KR20240127339A - Dispersants, compositions, dispersions, articles and copolymers for fluororesins - Google Patents
Dispersants, compositions, dispersions, articles and copolymers for fluororesins Download PDFInfo
- Publication number
- KR20240127339A KR20240127339A KR1020247018202A KR20247018202A KR20240127339A KR 20240127339 A KR20240127339 A KR 20240127339A KR 1020247018202 A KR1020247018202 A KR 1020247018202A KR 20247018202 A KR20247018202 A KR 20247018202A KR 20240127339 A KR20240127339 A KR 20240127339A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- fluororesin
- meth
- dispersant
- acrylate compound
- 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.)
- Pending
Links
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 53
- 229920001577 copolymer Polymers 0.000 title claims abstract description 37
- 239000006185 dispersion Substances 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 title claims description 8
- -1 acrylate compound Chemical class 0.000 claims abstract description 123
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000000470 constituent Substances 0.000 claims abstract description 34
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 19
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000001033 ether group Chemical group 0.000 claims abstract description 8
- 125000005647 linker group Chemical group 0.000 claims abstract description 7
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 12
- 125000006353 oxyethylene group Chemical group 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 abstract description 21
- 238000005516 engineering process Methods 0.000 abstract description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 33
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 31
- 239000004810 polytetrafluoroethylene Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- 239000002612 dispersion medium Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000010702 perfluoropolyether Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XVTQAXXMUNXFMU-UHFFFAOYSA-N methyl 2-(3-oxo-2-pyridin-2-yl-1h-pyrazol-5-yl)acetate Chemical compound N1C(CC(=O)OC)=CC(=O)N1C1=CC=CC=N1 XVTQAXXMUNXFMU-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 229940116423 propylene glycol diacetate Drugs 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QMGJMGFZLXYHCR-UHFFFAOYSA-N 1-(2-butoxypropoxy)butane Chemical compound CCCCOCC(C)OCCCC QMGJMGFZLXYHCR-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- WKYYYUWKFPFVEY-UHFFFAOYSA-N 2-ethylcyclohexan-1-one Chemical compound CCC1CCCCC1=O WKYYYUWKFPFVEY-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- XRLHGXGMYJNYCR-UHFFFAOYSA-N acetic acid;2-(2-hydroxypropoxy)propan-1-ol Chemical compound CC(O)=O.CC(O)COC(C)CO XRLHGXGMYJNYCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- JDJWQETUMXXWPD-UHFFFAOYSA-N butyl 2-methoxypropanoate Chemical compound CCCCOC(=O)C(C)OC JDJWQETUMXXWPD-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WHRLOJCOIKOQGL-UHFFFAOYSA-N ethyl 2-methoxypropanoate Chemical compound CCOC(=O)C(C)OC WHRLOJCOIKOQGL-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- DBLVXHJTZIDGHE-UHFFFAOYSA-N ethyl acetate;2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(C)=O.OCCOCCO DBLVXHJTZIDGHE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
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- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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Abstract
다양한 용제에의 불소 수지의 분산성을 향상시키는 기술을 제공한다. 공중합체를 포함하는 불소 수지용 분산제에 있어서, 공중합체는 Rf-Cb-R-O-X로 표시되는 (메타)아크릴레이트 화합물(a1)과, HO-(PO)p-Y로 표시되는 (메타)아크릴레이트 화합물(a2)을 포함하는 구성 모노머(a)를 중합하여 얻어진 공중합체를 포함하고, Rf는 퍼플루오로(폴리)에테르기이고, Cb는 에스테르 결합, 아미드 결합, 및 우레탄 결합으로 이루어지는 군으로부터 선택되는 어느 1개의 연결기이고, R은 탄소 원자 수 1 이상 8 이하의 알킬렌기이고, X 및 Y는 아크릴로일기 또는 메타크릴로일기이고, PO는 옥시프로필렌기이며, p는 2 이상 150 이하의 수이다. A technology for improving the dispersibility of a fluororesin in various solvents is provided. In a dispersant for a fluororesin including a copolymer, the copolymer includes a copolymer obtained by polymerizing a constituent monomer (a) including a (meth)acrylate compound (a1) represented by R f -Cb-ROX and a (meth)acrylate compound (a2) represented by HO-(PO) p Y, wherein R f is a perfluoro(poly)ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, R is an alkylene group having 1 to 8 carbon atoms, X and Y are acryloyl groups or methacryloyl groups, PO is an oxypropylene group, and p is a number of 2 to 150.
Description
본 발명은 불소 수지용 분산제 및 공중합체에 관한 것이다. The present invention relates to a dispersant and a copolymer for fluororesin.
일반적으로, 폴리테트라플루오로에틸렌(PTFE) 등의 불소 수지는 발수성이나 발유성이 우수한 한편 용제에의 분산성이 작은 것이 알려져 있다(예를 들면, 특허문헌 1). 특허문헌 1에는, 용제에의 불소 수지의 분산성을 향상시키기 위한 불소 수지용 분산제가 개시되어 있다. In general, fluororesins such as polytetrafluoroethylene (PTFE) are known to have excellent water and oil repellency, but poor dispersibility in solvents (e.g., Patent Document 1). Patent Document 1 discloses a dispersant for fluororesins that improves the dispersibility of fluororesins in solvents.
그러나, 특허문헌 1에 기재된 불소 수지용 분산제는 용제에의 불소 수지의 분산성이 충분하다고는 할 수 없어, 개선의 여지가 있었다. 이 때문에, 다양한 용제에의 불소 수지의 분산성을 향상시킬 수 있는 기술의 개발이 요망되고 있다. However, the dispersant for fluororesin described in Patent Document 1 cannot be said to have sufficient dispersibility of fluororesin in solvents, and thus there is room for improvement. Therefore, the development of a technology that can improve the dispersibility of fluororesin in various solvents is desired.
본 발명은 이하의 형태로서 실현할 수 있다. The present invention can be realized in the following forms.
(1) 본 발명의 하나의 형태에 의하면, 불소 수지용 분산제가 제공된다. 이 불소 수지용 분산제는 공중합체를 포함하는 불소 수지용 분산제로서, 상기 공중합체는 하기 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)과, 하기 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)을 포함하는 구성 모노머(a)를 중합하여 얻어진 공중합체를 포함하는 것을 특징으로 한다. (1) According to one aspect of the present invention, a dispersant for a fluororesin is provided. The fluororesin dispersant is a fluororesin dispersant comprising a copolymer, wherein the copolymer is characterized by including a copolymer obtained by polymerizing a constituent monomer (a) comprising a (meth)acrylate compound (a1) represented by the following general formula (1) and a (meth)acrylate compound (a2) represented by the following general formula (2).
Rf-Cb-R-O-X (1)R f -Cb-ROX (1)
(식 중, Rf는 퍼플루오로(폴리)에테르기이며, Cb는 에스테르 결합, 아미드 결합, 및 우레탄 결합으로 이루어지는 군으로부터 선택되는 어느 1개의 연결기이고, R은 탄소 원자 수 1 이상 8 이하의 알킬렌기이며, X는 아크릴로일기 또는 메타크릴로일기이다.)(In the formula, R f is a perfluoro(poly)ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, R is an alkylene group having 1 to 8 carbon atoms, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)p-Y (2)HO-(PO)p-Y (2)
(식 중, PO는 옥시프로필렌기이고, p는 2 이상 150 이하의 수이며, Y는 아크릴로일기 또는 메타크릴로일기이다.)(In the formula, PO is an oxypropylene group, p is a number greater than or equal to 2 and less than or equal to 150, and Y is an acryloyl group or a methacryloyl group.)
(2) 상기 형태의 불소 수지용 분산제에 있어서, 상기 Cb는 에스테르 결합이어도 된다. (2) In the dispersant for fluororesin of the above type, Cb may be an ester bond.
(3) 상기 형태의 불소 수지용 분산제에 있어서, 상기 구성 모노머(a)는, 또한, 하기 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)을 포함하고 있어도 된다. (3) In the dispersant for fluororesin of the above form, the constituent monomer (a) may further contain a (meth)acrylate compound (a3) represented by the following general formula (3).
AO-(EO)q-Z (3)AO-(EO)q-Z (3)
(식 중, A는 H 또는 CH3이고, EO는 옥시에틸렌기이고, q는 2 이상 150 이하의 수이며, Z는 아크릴로일기 또는 메타크릴로일기이다.)(In the formula, A is H or CH 3 , EO is an oxyethylene group, q is a number greater than or equal to 2 and less than or equal to 150, and Z is an acryloyl group or a methacryloyl group.)
(4) 상기 형태의 불소 수지용 분산제에 있어서, 상기 구성 모노머(a) 100질량부에 있어서, 상기 (메타)아크릴레이트 화합물(a1)이 30질량부 이상 80질량부 이하 포함되어 있어도 된다. (4) In the dispersant for fluororesin of the above form, the (meth)acrylate compound (a1) may be contained in an amount of 30 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the constituent monomer (a).
(5) 상기 형태의 불소 수지용 분산제에 있어서, 상기 Rf는 CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)이며, n은 0 이상의 수이어도 된다. (5) In the dispersant for fluororesin of the above type, R f is CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) n CF(CF 3 ), and n may be a number greater than or equal to 0.
(6) 상기 형태의 불소 수지용 분산제에 있어서, 상기 n이 0이어도 된다. (6) In the dispersant for fluororesin of the above form, n may be 0.
(7) 상기 형태의 불소 수지용 분산제와, 계면활성제를 포함하는 조성물이어도 된다. (7) It may also be a composition containing a dispersant for fluorine resin of the above type and a surfactant.
(8) 상기 형태의 불소 수지용 분산제와, 불소 수지를 포함하는 분산액이어도 된다. (8) It may be a dispersant for fluorine resin of the above form or a dispersion liquid containing fluorine resin.
(9) 상기 형태의 분산액이 함침 또는 도포된 물품이어도 된다. (9) It may also be an article impregnated or coated with a dispersion of the above form.
(10) 본 발명의 다른 형태에 의하면, 공중합체가 제공된다. 이 공중합체는 하기 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)과, 하기 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)을 포함하는 구성 모노머(a)를 중합하여 얻어졌다. (10) According to another embodiment of the present invention, a copolymer is provided. The copolymer is obtained by polymerizing a constituent monomer (a) including a (meth)acrylate compound (a1) represented by the following general formula (1) and a (meth)acrylate compound (a2) represented by the following general formula (2).
