JP7382445B2 - A fluorine-containing sulfonylimide, a method for producing a reactive fluorine-containing sulfonylimide, and a method for producing a copolymer. - Google Patents
A fluorine-containing sulfonylimide, a method for producing a reactive fluorine-containing sulfonylimide, and a method for producing a copolymer. Download PDFInfo
- Publication number
- JP7382445B2 JP7382445B2 JP2022078803A JP2022078803A JP7382445B2 JP 7382445 B2 JP7382445 B2 JP 7382445B2 JP 2022078803 A JP2022078803 A JP 2022078803A JP 2022078803 A JP2022078803 A JP 2022078803A JP 7382445 B2 JP7382445 B2 JP 7382445B2
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- JP
- Japan
- Prior art keywords
- containing sulfonylimide
- fluorine
- reactive fluorine
- sulfonylimide
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052731 fluorine Inorganic materials 0.000 title claims description 146
- 239000011737 fluorine Substances 0.000 title claims description 143
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 142
- 125000005463 sulfonylimide group Chemical group 0.000 title claims description 139
- 229920001577 copolymer Polymers 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000178 monomer Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 13
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 claims description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- -1 sulfonyl compound Chemical class 0.000 description 64
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 63
- 238000006243 chemical reaction Methods 0.000 description 56
- 239000000243 solution Substances 0.000 description 43
- 239000000203 mixture Substances 0.000 description 42
- 238000005481 NMR spectroscopy Methods 0.000 description 38
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- 239000002904 solvent Substances 0.000 description 18
- 150000001768 cations Chemical class 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 239000002216 antistatic agent Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 150000007960 acetonitrile Chemical class 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000003505 polymerization initiator Substances 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910001413 alkali metal ion Inorganic materials 0.000 description 10
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000011698 potassium fluoride Substances 0.000 description 6
- 235000003270 potassium fluoride Nutrition 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BRUZZEMTHTULBO-UHFFFAOYSA-N potassium;methylazanide Chemical compound [K+].[NH-]C BRUZZEMTHTULBO-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- VXRNSSZOLMMPBY-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonamide;potassium Chemical compound [K].NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VXRNSSZOLMMPBY-UHFFFAOYSA-N 0.000 description 1
- JHHBILFKAVPGAP-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl fluoride Chemical compound FS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O JHHBILFKAVPGAP-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- KHJQQUGSPDBDRM-UHFFFAOYSA-M 1-ethyl-1-methylpyrrolidin-1-ium;bromide Chemical compound [Br-].CC[N+]1(C)CCCC1 KHJQQUGSPDBDRM-UHFFFAOYSA-M 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
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004419 alkynylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- JUXVYADNSPUZHF-UHFFFAOYSA-N difluoromethanedisulfonyl fluoride Chemical compound FS(=O)(=O)C(F)(F)S(F)(=O)=O JUXVYADNSPUZHF-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- HTKPDYSCAPSXIR-UHFFFAOYSA-N octyltrimethylammonium ion Chemical compound CCCCCCCC[N+](C)(C)C HTKPDYSCAPSXIR-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- REOPKWVPPXKXEU-UHFFFAOYSA-N potassium;trifluoromethanesulfonamide Chemical compound [K].NS(=O)(=O)C(F)(F)F REOPKWVPPXKXEU-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- NRZWQKGABZFFKE-UHFFFAOYSA-N trimethylsulfonium Chemical compound C[S+](C)C NRZWQKGABZFFKE-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、含フッ素スルホニルイミドに関するものである。 The present invention relates to fluorine-containing sulfonylimides.
樹脂は、絶縁抵抗性が高いため、摩擦などの物理的な作用によって静電気を帯電しやすいという性質を有している。例えば、フラットディスプレイパネルの製造工程において、パネル面の傷や汚れを防止するために、パネル面に保護膜として樹脂フィルムを貼付することが行なわれているが、この樹脂フィルムをパネル面から剥がす際に、剥離帯電により静電気障害を起こすおそれがある。また、帯電した樹脂はごみや埃を吸着してしまうおそれがある。 Since resin has high insulation resistance, it has the property of being easily charged with static electricity due to physical effects such as friction. For example, in the manufacturing process of flat display panels, a resin film is pasted on the panel surface as a protective film to prevent scratches and dirt on the panel surface. In addition, there is a risk of electrostatic damage caused by peel-off charging. Furthermore, the charged resin may attract dirt and dust.
剥離帯電を防止するために、樹脂フィルムは、その粘着剤層に帯電防止剤を添加して樹脂フィルム表面の電気抵抗を低減させることが行なわれている。帯電防止剤としては、ビスパーフルオロアルカンスルホニルイミドリチウムなどが利用されている。 In order to prevent electrification from peeling off, an antistatic agent is added to the adhesive layer of the resin film to reduce the electrical resistance on the surface of the resin film. As the antistatic agent, lithium bisperfluoroalkanesulfonylimide and the like are used.
特許文献1には、アクリル系共重合体、ビストリフルオロメタンスルホニルイミドリチウムなどの帯電防止剤、腐食防止剤、及び多官能性架橋剤を含む粘着剤組成物が開示されている。 Patent Document 1 discloses an adhesive composition containing an acrylic copolymer, an antistatic agent such as lithium bistrifluoromethanesulfonylimide, a corrosion inhibitor, and a polyfunctional crosslinking agent.
樹脂フィルムの剥離帯電を防止するために、樹脂フィルムの粘着剤層に用いられる粘着剤組成物に帯電防止剤を添加することは有効な方法である。しかしながら、樹脂フィルムを高温高湿環境下で保存すると、粘着剤組成物に添加した帯電防止剤がブリードアウトして、粘着剤層の帯電防止効果が低下するおそれがある。 In order to prevent electrification during peeling of a resin film, it is an effective method to add an antistatic agent to the adhesive composition used for the adhesive layer of the resin film. However, if the resin film is stored in a high temperature and high humidity environment, the antistatic agent added to the adhesive composition may bleed out, which may reduce the antistatic effect of the adhesive layer.
本発明は、上記事情に鑑みてなされたものであって、その目的は、高温高湿環境下で保存してもブリードアウトが起こりにくい帯電防止剤として利用可能な化合物の中間体として用いることができる新規な含フッ素スルホニルイミドを提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is to use it as an intermediate for a compound that can be used as an antistatic agent that is unlikely to bleed out even when stored in a high temperature and high humidity environment. An object of the present invention is to provide a novel fluorine-containing sulfonylimide that can be produced.
本発明の発明者は、上記課題について鋭意検討した結果、帯電防止効果を有するパーフルオロアルカンスルホニルイミド塩に反応性官能基として(メタ)アクリロイル基を導入した反応性含フッ素スルホニルイミドを、他のモノマーと共重合させた共重合体は、優れた帯電防止性を有し、かつ高温高湿環境下で保存してもブリードアウトが発生しにくいことを見出して、本発明を完成させた。
すなわち、本発明は、以下の構成を有する。
As a result of intensive studies on the above-mentioned problems, the inventors of the present invention have developed a reactive fluorine-containing sulfonylimide in which a (meth)acryloyl group is introduced as a reactive functional group into a perfluoroalkanesulfonylimide salt having an antistatic effect. The present invention was completed based on the discovery that a copolymer copolymerized with a monomer has excellent antistatic properties and is less likely to bleed out even when stored in a high temperature, high humidity environment.
That is, the present invention has the following configuration.
[1]下記の一般式(I)で表される含フッ素スルホニルイミド。 [1] A fluorine-containing sulfonylimide represented by the following general formula (I).
ただし、上記の一般式(I)において、R2は水素原子、炭素数1~10の直鎖状あるいは分岐状のアルキル基、アルカリ金属イオンまたはオニウムカチオンを表し、Rf1はフッ素原子または炭素数1~4の直鎖状あるいは分岐状のパーフルオロアルキル基を表し、Rf2は炭素数1~4の直鎖状あるいは分岐状のパーフルオロアルキレン基を表し、A+はアルカリ金属イオンまたはオニウムカチオンを表し、Yはアルカリ金属イオン、オニウムカチオン、-炭素数1~10のアルキレン基-OH基または-(CH2)2-NH2基を表し、Yがアルカリ金属イオンまたはオニウムカチオンである場合、R2は水素原子、炭素数1~10の直鎖状あるいは分岐状のアルキル基である。 However, in the above general formula (I), R 2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkali metal ion or an onium cation, and Rf 1 represents a fluorine atom or a carbon number Represents a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms, Rf 2 represents a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms, and A + represents an alkali metal ion or an onium cation. , Y represents an alkali metal ion, onium cation, -alkylene group having 1 to 10 carbon atoms -OH group or -(CH 2 ) 2 -NH 2 group, and when Y is an alkali metal ion or onium cation, R 2 is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.
[2]前記Rf2が、炭素数3の直鎖状パーフルオロアルキレン基であることを特徴とする[1]に記載の含フッ素スルホニルイミド。
[3]前記R2および前記Yのどちらか一方と、前記A+とが、アルカリ金属イオンであることを特徴とする[1]または[2]に記載の含フッ素スルホニルイミド。
[4]前記R2が、炭素数1~4の直鎖状あるいは分岐状のアルキル基であることを特徴とする[1]または[2]に記載の含フッ素スルホニルイミド。
[2] The fluorine-containing sulfonylimide according to [1], wherein the Rf 2 is a linear perfluoroalkylene group having 3 carbon atoms.
[3] The fluorine-containing sulfonylimide according to [1] or [2], wherein either one of R 2 and Y and A + are alkali metal ions.
[4] The fluorine-containing sulfonylimide according to [1] or [2], wherein R 2 is a linear or branched alkyl group having 1 to 4 carbon atoms.
[5]下記の式(2i)で表される[1]に記載の含フッ素スルホニルイミド。 [5] The fluorine-containing sulfonylimide according to [1], which is represented by the following formula (2i).
[6]下記の式(3i)で表される[1]に記載の含フッ素スルホニルイミド。 [6] The fluorine-containing sulfonylimide according to [1], which is represented by the following formula (3i).
[7]下記の式(4i)で表される[1]に記載の含フッ素スルホニルイミド。 [7] The fluorine-containing sulfonylimide according to [1], which is represented by the following formula (4i).
[8]下記の式(6i)で表される[1]に記載の含フッ素スルホニルイミド。 [8] The fluorine-containing sulfonylimide according to [1], which is represented by the following formula (6i).
[9]下記の式(7i)で表される[1]に記載の含フッ素スルホニルイミド。 [9] The fluorine-containing sulfonylimide according to [1], which is represented by the following formula (7i).
[10]下記の一般式(8i)で表される[1]に記載の含フッ素スルホニルイミド。 [10] The fluorine-containing sulfonylimide according to [1], which is represented by the following general formula (8i).
本発明によれば、高温高湿環境下で保存してもブリードアウトが起こりにくい帯電防止剤として利用可能な化合物(反応性含フッ素スルホニルイミド)の中間体として用いることができる新規な含フッ素スルホニルイミドを提供することが可能となる。 According to the present invention, a novel fluorine-containing sulfonyl compound that can be used as an intermediate for a compound (reactive fluorine-containing sulfonylimide) that can be used as an antistatic agent that does not easily bleed out even when stored in a high temperature and high humidity environment It becomes possible to provide imide.
以下、本発明を適用した一実施形態である含フッ素スルホニルイミド、その含フッ素スルホニルイミドを用いて合成される反応性含フッ素スルホニルイミド(本実施形態の反応性含フッ素スルホニルイミドということもある)及びその溶液(本実施形態の反応性含フッ素スルホニルイミド溶液ということもある)、並びに反応性含フッ素スルホニルイミドに基づく繰り返し単位を含む反応性含フッ素スルホニルイミド含有共重合体(本実施形態の反応性含フッ素スルホニルイミド含有共重合体ということもある)及びその溶液(本実施形態の反応性含フッ素スルホニルイミド含有共重合体溶液ということもある)を詳細に説明する。 Hereinafter, a fluorine-containing sulfonylimide according to an embodiment of the present invention, and a reactive fluorine-containing sulfonylimide synthesized using the fluorine-containing sulfonylimide (sometimes referred to as the reactive fluorine-containing sulfonylimide of this embodiment) and its solution (also referred to as the reactive fluorine-containing sulfonylimide solution of the present embodiment), and a reactive fluorine-containing sulfonylimide-containing copolymer containing a repeating unit based on the reactive fluorine-containing sulfonylimide (the reactive fluorine-containing sulfonylimide solution of the present embodiment). The reactive fluorine-containing sulfonylimide-containing copolymer) and its solution (also referred to as the reactive fluorine-containing sulfonylimide-containing copolymer solution of the present embodiment) will be described in detail.
