outer panels, automotive parts, building materials, general industrial use, and the like.
本発明の塗料組成物は、例えば、アルミニウム板、鉄鋼板等の金属板、プラスチック等の被塗物素材に直接、又は被塗物素材にプライマーもしくはプライマー／中塗りを施した塗膜面に塗布されうる。また、本発明の塗料組成物が自動車用塗料である場合には、例えば、上塗りエナメル塗料及びクリヤートップコート用塗料であることができる。 The coating composition of the present invention is applied directly to an object material such as a metal plate such as an aluminum plate or an iron and steel plate, plastic, or a coated surface of the material to be coated with a primer or primer / intermediate coating. Can be done. Moreover, when the coating composition of this invention is a coating material for motor vehicles, it can be a top coat enamel coating material and a clear top coat coating material, for example.
本発明の塗料組成物を、被塗物素材に塗布する手段としては、例えば、ロールコーティング、スプレー塗装、刷毛塗り、吹き付け塗り、電着塗装等のそれ自体既知の任意の方法を用いることができる。また、塗布膜厚は、通常、硬化塗膜として約２〜約１００μｍ程度の範囲であり、常温乾燥又は焼付け乾燥により塗膜が形成されうる。塗膜の焼付けは、一般に約４０℃〜約３００℃、好ましくは約６０℃〜約２３０℃の温度で、約２０〜約６００秒間、好ましくは約３０〜約３００秒間行われる。 As a means for applying the coating composition of the present invention to the material to be coated, any known method such as roll coating, spray coating, brush coating, spray coating, electrodeposition coating, etc. can be used. . Further, the coating film thickness is usually in the range of about 2 to about 100 μm as a cured coating film, and the coating film can be formed by room temperature drying or baking drying. The coating is baked generally at a temperature of about 40 ° C. to about 300 ° C., preferably about 60 ° C. to about 230 ° C., for about 20 to about 600 seconds, preferably about 30 to about 300 seconds.
本発明の有機無機複合微粒子の分散体は、リビングポリマー（ａ）と、重合性不飽和基を有する無機微粒子（ｂ）と、所望による不飽和モノマー（ｃ）とを、溶媒の存在下で反応させることにより製造される。上記反応は、リビングポリマー（ａ）の成長末端が、活性な炭素ラジカルの状態で無機微粒子上の重合性不飽和基、又は不飽和モノマー（ｃ）の重合性不飽和基を攻撃し、リビングラジカル重合の反応機構により進行する。この反応機構においては、粒子どうしを結合して粘度が増大するか、又は系がゲル化する反応が起こらないので、低粘度の有機無機複合微粒子の分散体を製造することでき、無機微粒子に結合していない未反応のポリマーの生成がほとんどないので、他の有機材料と混合した場合でも、その特性を損なうことなく、無機微粒子に起因する新しい特性や機能を効率良く発揮することができる。 The dispersion of organic-inorganic composite fine particles of the present invention comprises a reaction between a living polymer (a), inorganic fine particles (b) having a polymerizable unsaturated group, and an unsaturated monomer (c) as desired in the presence of a solvent. Manufactured. In the above reaction, the growth terminal of the living polymer (a) attacks the polymerizable unsaturated group on the inorganic fine particle or the polymerizable unsaturated group of the unsaturated monomer (c) in an active carbon radical state, and the living radical It proceeds by the polymerization reaction mechanism. In this reaction mechanism, the viscosity increases due to the bonding of particles, or the reaction of gelation of the system does not occur, so it is possible to produce a dispersion of low-viscosity organic-inorganic composite fine particles. Since almost no unreacted polymer is produced, even when mixed with other organic materials, new characteristics and functions resulting from the inorganic fine particles can be efficiently exhibited without impairing the characteristics.
以下、実施例及び比較例を挙げて、本発明をより具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。なお、以下、「部」及び「％」は、いずれも質量基準によるものとする。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples. Hereinafter, both “parts” and “%” are based on mass.
［リビングポリマー（ａ）の製造］
［製造例１］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、ＢｌｏｃＢｕｉｌｄｅｒ ＭＡ（アルケマ株式会社製、商品名）７．５部、スチレン５０部、アクリル酸ブチル５０部、及び３−エトキシプロピオン酸エチル２０部を仕込んだ。その後、窒素をフラスコ中に通気させながら１２０℃に加熱し、同温度で８時間攪拌し、リビングポリマー（ａ１）の溶液を得た。リビングポリマー（ａ１）の数平均分子量（Ｍｎ）は５，２００、分子量分布（Ｍｗ／Ｍｎ）は１．３、重合率（％）（注１）は９９％であった。
[Production of Living Polymer (a)]
[Production Example 1]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet, 7.5 parts of BlocBuilder MA (trade name, manufactured by Arkema Co., Ltd.), 50 parts of styrene, 50 parts of butyl acrylate, and 3 -Charged 20 parts of ethyl ethoxypropionate. Thereafter, the mixture was heated to 120 ° C. while allowing nitrogen to pass through the flask and stirred at the same temperature for 8 hours to obtain a living polymer (a1) solution. The number average molecular weight (Mn) of the living polymer (a1) was 5,200, the molecular weight distribution (Mw / Mn) was 1.3, and the polymerization rate (%) (Note 1) was 99%.
（注１）重合率は下記式１により計算した。
重合率（％）
＝１００×（実測された不揮発分（％）／計算された不揮発分（％）） （式１）
式１における「実測された不揮発分（％）」は、重合溶液２．０ｇ〜２．２ｇを秤量し、熱風乾燥機で１３０℃、３時間加熱した後の乾燥残差の質量を、乾燥前の重合溶液の質量に対する百分率で表わしたものである。
(Note 1) The polymerization rate was calculated by the following formula 1.
Polymerization rate (%)
= 100 × (actually measured nonvolatile content (%) / calculated nonvolatile content (%)) (Formula 1)
The “measured non-volatile content (%)” in Equation 1 is obtained by weighing 2.0 g to 2.2 g of the polymerization solution and measuring the mass of the drying residual after heating at 130 ° C. for 3 hours with a hot air drier before drying. It is expressed as a percentage with respect to the mass of the polymerization solution.
式１における「計算された不揮発分（％）」は、下記式２により計算した。
計算された不揮発分（％）
＝１００×（使用した不飽和モノマーの質量＋使用したリビング重合開始剤の質量×リビング重合開始剤の実測された不揮発分（％）÷１００）／（全使用原料の質量） （式２）
式２における「リビング重合開始剤」は、モノマーや溶媒以外のリビング重合を行うため必須の開始剤、連鎖移動剤、停止剤等の成分である。例えば、アルケマ社のＢｌｏｃＢｕｉｌｄｅｒ ＭＡをリビング重合の開始剤として用いた場合、その実測された不揮発分（％）は２０％であったので、その値を、実測された不揮発分として使用した。
“Calculated non-volatile content (%)” in Equation 1 was calculated by Equation 2 below.
Calculated non-volatile content (%)
= 100 × (mass of unsaturated monomer used + mass of living polymerization initiator used × actually measured nonvolatile content of living polymerization initiator (%) ÷ 100) / (mass of all raw materials used) (Formula 2)
The “living polymerization initiator” in Formula 2 is a component such as an initiator, a chain transfer agent, and a terminator essential for performing living polymerization other than the monomer and the solvent. For example, when BlocBuilder MA manufactured by Arkema was used as an initiator for living polymerization, the actually measured non-volatile content (%) was 20%, so that value was used as the actually measured non-volatile content.
［製造例２〜７］
製造例１において、各成分、配合量及び重合時間を表１に記載した各成分、配合量及び重合時間に代えた以外は、製造例１と同様にして、リビングポリマー（ａ２）〜（ａ７）の溶液を得た。
[Production Examples 2 to 7]
In Production Example 1, living polymers (a2) to (a7) were prepared in the same manner as in Production Example 1, except that each component, blending amount and polymerization time were changed to the respective components, blending amount and polymerization time described in Table 1. Solution was obtained.