Rf-Cb-R-O-X (1)R f -Cb-ROX (1)
(식 중, Rf는 퍼플루오로(폴리)에테르기이고, Cb는 에스테르 결합, 아미드 결합, 및 우레탄 결합으로 이루어지는 군으로부터 선택되는 어느 1개의 연결기이고, R은 탄소 원자 수 1 이상 8 이하의 알킬렌기이며, X는 아크릴로일기 또는 메타크릴로일기이다.)(In the formula, R f is a perfluoro(poly)ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, R is an alkylene group having 1 to 8 carbon atoms, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)p-Y (2)HO-(PO)p-Y (2)
(식 중, PO는 옥시프로필렌기이고, p는 2 이상 150 이하의 수이며, Y는 아크릴로일기 또는 메타크릴로일기이다.)(In the formula, PO is an oxypropylene group, p is a number greater than or equal to 2 and less than or equal to 150, and Y is an acryloyl group or a methacryloyl group.)
또한, 본 발명은 여러 형태로 실현하는 것이 가능하며, 예를 들면, 불소 수지용 분산제의 제조 방법이나 공중합체의 제조 방법 등의 형태로 실현할 수 있다. In addition, the present invention can be realized in various forms, and for example, can be realized in the form of a method for producing a dispersant for fluororesin, a method for producing a copolymer, etc.
본 실시형태에 의하면, 다양한 용제에의 불소 수지의 분산성을 향상시킬 수 있다. According to the present embodiment, the dispersibility of the fluororesin in various solvents can be improved.
(발명을 실시하기 위한 형태)(Form for carrying out the invention)
A. 불소 수지용 분산제A. Dispersant for fluororesin
본 발명의 하나의 실시형태인 불소 수지용 분산제(이하, 간단히 「분산제」라고도 부름)는 공중합체(A)를 포함한다. 공중합체(A)는 하기 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)과, 하기 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)을 포함하는 구성 모노머(a)를 중합하여 얻어진 공중합체를 포함한다. A dispersant for a fluororesin, which is one embodiment of the present invention (hereinafter also simply referred to as a “dispersant”), includes a copolymer (A). The copolymer (A) includes a copolymer obtained by polymerizing a constituent monomer (a) including a (meth)acrylate compound (a1) represented by the following general formula (1) and a (meth)acrylate compound (a2) represented by the following general formula (2).
Rf-Cb-R-O-X (1)R f -Cb-ROX (1)
(식 중, Rf는 퍼플루오로(폴리)에테르기이고, Cb는 에스테르 결합, 아미드 결합, 및 우레탄 결합으로 이루어지는 군으로부터 선택되는 어느 1개의 연결기이고, R은 탄소 원자 수 1 이상 8 이하의 알킬렌기이며, X는 아크릴로일기 또는 메타크릴로일기이다.)(In the formula, R f is a perfluoro(poly)ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, R is an alkylene group having 1 to 8 carbon atoms, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)p-Y (2)HO-(PO)p-Y (2)
(식 중, PO는 옥시프로필렌기이고, p는 2 이상 150 이하의 수이며, Y는 아크릴로일기 또는 메타크릴로일기이다.)(In the formula, PO is an oxypropylene group, p is a number greater than or equal to 2 and less than or equal to 150, and Y is an acryloyl group or a methacryloyl group.)
본 실시형태의 불소 수지용 분산제는 다양한 용제에의 불소 수지의 분산성을 향상시킬 수 있다. 이러한 효과를 발휘하는 메커니즘은 확실하지 않다. 그러나, 추정 메커니즘으로서는, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1) 유래의 측쇄에 의해 불소 수지에 흡착하기 쉬워지고, 또, 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2) 유래의 측쇄인 옥시프로필렌기에 의해 용제에 녹기 쉬워진다고 생각된다. The dispersant for fluororesin of the present embodiment can improve the dispersibility of fluororesin in various solvents. The mechanism by which this effect is exerted is not certain. However, it is thought that the presumed mechanism is that the side chain derived from the (meth)acrylate compound (a1) represented by the general formula (1) makes it easy to adsorb to the fluororesin, and further, the side chain derived from the (meth)acrylate compound (a2) represented by the general formula (2) makes it easy to dissolve in the solvent, which is an oxypropylene group.
또, 구성 모노머(a)는, 또한, 하기 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)을 포함하는 것이 바람직하다. In addition, it is preferable that the constituent monomer (a) also includes a (meth)acrylate compound (a3) represented by the following general formula (3).
AO-(EO)q-Z (3)AO-(EO)q-Z (3)
(식 중, A는 H 또는 CH3이고, EO는 옥시에틸렌기이고, q는 2 이상 150 이하의 수이며, Z는 아크릴로일기 또는 메타크릴로일기이다.)(In the formula, A is H or CH 3 , EO is an oxyethylene group, q is a number greater than or equal to 2 and less than or equal to 150, and Z is an acryloyl group or a methacryloyl group.)
구성 모노머(a)가 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)을 포함함으로써, 불소 수지의 수분산성을 더욱 향상시킬 수 있다. 이러한 효과를 발휘하는 메커니즘은 확실하지 않다. 그러나, 추정 메커니즘으로서는, 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3) 유래의 측쇄인 옥시에틸렌기에 의해, 물과의 친화성이 높여졌다고 생각된다. By including a (meth)acrylate compound (a3) represented by the general formula (3) as the constituent monomer (a), the water dispersibility of the fluororesin can be further improved. The mechanism by which this effect is exerted is not certain. However, as a presumed mechanism, it is thought that the affinity for water is enhanced by the oxyethylene group, which is a side chain derived from the (meth)acrylate compound (a3) represented by the general formula (3).
본 명세서에 있어서, 「불소 수지」란 불소를 함유하는 수지를 의미한다. 불소 수지로서는 특별히 한정되지 않지만, 예를 들면, 폴리테트라플루오로에틸렌(PTFE), 테트라플루오로에틸렌퍼플루오로비닐에테르 공중합체(PFA), 테트라플루오로에틸렌-헥사플루오로프로필렌 공중합체(FEP), 테트라플루오로에틸렌-에틸렌 공중합체(ETFE), 폴리불화비닐리덴(PVDF), 폴리불화비닐(PVF), 클로로트리플루오로에틸렌-에틸렌 공중합체(FCTFE), 폴리클로로트리플루오로에틸렌(PCTFE) 등을 들 수 있다. 분산제에 의해 불소 수지의 분산성을 효과적으로 부여하는 관점에서, 불소 수지로서는 PTFE와 PFA가 바람직하고, PTFE가 보다 바람직하다. In this specification, "fluororesin" means a resin containing fluorine. The fluororesin is not particularly limited, and examples thereof include polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluorovinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), chlorotrifluoroethylene-ethylene copolymer (FCTFE), and polychlorotrifluoroethylene (PCTFE). From the viewpoint of effectively imparting dispersibility to the fluororesin by a dispersing agent, PTFE and PFA are preferable as the fluororesin, and PTFE is more preferable.
<(메타)아크릴레이트 화합물(a1)><(Meth)acrylate compound (a1)>
(메타)아크릴레이트 화합물(a1)은 하기 일반식 (1)로 표시된다. (Meth)acrylate compound (a1) is represented by the following general formula (1).
Rf-Cb-R-O-X (1)R f -Cb-ROX (1)
식 중, Rf는 퍼플루오로(폴리)에테르기이며, Cb는 에스테르 결합, 아미드 결합, 및 우레탄 결합으로 이루어지는 군으로부터 선택되는 어느 1개의 연결기이고, R은 탄소 원자 수 1 이상 8 이하의 알킬렌기이며, X는 아크릴로일기 또는 메타크릴로일기이다. 본 명세서에 있어서, 퍼플루오로(폴리)에테르기는 퍼플루오로폴리에테르기 또는 퍼플루오로에테르기를 의미한다. 또, 본 명세서에 있어서, 퍼플루오로에테르기는 퍼플루오로알킬기와 에테르 결합을 가지며, 퍼플루오로폴리에테르기는 퍼플루오로알킬기와 퍼플루오로알킬렌기와 에테르 결합을 갖는다. 또한, 에스테르 결합이란 「-C(=O)-O-」를 나타내고, 아미드 결합이란 「-C(=O)-NH-」를 나타내고, 우레탄 결합이란 「-NH-C(=O)-O-」를 나타낸다. In the formula, R f is a perfluoro(poly)ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, R is an alkylene group having 1 to 8 carbon atoms, and X is an acryloyl group or a methacryloyl group. In the present specification, the perfluoro(poly)ether group means a perfluoropolyether group or a perfluoroether group. In addition, in the present specification, the perfluoroether group has an ether bond with a perfluoroalkyl group, and the perfluoropolyether group has an ether bond with a perfluoroalkyl group and a perfluoroalkylene group. In addition, an ester bond represents "-C(=O)-O-", an amide bond represents "-C(=O)-NH-", and a urethane bond represents "-NH-C(=O)-O-".
일반식 (1) 중의 Cb는, 분산성을 향상시키는 관점에서, 에스테르 결합을 포함하는 것이 바람직하다. 또, Rf는, 분산성을 향상시키는 관점에서, CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)이며 n은 0 이상의 수인 것이 바람직하고, CF3CF2CF2OCF(CF3), 즉 n이 0인 것이 보다 바람직하다. 또, R은, 분산성을 향상시키는 관점에서, 탄소 원자 수 1∼6의 알킬렌기인 것이 바람직하고, 탄소 원자 수 1∼3의 알킬렌기인 것이 보다 바람직하고, C2H4인 것이 더욱 바람직하다. 또, 일반식 (1) 중의 X는, 분산성을 향상시키는 관점에서, 메타크릴로일기인 것이 바람직하다. 또한, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)은 일종을 단독으로 사용해도 되고, 2종 이상을 병용해도 된다. In the general formula (1), Cb preferably contains an ester bond from the viewpoint of improving dispersibility. In addition, from the viewpoint of improving dispersibility, R f is preferably CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) n CF(CF 3 ) where n is a number greater than or equal to 0, and more preferably CF 3 CF 2 CF 2 OCF(CF 3 ), that is, n is 0. In addition, from the viewpoint of improving dispersibility, R is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and still more preferably C 2 H 4 . In addition, X in the general formula (1) is preferably a methacryloyl group from the viewpoint of improving dispersibility. In addition, the (meth)acrylate compound (a1) represented by the general formula (1) may be used alone or in combination of two or more.