<反応性含フッ素スルホニルイミド>
本実施形態の反応性含フッ素スルホニルイミドは、下記の一般式(1)で表される。
<Reactive fluorine-containing sulfonylimide>
The reactive fluorine-containing sulfonylimide of this embodiment is represented by the following general formula (1).
上記の一般式(1)において、R1は、水素原子またはメチル基を表す。
R2は、水素原子、炭素数1~10の直鎖状あるいは分岐状のアルキル基、アルカリ金属イオンまたはオニウムカチオンを表す。アルカリ金属イオンの例としては、リチウム、ナトリウム、カリウムを挙げることができる。オニウムカチオンは、例えば、窒素、硫黄、酸素、リン、セレン、錫、ヨウ素、アンチモン等の孤立電子対を有する元素を含んだ化合物に陽イオン型の原子団が配位して生ずる少なくとも一つの有機基を有するカチオンであれば、特に制限されるものではない。オニウムカチオンとしては、アンモニウムカチオン類、ピロリジニウムカチオン類、イミダゾリウムカチオン類、ピリジニウムカチオン類、スルホニウムカチオン類、ホスホニウムカチオン類を用いることができる。アンモニウムカチオン類の例としては、テトラメチルアンモニウムカチオン、テトラエチルアンモニウムカチオン、テトラブチルアンモニウムカチオン、エチルトリメチルアンモニウムカチオン、トリメチルプロピルアンモニウムカチオン、トリメチルイソプロピルアンモニウムカチオン、ブチルトリメチルアンモニウムカチオン、ヘキシルトリメチルアンモニウムカチオン、オクチルトリメチルアンモニウムカチオン、ドデシルトリメチルアンモニウムカチオン、ビニルトリメチルアンモニウムカチオン、アリルトリメチルアンモニウムカチオン、トリエチルメチルアンモニウムカチオン、トリエチルプロピルアンモニウムカチオン、トリエチルメトキシメチルアンモニウムカチオン、トリブチルエチルアンモニウムカチオン、ジエチルジメチルアンモニウムカチオン、ジメチルジプロピルアンモニウムカチオン、ヘキサメトニウムカチオン等を挙げることができる。ピロリジニウムカチオン類の例としては、N,N-ジメチルピロリジニウムカチオン、N,N-ジエチルピロリジニウムカチオン、N,N-ジプロピルピロリジニウムカチオン、N-エチル-N-メチルピロリジニウムカチオン、N-メチル-N-プロピルピロリジニウムカチオン、N-ブチル-N-メチルピロリジニウムカチオン、N-ヘキシル-N-メチルピロリジニウムカチオン等を挙げることができる。イミダゾリウムカチオン類の例としては、1,3-ジメチルイミダゾリウムカチオン、1,3-ジエチルイミダゾリウムカチオン、1,3-ジプロピルイミダゾリウムカチオン、1-エチル-3-メチルイミダゾリウムカチオン、1-メチル-3-プロピルイミダゾリウムカチオン、1-ブチル-3-メチルイミダゾリウムカチオン、1-イソプロピル-3-プロピルイミダゾリウムカチオン、1-tert-ブチル-3-イソプロピルイミダゾリウムカチオン等を挙げることができる。ピリジニウムカチオン類の例としては、N-エチルピリジニウムカチオン、N-ブチルピリジニウムカチオン等を挙げることができる。スルホニウムカチオン類の例としては、トリメチルスルホニウムカチオン、トリエチルスルホニウムカチオン、トリブチルスルホニウムカチオン、ジエチルメチルスルホニウムカチオン、ジメチルプロピルスルホニウムカチオン、ヘキシルジメチルスルホニウムカチオン等を挙げることができる。ホスホニウムカチオン類の例としては、テトラメチルホスホニウムカチオン、テトラエチルホスホニウムカチオン、テトラプロピルホスホニウムカチオン、テトラブチルホスホニウムカチオン、テトラオクチルホスホニウムカチオン、テトラフェニルホスホニウムカチオン、エチルトリメチルホスホニウムカチオン、トリエチルメチルホスホニウムカチオン、ヘキシルトリメチルホスホニウムカチオン、トリメチルオクチルホスホニウムカチオン等を挙げることができる。
R2は、水素原子または炭素数1~10の直鎖状あるいは分岐状のアルキル基であることが好ましく、炭素数1~4の直鎖状あるいは分岐状のアルキル基であることが特に好ましい。
In the above general formula (1), R 1 represents a hydrogen atom or a methyl group.
R 2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkali metal ion or an onium cation. Examples of alkali metal ions include lithium, sodium, and potassium. Onium cations are at least one organic compound formed by the coordination of a cationic atomic group to a compound containing an element with a lone pair of electrons, such as nitrogen, sulfur, oxygen, phosphorus, selenium, tin, iodine, and antimony. There are no particular restrictions on the cation as long as it has a group. As onium cations, ammonium cations, pyrrolidinium cations, imidazolium cations, pyridinium cations, sulfonium cations, and phosphonium cations can be used. Examples of ammonium cations include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, ethyltrimethylammonium cation, trimethylpropylammonium cation, trimethylisopropylammonium cation, butyltrimethylammonium cation, hexyltrimethylammonium cation, octyltrimethylammonium cation. Cations, dodecyltrimethylammonium cation, vinyltrimethylammonium cation, allyltrimethylammonium cation, triethylmethylammonium cation, triethylpropylammonium cation, triethylmethoxymethylammonium cation, tributylethylammonium cation, diethyldimethylammonium cation, dimethyldipropylammonium cation, hexa Examples include methonium cations. Examples of pyrrolidinium cations include N,N-dimethylpyrrolidinium cation, N,N-diethylpyrrolidinium cation, N,N-dipropylpyrrolidinium cation, and N-ethyl-N-methylpyrrolidinium cation. Examples include N-methyl-N-propylpyrrolidinium cation, N-butyl-N-methylpyrrolidinium cation, and N-hexyl-N-methylpyrrolidinium cation. Examples of imidazolium cations include 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1,3-dipropylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1- Examples include methyl-3-propylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-isopropyl-3-propylimidazolium cation, and 1-tert-butyl-3-isopropylimidazolium cation. Examples of pyridinium cations include N-ethylpyridinium cation and N-butylpyridinium cation. Examples of sulfonium cations include trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, diethylmethylsulfonium cation, dimethylpropylsulfonium cation, hexyldimethylsulfonium cation, and the like. Examples of phosphonium cations include tetramethylphosphonium cation, tetraethylphosphonium cation, tetrapropylphosphonium cation, tetrabutylphosphonium cation, tetraoctylphosphonium cation, tetraphenylphosphonium cation, ethyltrimethylphosphonium cation, triethylmethylphosphonium cation, hexyltrimethylphosphonium cation. cation, trimethyloctylphosphonium cation, and the like.
R 2 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, particularly preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
Rf1は、フッ素原子または炭素数1~4の直鎖状あるいは分岐状のパーフルオロアルキル基を表す。
Rf2は、炭素数1~4の直鎖状あるいは分岐状のパーフルオロアルキレン基を表す。Rf2は、直鎖状パーフルオロアルキレン基であることが好ましく、炭素数3の直鎖状パーフルオロアルキレン基であることが特に好ましい。
Rf 1 represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms.
Rf 2 represents a linear or branched perfluoroalkylene group having 1 to 4 carbon atoms. Rf 2 is preferably a linear perfluoroalkylene group, particularly preferably a linear perfluoroalkylene group having 3 carbon atoms.
Xは、2価の有機基である連結基を表す。2価の有機基としては、2価の炭化水素基、酸素原子(エーテル結合)、硫黄原子(スルフィド結合)、カルボニル基、イミノ基、スルホン基及びこれらを組合せた基を挙げることができる。2価の炭化水素基は、炭素数が1~10の範囲内にあることが好ましい。2価の炭化水素基は、飽和炭化水素基であってもよいし、不飽和炭化水素基であってもよい。また、2価の炭化水素基は、直鎖状あるいは分岐状の鎖状炭化水素基であってもよいし、環状炭化水素基であってもよいし、さらにこれらを組合せた基であってもよい。鎖状炭化水素基の例としては、アルキレン基、アルケニレン基、アルキニレン基を挙げることができる。環状炭化水素基の例としては、シクロアルキレン基、フェニレン基を挙げることができる。イミノ基は、水素原子が、炭素数1~10の直鎖状あるいは分岐状のアルキル基で置換されていてもよい。2価の炭化水素基は、置換基を有していてもよい。置換基の例としては、ヒドロキシ基、炭素数が1~6のアルコキシ基を挙げることができる。 X represents a linking group which is a divalent organic group. Examples of the divalent organic group include a divalent hydrocarbon group, an oxygen atom (ether bond), a sulfur atom (sulfide bond), a carbonyl group, an imino group, a sulfone group, and a combination thereof. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms. The divalent hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the divalent hydrocarbon group may be a linear or branched chain hydrocarbon group, a cyclic hydrocarbon group, or a combination thereof. good. Examples of the chain hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group. Examples of the cyclic hydrocarbon group include a cycloalkylene group and a phenylene group. In the imino group, a hydrogen atom may be substituted with a linear or branched alkyl group having 1 to 10 carbon atoms. The divalent hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
2価の有機基を組合せた基としては、オキシアルキレン基(-O-アルキレン基-)、イミノアルキレン基(-NH-アルキレン基-)、エステル結合(-O-C(=O)-)、アミド結合(-C(=O)-NH-)、スルホンアミド結合(-S(=O)2-NH-)、ウレタン結合(-O-C(=O)-NH-)、ウレア結合(-NH-C(=O)-NH-)及びこれらを組合せた基を挙げることができる。 Groups combining divalent organic groups include oxyalkylene group (-O-alkylene group-), iminoalkylene group (-NH-alkylene group-), ester bond (-OC(=O)-), Amide bond (-C(=O)-NH-), sulfonamide bond (-S(=O) 2 -NH-), urethane bond (-O-C(=O)-NH-), urea bond (- Mention may be made of groups such as NH-C(=O)-NH-) and combinations thereof.
Xは、下記の一般式(2)で表される2価の有機基であることが好ましい。 It is preferable that X is a divalent organic group represented by the following general formula (2).
ただし、上記の一般式(2)において、*は、Cとの接合手を表す。 However, in the above general formula (2), * represents a bond with C.
A+は、アルカリ金属イオンまたはオニウムカチオンを表す。アルカリ金属イオン及びオニウムカチオンの例は上記と同じである。A+は、アルカリ金属イオンであることが好ましく、リチウムイオンであることが特に好ましい。 A + represents an alkali metal ion or an onium cation. Examples of alkali metal ions and onium cations are the same as above. A + is preferably an alkali metal ion, particularly preferably a lithium ion.
本実施形態の反応性含フッ素スルホニルイミドの製造方法について、R1が水素原子であり、R2がメチル基であって、Xが上記一般式(2)で表される2価の有機基であって、A+がカリウムイオンである反応性含フッ素スルホニルイミドを例にとって説明する。この反応性含フッ素スルホニルイミドカリウムは、下記の反応式1~4の反応により製造することができる。なお、下記の反応式1ie~4ie、1e~2eにおいて、Rf1、Rf2、は、上記の一般式(1)と同じである。 Regarding the method for producing a reactive fluorine-containing sulfonylimide of the present embodiment, R 1 is a hydrogen atom, R 2 is a methyl group, and X is a divalent organic group represented by the above general formula (2). This will be explained by taking as an example a reactive fluorine-containing sulfonylimide in which A + is a potassium ion. This reactive fluorine-containing potassium sulfonylimide can be produced by reactions according to Reaction Formulas 1 to 4 below. In addition, in the following reaction formulas 1ie to 4ie and 1e to 2e, Rf 1 and Rf 2 are the same as in the above general formula (1).