［製造例８］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、ジベンジルトリチオカーボネート１．０部、２，２’−アゾビスイソブチロニトリル０．０６部、及び３−エトキシプロピオン酸エチル３３部を仕込み、均一に溶解したことを確認した後、窒素雰囲気下で８０℃に昇温し、スチレン５０部、アクリル酸ブチル５０部の混合物を２時間かけて滴下した。次いで、同温度で窒素ガスを通気しながら１０時間攪拌することにより、リビングポリマー（ａ８）の溶液を得た。リビングポリマー（ａ８）の数平均分子量（Ｍｎ）は２５，０００、分子量分布（Ｍｗ／Ｍｎ）は１．６、不揮発分から求めた重合率は９９％であった。
[Production Example 8]
In a four-necked flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen gas inlet, 1.0 part of dibenzyltrithiocarbonate, 0.06 part of 2,2′-azobisisobutyronitrile, and 3 -After charging 33 parts of ethyl ethoxypropionate and confirming that it melt | dissolved uniformly, it heated up at 80 degreeC in nitrogen atmosphere, and the mixture of 50 parts of styrene and 50 parts of butyl acrylate was dripped over 2 hours. Subsequently, it stirred for 10 hours, ventilating nitrogen gas at the same temperature, and the solution of the living polymer (a8) was obtained. The number average molecular weight (Mn) of the living polymer (a8) was 25,000, the molecular weight distribution (Mw / Mn) was 1.6, and the polymerization rate determined from the nonvolatile content was 99%.
［製造例９］
温度計、サーモスタット、撹拌装置、還流冷却器、窒素ガス導入管及び滴下装置を備えた反応容器に、３−エトキシプロピオン酸エチル４５部、及び２，４−ジフェニル−４−メチル−１−ペンテン（以下、「ＭＳＤ」と略称する場合がある）１．５部を仕込み、気相に窒素ガスを通気し、攪拌しながら１６０℃に昇温した。１６０℃に達したら、メタクリル酸メチル５０部、メタクリル酸ブチル５０部及びジ−ｔｅｒｔ−アミルパーオキサイド７部からなる混合液を３時間かけて滴下し、同温度で２時間攪拌した。次いで、３０℃まで冷却し、３−エトキシプロピオン酸エチル１３部で希釈して固形分６５％のリビングポリマーの溶液を得た。リビングポリマー（ａ９）の数平均分子量は４，５００であった。また、プロトンＮＭＲでの解析によるとＭＳＤ由来のエチレン性不飽和基のうち９７％以上がポリマー鎖末端に存在し、２％は消失していた。
[Production Example 9]
In a reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, nitrogen gas introduction tube and dropping device, 45 parts of ethyl 3-ethoxypropionate and 2,4-diphenyl-4-methyl-1-pentene ( Hereinafter, 1.5 parts (which may be abbreviated as “MSD”) were charged, nitrogen gas was passed through the gas phase, and the temperature was raised to 160 ° C. while stirring. When the temperature reached 160 ° C., a mixed solution consisting of 50 parts of methyl methacrylate, 50 parts of butyl methacrylate and 7 parts of di-tert-amyl peroxide was added dropwise over 3 hours and stirred at the same temperature for 2 hours. Subsequently, it was cooled to 30 ° C. and diluted with 13 parts of ethyl 3-ethoxypropionate to obtain a living polymer solution having a solid content of 65%. The number average molecular weight of the living polymer (a9) was 4,500. Moreover, according to the analysis by proton NMR, 97% or more of the ethylenically unsaturated groups derived from MSD were present at the end of the polymer chain, and 2% had disappeared.
なお、上記プロトンＮＭＲでの解析は、溶媒として重クロロホルムを使用し、重合反応前後の、ＭＳＤの不飽和基のプロトンに基づくピーク（４．８ｐｐｍ、５．１ｐｐｍ）、リビングポリマー鎖末端のエチレン性不飽和基のプロトンに基づくピーク（５．０ｐｐｍ、５．２ｐｐｍ）及びＭＳＤに由来する芳香族プロトン（７．２ｐｐｍ）のピークを測定した後、上記ＭＳＤに由来する芳香族プロトン（７．２ｐｐｍ）は重合反応前後で変化しないと仮定し、これを基準として、各不飽和基（未反応、リビングポリマー鎖末端、消失）を定量化することによって行った。 The analysis by proton NMR described above uses deuterated chloroform as a solvent, peaks (4.8 ppm, 5.1 ppm) based on protons of unsaturated groups of MSD before and after the polymerization reaction, ethylenic properties of living polymer chain ends. After measuring the peak of the unsaturated group proton (5.0 ppm, 5.2 ppm) and the peak of the aromatic proton derived from MSD (7.2 ppm), the aromatic proton derived from the MSD (7.2 ppm) Was assumed to be unchanged before and after the polymerization reaction, and based on this, each unsaturated group (unreacted, living polymer chain end, disappearance) was quantified.
［製造例１０〜１５］
表２に示す配合とする以外は、製造例９と同様にして、固形分６５％のリビングポリマー（ａ１０）〜（ａ１５）の溶液を得た。
[Production Examples 10 to 15]
A solution of living polymers (a10) to (a15) having a solid content of 65% was obtained in the same manner as in Production Example 9 except that the formulation shown in Table 2 was used.
［製造例１６］
温度計、サーモスタット、撹拌装置、還流冷却器、窒素ガス導入管及び滴下装置を備えた反応容器に、３−エトキシプロピオン酸エチル４２部を仕込み、液相に窒素ガスを通気し、攪拌しながら１０５℃に昇温した。１０５℃に達したら、メタクリル酸メチル５０部、メタクリル酸ブチル５０部、２，２’−アゾビス（２−メチルブチロニトリル）１．０部、及びビス（ボロンジフルオロジメチルグリオキイシメイト）Ｃｏ（ＩＩ）０．００４部からなる混合液を３時間かけて滴下し、同温度で１時間攪拌した。次いで、３−エトキシプロピオン酸エチル１２部及び２，２’−アゾビス（２−メチルブチロニトリル）０．５部からなる混合液を１時間かけて滴下し、同温度で１時間攪拌し、固形分６５％のリビングポリマー（ａ１６）の溶液を得た。リビングポリマー（ａ１６）の数平均分子量は１，２００であった。
なお、エチレン性不飽和単量体及び溶媒は、いずれも使用前に、それらの中に窒素ガスを少なくとも１時間通気することにより脱気（脱酸素）した。
[Production Example 16]
A reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, nitrogen gas inlet tube and dropping device was charged with 42 parts of ethyl 3-ethoxypropionate, and nitrogen gas was passed through the liquid phase while stirring. The temperature was raised to ° C. When 105 ° C. is reached, 50 parts of methyl methacrylate, 50 parts of butyl methacrylate, 1.0 part of 2,2′-azobis (2-methylbutyronitrile), and bis (borondifluorodimethylglyoxymate) Co (II ) A mixed solution consisting of 0.004 parts was added dropwise over 3 hours and stirred at the same temperature for 1 hour. Next, a mixed solution consisting of 12 parts of ethyl 3-ethoxypropionate and 0.5 part of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 1 hour, stirred at the same temperature for 1 hour, and solid. A solution of living polymer (a16) with a content of 65% was obtained. The number average molecular weight of the living polymer (a16) was 1,200.
The ethylenically unsaturated monomer and the solvent were degassed (deoxygenated) by passing nitrogen gas through them for at least 1 hour before use.
［製造例１７及び１８］
表３に示す配合とする以外は、製造例１６と同様にして合成し、固形分６５％のリビングポリマー（ａ１７）及び（ａ１８）の溶液を得た。
[Production Examples 17 and 18]
The synthesis was performed in the same manner as in Production Example 16 except that the composition shown in Table 3 was obtained, to obtain a solution of living polymers (a17) and (a18) having a solid content of 65%.
