JP5938280B2 - Perfluoropolyether-modified silane compound, antifouling film forming composition, antifouling film, and article having this film - Google Patents
Perfluoropolyether-modified silane compound, antifouling film forming composition, antifouling film, and article having this film Download PDFInfo
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- JP5938280B2 JP5938280B2 JP2012141219A JP2012141219A JP5938280B2 JP 5938280 B2 JP5938280 B2 JP 5938280B2 JP 2012141219 A JP2012141219 A JP 2012141219A JP 2012141219 A JP2012141219 A JP 2012141219A JP 5938280 B2 JP5938280 B2 JP 5938280B2
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- perfluoropolyether
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- film
- compound
- silane compound
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- -1 Perfluoropolyether-modified silane compound Chemical class 0.000 title claims description 95
- 230000003373 anti-fouling effect Effects 0.000 title claims description 66
- 239000000203 mixture Substances 0.000 title claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 239000010408 film Substances 0.000 description 108
- 150000001875 compounds Chemical class 0.000 description 66
- 238000000034 method Methods 0.000 description 40
- 239000010702 perfluoropolyether Substances 0.000 description 39
- 239000000126 substance Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000000576 coating method Methods 0.000 description 24
- 239000000758 substrate Substances 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 16
- 238000001771 vacuum deposition Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000002194 synthesizing effect Effects 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229940104873 methyl perfluorobutyl ether Drugs 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- ZOTKGMAKADCEDH-UHFFFAOYSA-N 5-triethoxysilylpentane-1,3-diamine Chemical compound CCO[Si](OCC)(OCC)CCC(N)CCN ZOTKGMAKADCEDH-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- BRWBDEIUJSDQGV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-methoxyhexane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BRWBDEIUJSDQGV-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- LMMGAGCAEGFLMD-UHFFFAOYSA-N 2-(2-methyloxiran-2-yl)ethanol Chemical compound OCCC1(C)CO1 LMMGAGCAEGFLMD-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- QZXUQPKFNQQQAJ-UHFFFAOYSA-N 2-ethyl-2-methyloxirane Chemical compound CCC1(C)CO1 QZXUQPKFNQQQAJ-UHFFFAOYSA-N 0.000 description 1
- FGFSHJRPXHNROK-UHFFFAOYSA-N 2-methyl-2-(phenoxymethyl)oxirane Chemical compound C=1C=CC=CC=1OCC1(C)CO1 FGFSHJRPXHNROK-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000003669 anti-smudge Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 1
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
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- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyethers (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、新規なパーフルオロポリエーテル変性シラン化合物に関するものであり、詳しくは撥水性および汚れ付着防止性に優れるとともに、付着した汚れを容易に除去可能な防汚性被膜を形成することができるパーフルオロポリエーテル変性シラン化合物に関するものである。
更に本発明は、上記パーフルオロポリエーテル変性シラン化合物を含有する防汚性被膜形成用組成物、この防汚性被膜形成用組成物を用いて形成される防汚性被膜、およびこの防汚性被膜を有する物品に関する。
The present invention relates to a novel perfluoropolyether-modified silane compound. Specifically, it is excellent in water repellency and antifouling property and can form an antifouling film capable of easily removing adhering dirt. The present invention relates to a perfluoropolyether-modified silane compound.
Furthermore, the present invention provides an antifouling film-forming composition containing the perfluoropolyether-modified silane compound, an antifouling film formed using the antifouling film-forming composition, and the antifouling property. The present invention relates to an article having a coating.
パーフルオロポリエーテル基含有化合物は、パーフルオロポリエーテル基の自由エネルギーが低いため表面エネルギーが非常に小さく、これにより防汚性、撥水撥油性、耐薬品性、潤滑性、離型性などの様々な性質を有しており、これらの性質を利用して各種ディスプレイの保護剤、紙や繊維などの撥水撥油防汚剤、磁気記録媒体の潤滑剤、精密機器の防油剤、離型剤などに幅広く利用されている。しかし、一般にパーフルオロポリエーテル基含有化合物は各種基材に対する密着性が低く、これを用いて形成された被膜において、経時的な防汚性の低下や膜剥がれが発生する場合がある。 Perfluoropolyether group-containing compounds have very low surface energy due to the low free energy of perfluoropolyether groups, which makes it possible to prevent stains, water and oil repellency, chemical resistance, lubricity, mold release, etc. It has various properties, and these properties are used to protect various displays, water and oil and oil repellent and antifouling agents such as paper and fiber, magnetic recording medium lubricants, precision device oil and oil releasing agents, mold release Widely used in medicines. However, in general, the perfluoropolyether group-containing compound has low adhesion to various base materials, and in a film formed using the perfluoropolyether group-containing compound, deterioration of antifouling properties and film peeling over time may occur.
一方、被膜と基材との密着性を高める成分としては、シランカップリング剤が知られている。シランカップリング剤は、一分子中に有機官能基や有機材料との親和性に優れる構造と反応性アルコキシシラン基を有しており、このアルコキシシラン基が空気中の水分などにより自己縮合反応を引き起こしてシロキサンとなり被膜を形成する。これと同時に、基材表面と化学的結合を形成することで強固な密着性を発現することができる。こうして基材との密着性に優れる被膜を形成することができるため、現在シランカップリング剤は各種基材表面のコーティング剤成分や下塗剤（プライマー）として広く利用されている。 On the other hand, a silane coupling agent is known as a component that enhances the adhesion between the coating and the substrate. Silane coupling agents have a structure with excellent affinity with organic functional groups and organic materials and reactive alkoxysilane groups in one molecule, and these alkoxysilane groups undergo a self-condensation reaction due to moisture in the air. Causes siloxane to form a film. At the same time, strong adhesiveness can be expressed by forming a chemical bond with the substrate surface. Since a film having excellent adhesion to the substrate can be formed in this manner, silane coupling agents are currently widely used as coating agent components and primer (primers) on various substrate surfaces.
そこで近年、パーフルオロポリエーテル基含有化合物による上記性質を有し、かつ基材との密着性に優れる被膜を形成するための成分として、シランカップリング剤とパーフルオロ基含有化合物を化学的に結合させた化合物が提案されている（特許文献１〜５参照）。 Therefore, in recent years, a silane coupling agent and a perfluoro group-containing compound are chemically bonded as a component for forming a film having the above-described properties of a perfluoropolyether group-containing compound and excellent adhesion to a substrate. Have been proposed (see Patent Documents 1 to 5).
上記特許文献１〜４では、これら文献に記載の化合物によればパーフルオロポリエーテル基をシランカップリング構造によって基材表面に固定することができるため、優れた防汚性（撥水性、撥油性、汚れ付着防止性、付着汚れの拭き取り性など）を有する被膜を形成できるとされている。しかし、上記文献に記載の化合物はパーフルオロ基の長さ（分子量）が短い場合には撥油性能が不十分であり、十分なパーフルオロ基の長さ（分子量）を有するとしても、パーフルオロ基を含む分子全体の分子量に対するアルコキシシラン基が占める比率が低いため、形成される被膜は密着性や耐久性に劣るものとなる。 In the above Patent Documents 1 to 4, since the perfluoropolyether group can be fixed to the surface of the substrate by the silane coupling structure according to the compounds described in these documents, excellent antifouling properties (water repellency, oil repellency) It is said that a film having anti-smudge property, wipe-off property of adhered stains, etc.) can be formed. However, the compounds described in the above documents have insufficient oil repellency when the perfluoro group length (molecular weight) is short, and even if the perfluoro group length (molecular weight) is sufficient, Since the ratio of the alkoxysilane group to the molecular weight of the whole molecule including the group is low, the formed film is inferior in adhesion and durability.
一方、特許文献５に記載のパーフルオロポリエーテル変性シラン化合物は、一分子中にアルコキシシラン基を２個有し、また一分子中の加水分解性基の含有割合が多いため、高い反応性を有する。したがって穏和な条件でも、基材とパーフルオロポリエーテル変性シラン化合物との反応が進行し高い密着性を有する被膜を形成することができ、またパーフルオロポリエーテル変性シラン化合物同士の反応が進行して高分子化しやすく複雑な三次元構造を形成しやすい。そのため、特許文献５に記載のパーフルオロポリエーテル変性シラン化合物は、比較的穏和な条件で成膜を行うスピンコーティング法やディッピング法といったコーティング法のための成膜材料として適している。
他方、近年、基材表面への成膜方法として真空蒸着法が注目されている。真空蒸着法は、特別な装置が必要であり、また使用できる成膜材料に制限がある（高耐熱性であり昇温工程では容易に高分子化しないが、所定の温度になると高分子化する性質を有するものが望ましい。）などの点で、汎用性や生産性、コスト面において他の成膜方法に劣る点はあるものの、膜厚をコントロールしやすく、磁気記録媒体などの精密機器表面に均一な薄膜を形成することが可能であり、今後も幅広く利用される成膜法であるため、真空蒸着法に対応可能な成膜材料への要求が高まっている。真空蒸着法においては、成膜を良好に行うためには成膜材料が昇温工程で徐々に蒸発することが求められるが、特許文献５に記載のパーフルオロポリエーテル変性シラン化合物では昇温工程において急激に高分子化してしまうためか、高温まで昇温した後に急激に蒸発する傾向が見られるため、良好な性能を有する被膜を形成することは困難である。
On the other hand, the perfluoropolyether-modified silane compound described in Patent Document 5 has two alkoxysilane groups in one molecule and a high content of hydrolyzable groups in one molecule. Have. Therefore, even under mild conditions, the reaction between the substrate and the perfluoropolyether-modified silane compound can proceed to form a film having high adhesion, and the reaction between the perfluoropolyether-modified silane compounds can proceed. It is easy to polymerize and form complex three-dimensional structures. Therefore, the perfluoropolyether-modified silane compound described in Patent Document 5 is suitable as a film forming material for a coating method such as a spin coating method or a dipping method for forming a film under relatively mild conditions.
On the other hand, in recent years, vacuum deposition has attracted attention as a method for forming a film on a substrate surface. The vacuum deposition method requires a special apparatus, and there is a limit to the film forming material that can be used (high heat resistance and does not easily polymerize in the temperature raising step, but polymerizes at a predetermined temperature. In terms of versatility, productivity, and cost, it is easy to control the film thickness, and it is suitable for the surface of precision equipment such as magnetic recording media. Since it is possible to form a uniform thin film and it will continue to be widely used in the future, there is an increasing demand for a film forming material that can be applied to the vacuum deposition method. In the vacuum deposition method, in order to perform film formation satisfactorily, the film forming material is required to gradually evaporate in the temperature raising step, but in the perfluoropolyether-modified silane compound described in Patent Document 5, the temperature raising step is required. It is difficult to form a coating film having good performance because the polymer is rapidly polymerized or has a tendency to evaporate rapidly after being heated to a high temperature.
本発明は上記の課題に対してなされたものであり、その目的は、コーティング法のみならず真空蒸着法によっても良好な成膜が可能であって、基材との密着性に優れた防汚性被膜を形成可能な防汚性被膜形成用組成物を提供することにある。 The present invention has been made for the above-mentioned problems, and its purpose is to achieve good film formation not only by a coating method but also by a vacuum evaporation method, and has excellent antifouling properties with excellent adhesion to a substrate. An object of the present invention is to provide a composition for forming an antifouling film capable of forming a conductive film.