先ず、下記の反応式1ieに示すように、パーフルオロアルカンジスルホニルジフロライド(F-S(=O)2-Rf2-S(=O)2-F)と、パーフルオロアルカンスルホンアミド塩(Rf1-S(=O)2-N-HA+)とを反応させて、中間体1ieを合成する。この反応は、例えば、脱水アセトニトリル(dry-CH3CN)中、フッ化カリウムの存在下で行うことができる。 First, as shown in reaction formula 1ie below, perfluoroalkanedisulfonyl difluoride (FS(=O) 2 -Rf 2 -S(=O) 2 -F) and perfluoroalkanesulfonamide salt (Rf 1 -S(=O) 2 -N - HA + ) to synthesize intermediate 1ie. This reaction can be carried out, for example, in dry acetonitrile (dry-CH 3 CN) in the presence of potassium fluoride.
次に、下記の反応式2ieに示すように、中間体1ieとメチルアミンとをフッ化カリウムの存在下で反応させて、中間体1ieの末端のフッ素原子を、メチルアミノカリウム塩基(-N-CH3K+)で置換して、中間体2ieを合成する。この反応は、例えば、脱水テトラヒドロフラン(dry-THF)中で行うことができる。 Next, as shown in reaction formula 2ie below, intermediate 1ie and methylamine are reacted in the presence of potassium fluoride to convert the terminal fluorine atom of intermediate 1ie into methylaminopotassium base ( -N- CH 3 K + ) to synthesize intermediate 2ie. This reaction can be carried out, for example, in dry tetrahydrofuran (dry-THF).
次に、下記の反応式3ieに示すように、中間体2ieと2-クロロエタノールとを反応させて、中間体2ieのメチルアミノカリウム塩基のカリウムをヒドロキシエチル基(-CH2CH2OH)で置換して、中間体3ieを生成させる。この反応は、例えば、脱水アセトニトリル(dry-CH3CN)中、炭酸カリウムの存在下で行うことができる。 Next, as shown in reaction formula 3ie below, intermediate 2ie is reacted with 2-chloroethanol to convert potassium of the methylaminopotassium base of intermediate 2ie with a hydroxyethyl group (-CH 2 CH 2 OH). Substitution produces intermediate 3ie. This reaction can be carried out, for example, in dry acetonitrile (dry-CH 3 CN) in the presence of potassium carbonate.
そして最後に、下記の反応式1eに示すように、中間体3ieのヒドロキシエチル基のヒドロキシ基と、2-イソシアナトエチルアクリレートのイソシアネート基とを反応させて、ウレタン結合を形成させる。これによって、A+がカリウムイオンである反応性含フッ素スルホニルイミド1eが生成する。この反応は、例えば、脱水アセトニトリル(dry-CH3CN)とジブチルヒドロキシトルエン(BHT)を含む混合溶媒中、ジラウリン酸ジブチルすず(DBTL)存在下で行うことができる。 Finally, as shown in reaction formula 1e below, the hydroxyl group of the hydroxyethyl group of intermediate 3ie and the isocyanate group of 2-isocyanatoethyl acrylate are reacted to form a urethane bond. This produces a reactive fluorine-containing sulfonylimide 1e in which A + is a potassium ion. This reaction can be carried out, for example, in a mixed solvent containing dehydrated acetonitrile (dry-CH 3 CN) and dibutylhydroxytoluene (BHT) in the presence of dibutyltin dilaurate (DBTL).
A+が、リチウムイオンである反応性含フッ素スルホニルイミドは、例えば、次のようにして合成することができる。
下記の反応式4ieに示すように、上記中間体3ieと硫酸とを反応させイミドカリウムをイミド酸にした後、水酸化リチウムと反応させて、中間体4ieを得る。この反応は、例えば、中間体3ieの酢酸エチル溶液を硫酸水溶液で洗浄後、水酸化リチウムを加えることによって行うことができる。
A reactive fluorine-containing sulfonylimide in which A + is a lithium ion can be synthesized, for example, as follows.
As shown in Reaction Formula 4ie below, intermediate 3ie is reacted with sulfuric acid to convert potassium imide into imidic acid, and then reacted with lithium hydroxide to obtain intermediate 4ie. This reaction can be carried out, for example, by washing an ethyl acetate solution of intermediate 3ie with an aqueous sulfuric acid solution, and then adding lithium hydroxide.
次いで、下記の反応式2eに示すように、上記中間体4ieのヒドロキシエチル基のヒドロキシ基と、2-イソシアナトエチルアクリレートのイソシアネート基とを反応させて、ウレタン結合を形成させて、A+がリチウムイオンである反応性含フッ素スルホニルイミド2eを生成させる。この反応は、脱水アセトニトリルとジブチルヒドロキシトルエンを含む混合溶媒中、ジラウリン酸ジブチルすず存在下で行うことができる。 Next, as shown in reaction formula 2e below, the hydroxyl group of the hydroxyethyl group of the intermediate 4ie and the isocyanate group of 2-isocyanatoethyl acrylate are reacted to form a urethane bond, and A + is A reactive fluorine-containing sulfonylimide 2e, which is a lithium ion, is generated. This reaction can be carried out in a mixed solvent containing dehydrated acetonitrile and dibutylhydroxytoluene in the presence of dibutyltin dilaurate.
A+が、オニウムカチオンである反応性含フッ素スルホニルイミドは、例えば、A+がカリウムイオンである反応性含フッ素スルホニルイミドとオニウムカチオン溶液とを混合して、カリウムイオンとオニウムカチオンとを置換させることによって合成することができる。 The reactive fluorine-containing sulfonylimide in which A + is an onium cation can be prepared by, for example, mixing the reactive fluorine-containing sulfonylimide in which A + is a potassium ion and an onium cation solution to replace the potassium ion with the onium cation. It can be synthesized by
また、Xが、オキシアルキレン基を含む反応性含フッ素スルホニルイミドは、例えば、中間体3ieとグリシジル基を有する(メタ)アクリレートとを反応させることによって合成することができる。グリシジル基を有する(メタ)アクリレートの例としては、アクリル酸グリシジル、メタクリル酸グリシジルを挙げることができる。 Further, a reactive fluorine-containing sulfonylimide in which X contains an oxyalkylene group can be synthesized, for example, by reacting intermediate 3ie with a (meth)acrylate having a glycidyl group. Examples of (meth)acrylates having a glycidyl group include glycidyl acrylate and glycidyl methacrylate.
さらに、Xが、イミノアルキレン基を含む反応性含フッ素スルホニルイミドは、例えば、中間体1ieとアルキレンジアミンとを反応させ、末端にアミノ基を有する中間体を生成させ、次いで、その中間体のアミノ基と塩化アクリロイルもしくは塩化メタクリロイルとを反応させることによって合成することができる。アルキレンジアミンの例としては、エチレンジアミン、1,4-ジアミノブタン、1,6-ジアミノヘキサン、1,7-ジアミノヘプタンを挙げることができる。 Furthermore, a reactive fluorine-containing sulfonylimide in which X contains an iminoalkylene group can be obtained by, for example, reacting intermediate 1ie with an alkylene diamine to produce an intermediate having an amino group at the terminal, and then It can be synthesized by reacting the group with acryloyl chloride or methacryloyl chloride. Examples of alkylene diamines include ethylene diamine, 1,4-diaminobutane, 1,6-diaminohexane, and 1,7-diaminoheptane.
本実施形態の反応性含フッ素スルホニルイミドは、イミド塩を含有するので、帯電防止剤として利用されているパーフルオロアルカンスルホニルイミド塩と同様に優れた帯電防止効果を有する。また、本実施形態の反応性含フッ素スルホニルイミドは、反応性官能基を有するので、単独重合あるいは他のモノマーと共重合させることができる。単独重合あるいは共重合させることによって、高温環境下で保存してもブリードアウトしにくくなり、長期間にわたって安定して優れた帯電防止効果を発揮することができる。 Since the reactive fluorine-containing sulfonylimide of this embodiment contains an imide salt, it has an excellent antistatic effect similar to perfluoroalkanesulfonylimide salts used as antistatic agents. Moreover, since the reactive fluorine-containing sulfonylimide of this embodiment has a reactive functional group, it can be homopolymerized or copolymerized with other monomers. Homopolymerization or copolymerization makes it difficult to bleed out even when stored in a high-temperature environment, and can stably exhibit an excellent antistatic effect over a long period of time.
<反応性含フッ素スルホニルイミド含有共重合体>
本実施形態の反応性含フッ素スルホニルイミド含有共重合体は、上述の反応性含フッ素スルホニルイミドに基づく繰り返し単位と、この反応性含フッ素スルホニルイミド以外の他のモノマーに基づく繰り返し単位とを含む。
<Reactive fluorine-containing sulfonylimide-containing copolymer>
The reactive fluorine-containing sulfonylimide-containing copolymer of the present embodiment includes a repeating unit based on the above-described reactive fluorine-containing sulfonylimide and a repeating unit based on a monomer other than the reactive fluorine-containing sulfonylimide.
他のモノマーは、反応性含フッ素スルホニルイミドが有する反応性官能基((メタ)アクリロイル基)と重合可能な反応性官能基を有するものであることが好ましい。(メタ)アクリロイル基と重合可能な反応性官能基の例としては、ビニル基、ビニルエーテル基、アリル基、(メタ)アクリル基、(メタ)アクリルアミド基、スチリル基などを挙げることができる。これらの反応性官能基の中で好ましいのは、(メタ)アクリル基、(メタ)アクリルアミド基、スチリル基であり、特に好ましいのは(メタ)アクリル基である。 The other monomer preferably has a reactive functional group that can be polymerized with the reactive functional group ((meth)acryloyl group) possessed by the reactive fluorine-containing sulfonylimide. Examples of reactive functional groups that can be polymerized with (meth)acryloyl groups include vinyl groups, vinyl ether groups, allyl groups, (meth)acrylic groups, (meth)acrylamide groups, and styryl groups. Preferred among these reactive functional groups are (meth)acrylic group, (meth)acrylamide group, and styryl group, and particularly preferred is (meth)acrylic group.
他のモノマーは、樹脂シートや樹脂フィルムなどの樹脂成形品あるいは粘着剤の原料として利用できるものであることが好ましい。反応性含フッ素スルホニルイミドは、帯電防止剤として作用して、他のモノマーを原料とする樹脂成形品あるいは粘着剤の電気抵抗を低減して、帯電防止能力を向上させる。他のモノマーは、1種を単独で使用してもよいし、2種以上を組合せて使用してもよい。 The other monomers are preferably those that can be used as raw materials for resin molded products such as resin sheets and resin films, or adhesives. The reactive fluorine-containing sulfonylimide acts as an antistatic agent, reduces the electrical resistance of resin molded articles or adhesives made from other monomers, and improves the antistatic ability. The other monomers may be used alone or in combination of two or more.
反応性含フッ素スルホニルイミドと他のモノマーの配合割合は、他のモノマー100質量部に対する反応性含フッ素スルホニルイミドの量が、一般に0.01質量部以上50質量部以下の範囲内、好ましくは0.1質量部以上10質量部以下の範囲内となる割合である。反応性含フッ素スルホニルイミドと他のモノマーの配合割合がこの範囲にあると、他のモノマーの特性を維持しつつ、帯電防止効果を向上させることができる。 The blending ratio of the reactive fluorine-containing sulfonylimide and other monomers is such that the amount of the reactive fluorine-containing sulfonylimide is generally in the range of 0.01 parts by mass or more and 50 parts by mass or less, preferably 0.01 parts by mass or more and 50 parts by mass or less. The ratio is within the range of .1 part by mass or more and 10 parts by mass or less. When the blending ratio of the reactive fluorine-containing sulfonylimide and other monomers is within this range, the antistatic effect can be improved while maintaining the properties of the other monomers.