일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)로서는, 예를 들면, 측쇄형 퍼플루오로폴리에테르(PFPE)(메타)아크릴레이트 화합물과, 직쇄형 PFPE(메타)아크릴레이트 화합물 등을 들 수 있다. 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)로서는, 분산성을 향상시키는 관점에서, 측쇄형 PFPE(메타)아크릴레이트 화합물인 것이 바람직하다. As the (meth)acrylate compound (a1) represented by the general formula (1), examples thereof include a branched-chain perfluoropolyether (PFPE) (meth)acrylate compound and a linear PFPE (meth)acrylate compound. As the (meth)acrylate compound (a1) represented by the general formula (1), a branched-chain PFPE (meth)acrylate compound is preferable from the viewpoint of improving dispersibility.
측쇄형 PFPE(메타)아크릴레이트 화합물로서는, 예를 들면, 하기 일반식 (4)∼(7)로 표시되는 화합물을 들 수 있다. 이하의 식 중의 평균 반복단위 수 n은 0 이상의 수이며, 30 이하가 바람직하고, 25 이하가 보다 바람직하고, 20 이하가 더욱 바람직하고, 특히, 15 이하가 바람직하고, 10 이하가 보다 바람직하고, 8 이하가 더욱 바람직하고, 특히, 5 이하가 바람직하고, 3 이하가 보다 바람직하고, 1 이하가 더욱 바람직하고, 0인 것이 더한층 바람직하다. 이하의 식 중의 평균 반복 단위 수 m은 0 이상의 수이며, 20 이하가 바람직하고, 10 이하가 보다 바람직하고, 8 이하가 더욱 바람직하고, 특히, 5 이하가 바람직하고, 3 이하가 보다 바람직하고, 1 이하가 더욱 바람직하다. 또한, 하기 일반식 (4)∼(7)에서는, (모두) 메타크릴로일기를 갖는 화합물을 열거하고 있지만, 메타크릴로일기 대신에 아크릴로일기를 갖는 화합물에 대해서도 측쇄형 PFPE(메타)아크릴레이트 화합물에 포함된다. As the side-chain PFPE (meth)acrylate compound, for example, compounds represented by the following general formulae (4) to (7) can be mentioned. The average repeating unit number n in the following formulae is a number equal to or greater than 0, preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, particularly preferably 15 or less, more preferably 10 or less, even more preferably 8 or less, particularly preferably 5 or less, more preferably 3 or less, even more preferably 1 or less, and even more preferably 0. The average repeating unit number m in the following formulae is a number equal to or greater than 0, preferably 20 or less, more preferably 10 or less, even more preferably 8 or less, particularly preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less. In addition, although the following general formulas (4) to (7) list compounds having (all) a methacryloyl group, compounds having an acryloyl group instead of a methacryloyl group are also included in the side-chain PFPE (meth)acrylate compounds.
직쇄형 PFPE(메타)아크릴레이트 화합물로서는, 예를 들면, 하기 일반식 (8)∼(11)로 표시되는 화합물을 들 수 있다. 이하의 식 중의 평균 반복단위 수 n은 0 이상의 수이며, 30 이하가 바람직하고, 25 이하가 보다 바람직하고, 20 이하가 더욱 바람직하고, 특히, 15 이하가 바람직하고, 10 이하가 보다 바람직하고, 8 이하가 더욱 바람직하고, 0인 것이 더한층 바람직하다. 이하의 식 중의 평균 반복 단위 수 m은 0 이상의 수이며, 20 이하가 바람직하고, 15 이하가 보다 바람직하고, 10 이하가 더욱 바람직하고, 특히, 8 이하가 바람직하고, 5 이하가 보다 바람직하고, 3 이하가 더욱 바람직하다. 또한, 하기 일반식 (8)∼(11)에서는, 모두 메타크릴로일기를 갖는 화합물을 열거하고 있지만, 메타크릴로일기 대신에 아크릴로일기를 갖는 화합물에 대해서도 직쇄형 PFPE(메타)아크릴레이트 화합물에 포함된다. As the linear PFPE (meth)acrylate compound, for example, compounds represented by the following general formulae (8) to (11) can be mentioned. The average repeating unit number n in the following formulae is a number equal to or greater than 0, preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, particularly preferably 15 or less, more preferably 10 or less, even more preferably 8 or less, and still more preferably 0. The average repeating unit number m in the following formulae is a number equal to or greater than 0, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, particularly preferably 8 or less, more preferably 5 or less, and still more preferably 3 or less. In addition, although the following general formulas (8) to (11) all list compounds having a methacryloyl group, compounds having an acryloyl group instead of a methacryloyl group are also included in the linear PFPE (meth)acrylate compounds.
<(메타)아크릴레이트 화합물(a2)><(Meth)acrylate compound (a2)>
(메타)아크릴레이트 화합물(a2)은 하기 일반식 (2)로 표시된다. (Meth)acrylate compound (a2) is represented by the following general formula (2).
HO-(PO)p-Y (2)HO-(PO)p-Y (2)
식 중, PO는 옥시프로필렌기이고, p는 2 이상 150 이하의 수이며, Y는 아크릴로일기 또는 메타크릴로일기이다. In the formula, PO is an oxypropylene group, p is a number greater than or equal to 2 and less than or equal to 150, and Y is an acryloyl group or a methacryloyl group.
일반식 (2) 중의 옥시프로필렌기의 평균 반복단위 수 p는 특별히 한정되지 않지만, 분산성을 보다 향상시키는 관점에서, 3 이상 150 이하인 것이 바람직하다. 평균 반복단위 수 p의 하한값은 4 이상인 것이 보다 바람직하고, 8 이상인 것이 더욱 바람직하고, 특히, 10 이상인 것이 바람직하고, 12 이상인 것이 보다 바람직하다. 평균 반복단위 수 p의 상한값은 120 이하인 것이 보다 바람직하고, 100 이하인 것이 더욱 바람직하고, 70 이하인 것이 더한층 바람직하고, 50 이하인 것이 보다 바람직하고, 20 이하인 것이 더욱 바람직하고, 15 이하인 것이 특히 바람직하다. 또, 일반식 (2) 중의 Y는, 분산성을 향상시키는 관점에서, 메타크릴로일기인 것이 바람직하다. 또한, 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)은 일종을 단독으로 사용해도 되고, 2종 이상을 병용해도 된다. The average repeating unit number p of the oxypropylene group in the general formula (2) is not particularly limited, but from the viewpoint of further improving dispersibility, it is preferably 3 or more and 150 or less. The lower limit of the average repeating unit number p is more preferably 4 or more, still more preferably 8 or more, particularly preferably 10 or more, and still more preferably 12 or more. The upper limit of the average repeating unit number p is more preferably 120 or less, still more preferably 100 or less, still more preferably 70 or less, more preferably 50 or less, still more preferably 20 or less, and particularly preferably 15 or less. In addition, Y in the general formula (2) is preferably a methacryloyl group from the viewpoint of improving dispersibility. In addition, the (meth)acrylate compound (a2) represented by the general formula (2) may be used alone, or two or more may be used in combination.
<(메타)아크릴레이트 화합물(a3)><(Meth)acrylate compound (a3)>
(메타)아크릴레이트 화합물(a3)은 하기 일반식 (3)으로 표시된다. (Meth)acrylate compound (a3) is represented by the following general formula (3).
AO-(EO)q-Z (3)AO-(EO)q-Z (3)
식 중, A는 H 또는 CH3이고, EO는 옥시에틸렌기이고, q는 2 이상 150 이하의 수이며, Z는 아크릴로일기 또는 메타크릴로일기이다. In the formula, A is H or CH 3 , EO is an oxyethylene group, q is a number greater than or equal to 2 and less than or equal to 150, and Z is an acryloyl group or a methacryloyl group.
일반식 (3) 중의 옥시에틸렌기의 평균 반복단위 수 q는 특별히 한정되지 않지만, 분산성을 보다 향상시키는 관점에서, 3 이상 150 이하인 것이 바람직하다. 평균 반복단위 수 q의 하한값은 5 이상인 것이 보다 바람직하고, 10 이상인 것이 더욱 바람직하고, 특히, 15 이상인 것이 바람직하고, 20 이상인 것이 보다 바람직하다. 평균 반복단위 수 q의 상한값은 120 이하인 것이 보다 바람직하고, 100 이하인 것이 더욱 바람직하고, 70 이하인 것이 더한층 바람직하고, 40 이하인 것이 특히 바람직하다. 또, 일반식 (3) 중의 Z는, 분산성을 향상시키는 관점에서, 메타크릴로일기인 것이 바람직하다. 또한, 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)은 일종을 단독으로 사용해도 되고, 2종 이상을 병용해도 된다. The average number of repeating units q of the oxyethylene group in the general formula (3) is not particularly limited, but from the viewpoint of further improving dispersibility, it is preferably 3 or more and 150 or less. The lower limit of the average number of repeating units q is more preferably 5 or more, still more preferably 10 or more, particularly preferably 15 or more, and still more preferably 20 or more. The upper limit of the average number of repeating units q is more preferably 120 or less, still more preferably 100 or less, still more preferably 70 or less, and particularly preferably 40 or less. In addition, Z in the general formula (3) is preferably a methacryloyl group from the viewpoint of improving dispersibility. In addition, the (meth)acrylate compound (a3) represented by the general formula (3) may be used alone, or two or more may be used in combination.
본 실시형태의 공중합체(A)를 구성하는 구성 모노머(a)는, 발명의 목적에 반하지 않는 범위에서, 상기 성분 (a1), (a2) 및 (a3) 이외의 모노머를 포함하고 있어도 된다. 또, 본 실시형태의 불소 수지용 분산제는, 발명의 목적에 반하지 않는 범위에서, 공중합체(A) 이외의 공중합체를 포함해도 된다. The constituent monomer (a) constituting the copolymer (A) of the present embodiment may contain monomers other than the components (a1), (a2), and (a3) as long as it does not conflict with the purpose of the invention. In addition, the dispersant for fluororesin of the present embodiment may contain a copolymer other than the copolymer (A) as long as it does not conflict with the purpose of the invention.