本発明者らは、上記の課題を解決すべく、鋭意検討を行った結果、下記一般式（１）で表される新規なパーフルオロポリエーテル変性シラン化合物によれば、上記の各種成膜方法によって、高い防汚性および耐久性を有するとともに、基材に対する密着性に優れる被膜を形成できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-described various film forming methods are based on the novel perfluoropolyether-modified silane compound represented by the following general formula (1). Thus, it was found that a film having high antifouling properties and durability and excellent adhesion to a substrate can be formed, and the present invention has been completed.
すなわち本発明は、下記一般式（１）で表されるパーフルオロポリエーテル変性シラン化合物を提供する。 That is, the present invention provides a perfluoropolyether-modified silane compound represented by the following general formula (1).
上記構造を有する本発明のパーフルオロポリエーテル変性シラン化合物は、コーティング法のみならず真空蒸着法による処理にも十分に対応することができ、各種基材に対して良好な密着性を示すとともに、優れた防汚性と耐久性とを兼ね備えた防汚性被膜を形成することができる。 The perfluoropolyether-modified silane compound of the present invention having the above structure can sufficiently cope with the treatment by the vacuum deposition method as well as the coating method, and exhibits good adhesion to various substrates, An antifouling film having both excellent antifouling properties and durability can be formed.
本発明のパーフルオロポリエーテル変性シラン化合物は、一般式（１）においてｍが２であり、Ｒ1がトリメチレン基を表し、Ｒ3が２，３−ジヒドロキシプロピル基を表すものであることが好ましい。 In the perfluoropolyether-modified silane compound of the present invention, m in the general formula (1) is preferably 2, R 1 represents a trimethylene group, and R 3 represents a 2,3-dihydroxypropyl group. .
本発明のパーフルオロポリエーテル変性シラン化合物は、そのままで、または溶剤によって希釈して、防汚性被膜形成用組成物として使用することができる。
即ち本発明によって、本発明のパーフルオロポリエーテル変性シラン化合物を含む防汚性被膜形成用組成物が提供される。
The perfluoropolyether-modified silane compound of the present invention can be used as it is or diluted with a solvent as a composition for forming an antifouling film.
That is, the present invention provides an antifouling film-forming composition containing the perfluoropolyether-modified silane compound of the present invention.
また本発明は、本発明の防汚性被膜形成用組成物を成膜して得られた防汚性被膜を提供する。 Moreover, this invention provides the antifouling film obtained by forming into a film the composition for antifouling film formation of this invention.
また本発明は、本発明の防汚性被膜を有する物品を提供する。 The present invention also provides an article having the antifouling film of the present invention.
前記一般式（１）で表される構造を有する本発明のパーフルオロポリエーテル変性シラン化合物は、防汚性被膜形成用組成物成分として有用である。
本発明のパーフルオロポリエーテル変性シラン化合物を含む防汚性被膜形成用組成物を用いて基材表面上に成膜処理を行うことによって、基材表面に防汚性、密着性、耐久性に優れ、透明性も良好な防汚性被膜を形成することができる。
また、本発明のパーフルオロポリエーテル変性シラン化合物を含む防汚性被膜形成用組成物は、スピンコーティング法やディッピング法のみならず真空蒸着法による成膜にも適しており、いずれの成膜方法によっても性能が良好な防汚性被膜を形成することができる。
The perfluoropolyether-modified silane compound of the present invention having the structure represented by the general formula (1) is useful as a composition component for forming an antifouling film.
By performing a film forming treatment on the surface of the substrate using the composition for forming an antifouling film containing the perfluoropolyether-modified silane compound of the present invention, the surface of the substrate is antifouling, adhesive, and durable. An antifouling film excellent in transparency and excellent in transparency can be formed.
Further, the antifouling film forming composition containing the perfluoropolyether-modified silane compound of the present invention is suitable not only for spin coating method and dipping method but also for film formation by vacuum deposition method, and any film formation method Can also form an antifouling film with good performance.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のパーフルオロポリエーテル変性シラン化合物は、下記一般式（１）で表される化合物である。 The perfluoropolyether-modified silane compound of the present invention is a compound represented by the following general formula (1).
（一般式（１）中、ｎは１０〜４０の範囲の整数であり、ｍは１〜３の範囲の整数であり、Ｒ1は炭素数２〜４のアルキレン基を表し、Ｒ2は炭素数１〜６のアルキル基、フェニル基または炭素数１〜３のアルコキシ基を表し、Ｘは炭素数１〜３のアルコキシ基を表し、Ｒ3はヒドロキシ基とヒドロキシ基およびフェノキシ基からなる群から選ばれる１つまたは２つの置換基とによって置換された炭素数３〜５のアルキル基を表す。） (In general formula (1), n is an integer in the range of 10 to 40, m is an integer in the range of 1 to 3, R 1 represents an alkylene group having 2 to 4 carbon atoms, and R 2 is carbon. Represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkoxy group having 1 to 3 carbon atoms, X represents an alkoxy group having 1 to 3 carbon atoms, and R 3 represents a group consisting of a hydroxy group, a hydroxy group, and a phenoxy group. Represents an alkyl group having 3 to 5 carbon atoms substituted by one or two selected substituents.)
本発明のパーフルオロポリエーテル変性シラン化合物は、ディッピング法やスピンコーティング法といったコーティング法のみならず真空蒸着法においても成膜材料として好適に使用することができる。また、本発明のパーフルオロポリエーテル変性シラン化合物を用いて各種成膜方法によって基材表面に形成された被膜は、基材との密着性に優れるとともに、高い防汚性および耐久性を発揮することができる。本発明のパーフルオロポリエーテル変性シラン化合物が真空蒸着法のための成膜材料として好適である理由は、構造中に十分な長さのパーフルオロポリエーテル基と１個のアルコキシシラン基（−Ｓｉ（Ｒ2）Ｘ2）と１つ以上のヒドロキシ基を含む側鎖部分を有するため、真空蒸着時の昇温工程において急激に高分子化することなく徐々に蒸発することにあると考えられる。 The perfluoropolyether-modified silane compound of the present invention can be suitably used as a film forming material not only in a coating method such as a dipping method or a spin coating method but also in a vacuum deposition method. Moreover, the film formed on the surface of the substrate by various film forming methods using the perfluoropolyether-modified silane compound of the present invention has excellent adhesion to the substrate and exhibits high antifouling properties and durability. be able to. The reason why the perfluoropolyether-modified silane compound of the present invention is suitable as a film forming material for a vacuum deposition method is that a perfluoropolyether group having a sufficient length in the structure and one alkoxysilane group (-Si Since it has a side chain portion containing (R 2 ) X 2 ) and one or more hydroxy groups, it is considered that it gradually evaporates without rapidly polymerizing in the temperature raising step during vacuum deposition.
以下、一般式（１）について、更に詳細に説明する。 Hereinafter, the general formula (1) will be described in more detail.
一般式（１）中、ｎが１０未満の整数では、パーフルオロポリエーテル基の長さが十分ではないため、十分な防汚性を発現する被膜を形成することは困難である。他方、ｎが４０を超過する整数では、パーフルオロポリエーテル変性シラン化合物中のアルコキシシラン基およびヒドロキシ基の比率が相対的に低くなるため、形成される被膜の密着性と耐久性が低下する。したがって本発明では、一般式（１）中のｎは１０〜４０の範囲の整数とする。ｎは、形成される被膜の性能の観点から、１０〜３０の範囲の整数であることが好ましい。 In the general formula (1), when n is an integer less than 10, the length of the perfluoropolyether group is not sufficient, so that it is difficult to form a film exhibiting sufficient antifouling properties. On the other hand, when n is an integer exceeding 40, the ratio of alkoxysilane groups and hydroxy groups in the perfluoropolyether-modified silane compound is relatively low, so that the adhesion and durability of the formed film are lowered. Therefore, in this invention, n in General formula (1) is taken as the integer of the range of 10-40. n is preferably an integer in the range of 10 to 30 from the viewpoint of the performance of the coating film to be formed.
ｍは１〜３の範囲の整数であり、この範囲外である場合は、原料の入手が困難になるからである。形成される被膜の性能の点からは、ｍは２であることが好ましい。 This is because m is an integer in the range of 1 to 3, and when it is outside this range, it becomes difficult to obtain the raw material. From the viewpoint of the performance of the film to be formed, m is preferably 2.
Ｒ1は炭素数２〜４のアルキレン基を表す。炭素数が前記の範囲外である場合は、原料の入手が困難になるからである。形成される被膜の性能の点からは、Ｒ1はトリメチレン基であることが好ましい。 R 1 represents an alkylene group having 2 to 4 carbon atoms. This is because it is difficult to obtain raw materials when the carbon number is outside the above range. From the viewpoint of the performance of the formed film, R 1 is preferably a trimethylene group.
Ｒ2は、反応性と形成される被膜の性能の観点から、炭素数１〜６のアルキル基、フェニル基または炭素数１〜３のアルコキシ基とする。炭素数１〜６のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ｎ−ヘキシル基、イソヘキシル基などを挙げることができる。炭素数１〜３のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基などを挙げることができる。本発明においてＲ2は、形成される被膜の密着性と耐久性の観点から、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、またはイソプロポキシ基を表すことが好ましく、メチル基、エチル基、メトキシ基、またはエトキシ基を表すことがより好ましい。 R 2 is an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkoxy group having 1 to 3 carbon atoms from the viewpoint of reactivity and the performance of the formed film. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n- A hexyl group, an isohexyl group, etc. can be mentioned. As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, an isopropoxy group etc. can be mentioned, for example. In the present invention, R 2 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group from the viewpoint of adhesion and durability of the formed film. And more preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group.
Ｘは、反応性の観点から、炭素数１〜３のアルコキシ基とする。なお、一般式（１）中に２つ存在するＸは、同一であっても異なっていてもよい。Ｘは、形成される被膜の密着性と耐久性の観点から、メトキシ基、エトキシ基を表すことが好ましい。 X is an alkoxy group having 1 to 3 carbon atoms from the viewpoint of reactivity. Note that two Xs in the general formula (1) may be the same or different. X preferably represents a methoxy group or an ethoxy group from the viewpoint of the adhesion and durability of the coating film to be formed.
Ｒ3は、形成される被膜の性能の観点から、ヒドロキシ基とヒドロキシ基およびフェノキシ基からなる群から選ばれる１つまたは２つの置換基とによって置換された炭素数３〜５のアルキル基とする。Ｒ3の具体例としては、例えば、２，３−ジヒドロキシプロピル基、２−メチル−２，４−ジヒドロキシブチル基、２−メチル−２，３，４−トリヒドロキシブチル基、２−ヒドロキシ−３−フェノキシプロピル基、２−ヒドロキシ−２−メチル−３−フェノキシプロピル基などを挙げることができる。本発明においてＲ3は、形成される被膜の密着性と耐久性の観点から、炭素数３〜５のジまたはトリヒドロキシアルキル基を表すことが好ましく、２，３−ジヒドロキシプロピル基を表すことがより好ましい。 R 3 is a C 3-5 alkyl group substituted by a hydroxy group and one or two substituents selected from the group consisting of a hydroxy group and a phenoxy group from the viewpoint of the performance of the coating film to be formed. . Specific examples of R 3 include, for example, 2,3-dihydroxypropyl group, 2-methyl-2,4-dihydroxybutyl group, 2-methyl-2,3,4-trihydroxybutyl group, 2-hydroxy-3. -Phenoxypropyl group, 2-hydroxy-2-methyl-3-phenoxypropyl group, etc. can be mentioned. In the present invention, R 3 preferably represents a di- or trihydroxyalkyl group having 3 to 5 carbon atoms, and represents a 2,3-dihydroxypropyl group, from the viewpoints of adhesion and durability of the formed film. More preferred.