本実施形態の反応性含フッ素スルホニルイミド含有共重合体は、反応性含フッ素スルホニルイミドと他のモノマーとを共重合させることによって製造することができる。重合方法には、特に制限なく、例えば、乳化重合法、懸濁重合法、塊状重合法、溶液重合法などの公知の重合法を用いることができる。 The reactive fluorine-containing sulfonylimide-containing copolymer of this embodiment can be produced by copolymerizing the reactive fluorine-containing sulfonylimide and another monomer. The polymerization method is not particularly limited, and for example, known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization can be used.
本実施形態の反応性含フッ素スルホニルイミド含有共重合体は、上述の反応性含フッ素スルホニルイミドに基づく繰り返し単位が、他のモノマーに基づく単位と共重合しているので、ブリードアウトしにくくなり、長期間にわたって安定して優れた帯電防止効果を発揮することができる。このため、本実施形態の反応性含フッ素スルホニルイミド含有共重合体は、他のモノマーの種類によって異なるが、樹脂シートや樹脂フィルムなどの樹脂成形品あるいは粘着剤の材料として利用することができる。また、本実施形態の反応性含フッ素スルホニルイミド含有共重合体は、帯電防止剤として、他の樹脂材料に添加したり、他の重合体に架橋させてもよい。 In the reactive fluorine-containing sulfonylimide-containing copolymer of the present embodiment, the repeating unit based on the above-mentioned reactive fluorine-containing sulfonylimide is copolymerized with units based on other monomers, so it is difficult to bleed out. It can stably exhibit an excellent antistatic effect over a long period of time. Therefore, the reactive fluorine-containing sulfonylimide-containing copolymer of the present embodiment can be used as a material for resin molded products such as resin sheets and resin films, or adhesives, although this varies depending on the types of other monomers. Further, the reactive fluorine-containing sulfonylimide-containing copolymer of this embodiment may be added to other resin materials as an antistatic agent, or may be crosslinked to other polymers.
<反応性含フッ素スルホニルイミド溶液>
本実施形態の反応性含フッ素スルホニルイミド溶液は、溶媒と、上述の反応性含フッ素スルホニルイミドとを含む。反応性含フッ素スルホニルイミド溶液は、さらに反応性含フッ素スルホニルイミド以外の他のモノマーを含んでいてもよい。またさらに、重合開始剤を含んでいてもよい。
<Reactive fluorine-containing sulfonylimide solution>
The reactive fluorine-containing sulfonylimide solution of this embodiment includes a solvent and the above-mentioned reactive fluorine-containing sulfonylimide. The reactive fluorine-containing sulfonylimide solution may further contain a monomer other than the reactive fluorine-containing sulfonylimide. Furthermore, a polymerization initiator may be included.
溶媒は、反応性含フッ素スルホニルイミドを溶解するものであれば、特に制限なく使用することができる。溶媒としては、例えば、エステル系溶媒、エーテル系溶媒、ニトリル系溶媒、ケトン系溶媒を用いることができる。エステル系溶媒の例としては、酢酸エチル、酢酸イソプロピル、酢酸ブチルなどを挙げることができる。エーテル系溶媒は、鎖状であってもよいし、環状であってもよい。鎖状エーテル系溶媒の例としては、ジエチルエーテル、ジイソプロピルエーテル、t-ブチルメチルエーテル、シクロペンチルメチルエーテル、ジメトキシメタン、1,2-ジメトキシエタンを挙げることができる。環状エーテル系溶媒の例としては、テトラヒドロフラン、2-メチルテトラヒドロフラン、1,3-ジオキサン、4-メチル-1,3-ジオキソランを挙げることができる。ニトリル系溶媒の例としては、アセトニトリル、イソブチロニトリル、バレロニトリル、ベンゾニトリルを挙げることができる。ケトン系溶媒の例としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジイソブチルケトンを挙げることができる。 The solvent can be used without particular limitation as long as it dissolves the reactive fluorine-containing sulfonylimide. As the solvent, for example, ester solvents, ether solvents, nitrile solvents, and ketone solvents can be used. Examples of ester solvents include ethyl acetate, isopropyl acetate, butyl acetate, and the like. The ether solvent may be linear or cyclic. Examples of chain ether solvents include diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether, dimethoxymethane, and 1,2-dimethoxyethane. Examples of the cyclic ether solvent include tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, and 4-methyl-1,3-dioxolane. Examples of nitrile solvents include acetonitrile, isobutyronitrile, valeronitrile, and benzonitrile. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone.
他のモノマーは、反応性含フッ素スルホニルイミドの反応性官能基と重合可能な反応性官能基を有するものであることが好ましい。反応性官能基と重合可能な反応性官能基の例は、上述の反応性含フッ素スルホニルイミド含有共重合体で用いる他のモノマーの場合と同じである。
また、反応性含フッ素スルホニルイミドと他のモノマーの配合割合は、上述の反応性含フッ素スルホニルイミド含有共重合体の場合と同じである。
The other monomer preferably has a reactive functional group that can be polymerized with the reactive functional group of the reactive fluorine-containing sulfonylimide. Examples of the reactive functional group polymerizable with the reactive functional group are the same as those of other monomers used in the above-mentioned reactive fluorine-containing sulfonylimide-containing copolymer.
Further, the blending ratio of the reactive fluorine-containing sulfonylimide and other monomers is the same as in the case of the above-mentioned reactive fluorine-containing sulfonylimide-containing copolymer.
重合開始剤は、反応性含フッ素スルホニルイミドと他のモノマーとの重合反応を促進させるために添加する。重合開始剤としては、熱重合開始剤及び光重合開始剤を用いることができる。熱重合開始剤と光重合開始剤とを併用してもよい。
重合開始剤の配合割合は、他のモノマー100質量部に対する重合開始剤の量が、一般に1質量部以上10質量部以下の範囲内となる割合である。
The polymerization initiator is added to promote the polymerization reaction between the reactive fluorine-containing sulfonylimide and other monomers. As the polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator can be used. A thermal polymerization initiator and a photopolymerization initiator may be used together.
The blending ratio of the polymerization initiator is such that the amount of the polymerization initiator per 100 parts by mass of other monomers is generally in the range of 1 part by mass or more and 10 parts by mass or less.
反応性含フッ素スルホニルイミド溶液は、さらに、必要に応じて、他の添加剤を含んでいてもよい。他の添加剤の例としては、架橋剤、粘度調整剤、消泡剤、酸化防止剤、可塑剤、難燃剤、赤外線吸収剤、紫外線吸収剤、pH調整剤、キレート化剤、着色剤を挙げることができる。 The reactive fluorine-containing sulfonylimide solution may further contain other additives as necessary. Examples of other additives include crosslinking agents, viscosity modifiers, antifoaming agents, antioxidants, plasticizers, flame retardants, infrared absorbers, ultraviolet absorbers, pH adjusters, chelating agents, and colorants. be able to.
反応性含フッ素スルホニルイミド溶液は、溶剤と、反応性含フッ素スルホニルイミドと、さらに必要に応じて他のモノマーと重合開始剤とを混合することによって製造することができる。これら材料の混合順序に特には制限ない。例えば、溶剤に、反応性含フッ素スルホニルイミドと、他のモノマーと、重合開始剤とを投入してもよいし、反応性含フッ素スルホニルイミドと、他のモノマーと、重合開始剤とを含む混合物に、溶剤を加えてもよい。 The reactive fluorine-containing sulfonylimide solution can be produced by mixing a solvent, the reactive fluorine-containing sulfonylimide, and, if necessary, other monomers and a polymerization initiator. There is no particular restriction on the order in which these materials are mixed. For example, a reactive fluorine-containing sulfonylimide, other monomers, and a polymerization initiator may be added to a solvent, or a mixture containing a reactive fluorine-containing sulfonylimide, other monomers, and a polymerization initiator may be used. A solvent may be added to the solution.
本実施形態の反応性含フッ素スルホニルイミド溶液は、上述の反応性含フッ素スルホニルイミドを含むので、これを基材の上に塗布し、乾燥した後、反応性含フッ素スルホニルイミドを重合させることによって、反応性含フッ素スルホニルイミドに基づく繰り返し単位を有する重合体を含む樹脂層を形成することができる。この樹脂層は、反応性含フッ素スルホニルイミドが基材上に固定化されるので、長期間にわたって安定して優れた帯電防止効果を基材に付与できる。 Since the reactive fluorine-containing sulfonylimide solution of this embodiment contains the above-mentioned reactive fluorine-containing sulfonylimide, it is applied onto a base material, dried, and then polymerized with the reactive fluorine-containing sulfonylimide. , a resin layer containing a polymer having a repeating unit based on a reactive fluorine-containing sulfonylimide can be formed. In this resin layer, since the reactive fluorine-containing sulfonylimide is immobilized on the base material, it is possible to stably impart an excellent antistatic effect to the base material over a long period of time.
<反応性含フッ素スルホニルイミド含有共重合体溶液>
本実施形態の反応性含フッ素スルホニルイミド含有共重合体溶液は、溶媒と、上述の反応性含フッ素スルホニルイミド含有共重合体とを含む。
<Reactive fluorine-containing sulfonylimide-containing copolymer solution>
The reactive fluorine-containing sulfonylimide-containing copolymer solution of the present embodiment contains a solvent and the above-described reactive fluorine-containing sulfonylimide-containing copolymer.
溶媒は、反応性含フッ素スルホニルイミド含有共重合体を溶解するものであれば、特に制限なく使用することができる。溶媒としては、例えば、エステル系溶媒、エーテル系溶媒、ニトリル系溶媒、ケトン系溶媒を用いることができる。エステル系溶媒、エーテル系溶媒、ニトリル系溶媒およびケトン系溶媒の例は、上述の反応性含フッ素スルホニルイミド溶液の場合と同じである。 The solvent can be used without particular limitation as long as it dissolves the reactive fluorine-containing sulfonylimide-containing copolymer. As the solvent, for example, ester solvents, ether solvents, nitrile solvents, and ketone solvents can be used. Examples of the ester solvent, ether solvent, nitrile solvent, and ketone solvent are the same as in the case of the above-mentioned reactive fluorine-containing sulfonylimide solution.
反応性含フッ素スルホニルイミド含有共重合体溶液は、さらに、必要に応じて、他の添加剤を含んでいてもよい。他の添加剤の例は、上述の反応性含フッ素スルホニルイミド溶液の場合と同じである。 The reactive fluorine-containing sulfonylimide-containing copolymer solution may further contain other additives, if necessary. Examples of other additives are the same as those for the reactive fluorine-containing sulfonylimide solution described above.
反応性含フッ素スルホニルイミド含有共重合体溶液は、溶剤と、反応性含フッ素スルホニルイミド含有共重合体とを混合することによって製造することができる。また、反応性含フッ素スルホニルイミドと他のモノマーとを含む溶液を作成し、反応性含フッ素スルホニルイミドと他のモノマーとを共重合させることによっても製造することができる。 The reactive fluorine-containing sulfonylimide-containing copolymer solution can be produced by mixing a solvent and the reactive fluorine-containing sulfonylimide-containing copolymer. It can also be produced by preparing a solution containing the reactive fluorine-containing sulfonylimide and other monomers and copolymerizing the reactive fluorine-containing sulfonylimide and the other monomers.
本実施形態の反応性含フッ素スルホニルイミド含有共重合体溶液は、上述の反応性含フッ素スルホニルイミド含有共重合体を含むので、例えば、これを基材の上に塗布し、乾燥することによって、反応性含フッ素スルホニルイミド含有共重合体を含む樹脂層を形成することができる。この樹脂層は、反応性含フッ素スルホニルイミドがブリードアウトしにくいので、長期間にわたって安定して優れた帯電防止効果を基材に付与できる。 Since the reactive fluorine-containing sulfonylimide-containing copolymer solution of the present embodiment contains the above-described reactive fluorine-containing sulfonylimide-containing copolymer, for example, by applying this onto a substrate and drying it, A resin layer containing a reactive fluorine-containing sulfonylimide-containing copolymer can be formed. Since the reactive fluorine-containing sulfonylimide does not easily bleed out from this resin layer, it is possible to stably impart an excellent antistatic effect to the base material over a long period of time.