［製造例１９］
温度計、サーモスタット、撹拌装置、窒素ガス導入管及び滴下装置を備えた耐圧反応容器に、３−エトキシプロピオン酸エチル４２部を仕込み、気相に窒素ガスを通気し、攪拌しながら１８５℃に昇温した。１８５℃に達したら、メタクリル酸ブチル７０部、アクリル酸ブチル３０部、及びジ−ｔｅｒｔ−アミルパーオキサイド１．０部からなる混合液を２時間かけて滴下し、同温度で１５分間攪拌した。次いで、３−エトキシプロピオン酸エチル１２部及びジ−ｔｅｒｔ−アミルパーオキサイド０．２５部からなる混合液を３０分間かけて滴下し、同温度で３０分間攪拌し、固形分６５％のリビングポリマー（ａ１９）の溶液を得た。リビングポリマー（ａ１９）の数平均分子量は２，６００であった。
[Production Example 19]
A pressure-resistant reaction vessel equipped with a thermometer, thermostat, stirrer, nitrogen gas inlet tube and dropping device was charged with 42 parts of ethyl 3-ethoxypropionate, and nitrogen gas was bubbled into the gas phase, and the temperature was raised to 185 ° C. while stirring. Warm up. When the temperature reached 185 ° C., a mixed solution consisting of 70 parts of butyl methacrylate, 30 parts of butyl acrylate, and 1.0 part of di-tert-amyl peroxide was added dropwise over 2 hours and stirred at the same temperature for 15 minutes. Next, a mixed solution consisting of 12 parts of ethyl 3-ethoxypropionate and 0.25 part of di-tert-amyl peroxide was added dropwise over 30 minutes, stirred at the same temperature for 30 minutes, and a living polymer having a solid content of 65% ( A solution of a19) was obtained. The number average molecular weight of the living polymer (a19) was 2,600.
［製造例２０及び２１］
表４に示す配合とする以外は、製造例１９と同様にして合成し、固形分６５％のリビングポリマー（ａ２０）及び（ａ２１）の溶液を得た。
[Production Examples 20 and 21]
The synthesis was performed in the same manner as in Production Example 19 except that the formulation shown in Table 4 was obtained, to obtain a solution of living polymers (a20) and (a21) having a solid content of 65%.
［製造例２２］
温度計、サーモスタット、撹拌装置、還流冷却器、及び窒素ガス導入管を備えた反応容器に、臭化第一銅１．４部、メタクリル酸メチル５０部、及びアクリル酸ブチル５０部を仕込み、気相に窒素ガスを通気し、攪拌した。その後、２−ブロモプロピオン酸エチル３．６部、及びアセトニトリル８部からなる混合液を加え、７０℃まで昇温し、同温度で３０分間攪拌した。その後、ペンタメチルジエチレントリアミン０．２部を加え、重合を開始した。ペンタメチルジエチレントリアミンを随時加えることで、重合速度を制御しながら、重合率９９％に達したところで３０℃まで冷却し、３−エトキシプロピオン酸エチル４８部で希釈して固形分６５％のリビングポリマー（ａ２２）の溶液を得た。リビングポリマー（ａ２２）の数平均分子量（Ｍｎ）は４，８００、分子量分布は１．３であった。
配合を、表５に示す。
[Production Example 22]
A reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, and nitrogen gas introduction tube was charged with 1.4 parts of cuprous bromide, 50 parts of methyl methacrylate, and 50 parts of butyl acrylate. Nitrogen gas was bubbled through the phase and stirred. Then, the liquid mixture which consists of 3.6 parts of ethyl 2-bromopropionate and 8 parts of acetonitrile was added, and it heated up to 70 degreeC, and stirred for 30 minutes at the same temperature. Thereafter, 0.2 part of pentamethyldiethylenetriamine was added to initiate polymerization. By adding pentamethyldiethylenetriamine as needed, while controlling the polymerization rate, when the polymerization rate reaches 99%, it is cooled to 30 ° C., diluted with 48 parts of ethyl 3-ethoxypropionate and a living polymer (solid content 65%) A solution of a22) was obtained. The number average molecular weight (Mn) of the living polymer (a22) was 4,800, and the molecular weight distribution was 1.3.
The formulation is shown in Table 5.
［製造例２３］
温度計、サーモスタット、撹拌装置、還流冷却器、及び窒素ガス導入管を備えた反応容器に、エチル−２−メチル−２−メチルテラニルプロピオネート５．４部、２，２−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）（和光純薬株式会社製、商品名Ｖ−７０）６．２部、メタクリル酸メチル５０部、及びアクリル酸ブチル５０部を仕込み、気相に窒素ガスを通気しながら４０℃へ昇温し、同温度で５時間攪拌した。次いで、３−エトキシプロピオン酸エチル６０部で希釈して固形分６５％のリビングポリマー（ａ２３）の溶液を得た。リビングポリマー（ａ２３）の数平均分子量（Ｍｎ）は４，７００、分子量分布は１．３で、重合率は９９％であった。
配合を、表６に示す。
[Production Example 23]
In a reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, and nitrogen gas inlet tube, 5.4 parts of ethyl-2-methyl-2-methylterranyl propionate, 2,2-azobis (4 -Methoxy-2,4-dimethylvaleronitrile) (trade name V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 6.2 parts, methyl methacrylate 50 parts, and butyl acrylate 50 parts, and nitrogen gas in the gas phase The temperature was raised to 40 ° C. while aerated, and the mixture was stirred at the same temperature for 5 hours. Subsequently, the solution was diluted with 60 parts of ethyl 3-ethoxypropionate to obtain a living polymer (a23) solution having a solid content of 65%. The number average molecular weight (Mn) of the living polymer (a23) was 4,700, the molecular weight distribution was 1.3, and the polymerization rate was 99%.
The formulation is shown in Table 6.
［重合性不飽和基を有する無機微粒子（ｂ）の製造］
［製造例２４］
還流冷却器、温度計及び攪拌機を取り付けたセパラブルフラスコに、コロイダルシリカ（分散媒；イソプロパノール、シリカ濃度；３０質量％、平均一次粒子径；１２ｎｍ、商品名；ＩＰＡ−ＳＴ、日産化学工業社製）３３３部（シリカ微粒子は１００部）、３−アクリロイルオキシプロピルトリメトキシシラン５部、ｐ−メトキシフェノール０．２部及びイソプロパノール２３３部を配合した後、攪拌しながら昇温した。揮発成分の還流が始まったところで、プロピレングリコールモノメチルエーテルを加えて共沸留出させ、反応系内の溶剤を置換した。
[Production of inorganic fine particles (b) having a polymerizable unsaturated group]
[Production Example 24]
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) ) After mixing 333 parts (silica fine particles 100 parts), 3-acryloyloxypropyltrimethoxysilane 5 parts, p-methoxyphenol 0.2 parts and isopropanol 233 parts, the temperature was increased with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.
続いて、９５℃で２時間攪拌しながら脱水縮合反応を行った後、６０℃に温度を下げてテトラブチルアンモニウムフルオリドを０．０３部加えて更に１時間攪拌しながら反応させた。反応終了後、減圧状態で揮発成分を留出させ、さらにプロピレングリコールモノメチルエーテルを加えて共沸留出させた。プロピレングリコールモノメチルエーテルを加えて共沸留出する操作を数回行うことで溶剤を置換し、重合性不飽和基を有する無機微粒子（ｂ１）の分散体（実測された不揮発分４０％）を得た。 Subsequently, after performing a dehydration condensation reaction with stirring at 95 ° C. for 2 hours, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a dispersion of inorganic fine particles (b1) having a polymerizable unsaturated group (measured nonvolatile content: 40%). It was.
［製造例２５〜３１］
各成分、配合量を、表７に記載した各成分、配合量に代えた以外は、製造例２４と同様にして、重合性不飽和基を有する無機微粒子（ｂ２）〜（ｂ８）の分散体を得た。
[Production Examples 25-31]
Dispersions of inorganic fine particles (b2) to (b8) having polymerizable unsaturated groups in the same manner as in Production Example 24 except that the respective components and blending amounts were changed to the respective components and blending amounts described in Table 7. Got.