以上説明した一般式（１）の好ましい態様としては、一般式（１）においてｍが２であり、Ｒ1がトリメチレン基を表し、Ｒ3が２，３−ジヒドロキシプロピル基を表す、下記一般式（２）を挙げることができる。 As a preferable aspect of the general formula (1) described above, in the general formula (1), m is 2, R 1 represents a trimethylene group, and R 3 represents a 2,3-dihydroxypropyl group. (2) can be mentioned.
（一般式（２）中、ｎ、Ｒ2、およびＸは、それぞれ一般式（１）と同義である。） (In general formula (2), n, R 2 , and X are as defined in general formula (1).)
本発明のパーフルオロポリエーテル変性シラン化合物は、当分野で一般的に使用される方法によって合成することができる。そのような合成方法としては、例えば、下記の４段階：
パーフルオロポリエーテル化合物を合成する第１段階；
前記パーフルオロポリエーテル化合物をメチルエステル化してメチルエステル化パーフルオロポリエーテル化合物を合成する第２段階；
前記メチルエステル化パーフルオロポリエーテル化合物とアミノシラン化合物とを反応させてパーフルオロポリエーテル変性アミノシラン化合物を合成する第３段階；
前記パーフルオロポリエーテル変性アミノシラン化合物の２級アミノ基にエポキシアルコール化合物（エポキシ基とヒドロキシ基とを有する化合物）を反応させ、本発明のパーフルオロポリエーテル変性シラン化合物を合成する第４段階；
を含む合成方法を挙げることができる。
以下、上記合成方法について、更に詳細に説明する。
The perfluoropolyether-modified silane compound of the present invention can be synthesized by a method generally used in the art. Examples of such a synthesis method include the following four steps:
A first step of synthesizing a perfluoropolyether compound;
A second step of methylating the perfluoropolyether compound to synthesize a methylesterified perfluoropolyether compound;
A third step of synthesizing a perfluoropolyether-modified aminosilane compound by reacting the methyl esterified perfluoropolyether compound with an aminosilane compound;
A fourth step of synthesizing the perfluoropolyether-modified silane compound of the present invention by reacting the secondary amino group of the perfluoropolyether-modified aminosilane compound with an epoxy alcohol compound (compound having an epoxy group and a hydroxy group);
Can be mentioned.
Hereinafter, the synthesis method will be described in more detail.
パーフルオロポリエーテル化合物を合成する第１段階：
パーフルオロポリエーテル化合物は下記のように公知の方法により、ヘキサフルオロプロピレンオキシドとフッ化セシウムとを溶媒に添加し混合することにより、合成することができる［JAMES T.HILL,J.Macromol.Sci.Chem.,A8,(3),p499(1974)参照］。ここで前記溶媒としては、当分野で一般的に使用されるものを用いることができ、特に限定されないが、例えば、トリグリム（ｔｒｉｇｌｙｍｅ）、テトラグリム（ｔｅｔｒａｇｌｙｍｅ）、ブチルジグリム（ｂｕｔｙｌｇｌｙｍｅ）およびエチルジグリム（ｅｔｈｙｌｇｌｙｍｅ）などが挙げられる。これらの溶媒は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。パーフルオロポリエーテル化合物の重合度（分子量）はヘキサフルオロプロピレンオキシドの導入速度および反応温度により制御することができる。
First step of synthesizing perfluoropolyether compound:
The perfluoropolyether compound can be synthesized by adding hexafluoropropylene oxide and cesium fluoride to a solvent and mixing them by a known method as described below [JAMES T.HILL, J. Macromol.Sci. Chem., A8, (3), p499 (1974)]. Here, as the solvent, those commonly used in the art can be used, and are not particularly limited. For example, triglyme, tetraglyme, butylyglyme and ethylglymeme. Etc. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type. The degree of polymerization (molecular weight) of the perfluoropolyether compound can be controlled by the introduction rate of hexafluoropropylene oxide and the reaction temperature.
パーフルオロポリエーテル化合物をメチルエステル化してメチルエステル化パーフルオロポリエーテル化合物を合成する第２段階：
パーフルオロポリエーテル化合物はメタノールと混合して２０〜３０℃程度の温度で攪拌することにより、容易にメチルエステル化することができる。その後、精製、乾燥を行うことでメチルエステル化パーフルオロポリエーテル化合物を得ることができる。
ここで、ゲル透過クロマトグラフィー法により、メチルエステル化パーフルオロポリエーテル化合物の分子量を測定することで、その重合度を確認することができる。前記重合度は前記一般式（１）のｎに相当する。
Second step of synthesizing a methyl esterified perfluoropolyether compound by methyl esterifying the perfluoropolyether compound:
The perfluoropolyether compound can be easily methyl esterified by mixing with methanol and stirring at a temperature of about 20-30 ° C. Then, a methyl esterified perfluoropolyether compound can be obtained by performing purification and drying.
Here, the degree of polymerization can be confirmed by measuring the molecular weight of the methyl esterified perfluoropolyether compound by gel permeation chromatography. The degree of polymerization corresponds to n in the general formula (1).
メチルエステル化パーフルオロポリエーテル化合物とアミノシラン化合物とを反応させてパーフルオロポリエーテル変性アミノシラン化合物を合成する第３段階：
アミノシラン化合物としては、当分野で一般的に使用されるものを用いることができ、例えば、３−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、３−（２−アミノエチル）アミノプロピルトリメトキシシラン、３−（２−アミノエチル）アミノプロピルトリエトキシシランなどが挙げられる。これらのアミノシラン化合物は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
前記アミノシラン化合物の使用量は特に限定されないが、例えば、溶媒内でメチルエステル化パーフルオロポリエーテル化合物１．０モルに対して１．０〜３．０モル比で混合することができる。この時、反応温度は反応系の粘度と溶媒の沸点の観点から、６０〜８０℃程度の温度条件を維持することが好ましい。また、前記溶媒としては、当分野で一般的に使用されるものを用いることができ、特に限定されないが、例えば、トリフルオロベンゼン、１，３−ビストリフルオロベンゼン、１，３−ビス（トリフルオロメチル）ベンゼン、１，４−ビストリフルオロベンゼンなどが挙げられる。これらの溶媒は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
反応終了後、精製、乾燥を行うことで、パーフルオロポリエーテル変性アミノシラン化合物を得ることができる。
Third step of synthesizing a perfluoropolyether-modified aminosilane compound by reacting a methylesterified perfluoropolyether compound with an aminosilane compound:
As the aminosilane compound, those generally used in the art can be used, for example, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane. , 3- (2-aminoethyl) aminopropyltriethoxysilane and the like. These aminosilane compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
Although the usage-amount of the said aminosilane compound is not specifically limited, For example, it can mix in 1.0-3.0 molar ratio with respect to 1.0 mol of methyl esterified perfluoropolyether compounds in a solvent. At this time, the reaction temperature is preferably maintained at about 60 to 80 ° C. from the viewpoint of the viscosity of the reaction system and the boiling point of the solvent. In addition, as the solvent, those commonly used in the art can be used, and are not particularly limited. For example, trifluorobenzene, 1,3-bistrifluorobenzene, 1,3-bis (trifluoro Methyl) benzene, 1,4-bistrifluorobenzene and the like. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
After completion of the reaction, purification and drying can be performed to obtain a perfluoropolyether-modified aminosilane compound.
パーフルオロポリエーテル変性アミノシラン化合物の２級アミノ基にエポキシアルコール化合物（エポキシ基とヒドロキシ基を有する化合物）を反応させ、本発明のパーフルオロポリエーテル変性シラン化合物を合成する第４段階：
エポキシアルコール化合物としては、当分野で一般的に使用されるものを用いることができ、例えば、グリシドール、３−メチル−３，４−エポキシ−１−ブタノール、３−メチル−３，４−エポキシブタン−１，２−ジオール、フェニルグリシジルエーテル、フェニル−２−メチルグリシジルエーテルなどを挙げることができる。これらのエポキシアルコール化合物は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらの中でも、形成される被膜の密着性と耐久性の観点からは、グリシドールを使用することが好ましい。
エポキシアルコール化合物を、溶媒内で、前記第３段階で製造されたパーフルオロポリエーテル変性アミノシラン化合物１．０モルに対して、例えば、１．０〜２．０モル比で混合し、２０〜５０℃程度で撹拌することで反応を進行させることができる。また、前記溶媒としては、当分野で一般的に使用されるものを用いることができ、特に限定されないが、例えば、トリクロロトリフルオロエタン、トリフルオロベンゼン、１，３−ビストリフルオロベンゼン、１，３−ビス（トリフルオロメチル）ベンゼン、１，４−ビストリフルオロベンゼンなどが挙げられる。これらの溶媒は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
反応終了後、精製、乾燥を行うことにより、パーフルオロポリエーテル変性アミノシラン化合物の２級アミノ基にエポキシアルコール化合物のエポキシ基を反応および付加させた、本発明のパーフルオロポリエーテル変性シラン化合物を得ることができる。
Fourth step of synthesizing the perfluoropolyether-modified silane compound of the present invention by reacting the secondary amino group of the perfluoropolyether-modified aminosilane compound with an epoxy alcohol compound (compound having an epoxy group and a hydroxy group).
As an epoxy alcohol compound, what is generally used in this field can be used, for example, glycidol, 3-methyl-3,4-epoxy-1-butanol, 3-methyl-3,4-epoxybutane. -1,2-diol, phenyl glycidyl ether, phenyl-2-methyl glycidyl ether, and the like. These epoxy alcohol compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, it is preferable to use glycidol from the viewpoint of adhesion and durability of the formed film.
The epoxy alcohol compound is mixed in a solvent at a ratio of, for example, 1.0 to 2.0 moles with respect to 1.0 mole of the perfluoropolyether-modified aminosilane compound produced in the third stage in a solvent. The reaction can be advanced by stirring at about ° C. Moreover, as said solvent, what is generally used in this field | area can be used, Although it does not specifically limit, For example, a trichloro trifluoro ethane, trifluorobenzene, 1, 3-bis trifluorobenzene, 1, 3 -Bis (trifluoromethyl) benzene, 1,4-bistrifluorobenzene and the like. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
After completion of the reaction, purification and drying are performed to obtain the perfluoropolyether-modified silane compound of the present invention in which the epoxy group of the epoxy alcohol compound is reacted and added to the secondary amino group of the perfluoropolyether-modified aminosilane compound. be able to.
以上説明した合成方法によって、本発明のパーフルオロポリエーテル変性シラン化合物を得ることができる。 The perfluoropolyether-modified silane compound of the present invention can be obtained by the synthesis method described above.