以上、本発明の実施形態について説明したが、本発明の技術範囲は上記実施の形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。 Although the embodiments of the present invention have been described above, the technical scope of the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention.
次に、本発明の作用効果を実施例により説明する。なお、本実施例で化合物の構造は、プロトン核磁気共鳴スペクトル(1H-NMR)とフッ素の核磁気共鳴スペクトル(19F-NMR)により確認した。 Next, the effects of the present invention will be explained using examples. In this example, the structure of the compound was confirmed by proton nuclear magnetic resonance spectrum ( 1 H-NMR) and fluorine nuclear magnetic resonance spectrum ( 19 F-NMR).
[合成例1]反応性含フッ素スルホニルイミドカリウム(反応性含フッ素スルホニルイミド1)の合成
(中間体1iの合成)
温度計と還流管を備えたフラスコに、1,1,2,2,3,3-ヘキサフルオロプロパン-1,3-ジスルホニルジフロライドを152g(0.48mol)、フッ化カリウムを36g(0.63mol)、脱水アセトニトリルを480gの割合で仕込み、窒素雰囲気下で60℃に加熱した。次いで、トリフルオロメタンスルホンアミドカリウム84gを数回に分けて添加した後、さらに60℃で2時間加熱して、下記の反応式1iの反応により中間体1iを生成させた。反応終了後、不溶物を吸引濾過により濾別し、濾液を濃縮乾固して、粗生成物213gを得た。得られた粗生成物にエタノール109gを加えて60℃に加熱溶解した後、不溶物を3μmのメンブレンフィルターで濾別し、濾液をクロロホルム2004gに加え、生成物を晶析させた。晶析した生成物を吸引濾過により回収し、乾燥して、白色固体の中間体1iを得た。得られた中間体1iの量は、192g(収率:89%)であった。
[Synthesis Example 1] Synthesis of reactive fluorine-containing sulfonylimide potassium (reactive fluorine-containing sulfonylimide 1) (synthesis of intermediate 1i)
In a flask equipped with a thermometer and a reflux tube, add 152 g (0.48 mol) of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride and 36 g (0.48 mol) of potassium fluoride. 0.63 mol) and 480 g of dehydrated acetonitrile were charged, and the mixture was heated to 60° C. under a nitrogen atmosphere. Next, 84 g of potassium trifluoromethanesulfonamide was added in several portions, and the mixture was further heated at 60° C. for 2 hours to produce intermediate 1i by the reaction of reaction formula 1i below. After the reaction was completed, insoluble matter was filtered off by suction filtration, and the filtrate was concentrated to dryness to obtain 213 g of a crude product. After adding 109 g of ethanol to the obtained crude product and heating and dissolving it at 60° C., insoluble matter was filtered off using a 3 μm membrane filter, and the filtrate was added to 2004 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to obtain intermediate 1i as a white solid. The amount of intermediate 1i obtained was 192 g (yield: 89%).
(中間体1iの19F-NMR測定結果)
19F-NMR(376MHz,CD3CN):δ45.0(m,1F),-80.2(s,3F),-107.4(m,2F),-113.6(t,2F),-119.0(t,2F)
( 19F -NMR measurement results of intermediate 1i)
19 F-NMR (376MHz, CD 3 CN): δ45.0 (m, 1F), -80.2 (s, 3F), -107.4 (m, 2F), -113.6 (t, 2F) , -119.0 (t, 2F)
(中間体2iの合成)
温度計と還流管を備えたフラスコに、中間体1iを180g(0.37mol)、フッ化カリウムを69g(3.2mol)、脱水テトラヒドロフランを360gの割合で仕込み、窒素雰囲気下で60℃に加熱した。そこに、濃度2mol/Lのメチルアミン・テトラヒドロフラン溶液201g(CH3NH214g、0.45mol)を滴下した後、60℃で2.5時間加熱して、下記の反応式2iの反応により中間体2iを生成させた。反応終了後、濃縮乾固し、残渣に酢酸エチル1498gとイオン交換水220gとを加えて混合した後、分液して酢酸エチル相を回収した。回収した酢酸エチル相を、さらに濃度20質量%の水酸化カリウム水溶液100gで3回、濃度20質量%の塩化カリウム水溶液100gで3回洗浄した後、再度濃縮乾固した。得られた残渣に同質量のアセトニトリルを加えて溶解させ、淡黄色透明で、濃度50質量%の中間体2iのアセトニトリル溶液199g(固形分99g、収率:100%)を得た。
(Synthesis of intermediate 2i)
A flask equipped with a thermometer and a reflux tube was charged with 180 g (0.37 mol) of intermediate 1i, 69 g (3.2 mol) of potassium fluoride, and 360 g of dehydrated tetrahydrofuran, and heated to 60°C under a nitrogen atmosphere. did. Thereto, 201 g of methylamine/tetrahydrofuran solution (14 g of CH 3 NH 2 , 0.45 mol) with a concentration of 2 mol/L was added dropwise, and the mixture was heated at 60° C. for 2.5 hours to form an intermediate by the reaction of reaction formula 2i below. body 2i was generated. After the reaction was completed, the mixture was concentrated to dryness, and 1498 g of ethyl acetate and 220 g of ion-exchanged water were added to the residue and mixed, followed by liquid separation to recover the ethyl acetate phase. The recovered ethyl acetate phase was further washed three times with 100 g of a 20% by mass aqueous potassium hydroxide solution and three times with 100 g of a 20% by mass aqueous potassium chloride solution, and then concentrated to dryness again. The same mass of acetonitrile was added to and dissolved in the obtained residue to obtain 199 g (solid content: 99 g, yield: 100%) of a pale yellow and transparent acetonitrile solution of Intermediate 2i with a concentration of 50% by mass.
(中間体2iの1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,D2O):δ2.8(s,3H)
19F-NMR(376MHz,D2O):δ-79.1(s,3F),-112.1(t,2F),-112.4(t,2F),-119.1(t,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of intermediate 2i)
1 H-NMR (400 MHz, D 2 O): δ2.8 (s, 3H)
19 F-NMR (376 MHz, D 2 O): δ -79.1 (s, 3F), -112.1 (t, 2F), -112.4 (t, 2F), -119.1 (t, 2F)
(中間体3iの合成)
温度計と還流管を備えたフラスコに、濃度50質量%の中間体2iのアセトニトリル溶液を180g(固形分90g、0.17mol)、2-クロロエタノールを34g(0.42mol)、炭酸カリウムを21g(0.15mol)、脱水アセトニトリルを180gの割合で仕込み、窒素雰囲気下、80℃で43時間加熱して、下記の反応式3iの反応により中間体3iを生成させた。反応終了後、不溶物を吸引濾過により濾別し、濾液を濃縮乾固して、残渣に酢酸エチル705gと濃度10質量%のKCl水溶液125gとを加えて混合した後、分液して酢酸エチル相を回収した。回収した酢酸エチル相を、さらにイオン交換水100gで2回洗浄した後、濃縮乾固し、粗生成物を得た。得られた粗生成物にエタノール97gを加えて溶解させ、得られた溶液をクロロホルム1013gに加え、生成物を晶析させた。晶析した生成物を吸引濾過により回収し、乾燥して、白色固体の中間体3iを得た。得られた中間体3iの量は、75g(収率:79%)であった。
(Synthesis of intermediate 3i)
In a flask equipped with a thermometer and a reflux tube, add 180 g (solid content 90 g, 0.17 mol) of an acetonitrile solution of Intermediate 2i with a concentration of 50% by mass, 34 g (0.42 mol) of 2-chloroethanol, and 21 g of potassium carbonate. (0.15 mol) and dehydrated acetonitrile at a ratio of 180 g were heated at 80° C. for 43 hours in a nitrogen atmosphere to produce intermediate 3i by the reaction of reaction formula 3i below. After completion of the reaction, insoluble matter was filtered off by suction filtration, the filtrate was concentrated to dryness, and 705 g of ethyl acetate and 125 g of a KCl aqueous solution with a concentration of 10% by mass were added and mixed to the residue, and the layers were separated to obtain ethyl acetate. The phase was collected. The collected ethyl acetate phase was further washed twice with 100 g of ion-exchanged water, and then concentrated to dryness to obtain a crude product. 97 g of ethanol was added to the obtained crude product to dissolve it, and the obtained solution was added to 1013 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to yield intermediate 3i as a white solid. The amount of intermediate 3i obtained was 75 g (yield: 79%).
(中間体3iの1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,D2O):δ3.8-3.3(m,4H),3.1(s,3H)
19F-NMR(376MHz,D2O):δ-79.2(s,3F),-111.3(m,2F),-112.5(t,2F),-119.1(t,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of intermediate 3i)
1 H-NMR (400 MHz, D 2 O): δ3.8-3.3 (m, 4H), 3.1 (s, 3H)
19 F-NMR (376 MHz, D 2 O): δ -79.2 (s, 3F), -111.3 (m, 2F), -112.5 (t, 2F), -119.1 (t, 2F)
(反応性含フッ素スルホニルイミド1の合成)
温度計と還流管を備えたフラスコに、中間体3iを110g(0.20mol)、ジブチルヒドロキシトルエンを1g、ジラウリン酸ジブチルすずを2g、脱水アセトニトリルを331gの割合で仕込み、窒素雰囲気下で60℃に加熱した。そこに、2-イソシアナトエチルアクリレート49g(0.35mol)を滴下した後、60℃で30分加熱して、下記の反応式1の反応により反応性含フッ素スルホニルイミド1を生成させた。反応終了後、濃縮乾固し、残渣にエタノール119gとクロロホルム681gとを加えて混合した後、分液して下相を回収した。回収した下相に、さらにエタノール40gとクロロホルム768gを加えて混合した後、分液して再度下相を回収した。そして、同様に回収した下相に、さらにジブチルヒドロキシトルエン0.01gを加えた後、濃縮乾固して、反応性含フッ素スルホニルイミド1を得た。得られた反応性含フッ素スルホニルイミド1の量は、101g(収率:73%)であった。
(Synthesis of reactive fluorine-containing sulfonylimide 1)
A flask equipped with a thermometer and a reflux tube was charged with 110 g (0.20 mol) of Intermediate 3i, 1 g of dibutylhydroxytoluene, 2 g of dibutyltin dilaurate, and 331 g of dehydrated acetonitrile, and heated at 60°C under a nitrogen atmosphere. heated to. After 49 g (0.35 mol) of 2-isocyanatoethyl acrylate was added dropwise thereto, the mixture was heated at 60° C. for 30 minutes to produce reactive fluorine-containing sulfonylimide 1 by the reaction shown in Reaction Formula 1 below. After the reaction was completed, the mixture was concentrated to dryness, 119 g of ethanol and 681 g of chloroform were added and mixed to the residue, and the layers were separated to recover the lower phase. After further adding and mixing 40 g of ethanol and 768 g of chloroform to the collected lower phase, the mixture was separated and the lower phase was collected again. Then, 0.01 g of dibutylhydroxytoluene was further added to the lower phase recovered in the same manner, and the mixture was concentrated to dryness to obtain reactive fluorine-containing sulfonylimide 1. The amount of reactive fluorine-containing sulfonylimide 1 obtained was 101 g (yield: 73%).