（注２）ＩＰＡ−ＳＴ：日産化学工業（株）社製コロイダルシリカ、平均一次粒子径１０〜２０ｎｍ、分散媒、イソプロパノール、シリカ微粒子濃度、３０質量％（日産化学工業のホームページに記載されている説明から抜粋）
（注３）ＩＰＡ−ＳＴ−ＺＬ：日産化学工業（株）社製コロイダルシリカ、平均一次粒子径７０〜１００ｎｍ、分散媒、イソプロパノール、シリカ微粒子濃度、３０質量％（日産化学工業のホームページに記載されている説明から抜粋）
(Note 2) IPA-ST: Colloidal silica manufactured by Nissan Chemical Industries, Ltd., average primary particle size 10-20 nm, dispersion medium, isopropanol, silica fine particle concentration, 30% by mass (described on the website of Nissan Chemical Industries) (Excerpt from explanation)
(Note 3) IPA-ST-ZL: Colloidal silica manufactured by Nissan Chemical Industries, Ltd., average primary particle size 70-100 nm, dispersion medium, isopropanol, silica fine particle concentration, 30% by mass (described on the website of Nissan Chemical Industries) (Excerpt from explanation)
［アクリルポリマーの製造］
［製造例３２］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、３−エトキシプロピオン酸エチル３１部を仕込み、窒素雰囲気下で１２５℃に昇温し、スチレン２０部、アクリル酸イソボロニル２０部、アクリル酸２−エチルヘキシル３０部、アクリル酸２−ヒドロキシエチル３０部、２，２’−アゾビスイソブチロニトリル５部の混合物を４時間かけて滴下した。次いで、１２５℃で窒素ガスを通気しながら３０分間熟成させた後、更に３２部の−エトキシプロピオン酸エチル及び２，２’−アゾビスイソブチロニトリル０．５部の混合物を１時間かけて滴下し、その後１時間熟成させることにより、固形分濃度６０％のアクリルポリマー（ｄ１）の溶液を得た。アクリルポリマー（ｄ１）の重量平均分子量（Ｍｗ）は９，０００であり、分子量分布（Ｍｗ／Ｍｎ）は２．１であり、そして不揮発分から求めた重合率は９９％であった。
[Manufacture of acrylic polymer]
[Production Example 32]
A four-necked flask equipped with a reflux condenser, thermometer, stirrer and nitrogen gas inlet was charged with 31 parts of ethyl 3-ethoxypropionate, heated to 125 ° C. in a nitrogen atmosphere, 20 parts of styrene, acrylic acid A mixture of 20 parts of isobornyl, 30 parts of 2-ethylhexyl acrylate, 30 parts of 2-hydroxyethyl acrylate, and 5 parts of 2,2′-azobisisobutyronitrile was added dropwise over 4 hours. Then, after aging for 30 minutes while bubbling nitrogen gas at 125 ° C., a mixture of 32 parts of ethyl ethoxypropionate and 0.5 part of 2,2′-azobisisobutyronitrile was added over 1 hour. The solution was dropped and then aged for 1 hour to obtain a solution of acrylic polymer (d1) having a solid concentration of 60%. The weight average molecular weight (Mw) of the acrylic polymer (d1) was 9,000, the molecular weight distribution (Mw / Mn) was 2.1, and the polymerization rate determined from the nonvolatile content was 99%.
［有機無機複合微粒子の分散体の製造］
［実施例１］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、製造例１で得られたリビングポリマー（ａ１）の溶液１２８部と、製造例２４で製造された無機微粒子（ｂ１）の分散体２４４部とを仕込んだ。その後、窒素をフラスコ中に通気させながら１２０℃に加熱し、同温度で１０時間攪拌した。その後、３−エトキシプロピオン酸エチルを加え、減圧状態で共沸留出することで溶剤を置換し、有機無機複合微粒子の分散体（ｅ１）（実測された不揮発分４５％）を得た。有機無機複合微粒子の分散体（ｅ１）のガードナー粘度はＡ３であった。
[Production of dispersion of organic-inorganic composite fine particles]
[Example 1]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet, 128 parts of the solution of the living polymer (a1) obtained in Production Example 1 and inorganic fine particles produced in Production Example 24 ( 244 parts of the dispersion of b1) was charged. Thereafter, the mixture was heated to 120 ° C. while allowing nitrogen to pass through the flask, and stirred at the same temperature for 10 hours. Thereafter, ethyl 3-ethoxypropionate was added and the solvent was replaced by azeotropic distillation under reduced pressure to obtain a dispersion (e1) of organic-inorganic composite fine particles (measured nonvolatile content: 45%). The Gardner viscosity of the dispersion (e1) of organic-inorganic composite fine particles was A3.
次いで、有機無機複合微粒子の分散体（ｅ１）に、製造例３２で製造されたアクリルポリマー（ｄ１）の溶液２０６０部と、硬化剤（ｆ）としての、スミジュールＮ−３３００（住化バイエルウレタン社製、ヘキサメチレンジイソシアネート系イソシアヌレート型ポリイソシアネート、固形分１００％、ＮＣＯ含有率２２％）６１３部とを加え、ディスパーで攪拌して混合した。得られた混合物を、ガラス板上にアプリケーターで乾燥膜厚が３０μｍとなる条件で塗装し、熱風乾燥機を用い、１４０℃で３０分間乾燥し、塗膜の透明性及び耐擦り傷性を目視評価した。結果を表８に示す。 Next, 2060 parts of a solution of the acrylic polymer (d1) produced in Production Example 32 and Sumidur N-3300 (Suika Bayer Urethane) as a curing agent (f) were added to the dispersion of organic-inorganic composite fine particles (e1). And 613 parts of hexamethylene diisocyanate-based isocyanurate type polyisocyanate, solid content 100%, NCO content 22%), and stirred and mixed with a disper. The obtained mixture was coated on a glass plate with an applicator under a condition that the dry film thickness was 30 μm, and dried at 140 ° C. for 30 minutes using a hot air dryer, and the transparency and scratch resistance of the coating film were visually evaluated. did. The results are shown in Table 8.
［実施例２〜１７］
各成分及び配合量を、表８に記載した各成分及び配合量に代えた以外は、実施例１と同様にして、有機無機複合微粒子の分散体（ｅ２）〜（ｅ１７）を得た。それらのガードナー粘度を、表８に示す。また、実施例１と同様にして塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を、表８に示す。
[Examples 2 to 17]
Dispersions (e2) to (e17) of organic-inorganic composite fine particles were obtained in the same manner as in Example 1 except that the respective components and blending amounts were changed to the respective components and blending amounts described in Table 8. Their Gardner viscosities are shown in Table 8. Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 8.
［実施例１８］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、製造例３で得られたリビングポリマー（ａ３）の溶液６７．５部、製造例２４で製造された無機微粒子（ｂ１）の分散体２４４部、スチレン２５部、及びアクリル酸ブチル２５部を仕込んだ。その後、窒素をフラスコ中に通気させながら１２０℃に加熱し、同温度で１４時間攪拌した。その後、３−エトキシプロピオン酸エチルを加え、減圧状態で共沸留出することで溶剤を置換し、有機無機複合微粒子の分散体（ｅ１８）（実測された不揮発分４５％）を得た。有機無機複合微粒子の分散体（ｅ１８）のガードナー粘度はＡ２であった。
[Example 18]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet, 67.5 parts of a solution of the living polymer (a3) obtained in Production Example 3 and inorganic fine particles produced in Production Example 24 244 parts of the dispersion of (b1), 25 parts of styrene, and 25 parts of butyl acrylate were charged. Thereafter, the mixture was heated to 120 ° C. while bubbling nitrogen through the flask, and stirred at the same temperature for 14 hours. Thereafter, ethyl 3-ethoxypropionate was added, and the solvent was replaced by azeotropic distillation under reduced pressure to obtain a dispersion (e18) of organic-inorganic composite fine particles (measured nonvolatile content: 45%). The dispersion of organic-inorganic composite fine particles (e18) had a Gardner viscosity of A2.