また本発明は、本発明のパーフルオロポリエーテル変性シラン化合物を含有する防汚性被膜形成用組成物を提供する。本発明の防汚性被膜形成用組成物は、本発明のパーフルオロポリエーテル変性シラン化合物のみを含むものであってもよいが、通常は取り扱いを容易にするために、当該化合物を希釈するための溶剤を含む。本発明の防汚性被膜形成用組成物における上記パーフルオロポリエーテル変性シラン化合物の含有量は、特別に制限されるわけではないが、扱いやすさの観点から、０．０５〜５０質量％であることが好ましく、０．０５〜２０質量％であることがより好ましい。 Moreover, this invention provides the composition for antifouling film formation containing the perfluoro polyether modified silane compound of this invention. The composition for forming an antifouling film of the present invention may contain only the perfluoropolyether-modified silane compound of the present invention, but in order to dilute the compound for easy handling. Of solvents. The content of the perfluoropolyether-modified silane compound in the antifouling film-forming composition of the present invention is not particularly limited, but is 0.05 to 50% by mass from the viewpoint of ease of handling. It is preferable that it is 0.05 to 20% by mass.
前記溶剤は、当分野で一般的に使用されるものを用いることができ、特別に限定はされないが、例えば、パーフルオロヘプタン、パーフルオロヘキサン、ｍ−六フッ化キシレン（ｍ−ｘｙｌｅｎｅ ｈｅｘａｆｌｕｏｒｉｄｅ）、ベンゾトリフルオリド、メチルパーフルオロブチルエーテル、エチルパーフルオロブチルエーテル、パーフルオロ（２−ブチルテトラヒドロフラン）、１，１，１，２，３，３−ヘキサフルオロ−４−（１，１，２，３，３，３−ヘキサフルオロプロポキシ）−ペンタン、メチルパーフルオロヘキシルエーテルなどのフッ素変性炭化水素系溶剤などが挙げられる。これらの溶媒は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 As the solvent, those commonly used in the art can be used, and are not particularly limited. For example, perfluoroheptane, perfluorohexane, m-xylene hexafluoride, Benzotrifluoride, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), 1,1,1,2,3,3-hexafluoro-4- (1,1,2,3,3) , 3-hexafluoropropoxy) -pentane, and fluorine-modified hydrocarbon solvents such as methyl perfluorohexyl ether. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
また、本発明の防汚性被膜形成用組成物には、必要に応じて、加水分解縮合触媒を添加してもよい。このような触媒としては、有機酸（酢酸、クロロ酢酸、クエン酸、安息香酸、ジメチルマロン酸、蟻酸、プロピオン酸、グルタール酸、グリコール酸、マレイン酸、マロン酸、トルエンスルホン酸、シュウ酸など）、無機酸（塩酸、硝酸、硫酸、リン酸、ハロゲン化シランなど）、酸性ゾル状フィラー（酸性コロイダルシリカ、酸化チタニアゾルなど）、炭酸塩（水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム等の水酸化物、炭酸ナトリウム、炭酸カリウム、炭酸アンモニウムなど）、炭酸水素塩（炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素アンモニウムなど）、脂肪族アミン（メチルアミン、エチルアミン、ブチルアミン、ジメチルアミン、ジエチルアミン、ジブチルアミン、トリメチルアミン、トリエチルアミン、トリブチルアミンなど）、脂肪族ポリアミン（エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ヘキサメチレンジアミンなど）、芳香族アミン（アニリン、メチルアニリン、エチルアニリン、メチルベンジルアミンなど）、アミノアルコール（モノエタノールアミン、ジエタノールアミン、トリエタノールアミンなど）、複素環式アミン（ピリジン、モルホリン、ピロリジン、ピペリジンなど）、有機錫化合物（ジブチル錫ジラウレート、ジブチル錫ジメトキシドなど）、有機チタン化合物（テトラｎ−ブチルチタネートなど）、亜鉛化合物（ステアリン酸亜鉛など）、アルミ系の金属触媒等を挙げることができ、これらの１種または２種以上を使用することができる。 Moreover, you may add a hydrolysis-condensation catalyst to the composition for antifouling film formation of this invention as needed. Examples of such catalysts include organic acids (acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, oxalic acid, etc.) , Inorganic acid (hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, halogenated silane, etc.), acidic sol filler (acidic colloidal silica, titania sol etc.), carbonate (sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc.) Oxides, sodium carbonate, potassium carbonate, ammonium carbonate, etc.), bicarbonates (sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, etc.), aliphatic amines (methylamine, ethylamine, butylamine, dimethylamine, diethylamine, dibutylamine) , Trimethylamine, triethylamine, Butylamine), aliphatic polyamines (ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, etc.), aromatic amines (aniline, methylaniline, ethylaniline, methylbenzylamine, etc.), amino alcohols (monoethanolamine, diethanolamine, trimethylamine) Ethanolamine, etc.), heterocyclic amines (pyridine, morpholine, pyrrolidine, piperidine, etc.), organic tin compounds (dibutyltin dilaurate, dibutyltin dimethoxide, etc.), organic titanium compounds (tetran-butyl titanate, etc.), zinc compounds (stearin) Zinc acid, etc.), aluminum-based metal catalysts, and the like, and one or more of these can be used.
本発明の防汚性被膜形成用組成物には、本発明の効果を損なわない範囲において、本発明のパーフルオロポリエーテル変性シラン化合物に加え、微量の水分の混入や分解などによって生じるパーフルオロポリエーテル変性シラン化合物の部分加水分解縮合物が含まれていてもよい。 In the composition for forming an antifouling film of the present invention, in the range that does not impair the effects of the present invention, in addition to the perfluoropolyether-modified silane compound of the present invention, perfluoropolyester generated by mixing or decomposition of a small amount of water. A partial hydrolysis condensate of an ether-modified silane compound may be included.
また本発明は、本発明の防汚性被膜形成用組成物を成膜して得られた防汚性被膜および該防汚性被膜を有する物品を提供する。 The present invention also provides an antifouling film obtained by forming the antifouling film forming composition of the present invention and an article having the antifouling film.
本発明の防汚性被膜は、本発明の防汚性被膜形成用組成物を用いて、ガラス、有機ポリマー、金属などの各種基材に対して成膜処理を行い形成することができる。本発明の防汚性被膜形成用組成物によれば、高い透明性を有する被膜を形成することができるため、物品の外観に影響を与えることなく、防汚性を付与することが可能である。 The antifouling film of the present invention can be formed by subjecting various substrates such as glass, organic polymer, metal and the like to film formation using the composition for forming an antifouling film of the present invention. According to the composition for forming an antifouling film of the present invention, since a film having high transparency can be formed, it is possible to impart antifouling properties without affecting the appearance of the article. .
防汚性被膜を形成する成膜方法としては、特に限定されず、当分野で一般的に使用される各種成膜方法、例えば、スピンコーティング法、浸漬コーティング法、カーテンコーティング法、ディッピング法、ゾル−ゲル法および真空蒸着法などの公知の方法を用いることができる。形成される防汚性被膜は、膜厚が５〜５０ｎｍの範囲であることが好ましく、５〜３０ｎｍの範囲であることがより好ましい。膜厚が５ｎｍ未満の場合は被膜の防汚性、密着性、耐久性が低下する傾向があり、５０ｎｍを超過する場合は、光透過性が減少し、厚さが不均一となるため、反射特性の劣化干渉模様が発生する傾向があるためである。本発明の防汚性被膜形成用組成物により成膜される防汚性被膜の膜厚は、光学式膜厚測定法等の公知の膜厚測定方法によって測定することができる。 The film forming method for forming the antifouling film is not particularly limited, and various film forming methods generally used in the art such as spin coating method, dip coating method, curtain coating method, dipping method, sol -Well-known methods, such as a gel method and a vacuum evaporation method, can be used. The antifouling film to be formed preferably has a thickness in the range of 5 to 50 nm, and more preferably in the range of 5 to 30 nm. When the film thickness is less than 5 nm, the antifouling property, adhesion, and durability of the film tend to decrease. When the film thickness exceeds 50 nm, the light transmittance decreases and the thickness becomes nonuniform. This is because a characteristic degradation interference pattern tends to occur. The film thickness of the antifouling film formed by the composition for forming an antifouling film of the present invention can be measured by a known film thickness measuring method such as an optical film thickness measuring method.
本発明の防汚性被膜が形成される物品としては、特に限定されるものではなく、防汚効果を付与することが望ましい各種物品を挙げることができる。例えば、無機ガラスや透明な有機ポリマーから構成され、汚れの付着が実生活の中で大きな不便をもたらすレンズ類、ガラス窓類、液晶類、平板表示素子（ＰＤＰ）類、有機発光素子（ＥＬ）および電界放出ディスプレー（ＦＥＤ）などのフラットパネルディスプレー類、光学フィルター類の最外層として、本発明の防汚性被膜を形成することが好ましい。具体的には、眼鏡、カメラなどのレンズ類、各種製品の液晶表面、一般家庭用、産業用車両などの窓ガラス類、台所、浴室などの水周辺用品、建築外装材、そして美術用品などにも、本発明の防汚性被膜を形成することができる。
また、本発明の防汚性被膜と基材との間には、帯電防止層、反射防止層、電磁波シールド層などの多様な機能性層が形成されていてもよい。
The article on which the antifouling film of the present invention is formed is not particularly limited, and examples thereof include various articles that are desirably imparted with an antifouling effect. For example, lenses, glass windows, liquid crystals, flat panel display devices (PDP), organic light emitting devices (EL), which are composed of inorganic glass or transparent organic polymer, and the adhesion of dirt causes great inconvenience in real life. The antifouling film of the present invention is preferably formed as the outermost layer of flat panel displays such as field emission displays (FED) and optical filters. Specifically, for glasses such as glasses and cameras, liquid crystal surfaces of various products, window glass for general household and industrial vehicles, water peripheral products such as kitchens and bathrooms, exterior building materials, and art supplies In addition, the antifouling film of the present invention can be formed.
Various functional layers such as an antistatic layer, an antireflection layer, and an electromagnetic wave shielding layer may be formed between the antifouling film of the present invention and the substrate.
以下、実施例に基づいて本発明を具体的に説明するが、本発明はこれらによってなんら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by these.