구성 모노머(a)에 있어서, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)의 함유 비율은 특별히 한정되지 않지만, 분산성을 향상시키는 관점에서, 구성 모노머(a) 100질량부에 있어서, 5질량부 이상 95질량부 이하 포함되는 것이 바람직하다. 구성 모노머(a) 100질량부에 대하여, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)의 함유 비율의 하한값은 10질량부 이상인 것이 보다 바람직하고, 30질량부 이상인 것이 더욱 바람직하다. 구성 모노머(a) 100질량부에 대하여, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)의 함유 비율의 상한값은 80질량부 이하인 것이 보다 바람직하고, 70질량부 이하인 것이 더욱 바람직하고, 50질량부 이하인 것이 더한층 바람직하다. In the constituent monomer (a), the content ratio of the (meth)acrylate compound (a1) represented by the general formula (1) is not particularly limited, but from the viewpoint of improving dispersibility, it is preferably contained in an amount of 5 parts by mass or more and 95 parts by mass or less per 100 parts by mass of the constituent monomer (a). With respect to 100 parts by mass of the constituent monomer (a), the lower limit of the content ratio of the (meth)acrylate compound (a1) represented by the general formula (1) is more preferably 10 parts by mass or more, and further preferably 30 parts by mass or more. With respect to 100 parts by mass of the constituent monomer (a), the upper limit of the content ratio of the (meth)acrylate compound (a1) represented by the general formula (1) is more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less, and further preferably 50 parts by mass or less.
구성 모노머(a)에 있어서, 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)의 함유 비율은 특별히 한정되지 않지만, 분산성을 향상시키는 관점에서, 구성 모노머(a) 100질량부에 있어서, 5질량부 이상 95질량부 이하 포함되는 것이 바람직하다. 구성 모노머(a) 100질량부에 대하여, 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)의 함유 비율의 하한값은 10질량부 이상인 것이 보다 바람직하고, 15질량부 이상인 것이 더욱 바람직하고, 20질량부 이상인 것이 더한층 바람직하다. 구성 모노머(a) 100질량부에 대하여, 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)의 함유 비율의 상한값은 80질량부 이하인 것이 보다 바람직하고, 50질량부 이하인 것이 더욱 바람직하고, 40질량부 이하인 것이 더한층 바람직하고, 30질량부 이하인 것이 특히 바람직하다. In the constituent monomer (a), the content ratio of the (meth)acrylate compound (a2) represented by the general formula (2) is not particularly limited, but from the viewpoint of improving dispersibility, it is preferably contained in an amount of 5 parts by mass or more and 95 parts by mass or less per 100 parts by mass of the constituent monomer (a). With respect to 100 parts by mass of the constituent monomer (a), the lower limit of the content ratio of the (meth)acrylate compound (a2) represented by the general formula (2) is more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more. With respect to 100 parts by mass of the constituent monomer (a), the upper limit of the content ratio of the (meth)acrylate compound (a2) represented by the general formula (2) is more preferably 80 parts by mass or less, further preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.
구성 모노머(a)에 있어서, 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)의 함유 비율은 특별히 한정되지 않지만, 물에의 분산성을 향상시키는 관점에서, 구성 모노머(a) 100질량부에 있어서, 5질량부 이상 90질량부 이하 포함되는 것이 바람직하다. 구성 모노머(a) 100질량부에 대하여, 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)의 함유 비율의 하한값은 10질량부 이상인 것이 보다 바람직하고, 15질량부 이상인 것이 더욱 바람직하고, 25질량부 이상인 것이 더한층 바람직하고, 35질량부 이상인 것이 특히 바람직하다. 구성 모노머(a) 100질량부에 대하여, 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)의 함유 비율의 상한값은 80질량부 이하인 것이 보다 바람직하고, 60질량부 이하인 것이 더욱 바람직하고, 45질량부 이하인 것이 더한층 바람직하다. In the constituent monomer (a), the content ratio of the (meth)acrylate compound (a3) represented by the general formula (3) is not particularly limited, but from the viewpoint of improving dispersibility in water, it is preferably contained in an amount of 5 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the constituent monomer (a). With respect to 100 parts by mass of the constituent monomer (a), the lower limit of the content ratio of the (meth)acrylate compound (a3) represented by the general formula (3) is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, still more preferably 25 parts by mass or more, and particularly preferably 35 parts by mass or more. With respect to 100 parts by mass of the constituent monomer (a), the upper limit of the content ratio of the (meth)acrylate compound (a3) represented by the general formula (3) is more preferably 80 parts by mass or less, further preferably 60 parts by mass or less, and still more preferably 45 parts by mass or less.
구성 모노머(a)에 있어서, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)에 대한 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)의 질량비율(a2/a1)은, 분산성을 향상시키는 관점에서, 20% 이상인 것이 바람직하고, 30% 이상인 것이 보다 바람직하고, 40% 이상인 것이 더한층 바람직하다. 또, 구성 모노머(a)에 있어서, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)에 대한 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)의 질량비율(a2/a1)은, 분산성을 향상시키는 관점에서, 170% 이하인 것이 바람직하고, 130% 이하인 것이 보다 바람직하고, 80% 이하인 것이 더한층 바람직하고, 60% 이하인 것이 특히 바람직하다. In the constituent monomer (a), the mass ratio (a2/a1) of the (meth)acrylate compound (a2) represented by the general formula (2) to the (meth)acrylate compound (a1) represented by the general formula (1) is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more, from the viewpoint of improving dispersibility. In addition, in the constituent monomer (a), the mass ratio (a2/a1) of the (meth)acrylate compound (a2) represented by the general formula (2) to the (meth)acrylate compound (a1) represented by the general formula (1) is preferably 170% or less, more preferably 130% or less, even more preferably 80% or less, and especially preferably 60% or less, from the viewpoint of improving dispersibility.
본 실시형태에서 사용하는 공중합체(A)는 특별히 한정되지 않지만, 중량평균 분자량이 2,000∼200,000인 것이 바람직하고, 5,000∼100,000인 것이 보다 바람직하고, 10,000∼50,000인 것이 더욱 바람직하다. 중량평균 분자량이 상기 범위 내이면, 분산성이 우수한 불소 수지용 분산제가 얻어지기 쉽다. 본 명세서에 있어서, 중량평균 분자량은, GPC 컬럼 크로마토그래피법을 사용하여, 하기의 조건으로 측정할 수 있고, 표준 샘플로서 분자량 300, 2,000, 8,000, 및 20,000의 폴리에틸렌글리콜로 교정한 것을 사용했다. The copolymer (A) used in the present embodiment is not particularly limited, but preferably has a weight average molecular weight of 2,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. When the weight average molecular weight is within the above range, a dispersant for fluororesin having excellent dispersibility can be easily obtained. In the present specification, the weight average molecular weight can be measured using a GPC column chromatography method under the following conditions, and those corrected with polyethylene glycol having molecular weights of 300, 2,000, 8,000, and 20,000 were used as standard samples.
·장치: LC-10AD((주)시마즈세이사쿠쇼제)·Device: LC-10AD (manufactured by Shimadzu Seisakusho Co., Ltd.)
·검출기: RID-10A((주)시마즈세이사쿠쇼제)·Detector: RID-10A (manufactured by Shimadzu Corporation)
·컬럼: Shodex GPC KF-G, KF-803, KF802.5, KF-802, KF-801을 연결한 것 (모두 쇼와덴코(주)제)·Column: Shodex GPC KF-G, KF-803, KF802.5, KF-802, KF-801 connected (all manufactured by Showa Denko Co., Ltd.)
·용리액: 테트라히드로푸란·Eluent: Tetrahydrofuran
·샘플 주입: 0.5중량% 용액, 100μL·Sample injection: 0.5 wt% solution, 100 μL
·유속: 0.8mL/min·Flow rate: 0.8mL/min
·온도: 25℃·Temperature: 25℃
다음에 본 실시형태의 불소 수지용 분산제의 제조 방법을 설명한다. 불소 수지용 분산제의 제조 방법은 특별히 한정되지 않지만, 예를 들면, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)과, 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)과, 용제를 혼합 후 가열하는 방법을 들 수 있다. Next, a method for producing a dispersant for a fluororesin according to the present embodiment is described. The method for producing a dispersant for a fluororesin is not particularly limited, but, for example, a method of mixing a (meth)acrylate compound (a1) represented by the general formula (1), a (meth)acrylate compound (a2) represented by the general formula (2), and a solvent and then heating the mixture may be exemplified.
불소 수지용 분산제의 제조에 사용하는 용제는 물이어도 되고, 유기 용제이어도 된다. 유기 용제로서는, 예를 들면, 톨루엔, 크실렌 등의 방향족계 용제, 헥산 등의 지방족 탄화수소계 용제, 시클로헥산, 이소포론 등의 지환족 탄화수소계 용제, 아세톤, 메틸에틸케톤, 시클로헥사논 등의 케톤계 용제, 아세트산 에틸, 아세트산 부틸, 프로필렌글리콜디아세테이트 등의 에스테르계 용제, 에틸렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 디프로필렌글리콜메틸에테르아세테이트, 디에틸렌글리콜모노에틸아세테이트, 3-메톡시-3-메틸부틸아세테이트 등의 글리콜에테르에스테르계 용제, 에틸렌글리콜디메틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디부틸에테르, 프로필렌글리콜디부틸에테르, 디메틸트리글리콜, 메틸에틸디글리콜, 디메틸프로필렌디글리콜 등의 글리콜에테르계 용제, 디메틸술폭시드, 디메틸포름아미드, N-메틸-2-피롤리돈 등을 들 수 있고, 이 중에서도, 아세톤, 메틸에틸케톤, 아세트산 에틸, 에틸렌글리콜디메틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 메틸에틸디글리콜, 프로필렌글리콜모노메틸에테르아세테이트, 3-메톡시-3-메틸부틸아세테이트, 디메틸프로필렌디글리콜인 것이 바람직하다. 상기의 용제는 2종 이상을 병용해도 된다. The solvent used in the manufacture of a dispersant for fluororesin may be water or an organic solvent. As organic solvents, for example, aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane and isophorone, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, and propylene glycol diacetate, glycol ether ester solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl acetate, and 3-methoxy-3-methylbutyl acetate, and glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol dibutyl ether, dimethyl triglycol, methyl ethyl diglycol, and dimethyl propylene diglycol. Examples of the solvent include dimethyl sulfoxide, dimethyl formamide, N-methyl-2-pyrrolidone, and among these, acetone, methyl ethyl ketone, ethyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl ethyl diglycol, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl butyl acetate, and dimethyl propylene diglycol are preferable. Two or more of the above solvents may be used in combination.