次いで、有機無機複合微粒子の分散体（ｅ１８）に、製造例３２で製造されたアクリルポリマー（ｄ１）の溶液２０６０部と、硬化剤（ｆ）としての、スミジュールＮ−３３００（住化バイエルウレタン社製、ヘキサメチレンジイソシアネート系イソシアヌレート型ポリイソシアネート、固形分１００％、ＮＣＯ含有率２２％）６１３部とを加え、ディスパーで攪拌して混合した。得られた混合物から、実施例１と同様にして塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表８に示す。 Next, 2060 parts of a solution of the acrylic polymer (d1) produced in Production Example 32 and Sumidur N-3300 (Suika Bayer Urethane) as the curing agent (f) were added to the dispersion of organic-inorganic composite fine particles (e18). And 613 parts of hexamethylene diisocyanate-based isocyanurate type polyisocyanate, solid content 100%, NCO content 22%), and stirred and mixed with a disper. A coating film was formed from the obtained mixture in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 8.
［実施例１９］
各成分及び配合量を表８に記載した各成分及び配合量に代えた以外は、実施例１８と同様にして、有機無機複合微粒子の分散体（ｅ１９）を得た。有機無機複合微粒子の分散体（ｅ１９）のガードナー粘度を表８に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を、表８に示す。
[Example 19]
A dispersion (e19) of organic-inorganic composite fine particles was obtained in the same manner as in Example 18 except that the respective components and blending amounts were changed to the respective components and blending amounts shown in Table 8. Table 8 shows the Gardner viscosity of the organic-inorganic composite fine particle dispersion (e19). Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 8.
［比較例１］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、製造例２４で製造された無機微粒子の（ｂ１）分散体２４４部、スチレン５０部、アクリル酸ブチル５０部、３−エトキシプロピオン酸エチル２０部、及び過酸化ベンゾイル２．０部を仕込んだ。その後、窒素をフラスコ中に通気させながら１２０℃に加熱し、同温度で１０時間攪拌した。不揮発分から求めた重合率は９９％であった。その後、３−エトキシプロピオン酸エチルを加え、減圧状態で共沸留出することで溶剤を置換し、有機無機複合微粒子の分散体（ｅ２０）（実測された不揮発分４５％）を得た。有機無機複合微粒子の分散体（ｅ２０）のガードナー粘度を、表８に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を、表８に示す。
[Comparative Example 1]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a nitrogen gas inlet, (b1) 244 parts of a dispersion of inorganic fine particles produced in Production Example 24, 50 parts of styrene, 50 parts of butyl acrylate, 20 parts of ethyl 3-ethoxypropionate and 2.0 parts of benzoyl peroxide were charged. Thereafter, the mixture was heated to 120 ° C. while allowing nitrogen to pass through the flask, and stirred at the same temperature for 10 hours. The polymerization rate determined from the nonvolatile content was 99%. Thereafter, ethyl 3-ethoxypropionate was added, and the solvent was replaced by azeotropic distillation under reduced pressure to obtain a dispersion (e20) of organic-inorganic composite fine particles (measured nonvolatile content: 45%). Table 8 shows the Gardner viscosity of the organic-inorganic composite fine particle dispersion (e20). Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 8.
［比較例２］
過酸化ベンゾイル配合量を１．０部に減らした以外は、比較例１と同様に、有機無機複合微粒子の分散体（ｅ２１）（実測された不揮発分４５％）を得た。不揮発分から求めた重合率は９９％であった。しかし、有機無機複合微粒子の分散体（ｅ２１）は、ゲル状であり、粘度を測定することができなかった。また、有機無機複合微粒子の分散体（ｅ２１）は、アクリルポリマー（ｄ１）及び硬化剤（ｆ）と混合しなかったので、塗膜の透明性及び耐擦り傷性を評価することができなかった。
[Comparative Example 2]
A dispersion (e21) of organic-inorganic composite fine particles (measured nonvolatile content of 45%) was obtained in the same manner as in Comparative Example 1 except that the amount of benzoyl peroxide was reduced to 1.0 part. The polymerization rate determined from the nonvolatile content was 99%. However, the dispersion (e21) of organic-inorganic composite fine particles was in a gel form, and the viscosity could not be measured. Moreover, since the dispersion (e21) of organic-inorganic composite fine particles was not mixed with the acrylic polymer (d1) and the curing agent (f), the transparency and scratch resistance of the coating film could not be evaluated.
［比較例３］
重合性不飽和基を有する無機微粒子（ｂ１）の分散体を、重合性不飽和基を有する無機微粒子（ｂ３）の分散体に変更した以外は、比較例１と同様に、有機無機複合微粒子の分散体（ｅ２２）（実測された不揮発分４５％）を得た。不揮発分から求めた重合率は９９％であった。得られた有機無機複合微粒子の分散体（ｅ２２）のガードナー粘度を、表８に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表８に示す。
[Comparative Example 3]
Similar to Comparative Example 1, the dispersion of the inorganic fine particles (b1) having a polymerizable unsaturated group was changed to a dispersion of inorganic fine particles (b3) having a polymerizable unsaturated group. Dispersion (e22) (actually measured non-volatile content 45%) was obtained. The polymerization rate determined from the nonvolatile content was 99%. Table 8 shows the Gardner viscosity of the obtained dispersion (e22) of organic-inorganic composite fine particles. Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 8.
［比較例４］
重合性不飽和基を有する無機微粒子（ｂ１）の分散体を、重合性不飽和基を有する無機微粒子（ｂ３）の分散体に変更し、スチレン１２．５部、アクリル酸ブチル１２．５部、３−エトキシプロピオン酸エチル５部、及び過酸化ベンゾイル０．５部を仕込んだ以外は、比較例１と同様にして、有機無機複合微粒子の分散体（ｅ２３）（実測された不揮発分４５％）を得た。不揮発分から求めた重合率は９９％であった。有機無機複合微粒子の分散体（ｅ２３）のガードナー粘度を、表８に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表８に示す。
[Comparative Example 4]
The dispersion of inorganic fine particles (b1) having a polymerizable unsaturated group was changed to a dispersion of inorganic fine particles (b3) having a polymerizable unsaturated group, and 12.5 parts of styrene, 12.5 parts of butyl acrylate, Dispersion of organic-inorganic composite fine particles (e23) (45% of measured non-volatile content) in the same manner as in Comparative Example 1 except that 5 parts of ethyl 3-ethoxypropionate and 0.5 parts of benzoyl peroxide were charged. Got. The polymerization rate determined from the nonvolatile content was 99%. Table 8 shows the Gardner viscosity of the organic-inorganic composite fine particle dispersion (e23). Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 8.
［比較例５］
製造例３２で製造されたアクリルポリマー（ｄ１）の溶液２０６０部と、硬化剤（ｆ）としての、スミジュールＮ−３３００（住化バイエルウレタン社製、ヘキサメチレンジイソシアネート系イソシアヌレート型ポリイソシアネート、固形分１００％、ＮＣＯ含有率２２％）６１３部とをディスパーで攪拌した。得られた混合物から、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表８に示す。
[Comparative Example 5]
2060 parts of a solution of the acrylic polymer (d1) produced in Production Example 32 and Sumijour N-3300 (manufactured by Sumika Bayer Urethane Co., Ltd., hexamethylene diisocyanate isocyanurate type polyisocyanate, solid as a curing agent (f) Min. 100%, NCO content 22%) and 613 parts. From the obtained mixture, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 8.
［試験方法］
塗膜の透明性：塗膜の透明性を、下記基準により評価した。
◎：濁り無く透明である、
○：わずかに白く濁りが認められるが、透明性がある（向こう側を透かして見ることができる）、
△：白く濁りが認められるが、透明性がある（向こう側を透かして見ることができる）、
×：白濁著しく、透明性がない（向こう側を透かして見ることができない）。
[Test method]
Transparency of coating film: The transparency of the coating film was evaluated according to the following criteria.
A: Transparent without turbidity,
○: Slightly white and cloudy, but transparent (can see through the other side)
Δ: White and cloudy are recognized, but transparent (the other side can be seen through)
X: Extremely cloudy and not transparent (cannot see through the other side).