［実施例１］
１．パーフルオロポリエーテル変性シラン化合物の合成
パーフルオロポリエーテル化合物を合成する第１段階：
攪拌器、冷却ジャケット、温度計、圧力計が設置されたステンレス製高圧反応器にテトラグリム２．４９ｇ、フッ化セシウム１．６９ｇ、ヘキサフルオロプロピレン８７．７５ｇおよびヘキサフルオロプロピレンオキシド２２０ｇを投入し、−３５℃で反応させることで無色透明液状のパーフルオロポリエーテル化合物を得た。この化合物について、ＦＴ−ＩＲおよび19Ｆ−ＮＭＲによる同定を行った。ＦＴ−ＩＲにおいて−Ｃ（Ｏ）Ｆの吸収の存在を確認した。19Ｆ−ＮＭＲにおいて以下のピークを確認した。
この化合物のＦＴ−ＩＲおよび19Ｆ−ＮＭＲのスペクトルデータを以下に示す。
19Ｆ−ＮＭＲ
８３．３ｐｐｍ ｓ、３Ｆ、ＣＦ 3 ＣＦ2−
１３１．３ｐｐｍ ｍ、２Ｆ、ＣＦ3ＣＦ 2 −
８３．２ｐｐｍ ｍ、２Ｆ、ＣＦ3ＣＦ2ＣＦ 2 −
ｓ、３Ｆ、−ＣＦ（ＣＦ 3 ）Ｃ（Ｏ）Ｆ
１４６．２ｐｐｍ ｔ、１Ｆ、−ＯＣＦ（ＣＦ3）ＣＦ2−
８１．６ｐｐｍ ｍ、３Ｆ、−ＯＣＦ（ＣＦ 3 ）ＣＦ2−
ｍ、２Ｆ、−ＯＣＦ（ＣＦ3）ＣＦ 2 −
１３２．０ｐｐｍ ｔ、１Ｆ、−ＣＦ（ＣＦ3）Ｃ（Ｏ）Ｆ
ＦＴ−ＩＲ
１８８０ｃｍ-1（−Ｃ（Ｏ）Ｆ）
１１００〜１３４０ｃｍ-1（Ｃ−Ｆ）
[Example 1]
1. Synthesis of perfluoropolyether-modified silane compound First step of synthesizing perfluoropolyether compound:
Tetraglyme 2.49 g, cesium fluoride 1.69 g, hexafluoropropylene 87.75 g and hexafluoropropylene oxide 220 g were charged into a stainless steel high-pressure reactor equipped with a stirrer, cooling jacket, thermometer, and pressure gauge. A colorless transparent liquid perfluoropolyether compound was obtained by reacting at -35 ° C. This compound was identified by FT-IR and 19 F-NMR. The presence of absorption of -C (O) F was confirmed in FT-IR. The following peaks were confirmed in 19 F-NMR.
The spectrum data of FT-IR and 19 F-NMR of this compound are shown below.
19 F-NMR
83.3 ppm s, 3F, C F 3 CF 2 −
131.3 ppm m, 2F, CF 3 C F 2 −
83.2 ppm m, 2F, CF 3 CF 2 C F 2 −
s, 3F, -CF (C F 3 ) C (O) F
146.2 ppm t, 1F, —OC F (CF 3 ) CF 2 —
81.6 ppm m, 3F, -OCF (C F 3 ) CF 2-
m, 2F, -OCF (CF 3 ) C F 2-
132.0 ppm t, 1F, -C F (CF 3 ) C (O) F
FT-IR
1880cm -1 ( -C (O) F)
1100-1340cm -1 (C-F)
パーフルオロポリエーテル化合物をメチルエステル化してメチルエステル化パーフルオロポリエーテル化合物を合成する第２段階：
前記の第１段階で得られたパーフルオロポリエーテル化合物にメタノール５ｇを添加し、室温で１２時間攪拌し、未反応のメタノールを真空乾燥にて除去することで、無色透明液状のメチルエステル化パーフルオロポリエーテル化合物２２１ｇを得た。ゲル透過クロマトグラフィー（ＧＰＣ）測定により、このメチルエステル化パーフルオロポリエーテル化合物の分子量がＭＷ＝２３００であり、ヘキサフルオロプロピレンオキシドが約１３量体であることが確認された（以下、「メチルエステル化パーフルオロポリエーテル化合物１３量体」という）。
ゲル透過クロマトグラフィー（ＧＰＣ）の測定条件は以下の通りとした。
使用機器：Ｗａｔｅｒｓ ４１０ Ｄｅｆｆｅｒｅｎｔｉａｌ Ｒｅｆａｃｔｏｍｅｔｅｒ、Ｗａｔｅｒｓ ７１７ｐｌｕｓ Ａｕｔｏ Ｓａｍｐｌｅｒ、Ｗａｔｅｒｓ １５２５ Ｂｉｎａｒｙ ＨＰＬＣ Ｐｕｍｐ
使用溶剤：Ｒ−１１３（１，１，２−トリクロロ−１，２，２−トリフルオロエタン）
温度：２５℃
流量：１〜５μｌ／ｍｉｎ
Second step of synthesizing a methyl esterified perfluoropolyether compound by methyl esterifying the perfluoropolyether compound:
By adding 5 g of methanol to the perfluoropolyether compound obtained in the first step, stirring at room temperature for 12 hours, and removing unreacted methanol by vacuum drying, a colorless transparent liquid methyl esterified perester is obtained. 221 g of a fluoropolyether compound was obtained. Gel permeation chromatography (GPC) measurement confirmed that the molecular weight of this methyl esterified perfluoropolyether compound was MW = 2300 and hexafluoropropylene oxide was an approximately 13-mer (hereinafter referred to as “methyl ester”). Perfluoropolyether compound 13-mer) ”.
The measurement conditions of gel permeation chromatography (GPC) were as follows.
Equipment used: Waters 410 Differential Refractometer, Waters 717 plus Auto Sampler, Waters 1525 Binary HPLC Pump
Solvent used: R-113 (1,1,2-trichloro-1,2,2-trifluoroethane)
Temperature: 25 ° C
Flow rate: 1-5 μl / min
上記化合物について、ＦＴ−ＩＲおよび1Ｈ−ＮＭＲによる同定を行った。ＦＴ−ＩＲにおいて−Ｃ（Ｏ）Ｆの吸収の消失と−Ｃ（Ｏ）ＯＣＨ3の吸収の存在を確認した。1Ｈ−ＮＭＲにおいて−ＯＣＨ 3 のピークを確認した。
この化合物のＦＴ−ＩＲおよび1Ｈ−ＮＭＲのスペクトルデータを以下に示す。
ＦＴ−ＩＲ
１８００ｃｍ-1（−Ｃ（Ｏ）ＯＣＨ3）
1Ｈ−ＮＭＲ（Ｃ６Ｆ６）
４．３ｐｐｍ ｓ、−ＯＣＨ 3
The above compound was identified by FT-IR and 1 H-NMR. In FT-IR - C (O) and disappearance of the absorption of F - confirmed the presence of absorption of C (O) OCH 3. In 1 H-NMR, a peak of —OC H 3 was confirmed.
The spectrum data of FT-IR and 1 H-NMR of this compound are shown below.
FT-IR
1800 cm −1 ( −C (O) OCH 3 )
1 H-NMR (C6F6)
4.3 ppm s, —OC H 3
メチルエステル化パーフルオロポリエーテル化合物とアミノシラン化合物とを反応させてパーフルオロポリエーテル変性アミノシラン化合物を合成する第３段階：
前記の第２段階で得られたメチルエステル化パーフルオロポリエーテル化合物１３量体２０ｇ（８．７ミリモル）に反応溶媒として１，３−ビス（トリフルオロメチル）ベンゼン１０ｇを加え、３−（２−アミノエチル）アミノプロピルメチルジメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−６０２）１．９７ｇ（９．５７ミリモル）を添加した後、窒素雰囲気下で６５〜７５℃で６時間反応させ、メタノールで沈殿精製することで、微黄色透明液状のパーフルオロポリエーテル変性アミノシラン化合物２１．５０ｇ得た。
この化合物について、ＦＴ−ＩＲおよび1Ｈ−ＮＭＲによる同定を行った。ＦＴ−ＩＲにおいて−Ｃ（Ｏ）ＯＣＨ3の吸収の消失と−Ｃ（Ｏ）ＮＨ−の吸収の存在を確認した。1Ｈ−ＮＭＲにおいて以下のピークを確認した。この化合物のＦＴ−ＩＲおよび1Ｈ−ＮＭＲのスペクトルデータを以下に示す。
ＦＴ−ＩＲ
１７１０ｃｍ-1（−Ｃ（Ｏ）ＮＨ−）
１５３０ｃｍ-1（−Ｃ（Ｏ）ＮＨ−）
1Ｈ−ＮＭＲ（Ｃ６Ｆ６）
０．１１ｐｐｍ ｓ、３Ｈ、≡Ｓｉ−ＣＨ 3
０．７ｐｐｍ ｔ、２Ｈ、−ＣＨ 2 −Ｓｉ≡
１．７４ｐｐｍ ｍ、２Ｈ、−ＣＨ2ＣＨ 2 ＣＨ2−
２．９１ｐｐｍ ｍ、２Ｈ、−ＮＨ−ＣＨ 2 −
３．１６ｐｐｍ ｍ、２Ｈ、−ＣＨ 2 −ＮＨ−
３．４３ｐｐｍ ｍ、２Ｈ、−Ｃ（Ｏ）ＮＨ−ＣＨ 2 −
３．５６ｐｐｍ ｓ、６Ｈ、＝Ｓｉ−（ＯＣＨ 3 ） 2
Third step of synthesizing a perfluoropolyether-modified aminosilane compound by reacting a methylesterified perfluoropolyether compound with an aminosilane compound:
10 g of 1,3-bis (trifluoromethyl) benzene as a reaction solvent was added to 20 g (8.7 mmol) of the methyl esterified perfluoropolyether compound 13-mer obtained in the second step, and 3- (2 -Aminoethyl) After adding 1.97 g (9.57 mmol) of aminopropylmethyldimethoxysilane (trade name KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), the mixture was reacted at 65 to 75 ° C. for 6 hours under a nitrogen atmosphere. By precipitation purification with methanol, 21.50 g of a slightly yellow transparent liquid perfluoropolyether-modified aminosilane compound was obtained.
This compound was identified by FT-IR and 1 H-NMR. In FT-IR - C (O) and the disappearance of absorption of OCH 3 - C (O) NH - confirmed the presence of absorption. The following peaks were confirmed in 1 H-NMR. The spectrum data of FT-IR and 1 H-NMR of this compound are shown below.
FT-IR
1710 cm -1 ( -C (O) NH-)
1530 cm −1 (—C (O) NH— )
1 H-NMR (C6F6)
0.11 ppm s, 3H, ≡Si-C H 3
0.7 ppm t, 2H, —C H 2 —Si≡
1.74ppm m, 2H, -CH 2 C H 2 CH 2 -
2.91 ppm m, 2H, —NH—C H 2 —
3.16 ppm m, 2H, —C H 2 —NH—
3.43ppm m, 2H, -C (O ) NH-C H 2 -
3.56 ppm s, 6H, = Si- (OC H 3 ) 2
パーフルオロポリエーテル変性アミノシラン化合物の２級アミノ基にエポキシアルコール化合物（エポキシ基とヒドロキシ基とを有する化合物）を反応させ、本発明のパーフルオロポリエーテル変性シラン化合物を合成する第４段階：
前記の第３段階で得られたパーフルオロポリエーテル変性アミノシラン化合物２１．５０ｇ（８．６６ミリモル）に再び反応溶媒として１，３−ビス（トリフルオロメチル）ベンゼン１０ｇを加えた後、３−グリシドール０．７７ｇ（１０．４３ミリモル）を添加し、窒素雰囲気下で３５〜４５℃で６時間反応させ、メタノールで沈殿精製することで、微黄色透明液状のパーフルオロポリエーテル変性シラン化合物２２．１２ｇを得た。
この化合物について、ＦＴ−ＩＲおよび1Ｈ−ＮＭＲによる同定を行った。ＦＴ−ＩＲにおいてＯＨの吸収の存在を確認した。1Ｈ−ＮＭＲにおいて以下のピークを確認した。この化合物のＦＴ−ＩＲと1Ｈ−ＮＭＲのスペクトルデータを以下に示す。
ＦＴ−ＩＲ
３２５０〜３４１０ｃｍ-1（Ｏ−Ｈ、Ｎ−Ｈ）
２７８０〜３０００ｃｍ-1（Ｃ−Ｈ）
１７１０ｃｍ-1（−Ｃ（Ｏ）ＮＨ−）
１５３０ｃｍ-1（−ＣＯＮＨ−）
１１００〜１３４０ｃｍ-1（Ｃ−Ｆ）
1Ｈ−ＮＭＲ
０．１１ｐｐｍ ｓ、３Ｈ、≡Ｓｉ−ＣＨ 3
０．７ｐｐｍ ｔ、２Ｈ、−ＣＨ 2 −Ｓｉ≡
２．６５〜３．１５ ｍ、６Ｈ、−ＣＨ 2 −Ｎ（ＣＨ 2 −）−ＣＨ 2 −
３．４３ｐｐｍ ｍ、２Ｈ、−Ｃ（Ｏ）ＮＨ−ＣＨ 2 −
３．６３ｐｐｍ ｓ、６Ｈ、＝Ｓｉ−（ＯＣＨ 3 ） 2
３．７１〜４．３１ ｍ、５Ｈ、−ＣＨ（ＯＨ）ＣＨ 2 ＯＨ
Fourth step of synthesizing the perfluoropolyether-modified silane compound of the present invention by reacting an epoxy alcohol compound (compound having an epoxy group and a hydroxy group) with the secondary amino group of the perfluoropolyether-modified aminosilane compound:
After adding 10 g of 1,3-bis (trifluoromethyl) benzene as a reaction solvent again to 21.50 g (8.66 mmol) of the perfluoropolyether-modified aminosilane compound obtained in the third step, 3-glycidol 0.77 g (10.43 mmol) was added, reacted at 35 to 45 ° C. for 6 hours under a nitrogen atmosphere, and purified by precipitation with methanol to give 22.12 g of a slightly yellow transparent liquid perfluoropolyether-modified silane compound. Got.