중합 방법은 특별히 한정되지 않지만, 용액 중합인 것이 바람직하다. 중합 온도는 특별히 한정되지 않지만, 통상은 40∼120℃의 범위가 바람직하다. 중합 시간은 특별히 한정되지 않지만, 통상은 4∼15시간 정도인 것이 바람직하다. The polymerization method is not particularly limited, but solution polymerization is preferred. The polymerization temperature is not particularly limited, but is usually preferably in the range of 40 to 120°C. The polymerization time is not particularly limited, but is usually preferably about 4 to 15 hours.
중합을 행할 때 중합개시제를 사용해도 된다. 중합개시제로서는 특별히 한정되지 않지만, 예를 들면, 과산화벤조일, t-부틸퍼옥시피발레이트, t-부틸퍼옥시-2-에틸헥사노에이트, t-헥실퍼옥시이소프로필모노카보네이트, 1,1,3,3-테트라메틸부틸퍼옥시-2-에틸헥사노에이트 등의 과산화물, 아조비스이소부티로니트릴, 2,2'-아조비스-2-메틸부티로니트릴 등의 아조 화합물 등을 들 수 있다. 중합개시제의 사용량은 특별히 한정되지 않지만, 일반적으로, 구성 모노머(a) 100질량부에 대하여, 0.1∼5질량부인 것이 바람직하다. A polymerization initiator may be used when conducting polymerization. The polymerization initiator is not particularly limited, but examples thereof include peroxides such as benzoyl peroxide, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; azo compounds such as azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile; and the like. The amount of the polymerization initiator to be used is not particularly limited, but is generally preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the constituent monomer (a).
본 실시형태의 불소 수지용 분산제는, 발명의 목적에 반하지 않는 범위에서, 예를 들면, 다른 친수제, 그 밖의 발유제, 발수제, 방충제, 난연제, 주름방지제, 대전방지제, 유연처리제, 방부제, 방향제, 산화방지제, 계면활성제, 유화제, 분산제, 수지첨가제 등을 더 함유하고 있어도 된다. 계면활성제로서는 특별히 한정되지 않지만, 예를 들면, 비이온 계면활성제, 음이온 계면활성제, 양이온 계면활성제, 양쪽성 계면활성제 등을 들 수 있다. The dispersant for fluororesin of the present embodiment may further contain, for example, other hydrophilic agents, other oil repellents, water repellents, insect repellents, flame retardants, anti-wrinkle agents, antistatic agents, softening agents, preservatives, fragrances, antioxidants, surfactants, emulsifiers, dispersants, resin additives, etc., as long as it does not conflict with the purpose of the invention. The surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
본 실시형태의 불소 수지용 분산제에 사용하는 분산매는 특별히 한정되지 않는다. 분산매로서는, 예를 들면, 메탄올, 에탄올, 이소프로필알코올, n-부탄올, iso-부탄올, sec-부틸알코올, tert-부탄올, 테르피네올 등의 알코올류를 들 수 있다. 또, 분산매로서는, 예를 들면, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 메틸아밀케톤, 2-헵타논, 시클로헵타논, γ-부티로락톤, 시클로헥사논, 메틸시클로헥사논, 에틸시클로헥사논, 메틸-n-펜틸케톤, 메틸이소펜틸케톤 등의 케톤류를 들 수 있다. 또, 분산매로서는, 예를 들면, 아세트산 메틸, 아세트산 에틸, 아세트산 부틸, 아세트산 이소부틸, 락트산 메틸, 락트산 에틸, 락트산 부틸, 시클로헥실아세테이트 등의 에스테르류를 들 수 있다. 또, 분산매로서는, 예를 들면, 2-옥시프로피온산 메틸, 2-옥시프로피온산 에틸, 2-옥시프로피온산 프로필, 2-옥시프로피온산 부틸, 2-메톡시프로피온산 메틸, 2-메톡시프로피온산 에틸, 2-메톡시프로피온산 프로필, 2-메톡시프로피온산 부틸, 3-에톡시프로피온산 에틸 등의 모노카르복실산 에스테르류를 들 수 있다. 또, 분산매로서는, 예를 들면, 디메틸포름아미드, 디메틸술폭시드, 디메틸아세트아미드, N-메틸피롤리돈 등의 극성 용제를 들 수 있다. 또, 분산매로서는, 예를 들면, 에틸렌글리콜, 디에틸렌글리콜, 에틸렌글리콜모노아세테이트, 에틸렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜모노에틸에테르아세테이트, 에틸렌글리콜디메틸에테르, 디에틸렌글리콜모노아세테이트, 에틸렌글리콜디에틸에테르, 디에틸렌글리콜메틸에틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노부틸에테르아세테이트, 트리에틸렌글리콜디메틸에테르 등의 에틸렌글리콜류 및 그 에스테르류를 들 수 있다. 또, 분산매로서는, 예를 들면, 프로필렌글리콜, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노부틸에테르아세테이트, 디프로필렌글리콜모노아세테이트, 프로필렌글리콜디아세테이트, 디프로필렌글리콜메틸에테르아세테이트, 디프로필렌글리콜디메틸에테르 등의 프로필렌글리콜류 및 그 에스테르류를 들 수 있다. 또, 분산매로서는, 예를 들면, 3-메톡시-3-메틸-1-부탄올, 3-메톡시-3-메틸-1-부틸아세테이트 등의 용제를 들 수 있다. 또, 분산매로서는 클로로포름, 염화메틸렌, 1,1,1-트리클로로에탄 등의 할로겐계 용제나, 테트라히드로푸란, 디옥산 등의 에테르류를 들 수 있다. 또, 분산매로서는, 예를 들면, 벤젠, 톨루엔, 크실렌, 디페닐에테르, 디벤질에테르, 페네톨, 부틸페닐에테르, 에틸벤젠, 디에틸벤젠 등의 방향족류를 들 수 있다. 또, 분산매로서는, 예를 들면, 물을 들 수 있다. 상기의 분산매는 2종 이상을 병용해도 된다. 상기의 분산매 중에서도, N-메틸피롤리돈, 시클로헥사논, 톨루엔, 디메틸포름아미드, 에탄올, 디메틸아세트아미드, 메틸에틸케톤, 프로필렌글리콜메틸에테르아세테이트, 아세트산 에틸, 물이 분산성의 관점에서 바람직하다. The dispersion medium used in the dispersant for the fluororesin of the present embodiment is not particularly limited. Examples of the dispersion medium include alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, iso-butanol, sec-butyl alcohol, tert-butanol, and terpineol. In addition, examples of the dispersion medium include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, 2-heptanone, cycloheptanone, γ-butyrolactone, cyclohexanone, methylcyclohexanone, ethylcyclohexanone, methyl-n-pentyl ketone, and methyl isopentyl ketone. In addition, examples of the dispersion medium include esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methyl lactate, ethyl lactate, butyl lactate, and cyclohexyl acetate. In addition, examples of the dispersion medium include monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, and ethyl 3-ethoxypropionate. In addition, examples of the dispersion medium include polar solvents such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, and N-methylpyrrolidone. In addition, as a dispersion medium, examples thereof include ethylene glycol, diethylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol monoacetate, ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol dimethyl ether, and other ethylene glycols and their esters. In addition, as a dispersion medium, for example, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol methyl ether acetate, dipropylene glycol dimethyl ether, and other propylene glycols and their esters can be mentioned. In addition, as a dispersion medium, for example, solvents such as 3-methoxy-3-methyl-1-butanol and 3-methoxy-3-methyl-1-butyl acetate can be mentioned. In addition, as a dispersion medium, halogen solvents such as chloroform, methylene chloride, and 1,1,1-trichloroethane, and ethers such as tetrahydrofuran and dioxane can be mentioned. In addition, examples of dispersion media include aromatics such as benzene, toluene, xylene, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, and diethyl benzene. In addition, examples of dispersion media include water. Two or more of the above dispersion media may be used in combination. Among the above dispersion media, N-methyl pyrrolidone, cyclohexanone, toluene, dimethyl formamide, ethanol, dimethyl acetamide, methyl ethyl ketone, propylene glycol methyl ether acetate, ethyl acetate, and water are preferable from the viewpoint of dispersibility.
본 실시형태의 불소 수지용 분산제는 불소 수지에 대해 우수한 분산성을 부여할 수 있다. 이 때문에, 본 실시형태의 불소 수지용 분산제는, 예를 들면, 유리, 플라스틱, 금속, 전자기판, 섬유 제품, 피혁, 석재, 목재, 종이 등을 포함하는 여러 물품의 코팅제이며, 불소 수지를 포함하는 코팅제에 사용할 수 있다. 이 코팅제는, 예를 들면, 프라이팬 등의 조리 기구나, 자동차의 보디에 도포해도 된다. The dispersant for fluororesin of the present embodiment can provide excellent dispersibility to fluororesin. Therefore, the dispersant for fluororesin of the present embodiment is a coating agent for various articles including, for example, glass, plastic, metal, electronic substrates, textile products, leather, stone, wood, paper, etc., and can be used in a coating agent containing a fluororesin. This coating agent can be applied to, for example, cooking utensils such as frying pans, or the body of an automobile.
B. 다른 실시형태B. Other embodiments
본 발명의 다른 실시형태로서, 예를 들면, 상기의 불소 수지용 분산제와 계면활성제를 포함하는 조성물을 들 수 있다. 계면활성제로서는 특별히 한정되지 않지만, 예를 들면, 비이온 계면활성제, 음이온 계면활성제, 양이온 계면활성제, 양쪽성 계면활성제 등을 사용할 수 있다. 또, 본 발명의 다른 실시형태로서, 예를 들면, 상기의 불소 수지용 분산제와 불소 수지를 포함하는 분산액이나, 이 분산액이 함침 또는 도포된 물품 등을 들 수 있다. 본 실시형태의 분산액에는, 불소 수지 이외의 수지가 용해되어 있어도 된다. 또, 본 실시형태의 분산액은 다양한 물품에 함침 또는 도포하여 사용할 수 있다. 예를 들면, 본 실시형태의 분산액을 천에 함침함으로써, 텐트 등의 천에 사용해도 된다. 또, 본 실시형태의 분산액을 비이커 등에 도포함으로써, 비이커 등에의 인자(印字)에 사용해도 된다. 또, 본 발명의 다른 실시형태로서, 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)과, 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)을 포함하는 구성 모노머(a)를 중합하여 얻어진 공중합체(A)를 들 수 있다. 이 공중합체(A)와 상기의 분산액의 용도로서, 예를 들면, 전자기기나, OA 기기, 가전제품, 자동차 내장부품 등의 기구 슬라이딩부나, 기어, 끼워맞춤부 등에 사용함으로써, 윤활성 등을 부여해도 되고, 삐걱거림으로 인해 생기는 소리의 억제 효과를 부여해도 된다. 또, 상기 공중합체(A)는 레벨링제로서 사용되어도 된다. 상기 공중합체(A)가 레벨링제로서 물품에 도포됨으로써, 핀홀이나 도포 얼룩의 발생 등을 억제할 수 있으므로, 균질성과 평활성을 향상할 수 있다. As another embodiment of the present invention, for example, a composition containing the above-described dispersant for fluororesin and a surfactant can be mentioned. The surfactant is not particularly limited, and for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, etc. can be used. In addition, as another embodiment of the present invention, for example, a dispersion containing the above-described dispersant for fluororesin and a fluororesin, or an article impregnated or coated with the dispersion can be mentioned. The dispersion of the present embodiment may have a resin other than a fluororesin dissolved in it. In addition, the dispersion of the present embodiment can be used by impregnating or coating various articles. For example, by impregnating cloth with the dispersion of the present embodiment, it can be used on cloth for tents and the like. In addition, by applying the dispersion of the present embodiment to a beaker and the like, it can be used for printing on a beaker and the like. In addition, as another embodiment of the present invention, a copolymer (A) obtained by polymerizing a constituent monomer (a) containing a (meth)acrylate compound (a1) represented by general formula (1) and a (meth)acrylate compound (a2) represented by general formula (2) can be exemplified. As a use of this copolymer (A) and the dispersion liquid above, for example, by using it in sliding parts, gears, fitting parts, etc. of mechanisms such as electronic devices, OA devices, home appliances, and automobile interior parts, lubricity, etc. can be provided, and an effect of suppressing noise caused by squeaking can be provided. In addition, the copolymer (A) can be used as a leveling agent. By applying the copolymer (A) to an article as a leveling agent, the occurrence of pinholes or coating unevenness, etc. can be suppressed, and therefore homogeneity and smoothness can be improved.
실시예Example
이하, 실시예에 의해 본 발명을 더욱 구체적으로 설명하지만, 본 발명은 이하의 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be described more specifically by examples, but the present invention is not limited to the following examples.
(사용 원료)(Raw materials used)
일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)(Meth)acrylate compound (a1) represented by general formula (1)
(a1-1)(a1-1)
하기 일반식 (12)로 표시되는 화합물(SINOCHEM LANTIAN제, 상품명: AC-500)A compound represented by the following general formula (12) (manufactured by SINOCHEM LANTIAN, trade name: AC-500)
(a1-2)(a1-2)
하기 일반식 (13)으로 표시되는 화합물(SINOCHEM LANTIAN제, 상품명: AC-1000, 평균 반복단위 수 n: 4)A compound represented by the following general formula (13) (manufactured by SINOCHEM LANTIAN, trade name: AC-1000, average number of repeating units n: 4)
일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)(Meth)acrylate compound (a2) represented by general formula (2)
(a2-1) 폴리프로필렌글리콜모노메타크릴레이트(옥시프로필렌기의 평균 반복단위 수: 4∼6, 니치유(주)제, 상품명: 블렘머(등록상표) PP-1000)(a2-1) Polypropylene glycol monomethacrylate (average number of repeating units of oxypropylene group: 4∼6, manufactured by Nichiyu Co., Ltd., product name: Blemmer (registered trademark) PP-1000)
(a2-2) 폴리프로필렌글리콜모노메타크릴레이트(옥시프로필렌기의 평균 반복단위 수: 9, 니치유(주)제, 상품명: 블렘머(등록상표) PP-500)(a2-2) Polypropylene glycol monomethacrylate (average number of repeating units of oxypropylene group: 9, manufactured by Nichiyu Co., Ltd., trade name: Blemmer (registered trademark) PP-500)
(a2-3) 폴리프로필렌글리콜모노메타크릴레이트(옥시프로필렌기의 평균 반복단위 수: 13, 니치유(주)제, 상품명: 블렘머(등록상표) PP-800)(a2-3) Polypropylene glycol monomethacrylate (average number of repeating units of oxypropylene group: 13, manufactured by Nichiyu Co., Ltd., product name: Blemmer (registered trademark) PP-800)
일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)(Meth)acrylate compound (a3) represented by general formula (3)
(a3-1) 메톡시폴리에틸렌글리콜메타크릴레이트(옥시에틸렌기의 평균 반복단위 수: 23, 니치유(주)제, 상품명: 블렘머(등록상표) PME-1000)(a3-1) Methoxy polyethylene glycol methacrylate (average number of repeating units of oxyethylene group: 23, manufactured by Nichiyu Co., Ltd., product name: Blemmer (registered trademark) PME-1000)
(a3-2) 폴리에틸렌글리콜아크릴레이트(옥시에틸렌기의 평균 반복단위 수: 10, 니치유(주)제, 상품명: 블렘머(등록상표) AE-400)(a3-2) Polyethylene glycol acrylate (average number of repeating units of oxyethylene group: 10, manufactured by Nichiyu Co., Ltd., product name: Blemmer (registered trademark) AE-400)
용제solvent
(c-1) 메틸에틸케톤(MEK)(c-1) Methyl ethyl ketone (MEK)
(c-2) 에틸렌글리콜디메틸에테르(DMG)(c-2) Ethylene glycol dimethyl ether (DMG)
(c-3) 3-메톡시-3-메틸부틸아세테이트((주)쿠라레제, 상품명: 솔피트 AC)(c-3) 3-Methoxy-3-methylbutyl acetate (Kurareze Co., Ltd., product name: Solfit AC)
(c-4) 프로필렌글리콜메틸에테르아세테이트(PGMEA)(c-4) Propylene glycol methyl ether acetate (PGMEA)
(c-5) 디에틸렌글리콜디에틸렌에테르(DEDG)(c-5) Diethylene glycol diethylene ether (DEDG)
(c-6) 메틸에틸디글리콜(MEDG)(c-6) Methyl ethyl diglycol (MEDG)
(c-7) 아세트산 에틸(c-7) Ethyl acetate
(c-8) 에탄올(c-8) Ethanol
(실시예 1∼18, 비교예 1∼4)(Examples 1 to 18, Comparative Examples 1 to 4)
교반기, 온도계, 질소도입관 및 환류관을 갖춘 반응 용기에, 후술하는 표 1 및 표 2에 기재된 배합 비율로, (a1)∼(a3)의 화합물 및 용제를 가하고, 질소 치환을 행했다. 이어서, t-부틸퍼옥시피발레이트(니치유(주)제, 상품명: 퍼부틸(등록상표) PV)를, 상기 (a1)∼(a3)의 화합물의 합계량 100질량부에 대하여 3질량부가 되도록 가하고, 65℃에서 8시간 반응시킴으로써 공중합체 용액(분산제)을 얻었다. In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux tube, the compounds (a1) to (a3) and solvents were added at the mixing ratios described in Tables 1 and 2 below, and nitrogen substitution was performed. Next, t-butyl peroxypivalate (manufactured by NOF Co., Ltd., trade name: Perbutyl (registered trademark) PV) was added in an amount of 3 parts by mass based on 100 parts by mass of the total amount of the compounds (a1) to (a3), and the mixture was reacted at 65°C for 8 hours, thereby obtaining a copolymer solution (dispersant).
(실시예 19)(Example 19)
교반기, 온도계, 질소도입관 및 환류관을 갖춘 반응 용기에, 후술하는 표 2에 기재된 배합 비율로, (a1), (a2)의 화합물 및 용제로서 MEK 230부를 가하고, 질소 치환을 행했다. 이어서, t-부틸퍼옥시피발레이트(니치유(주)제, 상품명: 퍼부틸(등록상표) PV)를, 상기 (a1), (a2)의 화합물의 합계량 100질량부에 대하여 3질량부가 되도록 가하고, 65℃에서 8시간 반응시킴으로써 반응 용액을 얻었다. 이 반응 용액 중의 MEK를 감압 증류 제거한 후, 아세트산 에틸 230부를 첨가하고, 60℃에서 1시간 혼합함으로써, 공중합체 용액(분산제)을 얻었다. In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux tube, the compounds of (a1) and (a2) and 230 parts of MEK as a solvent were added at the mixing ratios described in Table 2 below, and nitrogen replacement was performed. Next, t-butyl peroxypivalate (manufactured by NOF Co., Ltd., trade name: Perbutyl (registered trademark) PV) was added in an amount of 3 parts by mass based on 100 parts by mass of the total amount of the compounds of (a1) and (a2), and the mixture was reacted at 65°C for 8 hours, thereby obtaining a reaction solution. After the MEK in the reaction solution was distilled off under reduced pressure, 230 parts of ethyl acetate was added, and mixing was performed at 60°C for 1 hour, thereby obtaining a copolymer solution (dispersant).
(실시예 20)(Example 20)
교반기, 온도계, 질소도입관 및 환류관을 갖춘 반응 용기에, 후술하는 표 2에 기재된 배합 비율로, (a1), (a2)의 화합물, 및 용제로서 MEK 230부를 가하고, 질소 치환을 행했다. 이어서, t-부틸퍼옥시피발레이트(니치유(주)제, 상품명: 퍼부틸(등록상표) PV)를, 상기 (a1), (a2)의 화합물의 합계량 100질량부에 대하여 3질량부가 되도록 가하고, 65℃에서 8시간 반응시킴으로써 반응 용액을 얻었다. 이 반응 용액 중의 MEK를 감압 증류 제거한 후, 에탄올 230부를 첨가하고, 60℃에서 1시간 혼합함으로써, 공중합체 용액(분산제)을 얻었다. In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux tube, the compounds of (a1) and (a2) and 230 parts of MEK as a solvent were added at the mixing ratios described in Table 2 below, and nitrogen replacement was performed. Next, t-butyl peroxypivalate (manufactured by NOF Co., Ltd., trade name: Perbutyl (registered trademark) PV) was added in an amount of 3 parts by mass based on 100 parts by mass of the total amount of the compounds of (a1) and (a2), and the mixture was reacted at 65°C for 8 hours, thereby obtaining a reaction solution. After the MEK in the reaction solution was distilled off under reduced pressure, 230 parts of ethanol was added, and mixing was performed at 60°C for 1 hour, thereby obtaining a copolymer solution (dispersant).
제작한 분산제를 사용하여, 이하의 평가를 행했다. 구체적으로는, 다양한 용매를 사용한 경우에 있어서의 하기의 각 성능에 대한 평가를 행했다. Using the manufactured dispersant, the following evaluations were conducted. Specifically, the following performances were evaluated when using various solvents.
(외관(투명성))(Appearance (Transparency))
제작한 분산제를, 외경 3.5cm의 스크루관병((주)마루엠제 No.8) 2개에, 한쪽은 높이가 10cm가 되도록, 다른 쪽은 높이가 1cm가 되도록 부었다. 문자(MS 고딕, 12포인트)가 인쇄된 용지 위에 각 스크루관병을 놓고, 상방으로부터의 문자의 시인에 의해 이하의 3단계로 외관을 평가했다. 또한, 함불소 공중합체 용액이 겔 모양으로 된 경우는, 평가 결과를 D로 하고, 투명성의 확인은 실시하지 않는 것으로 했다. The prepared dispersion was poured into two screw tube bottles (Marum Co., Ltd. No. 8) with an outer diameter of 3.5 cm, so that one side was 10 cm high and the other side was 1 cm high. Each screw tube bottle was placed on paper printed with characters (MS Gothic, 12 point), and the appearance was evaluated in the following three stages by viewing the characters from above. In addition, when the fluorinated copolymer solution became a gel, the evaluation result was set as D, and confirmation of transparency was not performed.
A: 투명(높이 10cm, 1cm 어느 쪽의 스크루관병에서도, 아래로 기재된 문자를 읽을 수 있음)A: Transparent (You can read the letters written below in either a 10cm or 1cm screw bottle)
B: 미탁(높이 10cm의 스크루관병의 아래에 기재한 문자는 읽을 수 없지만, 높이 1cm의 스크루관병 아래에 기재된 문자는 읽을 수 있음)B: Unreadable (the letters written under a 10cm tall screw bottle are unreadable, but the letters written under a 1cm tall screw bottle are readable)
C: 백탁(높이 10cm, 1cm 어느 쪽의 스크루관병에서도, 아래에 기재된 문자를 읽을 수 없음)C: White turbidity (the letters written below cannot be read in either the 10cm or 1cm screw-pipe bottles)
(NMP 분산성 평가)(NMP dispersibility assessment)
외경 3.0cm의 스크루관병((주)마루엠제 No.7)에, 분산제 1.67g(장입량)과, N-메틸피롤리돈(NMP)(분산매) 8.33g(장입량)을 혼합한 후, 폴리테트라플루오로에틸렌(PTFE)((주)세이신키교제, 상품명: TFW-2000(평균 입자직경 6㎛)) 10g(장입량)을 첨가했다. 그 후, 스크루관병을 상하로 30회 진탕함으로써, PTFE를 분산시켰다. 또한, 이 진탕만으로 PTFE가 분산되지 않는 경우, PTFE를 스패튤러로 용액까지 ?씨爭? 후, 진탕함으로써 분산시켰다. 그리고, 밤새 정치 후, 불필요한 거품을 일으키지 않도록 스패튤러로 교반하여 PTFE를 재분산시킨 후, 신속하게 분산액을 스테인레스강의 평직 철망(간사이카나아미(주)제)(200메시, 선 직경 0.05mm)으로 여과한 후, 20분간 정치시킴으로써 불필요한 액체 부분을 평직 철망으로 제거했다. 그 후, 150℃에서 20분간, 알루미늄 호일 위에서 평직 철망을 건조시켰다. 그리고, 사전에 측정해 둔 알루미늄 호일과 평직 철망의 합계 질량을 전체 질량에서 뺌으로써, PTFE 잔사의 질량을 산출했다. In a screw tube bottle (Marum Co., Ltd. No. 7) with an outer diameter of 3.0 cm, 1.67 g (charge amount) of a dispersant and 8.33 g (charge amount) of N-methylpyrrolidone (NMP) (dispersing medium) were mixed, and then 10 g (charge amount) of polytetrafluoroethylene (PTFE) (Seishin Kikyo Co., Ltd., trade name: TFW-2000 (average particle diameter 6 ㎛)) was added. Thereafter, the PTFE was dispersed by shaking the screw tube bottle up and down 30 times. In cases where the PTFE was not dispersed by this shaking alone, the PTFE was mixed into the solution with a spatula and then dispersed by shaking. Then, after standing overnight, the PTFE was redispersed by stirring with a spatula so as not to generate unnecessary bubbles, and the dispersion was quickly filtered through a stainless steel plain-weave wire mesh (manufactured by Kansai Kanaami Co., Ltd.) (200 mesh, wire diameter 0.05 mm), and the unnecessary liquid portion was removed with the plain-weave wire mesh by standing for 20 minutes. Thereafter, the plain-weave wire mesh was dried on aluminum foil at 150°C for 20 minutes. Then, the mass of the PTFE residue was calculated by subtracting the total mass of the aluminum foil and the plain-weave wire mesh, which had been measured in advance, from the total mass.
(톨루엔 분산성 평가)(Toluene dispersibility evaluation)
스크루관병((주)마루엠제 No.7)에, 분산제 1.67g(장입량)과, 톨루엔(분산매) 8.33g(장입량)을 혼합한 후, 폴리테트라플루오로에틸렌(PTFE)((주)세이신키교제, 상품명: TFW-2000(평균 입자직경 6㎛)) 10g(장입량)을 첨가했다. 그 후, 스크루관병을 상하로 30회 진탕함으로써, PTFE를 분산시켰다. 또한, 이 진탕만으로 PTFE가 분산되지 않는 경우, PTFE를 스패튤러로 용액까지 ?씨爭? 후, 진탕함으로써 분산시켰다. 그리고, 밤새 정치 후, 불필요한 거품을 일으키지 않도록 스패튤러로 교반하여 PTFE를 재분산시킨 후, 신속하게 분산액을 스테인레스강의 평직 철망(간사이카나아미(주)제)(200메시, 선 직경 0.05mm)으로 여과한 후, 20분간 정치시킴으로써 불필요한 액체 부분을 평직 철망으로부터 제거했다. 그 후, 150℃에서 20분간, 알루미늄 호일 위에서 평직 철망을 건조시켰다. 그리고, 사전에 측정해 둔 알루미늄 호일과 평직 철망의 합계 질량을 전체 질량으로부터 뺌으로써, PTFE 잔사의 질량을 산출했다. In a screw tube bottle (Marum Manufacturing Co., Ltd. No. 7), 1.67 g (charge amount) of a dispersant and 8.33 g (charge amount) of toluene (dispersing medium) were mixed, and then 10 g (charge amount) of polytetrafluoroethylene (PTFE) (Seishin Kikyo Manufacturing Co., Ltd., trade name: TFW-2000 (average particle diameter 6 ㎛)) was added. Thereafter, the PTFE was dispersed by shaking the screw tube bottle up and down 30 times. In cases where the PTFE was not dispersed by this shaking alone, the PTFE was mixed into the solution with a spatula and then dispersed by shaking. Then, after standing overnight, the PTFE was redispersed by stirring with a spatula so as not to generate unnecessary bubbles, and the dispersion was quickly filtered through a stainless steel plain-weave wire mesh (manufactured by Kansai Kanaami Co., Ltd.) (200 mesh, wire diameter 0.05 mm), and the unnecessary liquid portion was removed from the plain-weave wire mesh by standing for 20 minutes. Thereafter, the plain-weave wire mesh was dried on aluminum foil at 150°C for 20 minutes. Then, the mass of the PTFE residue was calculated by subtracting the total mass of the aluminum foil and the plain-weave wire mesh, which had been measured in advance, from the total mass.
NMP 분산성 평가 및 톨루엔 분산성 평가에는, PTFE 잔사의 질량을 PTFE의 장입량으로 나눈 값(%)을 사용했다. 이 값이 작을수록, 분산성이 우수하기 때문에 바람직하다. 구체적으로는, NMP 분산성 및 톨루엔 분산성을 이하의 5단계로 평가했다. For the evaluation of NMP dispersibility and toluene dispersibility, the value (%) obtained by dividing the mass of PTFE residue by the loading amount of PTFE was used. The smaller this value, the better the dispersibility, which is preferable. Specifically, the NMP dispersibility and toluene dispersibility were evaluated in the following five stages.
A: 4% 미만A: Less than 4%
B: 4% 이상 9% 미만B: 4% or more but less than 9%
C: 9% 이상 40% 미만C: 9% or more but less than 40%
D: 40% 이상 70% 미만D: 40% or more but less than 70%
E: 70% 이상E: 70% or more
(수분산성 평가)(Evaluation of water dispersibility)
스크루관병((주)마루엠제 No.7)에, 분산제 0.67g(장입량)과 물(분산매) 8.33g(장입량)과 비이온 계면활성제 1.00g(장입량)을 혼합한 후, 폴리테트라플루오로에틸렌(PTFE)((주)세이신키교제, 상품명: TFW-2000(평균 입자직경 6㎛)) 10g(장입량)을 첨가했다. 여기에서, 비이온 계면활성제로서 폴리옥시알킬렌 분기 데실에테르(다이이치코교세이야쿠(주)제 「노이겐 XL-70」)를 사용했다. 그 후, 스크루관병을 상하로 30회 진탕함으로써, PTFE를 분산시켰다. 또한, 이 진탕만으로 PTFE가 분산되지 않는 경우, PTFE를 스패튤러로 용액까지 ?씨爭? 후, 진탕함으로써 분산시켰다. 그리고, 밤새 정치 후, 불필요한 거품을 일으키지 않도록 스패튤러로 교반하여 PTFE를 재분산시킨 후, 신속하게 분산액을 스테인레스강의 평직 철망(간사이카나아미(주)제)(200메시, 선 직경 0.05mm)으로 여과한 후, 20분간 정치시킴으로써 불필요한 액체 부분을 평직 철망으로부터 제거했다. 그 후, 150℃에서 20분간, 알루미늄 호일 위에서 평직 철망을 건조시켰다. 그리고, 사전에 측정해 둔 알루미늄 호일과 평직 철망의 합계 질량을 전체 질량으로부터 뺌으로써, PTFE 잔사의 질량을 산출했다. In a screw tube bottle (Marum Co., Ltd. No. 7), 0.67 g (charged amount) of a dispersant, 8.33 g (charged amount) of water (dispersing medium), and 1.00 g (charged amount) of a nonionic surfactant were mixed, and then 10 g (charged amount) of polytetrafluoroethylene (PTFE) (Seishin Kikyo Co., Ltd., trade name: TFW-2000 (average particle diameter 6 μm)) was added. Here, polyoxyalkylene branched decyl ether ("Noigen XL-70" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used as the nonionic surfactant. Thereafter, the PTFE was dispersed by shaking the screw tube bottle up and down 30 times. In cases where the PTFE was not dispersed by this shaking alone, the PTFE was mixed into the solution with a spatula, and then dispersed by shaking. Then, after standing overnight, the PTFE was redispersed by stirring with a spatula so as not to generate unnecessary bubbles, and the dispersion was quickly filtered through a stainless steel plain-weave wire mesh (manufactured by Kansai Kanaami Co., Ltd.) (200 mesh, wire diameter 0.05 mm), and the unnecessary liquid portion was removed from the plain-weave wire mesh by standing for 20 minutes. Thereafter, the plain-weave wire mesh was dried on aluminum foil at 150°C for 20 minutes. Then, the mass of the PTFE residue was calculated by subtracting the total mass of the aluminum foil and the plain-weave wire mesh, which had been measured in advance, from the total mass.
수분산성의 평가에는, PTFE 잔사의 질량을 PTFE의 장입량으로 나눈 값(%)을 사용했다. 이 값이 작을수록, 분산성이 우수하기 때문에 바람직하다. 구체적으로는, 수분산성을 이하의 5단계로 평가했다. To evaluate the water dispersibility, the value (%) obtained by dividing the mass of PTFE residue by the PTFE loading amount was used. The smaller this value, the better the dispersibility, which is desirable. Specifically, the water dispersibility was evaluated in the following five stages.
A: 4% 미만A: Less than 4%
B: 4% 이상 9% 미만B: 4% or more but less than 9%
C: 9% 이상 40% 미만C: 9% or more but less than 40%
D: 40% 이상 70% 미만D: 40% or more but less than 70%
E: 70% 이상E: 70% or more
상기의 표 1 및 표 2의 결과로부터 이하를 알 수 있었다. 즉, 상기의 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1) 및 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)을 포함하는 구성 모노머(a)를 중합하여 얻어진 공중합체를 포함하는 분산제는, 구성 모노머(a)에 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1) 또는 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)을 포함하지 않는 경우와 비교하여, NMP 분산성 및 톨루엔 분산성이 현저하게 우수한 것을 알았다. 또한, 표에는 나타내지 않았지만, MEK에 대한 분산성은 톨루엔 분산성과 동일한 결과가 얻어졌다. From the results in Tables 1 and 2 above, the following could be known. That is, it was found that a dispersant including a copolymer obtained by polymerizing a constituent monomer (a) including a (meth)acrylate compound (a1) represented by the general formula (1) and a (meth)acrylate compound (a2) represented by the general formula (2) was remarkably excellent in NMP dispersibility and toluene dispersibility compared to a case where the constituent monomer (a) did not include the (meth)acrylate compound (a1) represented by the general formula (1) or the (meth)acrylate compound (a2) represented by the general formula (2). In addition, although not shown in the table, the same result as the toluene dispersibility was obtained for the dispersibility for MEK.
또, 상기의 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)을 더 포함하는 구성 모노머(a)를 중합하여 얻어진 공중합체를 포함하는 분산제는, 구성 모노머(a)에 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)을 포함하지 않는 경우와 비교하여, 수분산성이 현저하게 우수한 것을 알았다. 또, 표에는 나타내지 않았지만, 일반식 (3)으로 표시되는 (메타)아크릴레이트 화합물(a3)보다, 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)을 사용한 경우 쪽이 거품 발생이 적은 경향이 있었다. In addition, it was found that a dispersant including a copolymer obtained by polymerizing a constituent monomer (a) further including a (meth)acrylate compound (a3) represented by the general formula (3) above has remarkably excellent water dispersibility compared to a case where the constituent monomer (a) does not include the (meth)acrylate compound (a3) represented by the general formula (3). In addition, although not shown in the table, there was a tendency for less foaming to occur when a (meth)acrylate compound (a2) represented by the general formula (2) was used rather than a (meth)acrylate compound (a3) represented by the general formula (3).
<불가능·비실제적 사정><Impossible/Impractical Circumstances>
본 실시형태의 불소 수지용 분산제는 상기의 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1) 및 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)을 포함하는 구성 모노머를 중합하여 얻어진 공중합체(A)를 포함한다. 이 공중합체의 구조는 복잡하기 때문에, 일반식으로 나타내는 것은 곤란하다. 또한, 구조가 특정되지 않으면, 그것에 따라 정해지는 그 물질의 특성도 용이하게는 특정할 수 없다. 즉, 본 실시형태의 불소 수지용 분산제가 함유하는 공중합체를, 그 구조 또는 특성에 의해 직접 특정하는 것은 불가능하다. The dispersant for fluororesin of the present embodiment contains a copolymer (A) obtained by polymerizing a constituent monomer including a (meth)acrylate compound (a1) represented by the general formula (1) and a (meth)acrylate compound (a2) represented by the general formula (2). Since the structure of this copolymer is complex, it is difficult to express it by a general formula. Furthermore, if the structure is not specified, the properties of the substance determined by it cannot be easily specified. That is, it is impossible to directly specify the copolymer contained in the dispersant for fluororesin of the present embodiment by its structure or properties.
본 발명은, 상기의 실시형태에 한정되는 것은 아니고, 그 취지를 일탈하지 않는 범위에서 여러 구성으로 실현할 수 있다. 예를 들면, 발명의 개요의 난에 기재한 각 형태 중의 기술적 특징에 대응하는 실시형태, 실시예 중의 기술적 특징은, 상기의 과제의 일부 또는 전부를 해결하기 위해, 또는, 상기의 효과의 일부 또는 전부를 달성하기 위해, 적당하게, 바꾸기나, 조합을 행할 수 있다. 또, 그 기술적 특징이 본 명세서 중에 필수적인 것으로서 설명되어 있지 않으면, 적당하게, 삭제하는 것이 가능하다. The present invention is not limited to the above-described embodiments, and can be realized in various configurations without departing from the scope of the invention. For example, the technical features in the embodiments and examples corresponding to the technical features in each form described in the summary of the invention can be appropriately replaced or combined in order to solve part or all of the above-described problems, or to achieve part or all of the above-described effects. In addition, if the technical feature is not described as essential in this specification, it can be appropriately deleted.
Claims (10)
상기 공중합체는
하기 일반식 (1)로 표시되는 (메타)아크릴레이트 화합물(a1)과,
하기 일반식 (2)로 표시되는 (메타)아크릴레이트 화합물(a2)
을 포함하는 구성 모노머(a)를 중합하여 얻어진 공중합체를 포함하는 것을 특징으로 하는, 불소 수지용 분산제.
Rf-Cb-R-O-X (1)
(식 중, Rf는 퍼플루오로(폴리)에테르기이고, Cb는 에스테르 결합, 아미드 결합, 및 우레탄 결합으로 이루어지는 군으로부터 선택되는 어느 1개의 연결기이고, R은 탄소 원자 수 1 이상 8 이하의 알킬렌기이며, X는 아크릴로일기 또는 메타크릴로일기이다.)
HO-(PO)p-Y (2)
(식 중, PO는 옥시프로필렌기이고, p는 2 이상 150 이하의 수이며, Y는 아크릴로일기 또는 메타크릴로일기이다.)As a dispersant for fluororesin containing a copolymer,
The above copolymer
A (meth)acrylate compound (a1) represented by the following general formula (1),
(Meth)acrylate compound (a2) represented by the following general formula (2)
A dispersant for fluororesin, characterized in that it comprises a copolymer obtained by polymerizing a constituent monomer (a) including:
R f -Cb-ROX (1)
(In the formula, R f is a perfluoro(poly)ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, R is an alkylene group having 1 to 8 carbon atoms, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)pY (2)
(In the formula, PO is an oxypropylene group, p is a number greater than or equal to 2 and less than or equal to 150, and Y is an acryloyl group or a methacryloyl group.)
AO-(EO)q-Z (3)
(식 중, A는 H 또는 CH3이고, EO는 옥시에틸렌기이고, q는 2 이상 150 이하의 수이며, Z는 아크릴로일기 또는 메타크릴로일기이다.)A dispersant for a fluororesin, characterized in that in claim 1 or 2, the constituent monomer (a) further includes a (meth)acrylate compound (a3) represented by the following general formula (3).
AO-(EO)qZ (3)
(In the formula, A is H or CH 3 , EO is an oxyethylene group, q is a number greater than or equal to 2 and less than or equal to 150, and Z is an acryloyl group or a methacryloyl group.)
Rf-Cb-R-O-X (1)
(식 중, Rf는 퍼플루오로(폴리)에테르기이고, Cb는 에스테르 결합, 아미드 결합, 및 우레탄 결합으로 이루어지는 군으로부터 선택되는 어느 1개의 연결기이고, R은 탄소 원자 수 1 이상 8 이하의 알킬렌기이며, X는 아크릴로일기 또는 메타크릴로일기이다.)
HO-(PO)p-Y (2)
(식 중, PO는 옥시프로필렌기이고, p는 2 이상 150 이하의 수이며, Y는 아크릴로일기 또는 메타크릴로일기이다.)A copolymer obtained by polymerizing a constituent monomer (a) comprising a (meth)acrylate compound (a1) represented by the following general formula (1) and a (meth)acrylate compound (a2) represented by the following general formula (2).
R f -Cb-ROX (1)
(In the formula, R f is a perfluoro(poly)ether group, Cb is any one linking group selected from the group consisting of an ester bond, an amide bond, and a urethane bond, R is an alkylene group having 1 to 8 carbon atoms, and X is an acryloyl group or a methacryloyl group.)
HO-(PO)pY (2)
(In the formula, PO is an oxypropylene group, p is a number greater than or equal to 2 and less than or equal to 150, and Y is an acryloyl group or a methacryloyl group.)
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| JP2021212282A JP7136994B1 (en) | 2021-12-27 | 2021-12-27 | Dispersants for fluororesins, compositions, dispersions, articles and copolymers |
| PCT/JP2022/047006 WO2023127617A1 (en) | 2021-12-27 | 2022-12-21 | Dispersant for fluororesin, composition, dispersion liquid, article, and copolymer |
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| JP5446202B2 (en) | 2008-10-10 | 2014-03-19 | Ｄｉｃ株式会社 | Dispersant for fluororesin particles, fluororesin particle dispersion and fluororesin paint |
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