耐擦り傷性：染色物摩擦堅牢度試験機（大栄化学精器製作所製）を用いて評価した。磨き粉（ダルマ・クレンザー）を水で固練りして試験塗板の塗面に置き、その上を、５００ｇの加重を有する試験機端子で押さえて、２５往復させ、水洗した後、塗面を目視観察し、擦り傷の程度を下記基準にて評価した。
◎：擦り傷が全く又はほとんど観察されない（合格）、
○：少し擦り傷がみられるが、その程度は軽い（合格）、
△：擦り傷が目立つ（不合格）、
×：はっきりと著しい擦り傷が判る（不合格）。
Scratch resistance: Evaluated by using a dyeing friction fastness tester (manufactured by Daiei Chemical Seiki Seisakusho). The polishing powder (Dalma Cleanser) is kneaded with water and placed on the coating surface of the test coating plate, and it is pressed with a test machine terminal having a load of 500 g, reciprocated 25 times, washed with water, and the coating surface is visually observed. The degree of abrasion was evaluated according to the following criteria.
A: No or almost no scratches are observed (pass),
○: Some scratches are seen, but the degree is light (pass),
Δ: Scratches are conspicuous (failed),
X: A clear remarkable scratch is recognized (failed).
［実施例２０］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、製造例９で得られたリビングポリマー（ａ９）の溶液１３６部、製造例２４で製造された重合性不飽和基を有する無機微粒子（ｂ１）の分散体２４４部、及び２，２’−アゾビス（２−メチルブチロニトリル）２．０部を仕込んだ。その後、窒素をフラスコ中に通気させながら１２０℃に加熱し、同温度で１０時間攪拌した。その後、３−エトキシプロピオン酸エチルを加え、減圧状態で共沸留出することで溶剤を置換し、有機無機複合微粒子の分散体（ｅ２４）（実測された不揮発分４５％）を得た。有機無機複合微粒子の分散体（ｅ２４）のガードナー粘度はＡ３であった。
[Example 20]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet, 136 parts of the solution of the living polymer (a9) obtained in Production Example 9 and the polymerizable unsaturated produced in Production Example 24 244 parts of a dispersion of inorganic fine particles (b1) having a group and 2.0 parts of 2,2′-azobis (2-methylbutyronitrile) were charged. Thereafter, the mixture was heated to 120 ° C. while allowing nitrogen to pass through the flask, and stirred at the same temperature for 10 hours. Thereafter, ethyl 3-ethoxypropionate was added, and the solvent was replaced by azeotropic distillation under reduced pressure to obtain a dispersion (e24) of organic-inorganic composite fine particles (measured nonvolatile content: 45%). The Gardner viscosity of the dispersion (e24) of organic-inorganic composite fine particles was A3.
次いで、有機無機複合微粒子の分散体（ｅ２４）に、製造例３２で製造されたアクリルポリマー（ｄ１）の溶液２０６０部と、硬化剤（ｆ）としての、スミジュールＮ−３３００（住化バイエルウレタン社製、ヘキサメチレンジイソシアネート系イソシアヌレート型ポリイソシアネート、固形分１００％、ＮＣＯ含有率２２％）６１３部とを加え、ディスパーで攪拌して混合した。得られた混合物から、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。 Next, 2060 parts of a solution of the acrylic polymer (d1) produced in Production Example 32 and Sumidur N-3300 (Suika Bayer Urethane) as the curing agent (f) were added to the dispersion of organic-inorganic composite fine particles (e24). And 613 parts of hexamethylene diisocyanate-based isocyanurate type polyisocyanate, solid content 100%, NCO content 22%), and stirred and mixed with a disper. From the obtained mixture, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
［実施例２１〜４０］
各成分及び配合量を表９に記載される各成分及び配合量に代えた以外は、実施例２０と同様にして、有機無機複合微粒子の分散体（ｅ２５）〜（ｅ４４）を得た。それらのガードナー粘度を表９に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。
[Examples 21 to 40]
Dispersions (e25) to (e44) of organic-inorganic composite fine particles were obtained in the same manner as in Example 20 except that the respective components and blending amounts were changed to the respective components and blending amounts described in Table 9. Their Gardner viscosities are shown in Table 9. Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
［実施例４１］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、製造例１１で得たリビングポリマー（ａ１１）の溶液６９部、製造例２４で製造された重合性不飽和基を有する無機微粒子（ｂ１）の分散体２４４部、メタクリル酸メチル２５部、メタクリル酸ブチル２５部、及び２，２’−アゾビス（２−メチルブチロニトリル）２．０部を仕込んだ。その後、窒素をフラスコ中に通気させながら１２０℃に加熱し、同温度で１４時間攪拌した。不揮発分から求めた重合率は９９％であった。その後、３−エトキシプロピオン酸エチルを加え、減圧状態で共沸留出することで溶剤を置換し、有機無機複合微粒子の分散体（ｅ４５）（実測された不揮発分４５％）を得た。有機無機複合微粒子の分散体（ｅ４５）のガードナー粘度はＡ２であった。
[Example 41]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet, 69 parts of the solution of the living polymer (a11) obtained in Production Example 11 and the polymerizable unsaturated group produced in Production Example 24 244 parts of a dispersion of inorganic fine particles (b1) having, 25 parts of methyl methacrylate, 25 parts of butyl methacrylate, and 2.0 parts of 2,2′-azobis (2-methylbutyronitrile) were charged. Thereafter, the mixture was heated to 120 ° C. while bubbling nitrogen through the flask, and stirred at the same temperature for 14 hours. The polymerization rate determined from the nonvolatile content was 99%. Thereafter, ethyl 3-ethoxypropionate was added, and the solvent was replaced by azeotropic distillation under reduced pressure to obtain a dispersion (e45) of organic-inorganic composite fine particles (measured nonvolatile content: 45%). The Gardner viscosity of the dispersion (e45) of organic-inorganic composite fine particles was A2.
次いで、有機無機複合微粒子の分散体（ｅ４５）に、製造例３２で製造されたアクリルポリマー（ｄ１）の溶液２０６０部と、硬化剤（ｆ）としての、スミジュールＮ−３３００（住化バイエルウレタン社製、ヘキサメチレンジイソシアネート系イソシアヌレート型ポリイソシアネート、固形分１００％、ＮＣＯ含有率２２％）６１３部とを加え、ディスパーで攪拌して混合した。得られた混合物から、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。 Next, 2060 parts of a solution of the acrylic polymer (d1) produced in Production Example 32 and Sumidur N-3300 (Suika Bayer Urethane) as the curing agent (f) were added to the dispersion of organic-inorganic composite fine particles (e45). And 613 parts of hexamethylene diisocyanate-based isocyanurate type polyisocyanate, solid content 100%, NCO content 22%), and stirred and mixed with a disper. From the obtained mixture, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
［実施例４２］
各成分及び配合量を表９に記載した各成分及び配合量に代えた以外は、実施例４１と同様にして、有機無機複合微粒子の分散体（ｅ４６）を得た。不揮発分から求めた重合率は９９％であった。そのガードナー粘度を表９に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。
[Example 42]
A dispersion (e46) of organic-inorganic composite fine particles was obtained in the same manner as in Example 41 except that the respective components and blending amounts were changed to the respective components and blending amounts shown in Table 9. The polymerization rate determined from the nonvolatile content was 99%. The Gardner viscosity is shown in Table 9. Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
（実施例４３）
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、製造例２２で得たリビングポリマー（ａ２２）の溶液１５４部、及び製造例２４で製造された重合性不飽和基を有する無機微粒子（ｂ１）の分散体２４４部を仕込んだ。その後、窒素をフラスコ中に通気させながら７０℃に加熱し、その後、ペンタメチルジエチレントリアミンを随時加えることで、重合速度（付加反応速度）を制御しながら、同温度で１０時間攪拌した。その後、３−エトキシプロピオン酸エチルを加え、減圧状態で共沸留出することで溶剤を置換し、有機無機複合微粒子の分散体（ｅ４７）（実測された不揮発分４５％）を得た。有機無機複合微粒子の分散体（ｅ４７）のガードナー粘度はＡ３であった。
(Example 43)
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a nitrogen gas inlet, 154 parts of the solution of the living polymer (a22) obtained in Production Example 22 and the polymerizable unsaturated produced in Production Example 24 244 parts of a dispersion of inorganic fine particles (b1) having a group were charged. Thereafter, the mixture was heated to 70 ° C. while bubbling nitrogen through the flask, and then stirred at the same temperature for 10 hours while controlling the polymerization rate (addition reaction rate) by adding pentamethyldiethylenetriamine as needed. Thereafter, ethyl 3-ethoxypropionate was added, and the solvent was replaced by azeotropic distillation under reduced pressure to obtain a dispersion (e47) of organic-inorganic composite fine particles (measured nonvolatile content: 45%). The dispersion of organic-inorganic composite fine particles (e47) had a Gardner viscosity of A3.