This compound was identified by FT-IR and 1 H-NMR. The presence of OH absorption was confirmed in FT-IR. The following peaks were confirmed in 1 H-NMR. The spectrum data of FT-IR and 1 H-NMR of this compound are shown below.
FT-IR
3250 to 3410 cm −1 (OH, NH)
2780-3000cm -1 (C-H)
1710 cm -1 ( -C (O) NH-)
1530cm -1 (-CO NH -)
1100-1340cm -1 (C-F)
1 H-NMR
0.11 ppm s, 3H, ≡Si-C H 3
0.7 ppm t, 2H, —C H 2 —Si≡
2.65~3.15 m, 6H, -C H 2 -N (C H 2 -) - C H 2 -
3.43ppm m, 2H, -C (O ) NH-C H 2 -
3.63 ppm s, 6H, = Si- (OC H 3 ) 2
3.71~4.31 m, 5H, -C H ( O H) C H 2 O H
以上の同定結果から、前記の第４段階で得られたパーフルオロポリエーテル変性シラン化合物が、下記化学式ａで表される構造を有することが確認された。 From the above identification results, it was confirmed that the perfluoropolyether-modified silane compound obtained in the fourth step has a structure represented by the following chemical formula a.
２．真空蒸着法による防汚性被膜の形成
上記１．で得たパーフルオロポリエーテル変性シラン化合物の２０質量％溶液（溶媒はメチルパーフルオロブチルエーテル（東京化成工業株式会社製）を使用）０．２５ｍＬを、ステンレス製焼結フィルター（細孔径８０〜１００μｍ、直径１８ｍｍ、厚さ３ｍｍ）に含浸させ、５０℃で６０分間加熱処理してメチルパーフルオロブチルエーテルを蒸発除去した。
その後、ポリカーボネート系プラスチックレンズまたは金属板と、上記方法でパーフルオロポリエーテル変性シラン化合物を含浸させたステンレス製焼結フィルターとを真空蒸着機（商品名：ＣＥＳ−１０５０（シンクロン社製））に装着し、真空度１．５×１０-2Ｐa以下で、第一ステップとして３分２０秒で８００℃まで加熱昇温し、さらに第二ステップとして１分４０秒で８５０℃まで加熱昇温し、真空蒸着を行い、被膜を有する物品を得た。
光学式膜厚測定器にて、真空蒸着法にて得られた被膜の膜厚を測定したところ１５ｎｍであった。
この被膜を有する物品を用いて、下記の方法で、接触角、転落角、密着性、外観、耐久性の評価を行った。得られた結果を表１に示す。
2. Formation of antifouling film by vacuum deposition method 0.25 mL of a 20% by mass solution of the perfluoropolyether-modified silane compound obtained in (using methyl perfluorobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)) as a stainless sintered filter (pore size 80-100 μm, 18 mm in diameter and 3 mm in thickness) and heat-treated at 50 ° C. for 60 minutes to evaporate and remove methyl perfluorobutyl ether.
Thereafter, a polycarbonate plastic lens or metal plate and a stainless sintered filter impregnated with a perfluoropolyether-modified silane compound by the above method are mounted on a vacuum deposition machine (trade name: CES-1050 (manufactured by SYNCHRON)). Then, at a vacuum degree of 1.5 × 10 −2 Pa or less, the temperature was raised to 800 ° C. in 3 minutes and 20 seconds as the first step, and further heated to 850 ° C. in 1 minute and 40 seconds as the second step, Vacuum deposition was performed to obtain an article having a coating.
It was 15 nm when the film thickness of the film obtained by the vacuum evaporation method was measured with the optical film thickness measuring device.
Using the article having this film, the contact angle, the falling angle, the adhesion, the appearance, and the durability were evaluated by the following methods. The obtained results are shown in Table 1.
ポリカーボネート系プラスチックレンズ、金属板としては以下のものを使用した。
ポリカーボネート系プラスチックレンズは、レンズ基板（ＨＯＹＡ株式会社製ポリカーボネート製レンズ、屈折率１．５８９、度数−４．００）の表面上に、ハードコート膜（特開昭６３−１０６４０号公報に開示の保護膜を使用）と反射防止膜（ＳｉＯ2を蒸着材料として形成された蒸着層とＺｒＯ2を蒸着材料として形成された蒸着層が複数積層された多層膜）をこの順に積層して作製した。上記多層膜の最外層のＳｉＯ2蒸着層表面に、上記被膜を形成した。
金属板としては、株式会社ニラコ製のニッケル板（品番：ＮＩ−３１３３２４）を、超音波洗浄機にてアセトンで洗浄した後、２５℃で1 Nの塩酸水溶液で５分間処理した。その後水洗し、超音波洗浄機にてアセトンで洗浄した。洗浄後のニッケル板表面に、上記被膜を形成した。
The following were used as polycarbonate plastic lenses and metal plates.
A polycarbonate plastic lens is a protective film disclosed in Japanese Patent Application Laid-Open No. 63-10640 on the surface of a lens substrate (polycarbonate lens manufactured by HOYA Corporation, refractive index 1.589, power −4.00). A film was used) and an antireflection film (a multilayer film in which a plurality of vapor deposition layers formed using SiO 2 as a vapor deposition material and a plurality of vapor deposition layers formed using ZrO 2 as a vapor deposition material) were laminated in this order. The coating film was formed on the surface of the outermost SiO 2 vapor deposition layer of the multilayer film.
As a metal plate, a Nilaco nickel plate (product number: NI-313324) was washed with acetone in an ultrasonic washer and then treated with a 1 N aqueous hydrochloric acid solution at 25 ° C. for 5 minutes. Thereafter, it was washed with water and washed with acetone with an ultrasonic washer. The film was formed on the surface of the nickel plate after washing.
評価方法
（１）接触角
接触角計ＤＭ−５００（協和界面科学社製）を用いて、設置角度０°（水平）のステージ上に設置した物品の被膜表面に蒸留水（２．０μＬ）を滴下し、２０℃の雰囲気下で接触角（°）を測定した。接触角が大きいほど撥水性が良好であり、防汚性が良好であると判断する。
（２）転落角
接触角を測定した後ステージを水平（０°）から傾けていき、水滴の転がる角度を測定した。転落角が小さいほど撥水性が良好であり、防汚性が良好であると判断する。
（３）密着性
被膜を有する物品１枚をメチルパーフルオロブチルエーテル（３００ｍｌ）に浸漬し、超音波洗浄機を行いて２５℃で１分間処理を行い、取り出して乾燥後に、上記（１）と同様の方法で接触角を測定した。接触角が大きいほど密着性が良好と判断する。
（４）外観
目視にて、被膜を有する物品表面の透明性を確認し、下記の基準に従い評価を行った。
○：後述する比較例３と同等の透明性であり、透明性が良好。
×：後述する比較例３より透明性が劣る。
（５）摩擦耐久性
ＪＩＳ Ｌ ０８４９：２００４に従って、摩擦試験機Ｉ形（クロックメーター）を使用し、物品の被膜表面をキムワイプ（商品名：キムワイプ ワイパーＳ−２００（日本製紙クレシア株式会社製））にて摩擦した後に、上記（１）の方法で接触角の測定を行った。摩擦時の荷重は２ｋｇとし、摩擦回数は６００回とした。摩擦後の接触角が大きいほど耐久性が良好と判断する。
Evaluation Method (1) Contact Angle Using a contact angle meter DM-500 (manufactured by Kyowa Interface Science Co., Ltd.), distilled water (2.0 μL) is applied to the coating surface of the article placed on the stage at an installation angle of 0 ° (horizontal). It was dripped and the contact angle (°) was measured under an atmosphere of 20 ° C. It is judged that the larger the contact angle, the better the water repellency and the better the antifouling property.
(2) Falling angle After measuring the contact angle, the stage was tilted from the horizontal (0 °) to measure the angle at which the water droplets roll. It is judged that the smaller the falling angle, the better the water repellency and the better the antifouling property.
(3) Adhesiveness One article having a coating is immersed in methyl perfluorobutyl ether (300 ml), subjected to an ultrasonic cleaner, treated at 25 ° C. for 1 minute, taken out and dried, and then the same as (1) above The contact angle was measured by this method. The larger the contact angle, the better the adhesion.
(4) Appearance Visually, the transparency of the surface of the article having the coating was confirmed and evaluated according to the following criteria.
○: Transparency equivalent to that of Comparative Example 3 described later, and good transparency.
X: Transparency is inferior to the comparative example 3 mentioned later.
(5) Friction Durability According to JIS L 0849: 2004, using a friction tester I type (clock meter), the surface of the coated film of Kimwipe (trade name: Kimwipe Wiper S-200 (manufactured by Nippon Paper Crecia Co., Ltd.)) Then, the contact angle was measured by the method (1). The load during friction was 2 kg, and the number of frictions was 600. The greater the contact angle after friction, the better the durability.
３．ディッピング法による防汚性被膜の形成
上記１．で得たパーフルオロポリエーテル変性シラン化合物の０．１質量％溶液（溶媒は３Ｍ社製Ｎｏｖｅｃ７１００（ハイドロフルオロエーテル）を使用）をシャーレに入れ、スライドグラスまたは金属板を２５℃で３０秒間浸後、９０％ＲＨ９０℃の雰囲気中で３時間加熱処理を行い被膜を有する物品を得た。オージェ電子分光分析装置（ＡＥＳ、日立協和エンジニアリング株式会社製、シリコン換算）にて、ディッピング法にて得られた被膜の膜厚を測定したところ１５ｎｍであった。
この被膜を有する物品を用いて、下記の方法で、接触角、はじき性、拭き取り性、密着性、外観、耐久性の評価を行った。得られた結果を表２に示す。
3. Formation of antifouling film by dipping method A 0.1% by mass solution of the perfluoropolyether-modified silane compound obtained in 1 above (using 3M Novec7100 (hydrofluoroether) as a solvent) was placed in a petri dish, and the slide glass or metal plate was immersed at 25 ° C. for 30 seconds. Then, heat treatment was performed in an atmosphere of 90% RH 90 ° C. for 3 hours to obtain an article having a film. It was 15 nm when the film thickness of the film obtained by the dipping method was measured with an Auger electron spectroscopy analyzer (AES, manufactured by Hitachi Kyowa Engineering Co., Ltd., silicon conversion).
Using the article having this film, the contact angle, repellency, wiping property, adhesion, appearance, and durability were evaluated by the following methods. The obtained results are shown in Table 2.
スライドグラス、金属板としては以下のものを使用した。
スライドグラスは、商品名：マツナミスライドグラス白縁磨Ｎｏ．１、品番：Ｓ１１１１（松浪硝子工業株式会社製）を使用した。
金属板としては、ニッケル板およびアルミニウム板を使用した。ニッケル板としては、株式会社ニラコ製のニッケル板（品番：ＮＩ−３１３３２４）を、超音波洗浄機にてアセトンで洗浄した後、２５℃で１Ｎの塩酸水溶液で５分間処理した。その後水洗し、超音波洗浄機にてアセトンで洗浄した。洗浄後のニッケル板表面に、上記被膜を形成した。
アルミニウム板としては、ＴＰ技研株式会社製のアルミニウム板（品番：Ａ１０５０Ｐ）を、超音波洗浄機にてアセトンで洗浄した後、２５℃で５質量%の水酸化ナトリウム水溶液で５分間処理した。その後水で洗い出し、超音波洗浄機にてアセトンで洗浄した。洗浄後のアルミニウム板表面に、上記被膜を形成した。
The followings were used as slide glasses and metal plates.
The slide glass is trade name: Matsunami slide glass white edge polish No. 1. Product number: S1111 (manufactured by Matsunami Glass Industry Co., Ltd.) was used.
As the metal plate, a nickel plate and an aluminum plate were used. As a nickel plate, a nickel plate (product number: NI-313324) manufactured by Niraco Co., Ltd. was washed with acetone with an ultrasonic cleaner, and then treated with a 1N hydrochloric acid aqueous solution at 25 ° C. for 5 minutes. Thereafter, it was washed with water and washed with acetone with an ultrasonic washer. The film was formed on the surface of the nickel plate after washing.
As the aluminum plate, an aluminum plate manufactured by TP Giken Co., Ltd. (product number: A1050P) was washed with acetone with an ultrasonic cleaner, and then treated with a 5 mass% aqueous sodium hydroxide solution at 25 ° C for 5 minutes. Then, it was washed out with water and washed with acetone with an ultrasonic washing machine. The above-mentioned film was formed on the surface of the cleaned aluminum plate.
評価方法
（１）接触角
（株）マツボー製の携帯式接触角計（ＰＧ−Ｘ）を用いて、物品の被膜表面に蒸留水（２．５μＬ）を滴下し、２０℃の雰囲気下で接触角（°）を測定した。接触角が大きいほど撥水性が良好であり、防汚性が良好であると判断する。
（２）はじき性（汚れ付着防止性）
物品の被膜表面上に、油性ペン（商品名：ＰｅｎｔｅｌＰＥＮ ＥＮＮ５０ 丸芯中字（ぺんてる製））で５ｃｍの直線を引いたときの、被膜を有する物品表面でのインクのはじきの度合いを目視にて判定した。下記の基準に従い評価を行った。
○：インクをはじき滴状になり、インク汚れがほとんど付かない。
△：インクをはじくもののすべて滴状ではなく一部つながっており、
若干のインク汚れが付く。
×：インクの汚れが付く。
（３）拭き取り性
物品の被膜表面上に、油性ペン（商品名：ＰｅｎｔｅｌＰＥＮ ＥＮＮ５０ 丸芯中字（ぺんてる製））で５ｃｍの直線を引き、キムワイプ（商品名：キムワイプ ワイパーＳ−２００（日本製紙クレシア株式会社製））にて拭き取った（荷重１ｋｇ×１０往復）後のインク汚れの残存度合いを目視にて判定した。下記の基準に従い評価を行った。
○：インク汚れを全て拭き取ることができる
△：インク汚れの線の跡が若干残る
×：インク汚れの線の跡がはっきり残る
（４）密着性
被膜を有する物品１枚をメチルパーフルオロブチルエーテル（３００ｍｌ）に浸漬し、超音波洗浄機を行いて２５℃で１分間処理を行い、取り出して乾燥後に接触角を測定した。接触角が大きいほど密着性が良好と判断する。
（５）外観
目視にて、被膜を有する物品表面の透明性を確認し、下記の基準に従い評価を行った。
○：後述する比較例３と同等の透明性であり、透明性が良好。
×：後述する比較例３より透明性が劣る。
（６）摩擦耐久性
ＪＩＳ Ｌ ０８４９：２００４に従って、摩擦試験機Ｉ形（クロックメーター）を使用し、物品の被膜表面を綿ブロード布にて摩擦した後、上記（１）〜（３）の方法で接触角、はじき性、拭き取り性の評価を行った。摩擦時の荷重は１ｋｇとし、摩擦回数は１０００回とした。摩擦後の接触角が大きいほど耐久性が良好と判断する。
Evaluation method (1) Contact angle Using a portable contact angle meter (PG-X) manufactured by Matsubo Co., Ltd., distilled water (2.5 μL) was dropped on the surface of the coating film of the article and contacted in an atmosphere at 20 ° C. The angle (°) was measured. It is judged that the larger the contact angle, the better the water repellency and the better the antifouling property.
(2) Repellency (stain adhesion prevention)
The degree of ink repelling on the surface of the article having the coating is visually determined when a 5 cm straight line is drawn on the surface of the article coating with an oil-based pen (trade name: PentelPEN ENN50 round core middle letter (made by Pentel)). did. Evaluation was performed according to the following criteria.
○: The ink is repelled and the ink is hardly stained.
△: All of the ink repellent parts are connected, not in the form of drops,
Some ink stains.
X: The ink is stained.
(3) Wiping property A 5 cm straight line is drawn on the coating surface of the article with an oil-based pen (trade name: PentelPEN ENN50, round core middle character (manufactured by Pentel)), and Kimwipe (trade name: Kimwipe Wiper S-200 (Nippon Paper Crecia Co., Ltd.). The degree of residual ink stains after wiping (made by company 1)) was visually determined. Evaluation was performed according to the following criteria.
○: All ink stains can be wiped off. Δ: Some traces of ink stain lines remain. X: Clear traces of ink stain lines remain. (4) Adhesion One article having a coating is methylperfluorobutyl ether (300 ml). ), Followed by treatment with an ultrasonic cleaner at 25 ° C. for 1 minute, and after taking out and drying, the contact angle was measured. The larger the contact angle, the better the adhesion.
(5) Appearance Visually, the transparency of the surface of the article having the coating was confirmed and evaluated according to the following criteria.
○: Transparency equivalent to that of Comparative Example 3 described later, and good transparency.
X: Transparency is inferior to the comparative example 3 mentioned later.
(6) Friction durability According to JIS L 0849: 2004, the friction tester type I (clock meter) was used, and the coated surface of the article was rubbed with a cotton broad cloth, and then the methods (1) to (3) above. The contact angle, repellency, and wiping property were evaluated. The load during friction was 1 kg and the number of frictions was 1000. The greater the contact angle after friction, the better the durability.
［実施例２〜４、比較例１〜３］
実施例１で用いたパーフルオロポリエーテル変性シラン化合物（化学式ａ）を、表１〜４に記載の化合物（下記化学式ｂ〜ｇ）に変えた点以外は実施例１と同様に操作して実施例２〜４および比較例１〜３の被膜を有する物品を得た。これらの被膜を有する物品を用いて、実施例１と同様に評価を行った。得られた結果を、表１〜４に示す。
[Examples 2 to 4, Comparative Examples 1 to 3]
The same operation as in Example 1 was carried out except that the perfluoropolyether-modified silane compound (chemical formula a) used in Example 1 was changed to the compounds shown in Tables 1 to 4 (the following chemical formulas b to g). Articles having the coatings of Examples 2 to 4 and Comparative Examples 1 to 3 were obtained. Evaluation was performed in the same manner as in Example 1 using articles having these coatings. The obtained result is shown to Tables 1-4.
実施例２〜４、比較例１〜３で被膜の形成に使用した化合物の合成方法を、以下に示す。 A method for synthesizing the compounds used for forming the coating films in Examples 2 to 4 and Comparative Examples 1 to 3 is shown below.
［化学式ｂで表される化合物（実施例２で使用）の合成］
パーフルオロポリエーテル化合物を合成する第１段階において、ヘキサフルオロプロピレンオキシドの量を４２０ｇに増加した点以外は実施例１と同様に反応を行い、メチルエステル化パーフルオロポリエーテル化合物４２１ｇを得た。ゲル透過クロマトグラフィー測定によりこのメチルエステル化パーフルオロポリエーテル化合物の分子量がＭＷ＝４、４００であり、ヘキサフルオロプロピレンオキシドが約２６量体であることが確認された（メチルエステル化パーフルオロポリエーテル化合物２６量体）。
メチルエステル化パーフルオロポリエーテル化合物２６量体４０ｇ（９．０９ミリモル）に反応溶媒として１，３−ビス（トリフルオロメチル）ベンゼン２０ｇを加え、３−（２−アミノエチル）アミノプロピルメチルジメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−６０２）２．０６ｇ（１０ミリモル）を添加した後、窒素雰囲気下で６５〜７５℃で６時間反応させ、メタノールで沈殿精製することで、微黄色透明液状のパーフルオロポリエーテル変性アミノシラン化合物を４１．４８ｇを得た。
このパーフルオロポリエーテル変性アミノシラン化合物４１．５ｇ（９．０７ミリモル）に再び反応溶媒として１，３−ビス（トリフルオロメチル）ベンゼン２０ｇを加えた後、３−グリシドールを０．８１ｇ（１０．８８ミリモル）添加し、窒素雰囲気下で３５〜４５℃で６時間反応させ、メタノールで沈殿精製することで、微黄色透明液状のパーフルオロポリエーテル変性シラン化合物４２．２６ｇを得た。
化学式ａで表される化合物を同定した際と同様の方法で同定を行った結果、得られたパーフルオロポリエーテル変性シラン化合物は下記化学式ｂで表される構造を有することが確認された。
[Synthesis of Compound Represented by Chemical Formula b (Used in Example 2)]
In the first step of synthesizing the perfluoropolyether compound, the reaction was carried out in the same manner as in Example 1 except that the amount of hexafluoropropylene oxide was increased to 420 g to obtain 421 g of a methyl esterified perfluoropolyether compound. It was confirmed by gel permeation chromatography measurement that the molecular weight of this methyl esterified perfluoropolyether compound was MW = 4,400 and hexafluoropropylene oxide was about 26-mer (methyl esterified perfluoropolyether). Compound 26mer).
20 g of 1,3-bis (trifluoromethyl) benzene was added as a reaction solvent to 40 g (9.09 mmol) of 26-mer of methyl esterified perfluoropolyether compound, and 3- (2-aminoethyl) aminopropylmethyldimethoxysilane was added. (Trade name KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) After adding 2.06 g (10 mmol), the mixture is reacted at 65 to 75 ° C. for 6 hours under a nitrogen atmosphere, and purified by precipitation with methanol, which is slightly yellow transparent. 41.48 g of a liquid perfluoropolyether-modified aminosilane compound was obtained.
After adding 20 g of 1,3-bis (trifluoromethyl) benzene as a reaction solvent again to 41.5 g (9.07 mmol) of this perfluoropolyether-modified aminosilane compound, 0.81 g (10.88) of 3-glycidol was added. Mmol), reacted at 35 to 45 ° C. for 6 hours under a nitrogen atmosphere, and purified by precipitation with methanol to obtain 42.26 g of a slightly yellow transparent liquid perfluoropolyether-modified silane compound.
As a result of identification by the same method as that for identifying the compound represented by the chemical formula a, it was confirmed that the obtained perfluoropolyether-modified silane compound had a structure represented by the following chemical formula b.
［化学式ｃで表される化合物（実施例３で使用）の合成］
３−（２−アミノエチル）アミノプロピルメチルジメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−６０２）２．０６ｇ（１０ミリモル）に変えて３−（２−アミノエチル）アミノプロピルトリメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−６０３）２．２２ｇ（１０ミリモル）を使用した点以外は、上記の化学式ｂで表される化合物の合成と同様に操作を行い、微黄色透明液状のパーフルオロポリエーテル変性シラン化合物４２．２７ｇを得た。
化学式ａで表される化合物を同定した際と同様の方法で同定を行った結果、得られたパーフルオロポリエーテル変性シラン化合物は下記化学式ｃで表される構造を有することが確認された。
[Synthesis of Compound Represented by Chemical Formula c (Used in Example 3)]
3- (2-aminoethyl) aminopropyltrimethoxysilane (trade name KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.06 g (10 mmol) instead of 3- (2-aminoethyl) aminopropyltrimethoxysilane ( Except for using 2.22 g (10 mmol) of trade name KBM-603) manufactured by Shin-Etsu Chemical Co., Ltd., the same operation as in the synthesis of the compound represented by the chemical formula b was performed, and a slightly yellow transparent liquid par 42.27 g of a fluoropolyether-modified silane compound was obtained.
As a result of identification by the same method as that for identifying the compound represented by the chemical formula a, it was confirmed that the obtained perfluoropolyether-modified silane compound had a structure represented by the following chemical formula c.
［化学式ｄで表される化合物（実施例４で使用）の合成］
３−（２−アミノエチル）アミノプロピルメチルジメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−６０２）２．０６ｇ（１０ミリモル）に変えて３−（２−アミノエチル）アミノプロピルトリエトキシシラン（信越化学工業株式会社製商品名ＫＢＥ−６０３）２．６４ｇ（１０ミリモル）を使用した点以外は、上記の化学式ｂで表される化合物の合成と同様に操作を行い、微黄色透明液状のパーフルオロポリエーテル変性シラン化合物４２．６９ｇを得た。
化学式ａで表される化合物を同定した際と同様の方法で同定を行った結果、得られたパーフルオロポリエーテル変性シラン化合物は下記化学式ｄで表される構造を有することが確認された。
[Synthesis of Compound Represented by Chemical Formula d (Used in Example 4)]
3- (2-aminoethyl) aminopropylmethyldimethoxysilane (trade name KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 2.06 g (10 mmol), and 3- (2-aminoethyl) aminopropyltriethoxysilane ( Except that 2.64 g (10 mmol) of trade name KBE-603) manufactured by Shin-Etsu Chemical Co., Ltd. was used, the same operation as in the synthesis of the compound represented by the above chemical formula b was performed, and a slightly yellow transparent liquid par 42.69 g of a fluoropolyether-modified silane compound was obtained.
As a result of identification by the same method as that for identifying the compound represented by the chemical formula a, it was confirmed that the obtained perfluoropolyether-modified silane compound had a structure represented by the following chemical formula d.
［化学式ｅで表される化合物（比較例１で使用）の合成］
３−（２−アミノエチル）アミノプロピルメチルジメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−６０２）１．９７ｇ（９．５７ミリモル）に変えて３−（２−アミノエチル）アミノプロピルトリメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−６０３）２．１２ｇ（９．５７ミリモル）を使用し、３−グリシドール０．７７ｇ（１０．４３ミリモル）に変えて３−グリシドキシプロピルトリメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−４０３）２．４６ｇ（１０．４３ミリモル）を使用した点以外は、実施例１と同様に操作を行って、微黄色透明液状のパーフルオロポリエーテル変性シラン化合物２３．５８ｇを得た。
化学式ａで表される化合物を同定した際と同様の方法で同定を行った結果、得られたパーフルオロポリエーテル変性シラン化合物は下記化学式ｅで表される構造を有することが確認された。
[Synthesis of Compound Represented by Chemical Formula e (Used in Comparative Example 1)]
3- (2-aminoethyl) aminopropyltrimethoxysilane (trade name KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 1.97 g (9.57 mmol) and 3- (2-aminoethyl) aminopropyltrimethoxy Silane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.12 g (9.57 mmol) was used, and 3-glycidoxypropyltrimethoxy was changed to 0.77 g (10.43 mmol) of 3-glycidol. Except that 2.46 g (10.43 mmol) of silane (trade name KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used, the same operation as in Example 1 was carried out to obtain a slightly yellow transparent liquid perfluoropolyether. 23.58 g of a modified silane compound was obtained.
As a result of identification by the same method as that for identifying the compound represented by the chemical formula a, it was confirmed that the obtained perfluoropolyether-modified silane compound had a structure represented by the following chemical formula e.
［化学式ｆで表される化合物（比較例２で使用）の合成］
３−グリシドール０．７７ｇ（１０．４３ミリモル）に変えて３−グリシドキシプロピルトリエトキシシラン（信越化学工業株式会社製商品名ＫＢＥ−４０３）２．９０ｇ（１０．４３ミリモル）を使用した点以外は、実施例１と場合と同様に操作を行って、微黄色透明液状のパーフルオロポリエーテル変性シラン化合物２３．８７ｇを得た。
化学式ａで表される化合物を同定した際と同様の方法で同定を行った結果、得られたパーフルオロポリエーテル変性シラン化合物は下記化学式ｆで表される構造を有することが確認された。
[Synthesis of Compound Represented by Chemical Formula f (Used in Comparative Example 2)]
The point of using 2.90 g (10.43 mmol) of 3-glycidoxypropyltriethoxysilane (trade name KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.) instead of 0.77 g (10.43 mmol) of 3-glycidol Except for the above, the same operation as in Example 1 was performed to obtain 23.87 g of a slightly yellow transparent liquid perfluoropolyether-modified silane compound.
As a result of identification by the same method as that for identifying the compound represented by the chemical formula a, it was confirmed that the obtained perfluoropolyether-modified silane compound had a structure represented by the following chemical formula f.
［化学式ｇで表される化合物（比較例３で使用）の合成］
メチルエステル化パーフルオロポリエーテル化合物１３量体２０ｇ（８．７ミリモル）に反応溶媒として１，３−ビス（トリフルオロメチル）ベンゼン１０ｇを加え、３−（２−アミノエチル）アミノプロピルトリメトキシシラン（信越化学工業株式会社製商品名ＫＢＭ−６０３）２．１２ｇ（９．５７ミリモル）を添加した後、窒素雰囲気下で６５〜７５℃で６時間反応させ、メタノールで沈殿精製することで、微黄色透明液状のパーフルオロポリエーテル変性アミノシラン化合物２１．６０ｇを得た。
化学式ａで表される化合物を同定した際と同様の方法で同定を行った結果、得られたパーフルオロポリエーテル変性アミノシラン化合物は下記化学式ｇで表される構造を有することが確認された。
[Synthesis of Compound Represented by Chemical Formula g (Used in Comparative Example 3)]
10 g of 1,3-bis (trifluoromethyl) benzene as a reaction solvent was added to 20 g (8.7 mmol) of a 13-mer of methyl esterified perfluoropolyether compound, and 3- (2-aminoethyl) aminopropyltrimethoxysilane was added. After adding 2.12 g (9.57 mmol) (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), the mixture is reacted at 65 to 75 ° C. for 6 hours in a nitrogen atmosphere, and purified by precipitation with methanol. 21.60 g of a yellow transparent liquid perfluoropolyether-modified aminosilane compound was obtained.
As a result of identification by the same method as that for identifying the compound represented by the chemical formula a, it was confirmed that the obtained perfluoropolyether-modified aminosilane compound had a structure represented by the following chemical formula g.
以上の結果から、本発明のパーフルオロポリエーテル変性シラン化合物を含有する防汚性被膜形成用組成物は、各種基材に対して成膜方法を問わず高い防汚性および耐久性を有する防汚性被膜を形成することができ、しかも形成された防汚性被膜は基材との密着性も良好であることが示された。 From the above results, the antifouling film-forming composition containing the perfluoropolyether-modified silane compound of the present invention has high antifouling properties and durability for various substrates regardless of the film forming method. It was shown that a dirty film can be formed, and that the formed antifouling film has good adhesion to the substrate.
本発明のパーフルオロポリエーテル変性シラン化合物を含有する防汚性被膜形成用組成物によれば、各種物品に対して成膜方法を問わず良好な防汚性と密着性および基材との密着性を兼ね備えた防汚性被膜を形成することができる。このため、本発明のパーフルオロポリエーテル変性シラン化合物を含有する防汚性被膜形成用組成物は、ガラス類、有機ポリマー類、金属類などの各種基材に広く適用できるので、産業上きわめて利用価値が高い。 According to the composition for forming an antifouling film containing the perfluoropolyether-modified silane compound of the present invention, good antifouling properties and adhesion to various articles regardless of the film forming method, and adhesion to a substrate. It is possible to form an antifouling film having both properties. Therefore, the composition for forming an antifouling film containing the perfluoropolyether-modified silane compound of the present invention can be widely applied to various substrates such as glasses, organic polymers, metals, etc. High value.
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| CN106661436B (en) * | 2014-07-07 | 2018-10-26 | 大金工业株式会社 | The composition of amide silane compounds is modified containing perfluor (poly-) ether |
| JP6260579B2 (en) * | 2015-05-01 | 2018-01-17 | 信越化学工業株式会社 | Fluoropolyether group-containing polymer-modified silane, surface treatment agent and article |
| JP6390521B2 (en) * | 2015-06-03 | 2018-09-19 | 信越化学工業株式会社 | Fluoropolyether group-containing polymer-modified silane |
| EP3504300A1 (en) | 2016-08-25 | 2019-07-03 | General Electric Company | Reduced fouling of hydrocarbon oil |
| JP7116664B2 (en) * | 2017-11-07 | 2022-08-10 | 住友化学株式会社 | Composition |
| US20210214495A1 (en) * | 2018-05-16 | 2021-07-15 | Guangzhou Ur Materials Technology Co., Ltd. | Silane compound containing perfluoropolyether group, preparation method therefor, surface treatment agent and product thereof |
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| WO2021049240A1 (en) * | 2019-09-10 | 2021-03-18 | ダイキン工業株式会社 | Surface treatment agent |
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