(反応性含フッ素スルホニルイミド1の1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,CD3CN):δ6.4(w-w,1H),6.2(q,1H),5.9(w-w,1H),4.2-3.8(m,4H),4.2(t,2H),3.4(q,2H),3.1(s,3H)
19F-NMR(376MHz,CD3CN):δ-80.2(s,3F),-111.8(m,2F),-113.4(t,2F),-119.4(q,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of reactive fluorine-containing sulfonylimide 1)
1 H-NMR (400 MHz, CD 3 CN): δ6.4 (w-w, 1H), 6.2 (q, 1H), 5.9 (w-w, 1H), 4.2-3.8 (m, 4H), 4.2 (t, 2H), 3.4 (q, 2H), 3.1 (s, 3H)
19 F-NMR (376 MHz, CD 3 CN): δ-80.2 (s, 3F), -111.8 (m, 2F), -113.4 (t, 2F), -119.4 (q, 2F)
[合成例2]反応性含フッ素スルホニルイミドリチウム(反応性含フッ素スルホニルイミド2)の合成
(中間体4iの合成)
分液ロートに、本発明例1で合成した中間体3iを20g(38mmol)量り取り、これに濃度40質量%の硫酸水溶液60gと酢酸エチル206gとを加えて混合した後、分液して上相を回収した。回収した上相を、濃度40質量%の硫酸水溶液60gで2回洗浄した。洗浄後、濃度10質量%の水酸化リチウム水溶液30gを加えて混合して、下記の反応式4iの反応により中間体4iを生成させた後、分液して上相を回収した。回収した上相をイオン交換水20gで2回洗浄した後、濃縮し、アセトニトリルを加えて、濃度50質量%の中間体4iのアセトニトリル溶液36g(収率:96%)を得た。
[Synthesis Example 2] Synthesis of reactive fluorine-containing sulfonylimide lithium (reactive fluorine-containing sulfonylimide 2) (synthesis of intermediate 4i)
Weigh out 20g (38mmol) of Intermediate 3i synthesized in Inventive Example 1 into a separating funnel, add 60g of sulfuric acid aqueous solution with a concentration of 40% by mass and 206g of ethyl acetate, mix, and separate the layers. The phase was collected. The collected upper phase was washed twice with 60 g of an aqueous sulfuric acid solution having a concentration of 40% by mass. After washing, 30 g of lithium hydroxide aqueous solution having a concentration of 10% by mass was added and mixed to produce intermediate 4i by the reaction of reaction formula 4i below, and then the liquid was separated and the upper phase was collected. The collected upper phase was washed twice with 20 g of ion-exchanged water, concentrated, and acetonitrile was added to obtain 36 g (yield: 96%) of an acetonitrile solution of intermediate 4i with a concentration of 50% by mass.
(中間体4iの1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,D2O):δ4.0-3.3(m,4H),3.2(s,3H)
19F-NMR(376MHz,D2O):δ-79.3(s,3F),-111.4(m,2F),-112.6(t,2F),-119.1(t,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of intermediate 4i)
1 H-NMR (400 MHz, D 2 O): δ4.0-3.3 (m, 4H), 3.2 (s, 3H)
19 F-NMR (376 MHz, D 2 O): δ -79.3 (s, 3F), -111.4 (m, 2F), -112.6 (t, 2F), -119.1 (t, 2F)
(反応性含フッ素スルホニルイミド2の合成)
温度計、還流管を備えたフラスコに、濃度50質量%の中間体4iのアセトニトリル溶液を10.0g(固形分5.0g,9.9mmol)、ジブチルヒドロキシトルエンを0.05g、ジラウリン酸ジブチルすずを0.11g、脱水アセトニトリルを9.4gの割合で仕込み、窒素雰囲気下で60℃に加熱した。そこに、2-イソシアナトエチルアクリレート2.4g(17.1mmol)を滴下した後、60℃で30分加熱して、下記の反応式2の反応により反応性含フッ素スルホニルイミド2を生成させた。反応終了後、濃縮乾固し、乾固物にイオン交換水10.3gを加え溶解させた。得られた溶液をクロロホルム37gで2回洗浄した後、分液して上相を回収した。回収した上相にジブチルヒドロキシトルエン0.0005gを加えた後、濃縮した。濃縮後、酢酸エチルを加え、反応性含フッ素スルホニルイミド2の濃度が50質量%の酢酸エチル溶液を10.9g(収率:85%)を得た。
(Synthesis of reactive fluorine-containing sulfonylimide 2)
In a flask equipped with a thermometer and a reflux tube, add 10.0 g (solid content 5.0 g, 9.9 mmol) of an acetonitrile solution of Intermediate 4i with a concentration of 50% by mass, 0.05 g of dibutylhydroxytoluene, and dibutyltin dilaurate. 0.11 g of dehydrated acetonitrile and 9.4 g of dehydrated acetonitrile were charged, and the mixture was heated to 60° C. under a nitrogen atmosphere. Thereto, 2.4 g (17.1 mmol) of 2-isocyanatoethyl acrylate was added dropwise, and the mixture was heated at 60° C. for 30 minutes to generate reactive fluorine-containing sulfonylimide 2 by the reaction of reaction formula 2 below. . After the reaction was completed, the mixture was concentrated to dryness, and 10.3 g of ion-exchanged water was added to the dried product to dissolve it. The resulting solution was washed twice with 37 g of chloroform, then separated and the upper phase was collected. After adding 0.0005 g of dibutylhydroxytoluene to the collected upper phase, it was concentrated. After concentration, ethyl acetate was added to obtain 10.9 g (yield: 85%) of an ethyl acetate solution containing reactive fluorine-containing sulfonylimide 2 at a concentration of 50% by mass.
(反応性含フッ素スルホニルイミド2の1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,CD3CN):δ6.4(w-w,1H),6.2(q,1H),5.9(w-w,1H),4.4-3.3(m,4H),4.2(t,2H),3.4(q,2H),3.1(s,3H)
19F-NMR(376MHz,CD3CN):δ-80.2(s,3F),-111.8(m,2F),-113.4(t,2F),-119.4(q,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of reactive fluorine-containing sulfonylimide 2)
1 H-NMR (400 MHz, CD 3 CN): δ6.4 (w-w, 1H), 6.2 (q, 1H), 5.9 (w-w, 1H), 4.4-3.3 (m, 4H), 4.2 (t, 2H), 3.4 (q, 2H), 3.1 (s, 3H)
19 F-NMR (376 MHz, CD 3 CN): δ-80.2 (s, 3F), -111.8 (m, 2F), -113.4 (t, 2F), -119.4 (q, 2F)
[合成例3]反応性含フッ素スルホニルイミド・N-エチル-N-メチルピロリジニウム(反応性含フッ素スルホニルイミド3)の合成
分液ロートに、合成例1で合成した反応性含フッ素スルホニルイミド1を5.4g(7.9mmol)量り取り、これに濃度50質量%のN-エチル-N-メチルピロリジニウムブロミド水溶液4.7g(固形分2.4g,12.1mmol)と、イオン交換水20gと、クロロホルム13gとを加えて混合して、下記の反応式3の反応により反応性含フッ素スルホニルイミド3を生成させた後、分液して下相を回収した。回収した下相を、イオン交換水10gで3回洗浄した後、ジブチルヒドロキシトルエン0.003gを加え、濃縮、乾燥して、反応性含フッ素スルホニルイミド3を得た。得られた反応性含フッ素スルホニルイミド3の量は、35.4g(収率:90%)であった。
[Synthesis Example 3] Synthesis of reactive fluorine-containing sulfonylimide/N-ethyl-N-methylpyrrolidinium (reactive fluorine-containing sulfonylimide 3) In a separating funnel, place the reactive fluorine-containing sulfonylimide synthesized in Synthesis Example 1. Weigh out 5.4 g (7.9 mmol) of 1, add 4.7 g (solid content 2.4 g, 12.1 mmol) of an aqueous solution of N-ethyl-N-methylpyrrolidinium bromide with a concentration of 50% by mass, and perform ion exchange. 20 g of water and 13 g of chloroform were added and mixed to produce reactive fluorine-containing sulfonylimide 3 by the reaction shown in Reaction Formula 3 below, and then the layers were separated and the lower phase was collected. After washing the collected lower phase three times with 10 g of ion-exchanged water, 0.003 g of dibutylhydroxytoluene was added, and the mixture was concentrated and dried to obtain reactive fluorine-containing sulfonylimide 3. The amount of the obtained reactive fluorine-containing sulfonylimide 3 was 35.4 g (yield: 90%).
(反応性含フッ素スルホニルイミド3の1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,CD3CN):δ6.4(w-w,1H),6.2(q,1H),5.9(w-w,1H),4.4-3.3(m,14H),3.1(s,3H),2.9(s,3H),2.1(m,4H),1.3(t-t,3H)
19F-NMR(376MHz,CD3CN):δ-80.2(s,3F),-111.8(m,2F),-113.4(t,2F),-119.5(q,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of reactive fluorine-containing sulfonylimide 3)
1 H-NMR (400 MHz, CD 3 CN): δ6.4 (w-w, 1H), 6.2 (q, 1H), 5.9 (w-w, 1H), 4.4-3.3 (m, 14H), 3.1 (s, 3H), 2.9 (s, 3H), 2.1 (m, 4H), 1.3 (t-t, 3H)
19 F-NMR (376 MHz, CD 3 CN): δ-80.2 (s, 3F), -111.8 (m, 2F), -113.4 (t, 2F), -119.5 (q, 2F)
[合成例4]反応性含フッ素スルホニルイミドカリウム(反応性含フッ素スルホニルイミド4)の合成
(中間体5iの合成)
温度計と還流管を備えたフラスコに、1,1-ジフルオロメタン-1,1-ジスルホニルジフロライドを343g(1.59mol)、フッ化カリウムを115g(1.97mol)、脱水アセトニトリルを1627gの割合で仕込み、窒素雰囲気下で60℃に加熱した。次いで、ノナフルオロブタンスルホンアミドカリウム509g(1.51mol)を数回に分けて添加した後、さらに60℃で2時間加熱して、下記の反応式5iの反応により中間体5iを生成させた。反応終了後、不溶物を吸引濾過により濾別し、濾液を濃縮乾固して、粗生成物789gを得た。得られた粗生成物にエタノール397gを加えて60℃で加熱溶解した後、不溶物を3μmのメンブレンフィルターで濾別し、濾液をクロロホルム4032gに加え、生成物を晶析させた。晶析した生成物を吸引濾過により回収し、乾燥して、白色固体の中間体5iを得た。得られた中間体5iの量は、700g(収率:87%)であった。
[Synthesis Example 4] Synthesis of reactive fluorine-containing sulfonylimide potassium (reactive fluorine-containing sulfonylimide 4) (synthesis of intermediate 5i)
In a flask equipped with a thermometer and a reflux tube, add 343 g (1.59 mol) of 1,1-difluoromethane-1,1-disulfonyl difluoride, 115 g (1.97 mol) of potassium fluoride, and 1,627 g of dehydrated acetonitrile. and heated to 60° C. under a nitrogen atmosphere. Next, 509 g (1.51 mol) of potassium nonafluorobutanesulfonamide was added in several portions, and the mixture was further heated at 60° C. for 2 hours to produce intermediate 5i by the reaction of reaction formula 5i below. After the reaction was completed, insoluble materials were removed by suction filtration, and the filtrate was concentrated to dryness to obtain 789 g of a crude product. After adding 397 g of ethanol to the obtained crude product and dissolving it by heating at 60° C., insoluble matter was filtered off using a 3 μm membrane filter, and the filtrate was added to 4032 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to yield intermediate 5i as a white solid. The amount of intermediate 5i obtained was 700 g (yield: 87%).
(中間体5iの19F-NMR測定結果)
19F-NMR(376MHz,CD3CN):δ45.0(m.1F),-80.9(t,3F),-101.8(s,2F),-112.6(t,2F),-120.5(m,2F),-125.4(m,2F)
( 19F -NMR measurement results of intermediate 5i)
19 F-NMR (376MHz, CD 3 CN): δ45.0 (m.1F), -80.9 (t, 3F), -101.8 (s, 2F), -112.6 (t, 2F) , -120.5 (m, 2F), -125.4 (m, 2F)
(中間体6iの合成)
温度計と還流管を備えたフラスコに、中間体5iを443g(0.83mol)、フッ化カリウムを147g(2.53mol)、脱水テトラヒドロフランを802gの割合で仕込み、窒素雰囲気下で60℃に加熱した。そこに、プロピルアミン59.1g(1.00mol)を滴下した後、60℃で2.5時間加熱して、下記の反応式6iの反応により中間体6iを生成させた。反応終了後、濃縮乾固し、残渣に酢酸エチル2417g、イオン交換水360gを加えて混合した後、分液して酢酸エチル相を回収した。回収した酢酸エチル相を、さらに濃度20質量%の水酸化カリウム水溶液200gで2回、濃度20質量%の塩化カリウム水溶液220gで2回洗浄した後、再度、濃縮乾固した。得られた残渣に同質量のアセトニトリルを加え溶解させ、淡黄色透明で、濃度50質量%の中間体6iのアセトニトリル溶液982g(固形分491g、収率:97%)を得た。
(Synthesis of intermediate 6i)
A flask equipped with a thermometer and a reflux tube was charged with 443 g (0.83 mol) of Intermediate 5i, 147 g (2.53 mol) of potassium fluoride, and 802 g of dehydrated tetrahydrofuran, and heated to 60°C under a nitrogen atmosphere. did. After 59.1 g (1.00 mol) of propylamine was added dropwise thereto, the mixture was heated at 60° C. for 2.5 hours to produce intermediate 6i by the reaction of reaction formula 6i below. After the reaction was completed, the mixture was concentrated to dryness, and 2,417 g of ethyl acetate and 360 g of ion-exchanged water were added to the residue and mixed, followed by liquid separation to recover the ethyl acetate phase. The recovered ethyl acetate phase was further washed twice with 200 g of a 20% by mass aqueous potassium hydroxide solution and twice with 220g of a 20% by mass aqueous potassium chloride solution, and then concentrated to dryness again. The same mass of acetonitrile was added to and dissolved in the resulting residue to obtain 982 g (solid content: 491 g, yield: 97%) of a pale yellow and transparent acetonitrile solution of Intermediate 6i with a concentration of 50% by mass.
(中間体6iの1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,D2O):δ3.3(t,2H),1.5(m,2H),0.9(t,3H)
19F-NMR(376MHz,D2O):δ-80.7(t,3F),-106.5(s,2F),-111.4(t,2F),-120.3(m,2F),-125.0(m,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of intermediate 6i)
1 H-NMR (400 MHz, D 2 O): δ3.3 (t, 2H), 1.5 (m, 2H), 0.9 (t, 3H)
19 F-NMR (376 MHz, D 2 O): δ -80.7 (t, 3F), -106.5 (s, 2F), -111.4 (t, 2F), -120.3 (m, 2F), -125.0 (m, 2F)
(中間体7iの合成)
温度計と還流管を備えたフラスコに、濃度50質量%の中間体6iのアセトニトリル溶液を684g(固形分342g、0.56mol)、6-クロロ-1-ヘキサノールを212g(1.55mol)、炭酸カリウムを80g(0.58mol)、脱水アセトニトリルを433gの割合で仕込み、窒素雰囲気下、80℃で48時間加熱して、下記の反応式7iの反応により中間体7iを生成させた。反応終了後、不溶物を吸引濾過により濾別し、濾液を濃縮乾固した。得られた残渣に酢酸エチル1840gを加えて溶解させ、得られた溶液を濃度10質量%のKCl水溶液300gで2回洗浄した後、分液して酢酸エチル相を回収した。回収した酢酸エチル相を、さらにイオン交換水300gで2回洗浄した後、濃縮乾固し、粗生成物を得た。得られた粗生成物にエタノール203gを加えて溶解させ、得られた溶液をクロロホルム2032gに加え、生成物を晶析させた。晶析した生成物を吸引濾過により回収し、乾燥して、白色固体の中間体7iを得た。得られた中間体7iの量は、327g(収率:87%)であった。
(Synthesis of intermediate 7i)
In a flask equipped with a thermometer and a reflux tube, 684 g (solid content 342 g, 0.56 mol) of an acetonitrile solution of intermediate 6i with a concentration of 50% by mass, 212 g (1.55 mol) of 6-chloro-1-hexanol, and carbonic acid were added. 80 g (0.58 mol) of potassium and 433 g of dehydrated acetonitrile were charged, and the mixture was heated at 80° C. for 48 hours in a nitrogen atmosphere to produce intermediate 7i by the reaction of reaction formula 7i below. After the reaction was completed, insoluble materials were removed by suction filtration, and the filtrate was concentrated to dryness. 1840 g of ethyl acetate was added to the resulting residue to dissolve it, and the resulting solution was washed twice with 300 g of a KCl aqueous solution with a concentration of 10% by mass, and then separated to recover the ethyl acetate phase. The collected ethyl acetate phase was further washed twice with 300 g of ion-exchanged water, and then concentrated to dryness to obtain a crude product. 203 g of ethanol was added to the obtained crude product to dissolve it, and the obtained solution was added to 2032 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to yield intermediate 7i as a white solid. The amount of intermediate 7i obtained was 327 g (yield: 87%).
(中間体7iの1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,CD3CN):δ3.8-3.3(m,6H),1.8-1.3(m,10H),1.0(t,3H)
19F-NMR(376MHz,CD3CN):δ-80.7(t,3F),-107.3(s,2F),-111.5(t,2F),-120.4(m,2F),-125.0(m,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of intermediate 7i)
1 H-NMR (400 MHz, CD 3 CN): δ3.8-3.3 (m, 6H), 1.8-1.3 (m, 10H), 1.0 (t, 3H)
19 F-NMR (376 MHz, CD 3 CN): δ-80.7 (t, 3F), -107.3 (s, 2F), -111.5 (t, 2F), -120.4 (m, 2F), -125.0 (m, 2F)
(反応性含フッ素スルホニルイミド4の合成)
温度計と還流管を備えたフラスコに、中間体7iを13g(0.019mol)、ジブチルヒドロキシトルエンを0.02g、濃度12質量%のカリウムtert-ブトキシド(t-BuOK)・テトラヒドロフラン溶液を18g(カリウムtert-ブトキシド2.16g,0.019mol)、メタクリル酸グリシジル3g(0.020mol)、脱水テトラヒドロフランを30gの割合で仕込み、窒素雰囲気下、66℃で15時間加熱して、下記の反応式4の反応により反応性含フッ素スルホニルイミド4を生成させた。反応終了後、イオン交換水20gを加え、次いで塩酸を中性になるまで加えた後、濃縮乾固した。得られた残渣にエタノール20gに溶解させた後、不溶物を吸引濾過により濾別した。濾液にクロロホルム203gを加えて混合した後、分液して下相を回収した。回収した下相を濃縮乾固し、晶析した生成物を濾過により回収し、乾燥して、白色固体の反応性含フッ素スルホニルイミド4を得た。得られた反応性含フッ素スルホニルイミド4の量は、11g(収率:72%)であった。
(Synthesis of reactive fluorine-containing sulfonylimide 4)
In a flask equipped with a thermometer and a reflux tube, 13 g (0.019 mol) of Intermediate 7i, 0.02 g of dibutylhydroxytoluene, and 18 g ( 2.16 g (0.019 mol) of potassium tert-butoxide), 3 g (0.020 mol) of glycidyl methacrylate, and 30 g of dehydrated tetrahydrofuran were heated at 66°C for 15 hours under a nitrogen atmosphere to produce the following reaction formula 4. A reactive fluorine-containing sulfonylimide 4 was produced by the reaction. After the reaction was completed, 20 g of ion-exchanged water was added, and then hydrochloric acid was added until the mixture became neutral, and then concentrated to dryness. The resulting residue was dissolved in 20 g of ethanol, and insoluble matter was filtered off by suction filtration. After adding and mixing 203 g of chloroform to the filtrate, the mixture was separated and the lower phase was collected. The collected lower phase was concentrated to dryness, and the crystallized product was collected by filtration and dried to obtain reactive fluorine-containing sulfonylimide 4 as a white solid. The amount of the obtained reactive fluorine-containing sulfonylimide 4 was 11 g (yield: 72%).
(反応性含フッ素スルホニルイミド4の1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,CD3CN):δ6.1(t,1H),5.7(t,1H)4.3-4.2(m,5H),4.1-3.7(m,6H),2.0(t,3H)1.8-1.3(m,10H),1.0(t,3H)
19F-NMR(376MHz,CD3CN):δ-79.8(t,3F),-106.9(s,2F),-111.0(t,2F),-119.8(m,2F),-124.4(m,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of reactive fluorine-containing sulfonylimide 4)
1 H-NMR (400 MHz, CD 3 CN): δ6.1 (t, 1H), 5.7 (t, 1H) 4.3-4.2 (m, 5H), 4.1-3.7 ( m, 6H), 2.0 (t, 3H) 1.8-1.3 (m, 10H), 1.0 (t, 3H)
19 F-NMR (376 MHz, CD 3 CN): δ -79.8 (t, 3F), -106.9 (s, 2F), -111.0 (t, 2F), -119.8 (m, 2F), -124.4 (m, 2F)
[合成例5]反応性含フッ素スルホニルイミドカリウム(反応性含フッ素スルホニルイミド5)の合成
(中間体8iの合成)
温度計と還流管を備えたフラスコに、エチレンジアミンを37g(0.62mol)、脱水アセトニトリルを203gの割合で仕込み、窒素雰囲気下で60℃に加熱した。そこに、合成例1で合成した中間体1iを同量の脱水アセトニトリルに溶解して調製した溶液200g(中間体1iの量:100g、0.21mol)を滴下した後、60℃で2.5時間加熱して、下記の反応式8iの反応により中間体8iを生成させた。反応終了後、濃縮乾固し、残渣に酢酸エチル854gとイオン交換水87gとを加えて混合した後、分液して酢酸エチル相を回収した。回収した酢酸エチル相を、さらに濃度20質量%の水酸化カリウム水溶液100gで3回、濃度20質量%の塩化カリウム水溶液100gで2回、濃度40質量%の硫酸水溶液30gで1回洗浄した後、濃縮乾固した。得られた残渣にテトラヒドロフラン300gと炭酸カリウム88gとを加え60℃で2時間撹拌した後、不溶物を吸引濾過により濾別した。濾液を濃度50質量%の中間体8iのテトラヒドロフラン溶液になるまで濃縮し、淡黄色透明の溶液224g(固形分112g、収率:96%)を得た。
[Synthesis Example 5] Synthesis of reactive fluorine-containing sulfonylimide potassium (reactive fluorine-containing sulfonylimide 5) (synthesis of intermediate 8i)
A flask equipped with a thermometer and a reflux tube was charged with 37 g (0.62 mol) of ethylenediamine and 203 g of dehydrated acetonitrile, and heated to 60° C. under a nitrogen atmosphere. There, 200 g of a solution prepared by dissolving Intermediate 1i synthesized in Synthesis Example 1 in the same amount of dehydrated acetonitrile (amount of Intermediate 1i: 100 g, 0.21 mol) was added dropwise, and the mixture was heated to 60°C for 2.5 mol. After heating for a period of time, Intermediate 8i was produced by the reaction of Reaction Formula 8i below. After the reaction was completed, the mixture was concentrated to dryness, and 854 g of ethyl acetate and 87 g of ion-exchanged water were added to the residue and mixed, followed by liquid separation to recover the ethyl acetate phase. The recovered ethyl acetate phase was further washed three times with 100 g of a potassium hydroxide aqueous solution with a concentration of 20% by mass, twice with 100 g of a potassium chloride aqueous solution with a concentration of 20% by mass, and once with 30 g of a sulfuric acid aqueous solution with a concentration of 40% by mass, It was concentrated to dryness. 300 g of tetrahydrofuran and 88 g of potassium carbonate were added to the obtained residue, and the mixture was stirred at 60° C. for 2 hours, and then insoluble matter was filtered off by suction filtration. The filtrate was concentrated to a tetrahydrofuran solution of Intermediate 8i with a concentration of 50% by mass to obtain 224 g of a pale yellow transparent solution (solid content 112 g, yield: 96%).
(中間体8iの1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,CD3CN):δ3.0(t,2H),2.6(t,2H)
19F-NMR(376MHz,CD3CN):δ-80.2(t,3F),-111.3(t,2F),-113.4(t,2F),-119.1(t,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of intermediate 8i)
1 H-NMR (400 MHz, CD 3 CN): δ3.0 (t, 2H), 2.6 (t, 2H)
19 F-NMR (376 MHz, CD 3 CN): δ-80.2 (t, 3F), -111.3 (t, 2F), -113.4 (t, 2F), -119.1 (t, 2F)
(反応性含フッ素スルホニルイミド5の合成)
温度計と還流管を備えたフラスコに、濃度50質量%の中間体8iのテトラヒドロフラン溶液を100g(固形分50g,0.081mol)、炭酸カリウムを34g(0.245mol)、ジブチルヒドロキシトルエンを0.05g、脱水テトラヒドロフランを102gの割合で仕込み、窒素雰囲気下で60℃に加熱した。そこに、塩化アクリロイル8g(0.089mol)を滴下した後、60℃で2時間加熱して、下記の反応式5の反応により反応性含フッ素スルホニルイミド5を生成させた。反応終了後、反応液を濃縮乾固し、残渣をエタノール62gに溶解し、クロロホルム622gに加え生成物を晶析させた。晶析した生成物を吸引濾過により回収し、乾燥して、白色固体の反応性含フッ素スルホニルイミド5を得た。得られた反応性含フッ素スルホニルイミド5の量は、38g(収率:75%)であった。
(Synthesis of reactive fluorine-containing sulfonylimide 5)
In a flask equipped with a thermometer and a reflux tube, 100 g (solid content 50 g, 0.081 mol) of a tetrahydrofuran solution of Intermediate 8i with a concentration of 50% by mass, 34 g (0.245 mol) of potassium carbonate, and 0.5 g of dibutylhydroxytoluene were added. 05 g of dehydrated tetrahydrofuran were charged at a ratio of 102 g, and the mixture was heated to 60° C. under a nitrogen atmosphere. After 8 g (0.089 mol) of acryloyl chloride was added dropwise thereto, the mixture was heated at 60° C. for 2 hours to produce reactive fluorine-containing sulfonylimide 5 through the reaction of Reaction Formula 5 below. After the reaction was completed, the reaction solution was concentrated to dryness, and the residue was dissolved in 62 g of ethanol and added to 622 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to obtain reactive fluorine-containing sulfonylimide 5 as a white solid. The amount of reactive fluorine-containing sulfonylimide 5 obtained was 38 g (yield: 75%).
(反応性含フッ素スルホニルイミド5の1H-NMR測定結果と19F-NMR測定結果)
1H-NMR(400MHz,CD3CN):δ6.4(w-w,1H),6.2(q,1H),5.9(w-w,1H),3.6(t,2H),3.1(t,2H)
19F-NMR(376MHz,CD3CN):δ-80.7(t,3F),-111.8(t,2F),-114.0(t,2F),-119.3(t,2F)
( 1H -NMR measurement results and 19F -NMR measurement results of reactive fluorine-containing sulfonylimide 5)
1 H-NMR (400 MHz, CD 3 CN): δ6.4 (w-w, 1H), 6.2 (q, 1H), 5.9 (w-w, 1H), 3.6 (t, 2H) ), 3.1(t, 2H)
19 F-NMR (376 MHz, CD 3 CN): δ -80.7 (t, 3F), -111.8 (t, 2F), -114.0 (t, 2F), -119.3 (t, 2F)
[本発明例1]
始めに、撹拌機、温度計、還流冷却器、及び窒素導入管を備えた反応装置を用意し、反応装置に窒素ガスを封入した。次に、この反応装置に、2-エチルヘキシルアクリレートを10g、2-ヒドロキシエチルアクリレートを0.2g、帯電防止剤として合成例1で合成した反応性含フッ素スルホニルイミド1を0.01g、重合開始剤としてアゾビスイソブチロニトリルを0.02g、酢酸エチルを15gの割合で仕込み、撹拌しながら、65℃で7時間反応させることで、固形分濃度40%のアクリル系共重合体を得た。
[Example 1 of the present invention]
First, a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was prepared, and nitrogen gas was sealed in the reaction apparatus. Next, in this reaction apparatus, 10 g of 2-ethylhexyl acrylate, 0.2 g of 2-hydroxyethyl acrylate, 0.01 g of the reactive fluorine-containing sulfonylimide 1 synthesized in Synthesis Example 1 as an antistatic agent, and a polymerization initiator. As a result, 0.02 g of azobisisobutyronitrile and 15 g of ethyl acetate were charged and reacted at 65°C for 7 hours with stirring to obtain an acrylic copolymer with a solid content concentration of 40%.
次いで、上記アクリル系共重合体25gに、架橋剤であるコロネートL(日本ポリウレタン工業製、固形分濃度75%)0.5gを添加して、撹拌混合して粘着剤組成物を調製した。 Next, 0.5 g of Coronate L (manufactured by Nippon Polyurethane Industries, solid content concentration 75%), which is a crosslinking agent, was added to 25 g of the above acrylic copolymer, and the mixture was stirred and mixed to prepare an adhesive composition.
[粘着剤組成物の評価]
調製した粘着剤組成物を、ポリエステルフィルムに塗工し、90℃で3分間乾燥させて、厚さ25μmの粘着剤層が形成された積層フィルムを得た。
得られた積層フィルムの粘着剤層の表面抵抗を表面抵抗測定機(株式会社三菱ケミカルアナリテック社製、MCP-HT450)を用いて測定した。その結果を表1に示す。
[Evaluation of adhesive composition]
The prepared adhesive composition was applied to a polyester film and dried at 90° C. for 3 minutes to obtain a laminated film in which a 25 μm thick adhesive layer was formed.
The surface resistance of the adhesive layer of the obtained laminated film was measured using a surface resistance measuring device (MCP-HT450, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The results are shown in Table 1.
次に、積層フィルムを温度60℃、相対湿度90%RHに調整した恒温恒湿槽に、100時間保存した。保存後、積層フィルムを恒温恒湿槽から取り出し、60℃で30分乾燥した後、25℃まで放冷した。放冷後、ブリードアウトの状態を目視で観察し、皮膜の表面抵抗率を測定した。その結果を表1に示す。 Next, the laminated film was stored for 100 hours in a constant temperature and humidity chamber adjusted to a temperature of 60° C. and a relative humidity of 90% RH. After storage, the laminated film was taken out from the constant temperature and humidity bath, dried at 60°C for 30 minutes, and then allowed to cool to 25°C. After cooling, the state of bleed-out was visually observed and the surface resistivity of the film was measured. The results are shown in Table 1.
[本発明例2]
反応性含フッ素スルホニルイミド1の添加量を0.10gとしたこと以外は、本発明例1と同様にして粘着剤組成物を調製し、その粘着剤組成物を評価した。その結果を、表1に示す。
[Example 2 of the present invention]
A pressure-sensitive adhesive composition was prepared in the same manner as in Invention Example 1, except that the amount of reactive fluorine-containing sulfonylimide 1 was 0.10 g, and the pressure-sensitive adhesive composition was evaluated. The results are shown in Table 1.
[本発明例3]
反応性含フッ素スルホニルイミド1の添加量を1.00gとしたこと以外は、本発明例1と同様にして粘着剤組成物を調製し、その粘着剤組成物を評価した。その結果を、表1に示す。
[Example 3 of the present invention]
A pressure-sensitive adhesive composition was prepared in the same manner as in Invention Example 1, except that the amount of reactive fluorine-containing sulfonylimide 1 added was 1.00 g, and the pressure-sensitive adhesive composition was evaluated. The results are shown in Table 1.
[実施例4~15]
反応性含フッ素スルホニルイミド1の代わりに、上記合成例2~5で合成した反応性含フッ素スルホニルイミド2~5を、下記の表1に示す添加量で添加したこと以外は、本発明例1と同様にして粘着剤組成物を調製し、その粘着剤組成物を評価した。その結果を、表1に示す。
[Examples 4 to 15]
Example 1 of the present invention except that instead of reactive fluorine-containing sulfonylimide 1, reactive fluorine-containing sulfonylimides 2 to 5 synthesized in Synthesis Examples 2 to 5 above were added in the amounts shown in Table 1 below. A pressure-sensitive adhesive composition was prepared in the same manner as above, and the pressure-sensitive adhesive composition was evaluated. The results are shown in Table 1.
[比較例1~3]
反応性含フッ素スルホニルイミド1の代わりに、ビス(トリフルオロメタンスルホニル)イミドリチウムを下記の表1に示す添加量で添加したこと以外は、本発明例1と同様にして粘着剤組成物を調製し、その粘着剤組成物を評価した。その結果を、表1に示す。
[Comparative Examples 1 to 3]
An adhesive composition was prepared in the same manner as in Invention Example 1, except that lithium bis(trifluoromethanesulfonyl)imide was added in the amount shown in Table 1 below instead of the reactive fluorine-containing sulfonylimide 1. , evaluated the adhesive composition. The results are shown in Table 1.
[比較例4]
反応性含フッ素スルホニルイミド1を添加しなかったこと以外は、本発明例1と同様にして粘着剤組成物を調製し、その粘着剤組成物を評価した。その結果を、表1に示す。
[Comparative example 4]
A pressure-sensitive adhesive composition was prepared in the same manner as in Invention Example 1, except that the reactive fluorine-containing sulfonylimide 1 was not added, and the pressure-sensitive adhesive composition was evaluated. The results are shown in Table 1.
ビス(トリフルオロメタンスルホニル)イミドリチウムを用いた比較例1~3では、高温高湿環境下での保存前は、帯電防止剤が添加されていない比較例4と比較して表面抵抗率が低い値を示したが、高温高湿環境下(60℃、90%RH、100時間)での保存後は、表面抵抗率が大きく上昇した。これは、保存中に皮膜中のビス(トリフルオロメタンスルホニル)イミドリチウムがブリードアウトしたためであると考えられる。 In Comparative Examples 1 to 3 using bis(trifluoromethanesulfonyl)imide lithium, before storage in a high temperature and high humidity environment, the surface resistivity was lower than that of Comparative Example 4 in which no antistatic agent was added. However, after storage in a high temperature and high humidity environment (60° C., 90% RH, 100 hours), the surface resistivity increased significantly. This is thought to be because lithium bis(trifluoromethanesulfonyl)imide in the film bleed out during storage.
これに対して、反応性含フッ素スルホニルイミドを用いた本発明例1~15においては、高温高湿環境下での保存後でも、ブリードアウトが発生せず、表面抵抗率の上昇が抑えられていた。
以上の結果から、本発明によれば、高温高湿環境下で保存してもブリードアウトが起こりにくい帯電防止剤として利用可能な化合物を提供することが可能となることが確認された。
In contrast, in Examples 1 to 15 of the present invention using reactive fluorine-containing sulfonylimides, no bleed-out occurred and the increase in surface resistivity was suppressed even after storage in a high-temperature, high-humidity environment. Ta.
From the above results, it was confirmed that according to the present invention, it is possible to provide a compound that can be used as an antistatic agent that is unlikely to bleed out even when stored in a high temperature and high humidity environment.
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JP2002505356A (en) | 1998-03-03 | 2002-02-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Significantly fluorinated ionomer |
CN102936310A (en) | 2012-11-26 | 2013-02-20 | 山东华夏神舟新材料有限公司 | Perfluorinated ion exchange resin and preparation method thereof |
JP2014149409A (en) | 2013-01-31 | 2014-08-21 | Fujifilm Corp | Pattern forming method, compound, actinic ray-sensitive or radiation-sensitive resin composition and resist film used for the method, method for manufacturing electronic device, and electronic device |
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JP2013509619A (en) | 2009-10-30 | 2013-03-14 | スリーエム イノベイティブ プロパティズ カンパニー | Optical device with antistatic properties |
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---|---|---|---|---|
JP2002505356A (en) | 1998-03-03 | 2002-02-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Significantly fluorinated ionomer |
CN102936310A (en) | 2012-11-26 | 2013-02-20 | 山东华夏神舟新材料有限公司 | Perfluorinated ion exchange resin and preparation method thereof |
JP2014149409A (en) | 2013-01-31 | 2014-08-21 | Fujifilm Corp | Pattern forming method, compound, actinic ray-sensitive or radiation-sensitive resin composition and resist film used for the method, method for manufacturing electronic device, and electronic device |
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