次いで、有機無機複合微粒子の分散体（ｅ４７）に、製造例３２で製造されたアクリルポリマー（ｄ１）の溶液２０６０部と、硬化剤（ｆ）としての、スミジュールＮ−３３００（住化バイエルウレタン社製、ヘキサメチレンジイソシアネート系イソシアヌレート型ポリイソシアネート、固形分１００％、ＮＣＯ含有率２２％）６１３部とを加え、ディスパーで攪拌して混合した。得られた混合物から、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。 Next, 2060 parts of the solution of the acrylic polymer (d1) produced in Production Example 32 and Sumidur N-3300 (Suika Bayer Urethane) as the curing agent (f) were added to the dispersion of organic-inorganic composite fine particles (e47). And 613 parts of hexamethylene diisocyanate-based isocyanurate type polyisocyanate, solid content 100%, NCO content 22%), and stirred and mixed with a disper. From the obtained mixture, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
［実施例４４］
リビングポリマー（ａ２２）の溶液を、リビングポリマー（ａ２３）の溶液に変更し、さらに反応温度を４０℃とした以外は、実施例４３と同様にして、有機無機複合微粒子の分散体（ｅ４８）を得た。有機無機複合微粒子の分散体（ｅ４８）のガードナー粘度を、表９に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。
[Example 44]
The organic-inorganic composite fine particle dispersion (e48) was changed in the same manner as in Example 43 except that the living polymer (a22) solution was changed to the living polymer (a23) solution and the reaction temperature was 40 ° C. Obtained. Table 9 shows the Gardner viscosity of the organic-inorganic composite fine particle dispersion (e48). Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
［比較例６］
還流冷却器、温度計、攪拌機及び窒素ガス導入口を備えた四ツ口フラスコに、製造例２４で製造された無機微粒子（ｂ１）の分散体２４４部、メタクリル酸メチル５０部、メタクリル酸ブチル５０部、３−エトキシプロピオン酸エチル２０部、及び過酸化ベンゾイル２．０部を仕込んだ。その後、窒素をフラスコ中に通気させながら１２０℃に加熱し、同温度で１０時間攪拌した。不揮発分から求めた重合率は９９％であった。その後、３−エトキシプロピオン酸エチルを加え、減圧状態で共沸留出することで溶剤を置換し、有機無機複合微粒子の分散体（ｅ４９）（実測された不揮発分４５％）を得た。有機無機複合微粒子の分散体（ｅ４９）のガードナー粘度を表９に示す。また、実施例１と同様に塗膜枝を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。
[Comparative Example 6]
In a four-necked flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen gas inlet, 244 parts of a dispersion of inorganic fine particles (b1) produced in Production Example 24, 50 parts of methyl methacrylate, 50 of butyl methacrylate Part, 20 parts ethyl 3-ethoxypropionate, and 2.0 parts benzoyl peroxide. Thereafter, the mixture was heated to 120 ° C. while allowing nitrogen to pass through the flask, and stirred at the same temperature for 10 hours. The polymerization rate determined from the nonvolatile content was 99%. Thereafter, ethyl 3-ethoxypropionate was added and the solvent was replaced by azeotropic distillation under reduced pressure to obtain a dispersion (e49) of organic-inorganic composite fine particles (measured nonvolatile content: 45%). Table 9 shows the Gardner viscosity of the organic-inorganic composite fine particle dispersion (e49). Further, a coating film branch was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
［比較例７］
過酸化ベンゾイル配合量を１．０部に減らした以外は、比較例６と同様にして、有機無機複合微粒子の分散体（ｅ５０）（実測された不揮発分４５％）を得た。不揮発分から求めた重合率は９９％であった。しかしながら、有機無機複合微粒子の分散体（ｅ５０）は、ゲル状のため、粘度を測定することができなかった。また、有機無機複合微粒子の分散体（ｅ５０）は、アクリルポリマー（ｄ１）及び硬化剤（ｆ）と混合しなかったので、塗膜の透明性及び耐擦り傷性を評価することができなかった。
[Comparative Example 7]
A dispersion (e50) of organic-inorganic composite fine particles (measured nonvolatile content of 45%) was obtained in the same manner as in Comparative Example 6 except that the amount of benzoyl peroxide was reduced to 1.0 part. The polymerization rate determined from the nonvolatile content was 99%. However, since the dispersion (e50) of the organic / inorganic composite fine particles was in a gel state, the viscosity could not be measured. Further, since the dispersion (e50) of the organic / inorganic composite fine particles was not mixed with the acrylic polymer (d1) and the curing agent (f), the transparency and scratch resistance of the coating film could not be evaluated.
［比較例８］
重合性不飽和基を有する無機微粒子（ｂ１）の分散体を、重合性不飽和基を有する無機微粒子（ｂ３）の分散体に変更した以外は、比較例６と同様にして、有機無機複合微粒子の分散体（ｅ５１）（実測された不揮発分４５％）を得た。不揮発分から求めた重合率は９９％であった。有機無機複合微粒子の分散体（ｅ５１）のガードナー粘度を表９に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。
[Comparative Example 8]
Organic-inorganic composite fine particles were prepared in the same manner as in Comparative Example 6 except that the dispersion of the inorganic fine particles (b1) having a polymerizable unsaturated group was changed to a dispersion of inorganic fine particles (b3) having a polymerizable unsaturated group. A dispersion (e51) of (measured nonvolatile content: 45%) was obtained. The polymerization rate determined from the nonvolatile content was 99%. Table 9 shows the Gardner viscosity of the organic-inorganic composite fine particle dispersion (e51). Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
［比較例９］
重合性不飽和基を有する無機微粒子（ｂ１）の分散体を、重合性不飽和基を有する無機微粒子（ｂ３）の分散体に変更し、メタクリル酸メチル１２．５部、メタクリル酸ブチル１２．５部、３−エトキシプロピオン酸エチル５部、及び過酸化ベンゾイル０．５部を仕込んだ以外は、比較例６と同様にして、有機無機複合微粒子の分散体（ｅ５２）（実測された不揮発分４５％）を得た。不揮発分から求めた重合率は９９％であった。有機無機複合微粒子の分散体（ｅ５２）のガードナー粘度を表９に示す。また、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。
[Comparative Example 9]
The dispersion of inorganic fine particles (b1) having a polymerizable unsaturated group was changed to a dispersion of inorganic fine particles (b3) having a polymerizable unsaturated group, and 12.5 parts of methyl methacrylate and 12.5 of butyl methacrylate were obtained. In the same manner as in Comparative Example 6 except that 5 parts of ethyl 3-ethoxypropionate and 0.5 part of benzoyl peroxide were charged, a dispersion of organic-inorganic composite fine particles (e52) (measured nonvolatile content 45 %). The polymerization rate determined from the nonvolatile content was 99%. Table 9 shows the Gardner viscosity of the organic-inorganic composite fine particle dispersion (e52). Further, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
［比較例１０］
製造例３２で製造されたアクリルポリマー（ｄ１）の溶液２０６０部と、硬化剤（ｆ）としての、スミジュールＮ−３３００（住化バイエルウレタン社製、ヘキサメチレンジイソシアネート系イソシアヌレート型ポリイソシアネート、固形分１００％、ＮＣＯ含有率２２％）６１３部とをディスパーで攪拌した。得られた混合物から、実施例１と同様に塗膜を形成し、その透明性及び耐擦り傷性を目視評価した。結果を表９に示す。
[Comparative Example 10]
2060 parts of a solution of the acrylic polymer (d1) produced in Production Example 32 and Sumijour N-3300 (manufactured by Sumika Bayer Urethane Co., Ltd., hexamethylene diisocyanate isocyanurate type polyisocyanate, solid as a curing agent (f) Min. 100%, NCO content 22%) and 613 parts. From the obtained mixture, a coating film was formed in the same manner as in Example 1, and the transparency and scratch resistance were visually evaluated. The results are shown in Table 9.
Claims (6)
重合性不飽和基を有する無機微粒子（ｂ）が、無機微粒子と、加水分解性シリル基を有するモノマーとを反応させることにより得られ、前記無機微粒子が、粒子表面に、水酸基及び／又はアルコキシ基を有し、前記加水分解性シリル基を有するモノマーが、前記重合性不飽和基を有する、
ことを特徴とする、前記有機無機複合微粒子の分散体。 Inorganic fine particles produced by reacting living polymer (a) with inorganic fine particles (b) having a polymerizable unsaturated group in the presence of a solvent, or having living polymer (a) and a polymerizable unsaturated group A dispersion of organic-inorganic composite fine particles produced by reacting (b) and an unsaturated monomer (c) in the presence of a solvent,
The inorganic fine particle (b) having a polymerizable unsaturated group is obtained by reacting an inorganic fine particle with a monomer having a hydrolyzable silyl group, and the inorganic fine particle has a hydroxyl group and / or an alkoxy group on the particle surface. And the monomer having the hydrolyzable silyl group has the polymerizable unsaturated group ,
A dispersion of the organic-inorganic composite fine particles.
無機微粒子と、加水分解性シリル基を有するモノマーとを反応させることにより、重合性不飽和基を有する無機微粒子（ｂ）を得る工程、ここで、前記無機微粒子が、粒子表面に、水酸基及び／又はアルコキシ基を有し、前記加水分解性シリル基を有するモノマーが、前記重合性不飽和基を有する、及び
リビングポリマー（ａ）と重合性不飽和基を有する無機微粒子（ｂ）とを、溶媒の存在下で反応させる工程、又はリビングポリマー（ａ）と重合性不飽和基を有する無機微粒子（ｂ）と不飽和モノマー（ｃ）とを、溶媒の存在下で反応させる工程、
を含む、前記製造方法。 A method for producing a dispersion of organic-inorganic composite fine particles,
A step of obtaining inorganic fine particles (b) having a polymerizable unsaturated group by reacting inorganic fine particles with a monomer having a hydrolyzable silyl group , wherein the inorganic fine particles are formed on the particle surface with hydroxyl groups and / or Alternatively, the monomer having an alkoxy group and the hydrolyzable silyl group has the polymerizable unsaturated group , and the living polymer (a) and the inorganic fine particles (b) having the polymerizable unsaturated group are used as a solvent. Or a step of reacting the living polymer (a) with inorganic fine particles (b) having a polymerizable unsaturated group and an unsaturated monomer (c) in the presence of a solvent,
The said manufacturing method including.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010230461A JP5656546B2 (en) | 2010-06-10 | 2010-10-13 | Organic-inorganic composite fine particles, dispersion thereof, method for producing the dispersion, and coating composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010133432 | 2010-06-10 | ||
| JP2010133432 | 2010-06-10 | ||
| JP2010230461A JP5656546B2 (en) | 2010-06-10 | 2010-10-13 | Organic-inorganic composite fine particles, dispersion thereof, method for producing the dispersion, and coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012017446A JP2012017446A (en) | 2012-01-26 |
| JP5656546B2 true JP5656546B2 (en) | 2015-01-21 |
Family
ID=45602924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010230461A Active JP5656546B2 (en) | 2010-06-10 | 2010-10-13 | Organic-inorganic composite fine particles, dispersion thereof, method for producing the dispersion, and coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5656546B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5473874B2 (en) * | 2010-11-22 | 2014-04-16 | 関西ペイント株式会社 | Active energy ray-curable composition and method for producing the composition |
| JP5762212B2 (en) * | 2011-08-11 | 2015-08-12 | 関西ペイント株式会社 | Active energy ray-curable composition and method for producing the composition |
| JP7005907B2 (en) * | 2017-02-23 | 2022-02-10 | 三菱ケミカル株式会社 | Curable composition and membrane |
| JP2020105370A (en) * | 2018-12-27 | 2020-07-09 | 日本ペイント・オートモーティブコーティングス株式会社 | Clear coating composition and film formation method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69006472T2 (en) * | 1989-12-21 | 1994-09-01 | Minnesota Mining & Mfg | Dental compositions, processes for the production of molded dental articles via "photo-inferred polymerization" of dental compositions and molded dental articles produced thereby. |
| JP4046451B2 (en) * | 1999-02-04 | 2008-02-13 | 水谷ペイント株式会社 | Aqueous dispersion, method for producing the same, and coating composition |
| JP2004002559A (en) * | 2002-05-31 | 2004-01-08 | Asahi Kasei Corp | Inorganic substance-containing resin composition |
| JP2006219657A (en) * | 2005-01-13 | 2006-08-24 | Mitsubishi Rayon Co Ltd | Actinic-radiation-curing composition |
| JP5093656B2 (en) * | 2007-09-03 | 2012-12-12 | 国立大学法人京都大学 | Polymer solid electrolyte using ionic liquid polymer composite fine particles |
| US20110006245A1 (en) * | 2007-12-04 | 2011-01-13 | Hiroshi Handa | Polymer coated inorganic fine particle and method for preparing the same |
| JP5251324B2 (en) * | 2008-07-15 | 2013-07-31 | 東亞合成株式会社 | Liquid developer for electrostatic photography |
-
2010
- 2010-10-13 JP JP2010230461A patent/JP5656546B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012017446A (en) | 2012-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7407707B2 (en) | Radiation-curable coatings for metal substrates from multifunctional acrylate oligomers | |
| AU2005241027B2 (en) | Radiation-curable coatings for plastic susbtrates from multifunctional acrylate oligomers | |
| WO1997011129A1 (en) | Coating composition forming wear-resistant coat and article covered with the coat | |
| US20150024227A1 (en) | Block copolymer, process and composition | |
| JP5635778B2 (en) | Emulsion resin paint | |
| JP5656546B2 (en) | Organic-inorganic composite fine particles, dispersion thereof, method for producing the dispersion, and coating composition | |
| US6362301B1 (en) | Curable composition | |
| JP5762212B2 (en) | Active energy ray-curable composition and method for producing the composition | |
| DE60317103T2 (en) | MOISTURE-CURING, ISOCYANATE GROUPS-FREE ACRYLIC COATINGS | |
| JP5473874B2 (en) | Active energy ray-curable composition and method for producing the composition | |
| JP3765343B2 (en) | Non-aqueous dispersion type resin composition and curable coating | |
| JP4537552B2 (en) | (Meth) acrylic ester resin composition | |
| JP4673010B2 (en) | Curable water-based resin composition | |
| JPH0269507A (en) | Dispersing unit composition for ambient temperature curing type coating | |
| JP5635798B2 (en) | Emulsion resin paint | |
| JP2003119338A (en) | Curable resin composition | |
| JPS6067573A (en) | Cold-curing coating resin composition giving cured coating film having excellent appearance | |
| JP4058734B2 (en) | Oxidation-curing silicone-modified vinyl copolymer, one-component paint using the same, and method for producing oxidation-curing silicone-modified vinyl copolymer | |
| JP3446903B2 (en) | Curable composition | |
| JP2005171028A (en) | Dispersant containing ultraviolet-absorbing copolymer | |
| JPH05247402A (en) | Coating material for plastic member of automobile | |
| JP2017226751A (en) | Photosetting antiglare resin for metal | |
| Balgeman | Reversible Addition-Fragmentation Chain-Transfer Emulsion Polymerization and its Application to Waterborne Coatings | |
| WO2023013593A1 (en) | Aqueous resin composition, coating film, and article with coating film | |
| JPH04325579A (en) | Coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130524 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131031 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131112 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140110 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140603 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140728 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141028 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141125 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5656546 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |