CN116535950A - Method for preserving fluorine-containing composition, container containing fluorine-containing composition, and method for producing container containing fluorine-containing composition - Google Patents
Method for preserving fluorine-containing composition, container containing fluorine-containing composition, and method for producing container containing fluorine-containing composition Download PDFInfo
- Publication number
- CN116535950A CN116535950A CN202310051909.9A CN202310051909A CN116535950A CN 116535950 A CN116535950 A CN 116535950A CN 202310051909 A CN202310051909 A CN 202310051909A CN 116535950 A CN116535950 A CN 116535950A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- group
- containing composition
- container
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 161
- 239000011737 fluorine Substances 0.000 title claims abstract description 161
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 150
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 32
- 239000002335 surface treatment layer Substances 0.000 abstract description 26
- 238000004321 preservation Methods 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 104
- 125000002947 alkylene group Chemical group 0.000 description 83
- 239000007789 gas Substances 0.000 description 50
- 239000010410 layer Substances 0.000 description 31
- 125000004430 oxygen atom Chemical group O* 0.000 description 29
- 229920001296 polysiloxane Polymers 0.000 description 26
- 125000000217 alkyl group Chemical group 0.000 description 23
- 238000005299 abrasion Methods 0.000 description 22
- -1 perfluorocyclobutanediyl groups Chemical group 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 238000003860 storage Methods 0.000 description 16
- 150000001721 carbon Chemical group 0.000 description 15
- 239000003708 ampul Substances 0.000 description 14
- 125000004429 atom Chemical group 0.000 description 14
- 125000005647 linker group Chemical group 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- 229940125904 compound 1 Drugs 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 125000003367 polycyclic group Chemical group 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 125000004423 acyloxy group Chemical group 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001771 vacuum deposition Methods 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 125000003003 spiro group Chemical group 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000004419 alkynylene group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 125000004043 oxo group Chemical group O=* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 125000006661 (C4-C6) heterocyclic 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
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 1
- DEUJSGDXBNTQMY-UHFFFAOYSA-N 1,2,2-trifluoroethanol Chemical compound OC(F)C(F)F DEUJSGDXBNTQMY-UHFFFAOYSA-N 0.000 description 1
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 description 1
- TXOZSRCVHASUCW-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropan-1-ol Chemical compound OC(F)CC(F)(F)F TXOZSRCVHASUCW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PDCBZHHORLHNCZ-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(F)(F)F)C=C1 PDCBZHHORLHNCZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001054 5 membered carbocyclic group Chemical group 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- 125000004008 6 membered carbocyclic group Chemical group 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007771 Langmuir-Blodgett coating Methods 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical group C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical group C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007607 die coating method Methods 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
- 239000012153 distilled water Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XGQGTPFASZJKCD-UHFFFAOYSA-N fluorocyclopentane Chemical compound FC1[CH]CCC1 XGQGTPFASZJKCD-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000002872 norbornadienyl group Chemical group C12=C(C=C(CC1)C2)* 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229950008618 perfluamine Drugs 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- JAJLKEVKNDUJBG-UHFFFAOYSA-N perfluorotripropylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F JAJLKEVKNDUJBG-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
A method for preserving a fluorine-containing composition, a container containing a fluorine-containing composition, and a method for producing a container containing a fluorine-containing composition. Provided is a method for preserving a fluorine-containing composition, which can form a surface treatment layer excellent in water repellency on a substrate even when the fluorine-containing composition after preservation is used. In the method for storing a fluorine-containing composition, the concentration of carbon dioxide in a gas phase portion in a container containing a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is set to 4 to 380 ppm by volume at 25 ℃.
Description
Technical Field
The present application relates to a method for storing a fluorine-containing composition, a container containing a fluorine-containing composition, and a method for producing a container containing a fluorine-containing composition.
Background
Fluorochemical compounds have been attracting attention in recent years because they impart water and oil repellency, abrasion resistance, low fingerprint adhesion, fingerprint soil removability, lubricity, and the like to the surface of a substrate.
For example, patent document 1 describes a fluorine-containing compound having a reactive silyl group at the end.
Prior art literature
Patent literature
Patent document 1: international publication No. 2017/038830
Disclosure of Invention
Problems to be solved by the invention
It is known that: when a fluorine-containing composition containing a fluorine-containing compound is stored in a container and a surface treatment of a substrate is performed using the stored fluorine-containing composition, sufficient water repellency cannot be imparted to the substrate due to the storage state of the fluorine-containing composition.
The present invention has been made in view of the above circumstances, and an object of an embodiment of the present invention is to provide a method for preserving a fluorine-containing composition, which can form a surface-treated layer excellent in water repellency on a substrate even when the fluorine-containing composition after preservation is used.
Another object of the present invention is to provide a container containing a fluorine-containing composition which contains a fluorine-containing composition capable of forming a surface-treated layer excellent in water repellency.
Another object of the present invention is to provide a method for producing a container containing a fluorine-containing composition, which contains a fluorine-containing composition capable of forming a surface-treated layer excellent in water repellency.
Solution for solving the problem
Specific means for achieving the above-described object are as follows.
<1> a method for storing a fluorine-containing composition, wherein the concentration of carbon dioxide in a gas phase portion in a container containing a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is set to 4 to 380 ppm by volume at 25 ℃.
<2> the method for preserving a fluorine-containing composition according to <1>, wherein the concentration of carbon dioxide in the gas phase portion is 5 to 350 ppm by volume at 25 ℃.
<3> the method for preserving a fluorine-containing composition according to claim 1 or 2, wherein the gas phase portion accounts for 10 to 60% by volume of the volume inside the container.
<4> a method for storing a fluorine-containing composition, wherein the concentration of carbon dioxide in a gas phase portion in a sealed container containing a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is maintained at 25 ℃ to 4 to 380 ppm by volume.
<5> the method for preserving a fluorine-containing composition according to claim 4, wherein the concentration of carbon dioxide in the gas phase portion is 5 to 350 ppm by volume at 25 ℃.
<6> the method for preserving a fluorine-containing composition according to <4> or <5>, wherein the gas phase portion occupies 10 to 60% by volume of the volume inside the sealed container.
<7> a container containing a fluorine-containing composition, which is sealed in a state in which a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is contained, and the concentration of carbon dioxide in the gas phase portion is 4 to 380 ppm by volume at 25 ℃.
<8> the vessel containing a fluorine-containing composition according to <7>, wherein the concentration of carbon dioxide in the gas phase portion is 5 to 350 ppm by volume at 25 ℃.
<9> the vessel containing a fluorine-containing composition according to <7> or <8>, wherein the gas phase portion accounts for 10 to 60% by volume of the volume inside the vessel.
<10> a method for producing a container containing a fluorine-containing composition, comprising: a container containing a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is sealed, and the concentration of carbon dioxide in a gas phase portion in the container is set to 4 to 380 ppm by volume at 25 ℃.
<11> the process for producing a container containing a fluorine-containing composition according to <10>, wherein the concentration of carbon dioxide in the gas phase portion is 5 to 350 ppm by volume at 25 ℃.
<12> the process for producing a container containing a fluorine-containing composition according to <10> or <11>, wherein the gas phase portion accounts for 10 to 60% by volume of the volume inside the container.
ADVANTAGEOUS EFFECTS OF INVENTION
According to one embodiment of the present invention, there is provided a method for preserving a fluorine-containing composition capable of forming a surface-treated layer excellent in water repellency to a substrate even when the fluorine-containing composition after preservation is used.
According to another embodiment of the present invention, there is provided a container containing a fluorine-containing composition capable of forming a surface-treated layer excellent in water repellency.
According to another embodiment of the present invention, there is provided a method for producing a container containing a fluorine-containing composition, the container containing a fluorine-containing composition capable of forming a surface-treated layer excellent in water repellency.
Detailed Description
In the present application, numerical ranges shown in "to" are used as the minimum value and the maximum value, respectively, including numerical values described before and after "to".
In the numerical ranges described in stages in the present application, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. In addition, within the numerical ranges described in the present application, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment.
The meaning of the following terms in this application is as follows.
In this application, the compound represented by the formula (1) is referred to as the compound (1). Other compounds, groups, etc. of formula (I) are also based thereon.
Perfluoroalkyl refers to a group in which all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms. In addition, fluoroalkyl refers to a generic term for a part of fluoroalkyl and perfluoroalkyl. The partially fluoroalkyl group means an alkyl group in which 1 or more hydrogen atoms are replaced with fluorine atoms and which has 1 or more hydrogen atoms. That is, the fluoroalkyl group is an alkyl group having 1 or more fluorine atoms.
The "surface-treated layer" refers to a layer formed on the surface of a substrate by surface treatment.
< method for preserving fluorine-containing composition >
In the method for storing a fluorine-containing composition of the present application, the concentration of carbon dioxide in the gas phase portion in a container containing a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is set to 4 to 380 ppm by volume at 25 ℃.
In the present application, the gas phase means: the portion other than the portion occupied by the fluorine-containing composition is in the space inside the container for containing the fluorine-containing composition.
Carbon dioxide is a component contained in the atmosphere, and may contain a certain amount of a compound in a gas phase portion of a container for containing a fluorine-containing composition. Since carbon dioxide is an acidic substance, the carbon dioxide contained in the gas phase portion promotes hydrolysis of the reactive silyl group contained in the fluorine-containing compound.
Since the hydrolysis of the reactive silyl group is promoted, if the fluorine-containing composition is stored in a container, a condensation reaction of the fluorine-containing compound occurs. The condensation reaction of the fluorine-containing compound may cause deterioration of the fluorine-containing compound. It is difficult to form a surface treatment layer on a substrate due to deterioration of the fluorine-containing compound. On the other hand, when the surface treatment layer is formed, hydrolysis of the reactive silyl group is promoted, and thus a firm surface treatment layer is easily formed on the surface of the substrate.
The inventors of the present invention have found as a result of intensive studies that: the present invention has been completed by setting the concentration of carbon dioxide in the gas phase portion in the container containing the fluorine-containing composition to 4 to 380 ppm by volume at 25 ℃, and thereby forming a surface-treated layer excellent in water repellency on a substrate when the substrate is surface-treated with the fluorine-containing composition after storage. It was also found that: according to the present application, the fluorine composition after storage can form a surface-treated layer excellent in abrasion resistance.
Hereinafter, a method for storing the fluorine-containing composition of the present application will be described.
In the method for storing a fluorine-containing composition of the present application, a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is stored in a container.
(Container)
The container for containing the fluorine-containing composition is not particularly limited. Examples of the container include a storage tank as a fixed storage container, a gas filling bottle used for transportation, and a pressure-resistant container such as a secondary gas filling bottle (reserve tank). In addition, the container may be a simple container for temporary storage.
The material of the container is not particularly limited, and examples thereof include glass, carbon steel, manganese steel, chromium molybdenum steel, stainless steel, and aluminum alloy.
The shape of the lid for closing the container is not particularly limited, and may be circular or polygonal in plan view. Among them, the shape of the lid of the container is preferably polygonal, more preferably hexagonal to dodecagonal, from the viewpoint of improving the storage stability of the fluorine-containing composition.
The method for storing the fluorine-containing composition in the container is not particularly limited, and a generally known method can be used. The proportion of the gas phase portion in the volume of the container interior is preferably 60% by volume or less, more preferably 50% by volume or less, from the viewpoint of storage stability. The proportion of the gas phase portion in the volume of the container interior is preferably 10% by volume or more, more preferably 20% by volume or more, from the viewpoint of easy transportation.
From the above viewpoints, the ratio of the gas phase portion to the volume of the container interior is preferably 10 to 60% by volume, more preferably 20 to 50% by volume.
In the method for preserving a fluorine-containing composition of the present application, it is preferable that the container is sealed after the fluorine-containing composition is contained in the container.
The method of sealing the container is not particularly limited, and may be performed by closing a lid of the container, for example. When the container is closed, an inner lid may be used.
The concentration of carbon dioxide in the gas phase portion of the container containing the fluorine-containing composition is 4 to 380 ppm by volume, preferably 5 to 350 ppm by volume, more preferably 8 to 320 ppm by volume at 25 ℃.
The method for adjusting the concentration of carbon dioxide in the gas phase portion in the container is not particularly limited. For example, the fluorine-containing composition may be filled into the container after the container is replaced with an inert gas such as dry nitrogen or dry argon. Alternatively, the container may be replaced with an inert gas after the fluorine-containing composition is filled into the container.
The concentration of carbon dioxide in the gas phase portion in the container can be measured using TCD (thermal conductivity detector) of gas chromatography.
(fluorine-containing composition)
In the method for preserving a fluorine-containing composition of the present application, the fluorine-containing composition contains a fluorine-containing compound having a reactive silyl group. Hereinafter, details of the fluorine-containing compound having a reactive silyl group will be described.
The reactive silyl group is a group having a reactive group bonded to a Si atom.
The number of reactive silyl groups in the fluorine-containing compound is 1 or more, and is preferably 1 to 18, more preferably 2 to 12, and even more preferably 2 to 8, from the viewpoint of further improving the abrasion resistance of the surface-treated layer.
The reactive silyl group is preferably a group represented by the following formula 1.
-Si(R) n L 3-n …(1)
In the formula 1, R is a 1-valent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, and n is an integer of 0 to 2.
In the case where 1 molecule has a plurality of groups (1), the plurality of groups (1) may be the same or different from each other. The plurality of groups (1) are preferably the same from the viewpoints of easiness of raw material acquisition and easiness of production of fluorine-containing compounds.
R is a hydrocarbon group of 1 valence, preferably a saturated hydrocarbon group of 1 valence. The number of carbon atoms of R is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 to 2.
L is a hydrolyzable group or a hydroxyl group.
The hydrolyzable group is a group that forms a hydroxyl group by hydrolysis reaction. That is, the hydrolyzable silyl group represented by Si-L is hydrolyzed to form a silanol group represented by Si-OH. Regarding silanol groups, the silanol groups react further to form Si-O-Si bonds. In addition, silanol groups undergo a dehydration condensation reaction with silanol groups derived from oxides present on the substrate surface, thereby enabling the formation of si—o—si bonds.
Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group and an isocyanato group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The aryloxy group is preferably an aryloxy group having 3 to 10 carbon atoms. Wherein the aryl of the aryloxy group comprises a heteroaryl group. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
Among them, from the viewpoint of easiness in producing a fluorine-containing compound, L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. L is preferably an alkoxy group having 1 to 4 carbon atoms, from the viewpoint of less outgas during coating and more excellent storage stability of the fluorine-containing compound. In the case where long-term storage stability of the fluorine-containing compound is required, L is more preferably ethoxy. When the reaction time after the application is short, L is more preferably methoxy.
n is an integer of 0 to 2, preferably 0 or 1, more preferably 0. The presence of a plurality of L's makes the adhesion of the surface treatment layer to the substrate stronger.
When n is 1 or less, a plurality of L's present in 1 molecule may be the same or different from each other. The plurality of L's are preferably the same from the viewpoints of easiness in obtaining the raw material and easiness in producing the fluorine-containing compound. When n is 2, the plurality of R's in the 1 molecule may be the same or different from each other. From the viewpoints of easiness in obtaining raw materials and easiness in producing fluorine-containing compounds, the plurality of R's are preferably the same.
The fluorine-containing compound preferably has a poly (oxyfluoroalkylene) chain from the viewpoint of improving the water repellency of the surface-treated layer.
The poly (oxyfluoroalkylene) chain is represented by the following formula 2.
(OX) m …(2)
In formula 2, X is a fluoroalkylene group having 1 or more fluorine atoms.
The number of carbon atoms of the fluoroalkylene group is preferably 1 to 6, more preferably 2 to 4, from the viewpoint of improving the weather resistance and corrosion resistance of the surface-treated layer.
The fluoroalkylene group may be any of linear, branched and cyclic.
The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times, more preferably 1.7 to 2 times, the number of carbon atoms, from the viewpoint of improving the corrosion resistance of the surface-treated layer.
Among them, the fluoroalkylene group is preferably a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (i.e., a perfluoroalkylene group).
As specific examples of (OX), there may be mentioned-OCHF-, -OCF 2 CHF-、-OCHFCF 2 -、-OCF 2 CH 2 -、-OCH 2 CF 2 -、-OCF 2 CF 2 CHF-、-OCHFCF 2 CF 2 -、-OCF 2 CF 2 CH 2 -、-OCH 2 CF 2 CF 2 -、-OCF 2 CF 2 CF 2 CH 2 -、-OCH 2 CF 2 CF 2 CF 2 -、-OCF 2 CF 2 CF 2 CF 2 CH 2 -、-OCH 2 CF 2 CF 2 CF 2 CF 2 -、-OCF 2 CF 2 CF 2 CF 2 CF 2 CH 2 -、-OCH 2 CF 2 CF 2 CF 2 CF 2 CF 2 -、-OCF 2 -、-OCF 2 CF 2 -、-OCF 2 CF 2 CF 2 -、-OCF(CF 3 )CF 2 -、-OCF 2 CF 2 CF 2 CF 2 -、-OCF(CF 3 )CF 2 CF 2 -、-OCF 2 CF 2 CF 2 CF 2 CF 2 -、-OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -、-O-cycloC 4 F 6 -、-O-cycloC 5 F 8 -and-O-cyclics 6 F 10 -。
Here, -CycloC 4 F 6 -perfluorocyclobutanediyl. As perfluorocyclobutanediyl groups, perfluorocyclobutane-1, 2-diyl groups and perfluorocyclobutane-1, 3-diyl groups are mentioned. -cyclioc 5 F 8 -perfluorocyclopentanediyl. As perfluorocyclopentanediyl groups, perfluorocyclopentane-1, 2-diyl and perfluorocyclopentane-1, 3-diyl are mentioned. -cyclioc 6 F 10 -perfluorocyclohexanediyl. Examples of the perfluorocyclohexanediyl group include perfluorocyclohexane-1, 2-diyl group, perfluorocyclohexane-1, 3-diyl group and perfluorocyclohexane-1, 4-diyl group.
The repetition number m of (OX) is an integer of 2 or more, more preferably an integer of 2 to 200, still more preferably an integer of 5 to 150, particularly preferably an integer of 5 to 100, and most preferably an integer of 10 to 50.
(OX) m More than 2 (OX) may be contained.
The bonding order of 2 or more (OX) is not limited, and may be any of random, alternating, and block.
The inclusion of 2 or more (OX) means: in the fluorine-containing compound, there are 2 or more types (OX) having different carbon numbers; 2 or more (OX) having different numbers of hydrogen atoms and 2 or more (OX) having different positions of hydrogen atoms; and 2 or more types (OX) in which the presence or absence of a side chain or the type of the side chain (for example, the number of side chains, the number of carbon atoms in the side chain, etc.) are different even if the number of carbon atoms is the same.
Regarding the configuration of 2 or more (OX), for example, { (OCF) 2 ) m21 (OCF 2 CF 2 ) m22 The structure shown represents m21 (OCF) 2 ) And m22 (OCF) 2 CF 2 ) A random configuration was performed. In addition, (OCF) 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 ) m25 The structure shown represents m25 (OCF) 2 CF 2 ) And m25 (OCF) 2 CF 2 CF 2 CF 2 ) An alternating configuration is performed.
Wherein (OX) m Preferably [ (OCH) ma F (2-ma) ) m11 (OC 2 H mb F (4-mb) ) m12 (OC 3 H mc F (6-mc) ) m13 (OC 4 H md F (8-md) ) m14 (OC 5 H me F (10-me) ) m15 (OC 6 H mf F (12-mf) ) m16 (O-cycloC 4 H mg F (6-mg) ) m17 (O-cycloC 5 H mh F (8-mh) ) m18 (O-cycloC 6 H mi F (10-mi) ) m19 ]. Here, -CycloC 4 H mg F (6-mg) Refers to fluorocyclobutanediyl. Examples of fluorocyclobutane diyl include fluorocyclobutane-1, 2-diyl and fluorocyclobutane-1, 3-diyl. -cyclioc 5 H mh F (8-mh) Refer to fluorocyclopentadienyl. As fluorocyclopentane diyl groups, fluorocyclopentane-1, 2-diyl groups and fluorocyclopentane-1, 3-diyl groups are exemplified. -cyclioc 6 H mi F (10-mi) Refers to fluorocyclohexanediyl. Examples of fluorocyclohexanediyl include fluorocyclohexane-1, 2-diyl, fluorocyclohexane-1, 3-diyl and fluorocyclohexane-1, 4-diyl.
ma is 0 or 1, mb is an integer of 0 to 3, mc is an integer of 0 to 5, md is an integer of 0 to 7, me is an integer of 0 to 9, mf is an integer of 0 to 11, mg is an integer of 0 to 5, mh is an integer of 0 to 7, and mi is an integer of 0 to 9.
m11, m12, m13, m14, m15, m16, m17, m18 and m19 are each independently integers of 0 or more, preferably 100 or less.
m11+m12+m13+m14+m15+m16+m17+m18+m19 is an integer of 2 or more, more preferably an integer of 2 to 200, still more preferably an integer of 5 to 150, still more preferably an integer of 5 to 100, particularly preferably an integer of 10 to 50.
Among them, m12 is preferably an integer of 2 or more, and particularly preferably an integer of 2 to 200.
In addition, C 3 H mc F (6-mc) 、C 4 H md F (8-md) 、C 5 H me F (10-me) And C 6 H mf F (12-mf) Can be straight-chain or branched, so that the table can be usedThe surface treatment layer is preferably linear from the viewpoint of improving the abrasion resistance.
The above formula indicates the type and number of units, and does not indicate the arrangement of the units. That is, m11 to m19 represent the number of units, for example, (OCH) ma F (2-ma) ) m11 Not representing m11 (OCH) ma F (2-ma) ) Blocks obtained by continuous unit formation. Likewise, (OCH) ma F (2-ma) )～(O-cycloC 6 H mi F (10-mi) ) The order of description of (2) does not indicate that they are arranged in the order of description.
In the above formula, when 2 or more of m11 to m19 are not 0 (that is, when (OX) m In the case of a composition of 2 or more types of units), the arrangement of the different units may be any of random arrangement, alternating arrangement, block arrangement, and a combination of these arrangements.
Further, the above units may be different from each other when the units include 2 or more units. For example, when m11 is 2 or more, a plurality of (OCH ma F (2-ma) ) May be the same or different.
(OX) m Preferably has the following structure.
{(OCF 2 ) m21 (OCF 2 CF 2 ) m22 }、
(OCF 2 CF 2 ) m23 、
(OCF 2 CF 2 CF 2 ) m24 、
(OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 ) m25 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 ) m26 (OCF 2 ) m27 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 ) m26 (OCF 2 CF 2 ) m27 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) m26 (OCF 2 ) m27 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) m26 (OCF 2 CF 2 ) m27 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 -OCF 2 ) m28 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 -OCF 2 CF 2 ) m28 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -OCF 2 ) m28 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -OCF 2 CF 2 ) m28 、
(OCF 2 -OCF 2 CF 2 CF 2 CF 2 CF 2 ) m28 、
(OCF 2 -OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) m28 、
(OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 CF 2 ) m28 、
(OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) m28 。
Wherein m21 is an integer of 1 or more, m22 is an integer of 1 or more, m21+m22 is an integer of 2 to 500, m23 and m24 are each independently an integer of 2 to 500, m25 is an integer of 1 to 250, m26 and m27 are each independently an integer of 1 or more, m26+m27 is an integer of 2 to 500, and m28 is an integer of 1 to 250.
From the viewpoint of easiness in producing a fluorine-containing compound, (OX) m More preferably has the following structure.
{(OCF 2 ) m21 (OCF 2 CF 2 ) m22 }、
(OCF 2 CF 2 CF 2 ) m24 、
(OCF 2 CF 2 ) 2 {(OCF 2 ) m21 (OCF 2 CF 2 ) m22-2 }、
(OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 ) m25-1 OCF 2 CF 2 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 -OCF 2 ) m28 、
(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -OCF 2 ) m28 、
(OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 CF 2 ) m28-1 OCF 2 CF 2 、
(OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) m28-1 OCF 2 CF 2 。
Wherein the number of m22, m25 and m28 is selected such that m22-2, m25-1 and m28-1 are integers of 1 or more.
Among them, (OX) is a layer having a surface treatment layer having more excellent abrasion resistance m Preferably { (OCF) 2 ) m21 (OCF 2 CF 2 ) m22 }。
At { (OCF) 2 ) m21 (OCF 2 CF 2 ) m22 Among the above, m22/m21 is preferably 0.1 to 10, more preferably 0.2 to 5.0, still more preferably 0.2 to 2.0, particularly preferably 0.2 to 1.5, and most preferably 0.2 to 0.85, from the viewpoint of further excellent abrasion resistance of the surface-treated layer.
The number average molecular weight (Mn) of the poly (oxyfluoroalkylene) chain is preferably 1,000 to 20,000, more preferably 1,500 to 15,000, particularly preferably 2,000 to 10,000.
If Mn is 1,000 or more, the fluidity of the molecular chain of the fluorine-containing compound and the fluorine content become high, and therefore the abrasion resistance of the surface-treated layer is more excellent.
The fluorine-containing compound is preferably a compound represented by the following formula 3 from the viewpoint of further excellent abrasion resistance of the surface-treated layer.
[A-(OX) m -] j Y 1 [-Si(R) n L 3-n ] g …(3)
In the formula 3, A is perfluoroalkyl or-Y 2 [-Si(R) n L 3-n ] k ，Y 1 A linking group of valence (j+g), Y 2 A (k+1) -valent linking group, j is an integer of 1 or more, g is an integer of 1 or more, k is an integer of 1 or more, and R, L, n, X and m are as defined above.
The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 3, from the viewpoint of further excellent abrasion resistance of the surface-treated layer.
The perfluoroalkyl group may be any of linear, branched, and cyclic.
Wherein, A is-Y 2 [-Si(R) n L 3-n ] k In the case of (2), j is preferably 1 to 3.
Examples of perfluoroalkyl groups include CF 3 -、CF 3 CF 2 -、CF 3 CF 2 CF 2 -、CF 3 CF 2 CF 2 CF 2 -、CF 3 CF 2 CF 2 CF 2 CF 2 -、CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 -and CF 3 CF(CF 3 )-。
The perfluoroalkyl group is preferably CF from the viewpoint of more excellent water repellency of the surface treatment layer 3 -、CF 3 CF 2 -or CF 3 CF 2 CF 2 -。
Y 2 A linking group of valence (k+1).
As Y 2 As long as the effect of the present application is not impaired, there may be mentioned, for example, a group optionally having an etheric oxygen atom or a valence of 2An alkylene group, a carbon atom, a nitrogen atom, a silicon atom, and a 2-8-valent organopolysiloxane residue; si (R) is removed from the following formulae (3-1A), (3-1B) and (3-1A-1) to (3-1A-7) n L 3-n And the resulting group.
In addition, Y 2 The group (g 2-1) to the group (g 2-14) may be mentioned below.
Y 1 A linking group of valence (j+g).
Y 1 Examples of the group that does not impair the effect of the present application include an alkylene group optionally having an etheric oxygen atom or an organopolysiloxane residue of 2-valent atoms, a carbon atom, a nitrogen atom, a silicon atom, and an organopolysiloxane residue of 2 to 8-valent atoms; si (R) is removed from the following formulae (3-1A), (3-1B) and (3-1A-1) to (3-1A-7) n L 3-n And the resulting group.
In addition, Y 1 The following groups (g 2-1) to (g 2-14) may be used.
j is an integer of 1 or more. From the viewpoint of more excellent water repellency of the surface treatment layer, j is preferably 1 to 6. From the viewpoint of easy production of the fluorine-containing compound, j is particularly preferably 1.
g is an integer of 1 or more. From the viewpoint of further excellent abrasion resistance of the surface treatment layer, g is preferably 1 to 15, more preferably 1 to 6, further preferably 2 to 4, particularly preferably 2 or 3. On the other hand, from the viewpoint of more excellent fingerprint removability of the surface treatment layer, g is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
k is an integer of 1 or more. From the viewpoint of further excellent abrasion resistance of the surface treatment layer, k is preferably 1 to 15, more preferably 1 to 6, further preferably 2 to 4, particularly preferably 2 or 3. On the other hand, k is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1, from the viewpoint of more excellent fingerprint removability of the surface treatment layer.
At A is-Y 2 [-Si(R) n L 3-n ] k In this case, k+g is preferably 2 to 25, more preferably 4 to 18, and particularly preferably 6 to 12, from the viewpoint of further excellent abrasion resistance of the surface treatment layer. Another partyFrom the viewpoint of further excellent fingerprint removability of the surface-treated layer, k+g is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2.
In the compound (3), a plurality of [ -Si (R) n L 3-n ]In the case of (C), a plurality of [ -Si (R) n L 3-n ]May be the same or different from each other.
The compound (3) is preferably a compound represented by the following formula (3-1) or a compound represented by the following formula (3-2), and particularly preferably a compound represented by the following formula (3-2), from the viewpoint of further excellent abrasion resistance of the surface-treated layer.
[R f1 -(OX) m -] j1 Y 10 [-Si(R) n L 3-n ] g1 …(3-1)
[L 3-n (R) n Si-] k2 Y 12 -(OX) m -Y 11 [-Si(R) n L 3-n ] g2 …(3-2)
In the formula (3-1), X, L, R, m, n is defined as the same as each group in the formula (3). Y is Y 10 A linking group having a valence of (j1+g1), its specific example being Y in formula (3) 1 The same applies. R is R f1 Suitable means and specific examples of perfluoroalkyl groups are as described above. j1 and g1 are defined as the same as j and g in formula (3), respectively.
In the formula (3-2), X, L, R, m, n is defined as the same as each group in the formula (3). Y is Y 11 A linking group having a valence of (g2+1), and its specific example is Y in formula (3) 1 The same applies. Y is Y 12 A linking group having a valence of (k2+1), its specific example being Y in formula (3) 1 The same applies. k2 and g2 are defined as the same as k and g in formula (3), respectively.
Having a plurality of [ R ] in the compound (3-1) f1 -(OX) m -]In the case of (1), a plurality of [ R ] f1 -(OX) m -]May be the same or different. The compound (3-1) and the compound (3-2) have a plurality of [ -Si (R) n L 3-n ]In the case of (C), a plurality of [ -Si (R) n L 3-n ]May be the same or different.
-Y in formula (3-1) 10 [-Si(R) n L 3-n ] g1 The group shown, and-Y in formula (3-2) 11 [-Si(R) n L 3-n ] g2 The radicals shown and Y 12 [-Si(R) n L 3-n ] k2 The groups shown are preferably groups (3-1A) or groups (3-1B), respectively.
-Q a -X 31 (-Q b -Si(R) n L 3-n ) h (-R 31 ) i …(3-1A)
-Q c -[CH 2 C(R 32 )(-Q d -Si(R) n L 3-n )] y -R 33 …(3-1B)
In the formulae (3-1A) and (3-1B), R, L and n are as defined above.
Q a Is a single bond or a 2-valent linking group.
Examples of the 2-valent linking group include a 2-valent hydrocarbon group, a 2-valent heterocyclic group, -O-, -S-, -SO 2 -、-N(R d )-、-C(O)-、-Si(R a ) 2 And a group obtained by combining 2 or more of them.
The 2-valent hydrocarbon group may be a 2-valent saturated hydrocarbon group, a 2-valent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group. The saturated hydrocarbon group having a valence of 2 may be linear, branched or cyclic, and examples thereof include alkylene groups. The number of carbon atoms is preferably 1 to 20. The 2-valent aromatic hydrocarbon group is preferably a group having 5 to 20 carbon atoms, and examples thereof include phenylene groups. In addition, the compound may be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms.
R is as described above a Is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. R is as described above d Is a hydrogen atom or an alkyl group (the number of carbon atoms is preferably 1 to 10).
Examples of the groups obtained by combining 2 or more of them include groups having-OC (O) -, -C (O) O-, -C (O) N (R) d )-、-N(R d )C(O)-、-N(R d )C(O)N(R d )-、-N(R d )C(O)O-、-OC(O)N(R d )-、-SO 2 N(R d )-、-N(R d )SO 2 -、-C(O)N(R d ) -an alkylene group; having the formula-N (R) d ) C (O) -alkylene; an alkylene group having an etheric oxygen atom; alkylene having-OC (O) -group; alkylene having-C (O) O-; with-SO 2 N(R d ) -an alkylene group; alkylene-Si (R) a ) 2 -phenylene-Si (R) a )2。
X 31 Is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a 2-8-valent organopolysiloxane residue, or a group having a (h+i+1) -valent ring.
The alkylene group may optionally have an-O-, a silylene skeleton group, a 2-valent organopolysiloxane residue, or a dialkylsilylene group (dialkyl silylene group). The alkylene group optionally has a plurality of groups selected from the group consisting of-O-, a silylene backbone group, a 2-valent organopolysiloxane residue, and a dialkylsilylene group.
X 31 The number of carbon atoms of the alkylene group is preferably 1 to 20, particularly preferably 1 to 10.
Examples of the organopolysiloxane residue having a valence of 2 to 8 include organopolysiloxane residues having a valence of 2 and organopolysiloxane residues having a valence of (w2+1) described below.
In the formula (3-1A), X 31 In the case of a group having a ring with a valence of (h+i+1), Q a 、(-Q b -Si(R) n L 3-n ) And R is 31 Directly bonded to the atoms constituting the ring. Wherein the ring is a ring other than an organopolysiloxane ring.
X 31 The ring in (a) may be any of a single ring, a condensed ring, a bridged ring, a spiro ring, and a condensed ring, and the atoms constituting the ring may be a carbocycle formed of only carbon atoms, or may be a heterocycle formed of a heteroatom having a valence of 2 or more and a carbon atom. The bond between atoms constituting the ring may be a single bond or multiple bonds. The ring may be aromatic or non-aromatic.
The monocyclic ring is preferably a 4-to 8-membered ring, more preferably a 5-and 6-membered ring. As a condensed partThe polycyclic ring is preferably a fused polycyclic ring obtained by fusing 2 or more 4-to 8-membered rings, more preferably a fused polycyclic ring obtained by bonding 2 or 3 rings selected from 5-and 6-membered rings and a fused polycyclic ring obtained by bonding 1 or 2 rings selected from 5-and 6-membered rings to 1 4-membered ring. The bridged ring is preferably a bridged ring having a 5-membered ring or a 6-membered ring as the largest ring, and the spiro ring is preferably a spiro ring formed from 2 4-membered to 6-membered rings. The polycyclic ring is preferably a polycyclic ring in which 2 or 3 rings selected from the group consisting of 5-membered and 6-membered rings are bonded by a single bond, 1 to 3 carbon atoms, or 1 heteroatom having a valence of 2 or 3. In the collective polycyclic ring, Q is preferably bonded to each ring a 、(-Q b -Si(R) n L 3-n ) And R is 31 (i=1 or more).
The hetero atoms constituting the ring are preferably a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably a nitrogen atom and an oxygen atom. The number of hetero atoms constituting the ring is preferably 3 or less. In the case where the number of hetero atoms constituting the ring is 2 or more, these hetero atoms may be different.
As X 31 The ring in (2) is preferably 1 selected from the group consisting of an aliphatic ring having 3 to 8 ring members, a benzene ring, a heterocyclic ring having 3 to 8 ring members, a condensed polycyclic ring obtained by condensing 2 or 3 of these rings, a bridged ring having a 5-or 6-membered ring as the largest ring, and a polycyclic ring having 2 or more of these rings and a single bond as a linking group, an alkylene group having 3 or less carbon atoms, an oxygen atom, or a sulfur atom, from the viewpoint of easier production of a compound and further excellent abrasion resistance of a surface-treated layer.
The ring is preferably a benzene ring, a 5-or 6-membered aliphatic ring, a 5-or 6-membered heterocyclic ring having a nitrogen atom or an oxygen atom, or a fused polycyclic ring of a 5-or 6-membered carbocyclic ring and a 4-to 6-membered heterocyclic ring.
Specific examples of the ring include a ring shown below, and a 1, 3-cyclohexadiene ring, a 1, 4-cyclohexadiene ring, an anthracene ring, a cyclopropane ring, a decalin ring, a norbornene ring, a norbornadiene ring, a furan ring, a pyrrole ring, a thiophene ring, a pyrazine ring, a morpholine ring, an aziridine ring, an isoquinoline ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, a pyran ring, a pyridazine ring, a pyrimidine ring, and an indene ring. The ring having an oxo group (=o) is also shown below.
X 31 The bonds of atoms constituting the ring not constituting the ring being with Q a 、(-Q b -Si(R) n L 3-n ) Or R is 31 And a bonded connection. With the remaining linkages, the remaining linkages are bonded to hydrogen atoms or substituents. Examples of the substituent include a halogen atom, an alkyl group (optionally including an etheric oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, an oxo group (=o), and the like.
In addition, 1 carbon atom constituting the ring has 2 and Q a 、(-Q b -Si(R) n L 3-n ) Or R is 31 In the case of bonded linkages, Q may be bonded to 1 carbon atom a And (-Q) b -Si(R) n L 3-n ) There may also be 2 (-Q) bonded thereto b -Si(R) n L 3-n ). Preferably Q a And (-Q) b -Si(R) n L 3-n ) Or R is 31 Bonded to different ring-forming atoms. h (-Q) b -Si(R) n L 3-n ) May be bonded to different ring-forming atoms, 2 of which may be bonded to 1 ring-forming carbon atom, and further, 2 (-Q) b -Si(R) n L 3-n ) More than 2 ring-forming carbon atoms may also be present. i R 31 May be bonded to different ring-forming atoms, 2 of which may be bonded to 1 ring-forming carbon atom, and further, 2R 31 More than 2 ring-forming carbon atoms may be present.
Q b Is a single bond or a 2-valent linking group.
Definition of a 2-valent linking group with Q as described above a The definitions stated in the description are to be understood in the same sense.
R 31 Is a hydrogen atom, a hydroxyl group or an alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
At X 31 In the case of a single bond or alkylene, h is 1, i is 0,
at X 31 In the case of a nitrogen atom, h is an integer of 1 to 2, i is an integer of 0 to 1, satisfying h+i=2,
at X 31 In the case of a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, satisfying h+i=3,
at X 31 In the case of an organopolysiloxane residue having a valence of 2 to 8, h is an integer of 1 to 7, i is an integer of 0 to 6, and h+i=1 to 7 is satisfied.
At X 31 In the case of a group having a ring with a valence of (h+i+1), h is an integer of 1 to 7, i is an integer of 0 to 6, and h+i=1 to 7 is satisfied.
There are more than 2 (-Q) b -Si(R) n L 3-n ) In the case of (C), more than 2 (-Q) b -Si(R) n L 3-n ) May be the same or different. With more than 2R 31 In the case of (C), more than 2 (-R) 31 ) May be the same or different.
Q c Is a single bond or a 2-valent linking group.
Definition of a 2-valent linking group with Q as described above a The definitions stated in the description are to be understood in the same sense.
The number of carbon atoms of the alkylene group optionally having an etheric oxygen atom is preferably 1 to 10, particularly preferably 2 to 6.
R 32 The hydrogen atom or the alkyl group having 1 to 10 carbon atoms is preferable from the viewpoint of easy production of the compound.
The alkyl group is preferably a methyl group.
Q d Is a single bond or an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6. Q from the viewpoint of easy production of the compound d Preferably a single bond or CH 2 -。
R 33 The hydrogen atom or halogen atom is preferably a hydrogen atom from the viewpoint of easy production of the compound.
y is an integer of 1 to 10, preferably an integer of 1 to 6.
More than 2 [ CH ] 2 C(R 32 )(-Q d -Si(R) n L 3-n )]May be the same or different.
As the group (3-1A), the groups (3-1A-1) to (3-1A-7) are preferable.
-(X 32 ) s1 -Q b1 -Si(R) n L 3-n …(3-1A-1)
-(X 33 ) s2 -Q a2 -N[-Q b2 -Si(R) n L 3-n ] 2 …(3-1A-2)
-Q a3 -Si(R g )[-Q b3 -Si(R) n L 3-n ] 2 …(3-1A-3)
-[Q e ] s4 -Q a4 -(O) t4 -C[-(O) u4 -Q b4 -Si(R) n L 3-n ] 3-w1 (-R 31 ) w1 …(3-1A-4)
-Q a5 -Si[-Q b5 -Si(R) n L 3-n ] 3 …(3-1A-5)
-[Q e ] v -Q a6 -Z a [-Q b6 -Si(R) n L 3-n ] w2 …(3-1A-6)
-[Q e ] s4 -Q a4 -(O) t4 -Z c [-(O-Q b4 ) u4 -Si(R) n L 3-n ] w3 (-OH) w4 …(3-1A-7)
In the formulae (3-1A-1) to (3-1A-7), R, L and n are as defined above.
In the group (3-1A-1), X 32 is-O-, -C (O) O-, -SO 2 N(R d )-、-N(R d )SO 2 -、-N(R d ) C (O) -or-C (O) N (R) d ) - (wherein, in the formula, N and Q b1 Bonding).
R d Is defined as above.
s1 is 0 or 1.
Q b1 Is an alkylene group. The alkylene group may optionally have an-O-, a silaphenylene skeleton group, a 2-valent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group optionally has a plurality of groups selected from the group consisting of-O-, a silylene backbone group, a 2-valent organopolysiloxane residue, and a dialkylsilylene group.
In the case where the alkylene group has an-O-, a silylene skeleton group, a 2-valent organopolysiloxane residue, or a dialkylsilylene group, it is preferable to have these groups between carbon atoms.
Q b1 The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.
As Q b1 In the case where s1 is 0, it is preferably-CH 2 OCH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 Si(CH 3 ) 2 OSi(CH 3 ) 2 CH 2 CH 2 -. In (X) 32 ) s1 In the case of-O-, preference is given to-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 CH 2 -. In (X) 32 ) s1 is-C (O) N (R) d ) In the case of-an alkylene group having 2 to 6 carbon atoms (wherein, in the formula, N and Q b1 Bonding). If Q b1 These groups facilitate the production of the compound.
As specific examples of the group (3-1A-1), the following groups are given. In the following formula, AND (OX) m The bonding locations.
In the group (3-1A-2), X 33 is-O-, -NH-, -C (O) O- -OC (O) -, SO 2 N(R d )-、-N(R d )SO 2 -、-N(R d )C(O)-、-OC(O)N(R d ) -or-C (O) N (R) d )-。
R d Is defined as above.
Q a2 Is a single bond, alkylene, -C (O) -; or having an etheric oxygen atom, -C (O) -, -C (O) O-, -OC (O) -, -C (O) N (R) between carbon atoms of an alkylene group having 2 or more carbon atoms d )-、-N(R d )C(O)-、-N(R d )C(O)N(R d )-、-N(R d )C(O)O-、-OC(O)N(R d )-、-SO 2 N(R d )-、-N(R d )SO 2 -、-C(O)N(R d ) -or-NH-groups.
Q a2 The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6.
Q a2 The alkylene group having 2 or more carbon atoms has an etheric oxygen atom, -C (O) -, -C (O) O-, -OC (O) -, -C (O) N (R) d )-、-N(R d )C(O)-、-N(R d )C(O)N(R d )-、-N(R d )C(O)O-、-OC(O)N(R d )-、-SO 2 N(R d )-、-N(R d )SO 2 -、-C(O)N(R d ) The number of carbon atoms of the-or-NH-group is preferably 2 to 10, particularly preferably 2 to 6.
Q from the viewpoint of easy production of the compound a2 preferably-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 -、-CH 2 NHCH 2 CH 2 -、-CH 2 OC(O)CH 2 CH 2 -or-C (O) -.
s2 is 0 or 1 (wherein, at Q a2 In the case of a single bond, 0. ). From the viewpoint of easy production of the compound, 0 is preferred.
Q b2 Is alkylene or alkylene having 2 or more carbon atoms and having 2 valences between carbon atomsAn organopolysiloxane residue, an etheric oxygen atom or a group of-NH-.
Q b2 The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.
Q b2 The number of carbon atoms of the organopolysiloxane residue, the etheric oxygen atom or the group of-NH-having a valence of 2 between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, particularly preferably 2 to 6.
As Q b2 From the viewpoint of easy production of the compound, it is preferably-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 CH 2 - (wherein, the right side is bonded to Si).
2 [ -Q b2 -Si(R) n L 3-n ]May be the same or different.
As specific examples of the group (3-1A-2), the following groups are given. In the following formula, AND (OX) m The bonding locations.
In the group (3-1A-3), Q a3 The alkylene group which is a single bond or optionally has an etheric oxygen atom is preferably a single bond from the viewpoint of easy production of the compound.
The number of carbon atoms of the alkylene group optionally having an etheric oxygen atom is preferably 1 to 10, particularly preferably 2 to 6.
R g Is a hydrogen atom, a hydroxyl group or an alkyl group. R is R g The number of carbon atoms of the alkyl group is preferably 1 to 4.
Q b3 A group which is an alkylene group or an organopolysiloxane residue having an etheric oxygen atom or a valence of 2 between carbon atoms of an alkylene group having 2 or more carbon atoms.
Q b3 The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.
Q b3 The carbon atom of the alkylene group having 2 or more carbon atomsThe number of carbon atoms of the group having an etheric oxygen atom or a 2-valent organopolysiloxane residue between atom-carbon atoms is preferably 2 to 10, particularly preferably 2 to 6.
Q from the viewpoint of easy production of the compound b3 preferably-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
2 [ -Q b3 -Si(R) n L 3-n ]May be the same or different.
Specific examples of the group (3-1A-3) include the following groups. In the following formula, AND (OX) m The bonding locations.
In the group (3-1A-4), Q e is-C (O) O-, -OC (O) -, -SO 2 N(R d )-、-N(R d )SO 2 -、-N(R d )C(O)-、-OC(O)N(R d ) -or-C (O) N (R) d )-。
R 31 Is defined as above.
s4 is 0 or 1.
Q a4 Is a single bond or an alkylene group optionally having an etheric oxygen atom.
The number of carbon atoms of the alkylene group optionally having an etheric oxygen atom is preferably 1 to 10, particularly preferably 2 to 6.
t4 is 0 or 1 (wherein, at Q a4 In the case of a single bond, 0).
as-Q a4 -(O) t4 In the case where s4 is 0, it is preferably a single bond, -CH, from the viewpoint of easy production of the compound 2 O-、-CH 2 OCH 2 -、-CH 2 OCH 2 CH 2 O-、-CH 2 OCH 2 CH 2 OCH 2 -、-CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 - (wherein, left side and%OX) m Bonding), in the case of s4 being 1, it is preferably a single bond, -CH 2 -、-CH 2 CH 2 -。
Q b4 Is alkylene, said alkylene optionally having the formula-O-, -C (O) N (R) d )-(R d Definition of (c) is as described above), a silylene backbone group, a 2-valent organopolysiloxane residue or a dialkylsilylene group.
In the case where the alkylene group has an-O-or a silaphenylene skeleton group, it is preferable to have an-O-or a silaphenylene skeleton group between carbon atoms. In addition, the alkylene group has-C (O) N (R) d ) In the case of a dialkylsilylene radical or a 2-valent organopolysiloxane residue, preference is given to radicals between carbon atoms and carbon atoms or to radicals (O) u4 The one-sided end of the bond has these groups.
Q b4 The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.
u4 is 0 or 1.
As- (O) u4 -Q b4 From the viewpoint of easy production of the compound, it is preferably-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OSi(CH 3 ) 2 CH 2 CH 2 CH 2 -、-OSi(CH 3 ) 2 OSi(CH 3 ) 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 Si(CH 3 ) 2 PhSi(CH 3 ) 2 CH 2 CH 2 - (wherein, the right side is bonded to Si).
w1 is an integer of 0 to 2, preferably 0 or 1, particularly preferably 0.
There are more than 2 [ - (O) u4 -Q b4 -Si(R) n L 3-n ]In the case of (2) or more [ - (O) u4 -Q b4 -Si(R) n L 3-n ]Can be the same or different Different.
With more than 2R 31 In the case of (C), more than 2 (-R) 31 ) May be the same or different.
As specific examples of the group (3-1A-4), the following groups are given. In the following formula, AND (OX) m The bonding locations.
/>
In the group (3-1A-5), Q a5 Is an alkylene group optionally having an etheric oxygen atom.
The number of carbon atoms of the alkylene group optionally having an etheric oxygen atom is preferably 1 to 10, particularly preferably 2 to 6.
As Q a5 From the viewpoint of easy production of the compound, it is preferably-CH 2 OCH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 - (wherein, the right side is bonded to Si).
Q b5 A group which is an alkylene group or an organopolysiloxane residue having an etheric oxygen atom or a valence of 2 between carbon atoms of an alkylene group having 2 or more carbon atoms.
Q b5 The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.
Q b5 The number of carbon atoms of the group having an etheric oxygen atom or a 2-valent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, particularly preferably 2 to 6.
As Q b5 From the viewpoint of easy production of the compound, it is preferably-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 CH 2 - (wherein, right side and Si (R)) n L 3-n Bonding).
3 [ -Q b5 -Si(R) n L 3-n ]May be the same or different.
As specific examples of the group (3-1A-5), the following groups are given. In the following formula, AND (OX) m The bonding locations.
Q in group (3-1A-6) e Is as defined in the above group (3-1A-4).
v is 0 or 1.
Q a6 Is an alkylene group optionally having an etheric oxygen atom.
The number of carbon atoms of the alkylene group optionally having an etheric oxygen atom is preferably 1 to 10, particularly preferably 2 to 6.
As Q a6 From the viewpoint of easy production of the compound, it is preferably-CH 2 OCH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 - (wherein, right side and Z a Bonding).
Z a An organopolysiloxane residue having a valence of (w2+1).
w2 is an integer of 2 to 7.
As the (w2+1) valent organopolysiloxane residue, the following groups can be mentioned. Wherein R in the formula a As described above.
Q b6 Organopolysiloxane residue having an etheric oxygen atom or a valence of 2 between carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atomsIs a group of (2).
Q b6 The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.
Q b6 The number of carbon atoms of the group having an etheric oxygen atom or a 2-valent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, particularly preferably 2 to 6.
As Q b6 From the viewpoint of easy production of the compound, it is preferably-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -。
w2 [ -Q b6 -Si(R) n L 3-n ]May be the same or different.
As specific examples of the group (3-1A-6), the following groups are given. In the following formula, AND (OX) m The bonding locations.
In the group (3-1A-7), Z c A hydrocarbon group having a valence of (w3+w4+1).
w3 is an integer of 4 or more.
w4 is an integer of 0 or more.
Q e 、s4、Q a4 、t4、Q b4 And u4 are as defined and preferred for each symbol in the group (3-1A-4).
Z c May be formed of a hydrocarbon chain, or may have an etheric oxygen atom between carbon atoms of the hydrocarbon chain, and is preferably formed of a hydrocarbon chain.
Z c The valence number of (2) is preferably 5 to 10, more preferably 5 to 8, and still more preferably 5 to 6.
Z c The number of carbon atoms of (2) is preferably 7 to 50, more preferably 10 to 40, and still more preferably 15 to 30.
w3 is preferably 4 to 10, more preferably 4 to 8, and still more preferably 4 to 5.
w4 is preferably 0 to 10, more preferably 0 to 8, and still more preferably 0.
There are more than 2 [ - (O-Q) b4 ) u4 -Si(R) n L 3-n ]In the case of (2) or more [ - (O-Q) b4 ) u4 -Si(R) n L 3-n ]May be the same or different.
As specific examples of the group (3-1A-7), the following groups are given. In the following formula, AND (OX) m The bonding locations.
Y in the formula (3-1) 10 May be a group (g 2-1) (where j1=d1+d3, g1=d2+d4), a group (g 2-2) (where j1=e1, g1=e2), a group (g 2-3) (where j1=1, g1=2), a group (g 2-4) (where j1=h1, g1=h2), a group (g 2-5) (where j1=i1, g1=i2), a group (g 2-6) (where j1=1, g1=1), or a group (g 2-7) (where j1=1, g1=i3).
In addition, Y in formula (3-2) 11 And Y 12 Each independently may be a group (g2-1) (wherein g2=d2+d4, k2=d2+d4), a group (g2-2) (wherein g2=e2, k2=e2.), a group (g 2-3) (wherein g2=2, k2=2.), a group (g 2-4) (wherein g2=h2, k2=h2.), a group (g 2-5) (wherein g2=i2, k2=i2.), a group (g 2-6) (wherein g2=1, k2=1.), or a group (g 2-7) (wherein g2=i3, k2=i3.).
(-A 1 -Q 12 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -) e2 …(g2-2)
-A 1 -Q 13 -N(-Q 23 -) 2 …(g2-3)
(-A 1 -Q 14 -) h1 Z 1 (-Q 24 -) h2 …(g2-4)
(-A 1 -Q 15 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 …(g2-5)
-A 1 -Q 26 - (g2-6)
-A 1 -Q 12 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 …(g2-7)
Wherein in the formulae (g 2-1) to (g 2-7), A 1 Side connection (OX) m ，Q 22 、Q 23 、Q 24 、Q 25 Or Q 26 Side-attached to [ -Si (R) n L 3-n ]。
A 1 Is a single bond, -C (O) NR 6 -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR 6 -, -O-or SO 2 NR 6 -。
Q 11 Is a single bond, -O-, alkylene, or-C (O) NR between carbon atoms of an alkylene group having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 -or-O-groups.
Q 12 Is a single bond, alkylene, or an alkylene group having 2 or more carbon atoms with-C (O) NR between carbon atoms 6 -、-C(O)-、-NR 6 -or-O-group, at Y 10 、Y 11 Or Y 12 Having more than 2Q' s 12 In the case of (1), more than 2Q 12 May be the same or different.
Q 13 Is a single bond (wherein A 1 is-C (O) -. ) Alkylene having-C (O) NR between carbon atoms of alkylene having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 -either-O-groups, or-C (O) -groups at the N-terminal end of the alkylene group.
Q 14 Bonded Z 1 When the atom in (a) is a carbon atom, Q 14 Is Q 12 ，Q 14 Bonded Z 1 When the atom in (B) is a nitrogen atom, Q 14 Is Q 13 ，Y 10 、Y 11 Or Y 12 Having more than 2Q' s 14 In the time-course of which the first and second contact surfaces,more than 2Q 14 May be the same or different.
Q 15 Is alkylene or has-C (O) NR between carbon atoms of alkylene having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 -or-O-, Y 10 、Y 11 Or Y 12 Having more than 2Q' s 15 At least 2Q 15 May be the same or different.
Q 22 Is an alkylene group; having-C (O) NR between carbon atoms of alkylene groups having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 -or-O-groups; having-C (O) NR at the terminal of the alkylene group on the side not bonded to Si 6 -、-C(O)-、-NR 6 -or-O-groups; or having-C (O) NR between carbon atoms of alkylene groups having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 Or O-and having-C (O) NR at one terminal not bonded to Si 6 -、-C(O)-、-NR 6 -or-O-, Y 10 、Y 11 Or Y 12 Having more than 2Q' s 22 At least 2Q 22 May be the same or different.
Q 23 Is alkylene or has-C (O) NR between carbon atoms of alkylene having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 -or-O-, 2Q 23 May be the same or different.
Q 24 Bonded Z 1 When the atom in (a) is a carbon atom, Q 24 Is Q 22 ，Q 24 Bonded Z 1 When the atom in (B) is a nitrogen atom, Q 24 Is Q 23 ，Y 10 、Y 11 Or Y 12 Having more than 2Q' s 24 At least 2Q 24 May be the same or different.
Q 25 Is alkylene or has-C (O) NR between carbon atoms of alkylene having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 -or-O-, Y 10 、Y 11 Or Y 12 Having more than 2Q' s 25 At least 2Q 25 May be the same or different.
Q 26 Is alkylene or has-C (O) NR between carbon atoms of alkylene having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 -or-O-groups.
Z 1 Is a group having a ring structure of h1+h2 valence, said ring structure having a valence of Q 14 Directly bonded to carbon or nitrogen atoms and having a bond with Q 24 A directly bonded carbon atom or nitrogen atom.
R e1 Is a hydrogen atom or an alkyl group, Y 10 、Y 11 Or Y 12 Having more than 2R e1 At least 2R e1 May be the same or different.
R e2 Is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.
R e3 Is alkyl. R is R 6 Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
d1 is an integer of 0 to 3, preferably 1 or 2. d2 is an integer of 0 to 3, preferably 1 or 2. d1+d2 is an integer of 1 to 3.
d3 is an integer of 0 to 3, preferably 0 or 1. d4 is an integer of 0 to 3, preferably 2 or 3. d3+d4 is an integer of 1 to 3.
In Y 10 Wherein d1+d3 is an integer of 1 to 5, preferably 1 or 2, in Y 11 And Y 12 D1+d3 is 1.
In Y 10 Wherein d2+d4 is an integer of 1 to 5, preferably 4 or 5, in Y 11 And Y 12 D2+d4 is an integer of 3 to 5, preferably 4 or 5.
e1+e2 is 3 or 4. In Y 10 Wherein e1 is an integer of 1 to 3, preferably 1 or 2, in Y 11 And Y 12 In which e1 is 1. In Y 10 Wherein e2 is an integer from 1 to 3, preferably 2 or 3, in Y 11 And Y 12 Wherein e2 is 2 or 3.
In Y 10 Wherein h1 is an integer of 1 or more, preferably 1 or 2, and Y 11 And Y 12 In which h1 is 1. h2 is an integer of 1 or more, preferably 2 or 3.
i1+i2 is 3 or 4. In Y 10 Wherein i1 is an integer of 1 to 3, preferably 1 or 2, and Y 11 And Y 12 In which i1 is 1. In Y 10 Wherein i2 is an integer of 1 to 3, preferably 2 or 3, and Y 11 And Y 12 Wherein i2 is 2 or 3.
i3 is 2 or 3.
Q from the viewpoint of easiness in producing the compound (3-1) and the compound (3-2) and the viewpoint of more excellent abrasion resistance of the surface-treated layer 11 、Q 12 、Q 13 、Q 14 、Q 15 、Q 22 、Q 23 、Q 24 、Q 25 And Q 26 The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4. Wherein the lower limit of the number of carbon atoms of the alkylene group when a specific bond is present between carbon atoms is 2.
As Z 1 The ring structure of (a) may be the same as the ring structure described above, and the preferred embodiment is also the same. It should be noted that due to Q 14 、Q 24 Directly bonded to Z 1 In (2), thus, for example, alkylene is not attached to the ring structure and Q 14 、Q 24 And is bonded to the alkylene group.
From the viewpoint of easy production of the compound (3-1) and the compound (3-2), R e1 、R e2 Or R is e3 The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 3, particularly preferably 1 to 2.
From the viewpoint of easy production of the compound (3-1) and the compound (3-2), R e2 The number of carbon atoms of the alkyl portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, particularly preferably 1 to 2.
From the viewpoint of ease of production of the compound (3-1) and the compound (3-2) and further excellent abrasion resistance of the surface treatment layer, h1 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1.
H2 is preferably 2 to 6, more preferably 2 to 4, particularly preferably 2 or 3, from the viewpoint of easiness in producing the compound (3-1) and the compound (3-2) and further excellent abrasion resistance of the surface treatment layer.
As Y 10 Examples of the other modes of (a) include a group (g 2-8) (where j1=d1+d3, g1=d2×k3+d4×k3), a group (g 2-9) (where j1=e1, g1=e2×k3.), a group (g 2-10) (where j1=1, g1=2×k3.), a group (g 2-11) (where j1=h1, g1=h2×k3.), a group (g 2-12) (where j1=i1, g1=i2×k3.), a group (g 2-13) (where j1=1, g1=k3.), and a group (g 2-14) (where j1=1, g1=i3×k3.).
As Y 11 And Y 12 Examples of the other modes of (a) include a group (g 2-8) (where k2=d2×k3, g2=d4×k3), a group (g 2-9) (where k2=e2×0k3, g2=e2×1k3), a group (g 2-10) (where k2=2×k3, g2=2×k3), a group (g 2-11) (where k2=h2×k3, g2=h2×k3), a group (g 2-12) (where k2=i2×k3, g2=i2×k3), a group (g 2-13) (where k2=k3, g2=k3), or a group (g 2-14) (where k2=i3×k3, g2=i3×k3).
(-A 1 -Q 12 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 …(g2-9)
-A 1 -Q 13 -N(-Q 23 -G 1 ) 2 …(g2-10)
(-A 1 -Q 14 -) h1 Z 1 (-Q 24 -G 1 ) h2 …(g2-11)
(-A 1 -Q 15 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -G 1 ) i2 …(g2-12)
-A 1 -Q 26 -G 1 …(g2-13)
-A 1 -Q 12 -CH(-Q 22 -G 1 )-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 …(g2-14)
Wherein in the formulae (g 2-8) to (g 2-14), A 1 Side connection (OX) m ，G 1 Side-attached to [ -Si (R) n L 3-n ]。G 1 Is a group (g 3), Y 10 、Y 11 Or Y 12 Has more than 2G 1 May be the same or different. G removal 1 The other symbols are the same as those in the formulae (g 2-1) to (g 2-7).
-Si(R 8 ) 3-k3 (-Q 3 -) k3 …(g3)
Wherein in formula (g 3), the Si side is bonded to Q 22 、Q 23 、Q 24 、Q 25 And Q 26 ，Q 3 Side-attached to [ -Si (R) n L 3-n ]。R 8 Is alkyl. Q (Q) 3 Is alkylene having-C (O) NR between carbon atoms of alkylene having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 -or-O-, or (OSi (R) 9 ) 2 ) p O-, more than 2Q 3 May be the same or different. k3 is 2 or 3.R is R 6 Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R is R 9 Is alkyl, phenyl or alkoxy, 2R 9 May be the same or different. p is an integer of 0 to 5, and when p is 2 or more (OSi (R 9 ) 2 ) May be the same or different.
Q from the viewpoint of easiness in producing the compound (3-1) and the compound (3-2) and the viewpoint of further excellent abrasion resistance of the surface-treated layer 3 The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4. Wherein the lower limit of the number of carbon atoms of the alkylene group when a specific bond is present between carbon atoms is 2.
From the viewpoint of easy production of the compound (3-1) and the compound (3-2), R 8 The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 3, particularly preferably 1 to 2.
From the viewpoint of easy production of the compound (3-1) and the compound (3-2), R 9 The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 3, particularly preferably 1 to 2.
R is from the viewpoint of excellent storage stability of the compound (3-1) and the compound (3-2) 9 The number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 3, particularly preferably 1 to 2.
p is preferably 0 or 1.
Examples of the compounds (3-1) and (3-2) include compounds represented by the following formulas. The compound of the following formula is preferable from the viewpoints of easy industrial production, easy handling and more excellent abrasion resistance of the surface treatment layer. R in the compound of the formula f And Q f Respectively with [ R ] in the above formula (3-1) f1 -(OX) m -]And- (OX) in formula (3-2) m The same, preferably the same.
As Y 10 The compound (3-1) which is the group (g 2-1) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-2) is exemplified by the compounds of the following formula.
/>
As Y 10 The compound (3-1) which is the group (g 2-3) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-4) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-5) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-6) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-7) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-8) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-9) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-10) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-11) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-12) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-13) is exemplified by the compounds of the following formula.
As Y 10 The compound (3-1) which is the group (g 2-14) is exemplified by the compounds of the following formula.
As Y 11 And Y 12 The compound (3-2) which is the group (g 2-1) is exemplified by the compounds of the following formula.
As Y 11 And Y 12 The compound (3-2) which is the group (g 2-2) is exemplified by the compounds of the following formula.
/>
As Y 11 And Y 12 Is a group (g 2-3)The compound (3-2) may be, for example, a compound of the following formula.
As Y 11 And Y 12 The compound (3-2) which is the group (g 2-4) is exemplified by the compounds of the following formula.
As Y 11 And Y 12 The compound (3-2) which is the group (g 2-5) is exemplified by the compounds of the following formula.
As Y 11 And Y 12 The compound (3-2) which is the group (g 2-6) is exemplified by the compounds of the following formula.
As Y 11 And Y 12 The compound (3-2) which is the group (g 2-7) is exemplified by the compounds of the following formula.
As Y 11 And Y 12 The compound (3-2) which is the group (g 2-9) is exemplified by the compounds of the following formula.
/>
Specific examples of the fluorine-containing compound include compounds described in the following documents.
Japanese patent application laid-open No. 11-029585 discloses a perfluoropolyether-modified aminosilane.
A silicon-containing organic fluoropolymer described in japanese patent No. 2874715.
JP-A-2000-144097 discloses an organosilicon compound.
Japanese patent application laid-open No. 2000-327772 discloses a perfluoropolyether-modified aminosilane.
JP 2002-506887A describes a fluorinated siloxane.
JP-A2008-534696 discloses an organosilicon compound.
A polymer which is fluorinated and contains modified hydrogen as described in Japanese patent No. 4138936.
U.S. patent application publication No. 2010/012972, international publication No. 2014/126064, japanese patent application laid-open No. 2014-070163.
An organosilicon compound described in International publication No. 2011/060047 and International publication No. 2011/059430.
A fluorine-containing organosilane compound described in International publication No. 2012/064649.
JP 2012-72272A discloses a polymer containing a fluorooxyalkylene group.
The fluorine-containing ether compound described in International publication No. 2013/042732, international publication No. 2013/121984, international publication No. 2013/121985, international publication No. 2013/121986, international publication No. 2014/163004, japanese patent application laid-open No. 2014-080473, international publication No. 2015/087902, international publication No. 2017/038830, international publication No. 2017/038832, and International publication No. 2017/187775.
JP-A2014-218639, international publication No. 2017/022437, international publication No. 2018/079743, and International publication No. 2018/143433 disclose a perfluoro (poly) ether-containing silane compound.
JP-A2015-199906, JP-A2016-204656, JP-A2016-210854, and JP-A2016-222859 disclose polymer-modified silanes containing fluoropolyether groups.
A fluorine-containing ether compound described in International publication No. 2018/216630, international publication No. 2019/039226, international publication No. 2019/039341, international publication No. 2019/039186, international publication No. 2019/044479, japanese patent application laid-open No. 2019-44158, and Japanese patent application No. 2017-251611.
The number average molecular weight (Mn) of the fluorine-containing compound is preferably 1,000 to 20,000, more preferably 2,000 to 18,000, particularly preferably 3000 to 1,5000.
If Mn is 1,000 or more, the fluidity of the molecular chain of the fluorine-containing compound and the fluorine content become high, and therefore the fingerprint removability of the fluorine-containing compound is more excellent. When Mn is 20,000 or less, the tackiness is easily adjusted to an appropriate range, and the solubility is improved, so that the film-forming processability is excellent.
The fluorine-containing composition may contain other components than the fluorine-containing compound having a reactive silyl group. As the other component, a liquid medium may be mentioned. In the method for preserving a fluorine-containing composition of the present application, the fluorine-containing composition may contain no other components, and only the fluorine-containing compound may be preserved.
Examples of the liquid medium include water and an organic solvent. Examples of the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent.
The organic solvent contained in the fluorine-containing composition may be 1 or 2 or more.
Specific examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. Examples of the fluoroalkanes include C 6 F 13 H (product name "AC-2000", manufactured by AGC Co., ltd.), C 6 F 13 C 2 H 5 (product name "AC-6000", manufactured by AGC Co., ltd.) and C 2 F 5 CHFCHFCF 3 (product name "Vertrel", manufactured by DuPont).
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1, 3-bis (trifluoromethyl) benzene and 1, 4-bis (trifluoromethyl) benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Examples of the fluoroalkyl ether include CF 3 CH 2 OCF 2 CF 2 H (product name "AE-3000", manufactured by AGC Co., ltd.), C 4 F 9 OCH 3 (product name "Novec-7100", manufactured by 3M Co., ltd.), C 4 F 9 OC 2 H 5 (product name "Novec-7200", manufactured by 3M Co., ltd.) and C 2 F 5 CF(OCH 3 )C 3 F 7 (product name "Novec-7300", manufactured by 3M company).
Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Examples of the fluoroalcohol include 2, 3-tetrafluoropropanol, 2-trifluoroethanol and hexafluoroisopropanol.
The non-fluorine-based organic solvent is preferably a compound composed of only a hydrogen atom and a carbon atom or a compound composed of only a hydrogen atom, a carbon atom and an oxygen atom. Specific examples of the non-fluorinated organic solvent include hydrocarbons, ketones, ethers, esters, and alcohols.
Specific examples of the hydrocarbon include hexane, heptane and cyclohexane.
Specific examples of the ketone include acetone, methyl ethyl ketone and methyl isobutyl ketone.
Specific examples of the ether include diethyl ether, tetrahydrofuran and tetraethyleneglycol dimethyl ether.
Specific examples of the ester include ethyl acetate and butyl acetate.
Specific examples of the alcohol include isopropyl alcohol.
The content of the fluorine-containing compound in the fluorine-containing composition is preferably 0.01 to 50.00 mass%, particularly preferably 1.00 to 30.00 mass%, relative to the total mass of the fluorine-containing composition.
The content of the liquid medium in the fluorine-containing composition is preferably 50.00 to 99.99 mass%, particularly preferably 70.00 to 99.00 mass%, based on the total mass of the fluorine-containing composition.
The fluorochemical composition may contain other ingredients in addition to the liquid medium.
Examples of the other components include by-products produced in the production process of the fluorine-containing compound, and compounds which are unavoidable in the production of unreacted raw materials.
When the fluorine-containing composition contains other components, the content of the other components is preferably 10 mass% or less, more preferably 5 mass% or less, and particularly preferably 1 mass% or less, relative to the total mass of the fluorine-containing composition.
The fluorine-containing composition stored by the storage method of the present application is useful as a surface treatment agent for forming a surface treatment layer excellent in water repellency to a substrate.
The surface treatment layer may be formed by a dry coating method or a wet coating method.
Specific examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method. Among them, the vacuum vapor deposition method is preferable from the viewpoint of suppressing decomposition of the fluorine-containing composition and the viewpoint of simplicity of the apparatus.
Specific examples of the wet coating method include spin coating, wiping, spraying, doctor blading (squeegeee coating), dip coating, die coating, inkjet, flow coating, roll coating, casting, langmuir-Blodgett, and gravure coating.
As the substrate to be formed with the surface treatment layer, a substrate in which the surface to be formed with the surface treatment layer is glass, metal or resin is preferable, and a substrate in which the surface to be formed with the surface treatment layer is glass or metal is particularly preferable. The surface to be formed with the surface treatment layer may be a metal substrate, or may be a composite substrate having a metal layer on the surface of a body made of a non-metal such as a resin, glass, or ceramic. The substrate formed of metal may be a composite metal substrate having a metal layer formed of a metal different from the metal of the main body on the surface of the metal main body.
The surface treatment layer may be formed directly on the surface of the substrate or may be formed on the substrate via a spacerOther films on the substrate surface are formed on the substrate. Specific examples of the other film include compounds described in paragraphs 0089 to 0095 of International publication No. 2011/016458 and SiO-utilizing films 2 And a base film formed on the surface of the substrate by subjecting the substrate to a base treatment.
The method for storing the fluorine-containing composition of the present application may be a method in which the concentration of carbon dioxide in the gas phase portion in a sealed container containing a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is maintained at 25 ℃ to 4 to 380 ppm by volume.
The method of maintaining the concentration of carbon dioxide in the gas phase portion in the closed container at 4 to 380 ppm by volume at 25 ℃ is not particularly limited, and examples thereof include a method of maintaining the temperature change in the environment in which the closed container is stored at 20 ℃ or less without opening the lid of the closed container.
The concentration of carbon dioxide in the gas phase portion is preferably 5 to 350 ppm by volume at 25 ℃. The proportion of the gas phase portion in the volume of the inside of the closed vessel is preferably 10 to 60% by volume.
Preferred modes of the fluorine-containing composition and the closed vessel are as described above.
< Container containing fluorine-containing composition >
The container containing the fluorine-containing composition of the present application is sealed in a state in which the fluorine-containing composition containing the fluorine-containing compound having a reactive silyl group is contained, and the concentration of carbon dioxide in the gas phase portion is 4 to 380 ppm by volume at 25 ℃.
The concentration of carbon dioxide in the gas phase portion is preferably 5 to 350 ppm by volume at 25 ℃. The proportion of the gas phase portion in the volume of the container interior is preferably 10 to 60% by volume.
Preferred modes of the fluorochemical composition and container are as described above.
< method for producing Container containing fluorine-containing composition >
The method for manufacturing a container containing a fluorine-containing composition of the present application comprises: the container in which the fluorine-containing composition containing the fluorine-containing compound having a reactive silyl group is contained is sealed, and the concentration of carbon dioxide in the gas phase portion in the container is set to 4 to 380 ppm by volume at 25 ℃.
The concentration of carbon dioxide in the gas phase portion is preferably 5 to 350 ppm by volume at 25 ℃. The proportion of the gas phase portion in the volume of the container interior is preferably 10 to 60% by volume.
Preferred modes of the fluorochemical composition and container are as described above.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 and 7 to 9 are comparative examples, and examples 2 to 6 and examples 10 to 20 are examples.
[ Synthesis of Compound 1 ]
The following compound 1 was obtained according to the method described in synthesis examples 11 to 15 of Japanese patent application laid-open No. 2014-218639. In compound 1, m is 18 and n is 22. Compound 1 had a number average molecular weight of 4600.
The number m (CF 2 O) chain and n (CF) 2 CF 2 O) chains are randomly arranged.
[ Synthesis of Compound 2, and preparation of composition 1 ]
The following compound 2 was obtained according to the method for synthesizing Compound A-2 described in International publication No. 2020/071330. In compound 2, n is 13. Compound 2 had a number average molecular weight of 5035.
Next, the obtained compound 1 was treated with C 4 F 9 OC 2 H 5 (product name "Novec-7200", manufactured by 3M company) to give a composition 1 having a concentration of 20% by mass of the compound 1.
[ storage in Container ]
Next, each of the obtained compounds or compositions is contained in a container.
For examples 1 to 9, 100g of Compound 1 was contained in a glass 100mL ampoule (product name "syringe ampoule", manufactured by MARUMU Co., ltd., actual volume of 124 mL). The proportion of the gas phase portion in the volume of the interior of the container was 49.6% by volume.
For examples 10 to 11, 165g of Compound 1 was contained in a glass 100mL ampoule (product name "syringe ampoule", manufactured by MARUMU Co., ltd., actual volume of 124 mL). The proportion of the gas phase portion in the volume of the interior of the container was 16.8% by volume.
For examples 12 to 13, 85g of Compound 1 was contained in a glass 100mL ampoule (product name "syringe ampoule", manufactured by MARUMU Co., ltd., actual volume of 124 mL). The proportion of the gas phase portion in the volume of the interior of the container was 57.2% by volume.
For example 14, 10g of Compound 1 was contained in a glass 10mL ampoule (product name "syringe ampoule", manufactured by MARUMU Co., ltd., actual volume of 12.4 mL). The proportion of the gas phase portion in the volume of the interior of the container was 49.6% by volume.
For example 15, 100g of composition 1 was contained in a glass 100mL ampoule (product name "syringe ampoule", manufactured by MARUMU Co., ltd., actual volume of 124 mL). The proportion of the gas phase portion in the volume of the interior of the container was 46.2% by volume.
For example 16, 1000g of composition 1 was contained in a 1000mL bottle made of glass (product name "bottle", manufactured by MARUMU Co., ltd., actual capacity 1120 mL). The proportion of the gas phase portion in the volume of the interior of the container was 40.5% by volume.
For examples 17 to 19, 100g of Compound 2 was contained in a glass 100mL ampoule (product name "syringe ampoule", manufactured by MARUMU Co., ltd., actual volume of 124 mL). The proportion of the gas phase portion in the volume of the interior of the container was 55.2% by volume.
For example 20, 10g of Compound 2 was contained in a glass 10mL ampoule (product name "syringe ampoule", manufactured by MARUMU Co., ltd., actual volume of 12.4 mL). The proportion of the gas phase portion in the volume of the interior of the container was 55.2% by volume.
Next, dry nitrogen was supplied into the container for examples 1 to 6 and examples 10 to 20 until the concentration of carbon dioxide in the gas phase portion became the concentration shown in table 1. For examples 8 to 9, carbon dioxide was supplied into the vessel until the concentration of carbon dioxide in the gas phase became the concentration shown in table 1. For example 7, the supply of dry nitrogen and carbon dioxide gas into the vessel was not performed. Thereafter, the container was closed.
After the concentration of carbon dioxide in the gas phase was adjusted as described above, the mixture was stored at 25℃for 30 days in a constant temperature bath. After 30 days of storage, the concentration of carbon dioxide in the gas phase portion was the same as that in the gas phase portion when the container was closed, and the concentration of carbon dioxide was maintained during storage.
[ whether or not a condensate was formed ]
The stored compound 1 was filtered using a membrane filter and a suction filter made of PTFE having a pore size of 1. Mu.m, and the condensate was separated. Whether or not a condensate was formed was evaluated visually and according to the following criteria. The results obtained are shown in Table 1. The amount of the condensate produced is shown in Table 1.
A: no condensate was produced.
B: the formation of a few condensates was confirmed, but there was no problem in practical use.
C: the formation of condensate was confirmed to be practically problematic.
[ vacuum deposition ]
Vacuum vapor deposition was performed on the substrate using the stored compound 1. Vacuum deposition was performed using a vacuum deposition apparatus (product name "VTR-350M", manufactured by ULVAC Co.). 0.5g of the stored compound 1 was filled into a molybdenum boat in a vacuum vapor deposition apparatus, and the pressure in the vacuum vapor deposition apparatus was 1X 10 -3 The exhaust is performed in the following manner. The boat is heated at a rate of 10 ℃/min or less, and the shutter is opened at a time point when the vapor deposition rate by the crystal oscillation film thickness meter exceeds 1 nm/sec, thereby starting film formation on the substrate surface. Closing the shutter at a time when the film thickness becomes about 50nm, ending on the substrate surfaceIs formed into a film. The substrate on which the compound 1 was deposited after storage was heat-treated at 200℃for 30 minutes, and washed with isopropyl alcohol, whereby an article having a surface-treated layer on the surface of the substrate was obtained.
As the base material, chemically strengthened glass is used.
[ evaluation ]
The following evaluation was performed on the obtained article.
< method for measuring contact Angle >
The contact angle of about 2. Mu.L of distilled water placed on the surface of the surface-treated layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa interface science Co., ltd.). The surface treatment layer was measured at 5 different points on the surface, and the average value was calculated. The 2 theta method was used for calculation of the contact angle.
< initial Water contact Angle >
The initial water contact angle was measured for the surface treatment layer using the aforementioned measurement method. The evaluation criteria are as follows.
A (excellent): 115 degrees or more.
B (good): 110 degrees or more and less than 115 degrees.
C (pass): 100 degrees or more and less than 110 degrees.
D (reject): less than 100 degrees.
< abrasion resistance (rubber) >)
For the surface-treated layer, a cross-over tester (manufactured by KNT Co., ltd.) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) to apply a scratch Rubber (manufactured by Rubber Eraser, minoan Co.) to the surface under load: 4.9N, speed: after 1 ten thousand rounds at 60rpm, the water contact angle was measured. The smaller the decrease in water repellency (water contact angle) after rubbing, the smaller the decrease in performance due to rubbing, and the more excellent the rubbing resistance. The evaluation criteria are as follows.
A (excellent): the change in water contact angle after 1 ten thousand passes is 2 degrees or less.
B (good): the change in water contact angle after 1 ten thousand passes exceeds 2 degrees and is 5 degrees or less.
C (pass): the change in water contact angle after 1 ten thousand passes exceeds 5 degrees and is 10 degrees or less.
D (reject): the change in water contact angle after 1 ten thousand passes exceeds 10 degrees.
< abrasion resistance (Steel wool) >
For the surface-treated layer, steel wool BONSTAR (# 0000) was subjected to pressure in accordance with JIS L0849:2013 (ISO 105-X12:2001) using a round trip tester (manufactured by KNT Co.). 98.07kPa, speed: after 1 ten thousand rounds under 320 cm/min, the water contact angle was measured. The smaller the decrease in water repellency (water contact angle) after rubbing, the smaller the decrease in performance due to rubbing, and the more excellent the rubbing resistance. The evaluation criteria are as follows.
A (excellent): the change in water contact angle after 1 ten thousand passes is 2 degrees or less.
B (good): the change in water contact angle after 1 ten thousand passes exceeds 2 degrees and is 5 degrees or less.
C (pass): the change in water contact angle after 1 ten thousand passes exceeds 5 degrees and is 10 degrees or less.
D (reject): the change in water contact angle after 1 ten thousand passes exceeds 10 degrees.
TABLE 1
As shown in table 1, it can be seen that: when the concentration of carbon dioxide in the gas phase portion in the container is set to be in the range of 4 to 380 ppm by volume at 25 ℃, a surface-treated layer excellent in abrasion resistance can be formed on the substrate when the surface treatment is performed using the stored fluorine-containing composition.
Claims (12)
1. A method for preserving a fluorine-containing composition, wherein the concentration of carbon dioxide in a gas phase portion in a container is set to 4 to 380 ppm by volume at 25 ℃,
the container houses a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group.
2. The method for preserving a fluorine-containing composition according to claim 1, wherein a concentration of carbon dioxide in the gas phase portion is 5 to 350 ppm by volume at 25 ℃.
3. The method for preserving a fluorine-containing composition according to claim 1 or 2, wherein the gas phase portion accounts for 10 to 60% by volume of the volume inside the container.
4. A method for preserving a fluorine-containing composition, wherein the concentration of carbon dioxide in a gas phase portion in a closed vessel is maintained at 25 ℃ at 4 to 380 ppm by volume,
the sealed container contains a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group.
5. The method for preserving a fluorine-containing composition according to claim 4, wherein a concentration of carbon dioxide in the gas phase portion is 5 to 350 ppm by volume at 25 ℃.
6. The method for preserving a fluorine-containing composition according to claim 4 or 5, wherein the gas phase portion accounts for 10 to 60% by volume of the volume inside the closed container.
7. A container containing a fluorine-containing composition, wherein the container is sealed in a state in which the fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is contained, and the concentration of carbon dioxide in a gas phase portion is 4 to 380 ppm by volume at 25 ℃.
8. The container filled with the fluorine-containing composition according to claim 7, wherein the concentration of carbon dioxide in the gas phase portion is 5 to 350 ppm by volume at 25 ℃.
9. The container filled with the fluorine-containing composition according to claim 7 or 8, wherein the gas phase portion accounts for 10 to 60% by volume of the container interior.
10. A method of making a container containing a fluorine-containing composition comprising: a container containing a fluorine-containing composition containing a fluorine-containing compound having a reactive silyl group is sealed,
the concentration of carbon dioxide in the gas phase portion in the container is set to 4 to 380 ppm by volume at 25 ℃.
11. The method for producing a container containing a fluorine-containing composition according to claim 10, wherein the concentration of carbon dioxide in the gas phase portion is 5 to 350 ppm by volume at 25 ℃.
12. The method for producing a container filled with a fluorine-containing composition according to claim 10 or 11, wherein the gas phase portion accounts for 10 to 60% by volume of the container interior.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-015928 | 2022-02-03 | ||
| JP2022190796A JP2023113562A (en) | 2022-02-03 | 2022-11-29 | Method for storing fluorinated composition, container storing fluorinated composition, and method for producing container storing fluorinated composition |
| JP2022-190796 | 2022-11-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116535950A true CN116535950A (en) | 2023-08-04 |
Family
ID=87442383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310051909.9A Pending CN116535950A (en) | 2022-02-03 | 2023-02-02 | Method for preserving fluorine-containing composition, container containing fluorine-containing composition, and method for producing container containing fluorine-containing composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116535950A (en) |
-
2023
- 2023-02-02 CN CN202310051909.9A patent/CN116535950A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20200157376A1 (en) | Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method | |
| CN113165346B (en) | Fluorine-containing ether compound, composition, and article | |
| US11208529B2 (en) | Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method | |
| CN113439111B (en) | Composition and article | |
| WO2013042733A1 (en) | Fluorine-containing ether composition, method for producing same, coating fluid, and method for manufacturing substrate having surface-treated layer | |
| CN114867730A (en) | Fluorine-containing ether compound, surface treatment agent, fluorine-containing ether composition, coating liquid, article, and method for producing article | |
| JP2023536937A (en) | Hydrophobic/oleophobic coating layer, manufacturing method thereof, and product | |
| CN116535950A (en) | Method for preserving fluorine-containing composition, container containing fluorine-containing composition, and method for producing container containing fluorine-containing composition | |
| JP7472794B2 (en) | Substrate with water- and oil-repellent layer, deposition material, and method for producing substrate with water- and oil-repellent layer | |
| CN116535952A (en) | Method for preserving fluorine-containing composition, container containing fluorine-containing composition, and method for producing container containing fluorine-containing composition | |
| KR101369478B1 (en) | Manufacturing method of macromolecular compounds | |
| JP2023113562A (en) | Method for storing fluorinated composition, container storing fluorinated composition, and method for producing container storing fluorinated composition | |
| KR20230154891A (en) | Fluorinated ether compounds, surface treatment agents, fluorinated ether compositions, coating solutions, articles, methods for producing articles, and compounds | |
| JP7468355B2 (en) | Substrate with water- and oil-repellent layer, deposition material, and method for producing substrate with water- and oil-repellent layer | |
| JP2023113563A (en) | Method for storing fluorinated composition, container storing fluorinated composition, and method for producing container storing fluorinated composition | |
| CN113891919A (en) | Substrate with water-repellent and oil-repellent layer | |
| JP2021172842A (en) | Substrate with water and oil repellent layer, vapor deposition material, and manufacturing method of substrate with water and oil repellent layer | |
| WO2024038865A1 (en) | Compound, composition, surface treatment agent, coating liquid, article, and article manufacturing method | |
| CN113227440A (en) | Vapor deposition material, substrate with base layer using same, and method for producing substrate with water-and oil-repellent layer | |
| KR20230157337A (en) | Method for producing a substrate with a surface treatment agent and a surface treatment layer | |
| KR20210106426A (en) | Method for manufacturing a water-and-oil-repellent layer-forming substrate, vapor deposition material, and water-and-oil-repellent layer-forming substrate | |
| WO2022196503A1 (en) | Surface treatment agent and method for producing base material having surface treated layer | |
| WO2024038873A1 (en) | Compound, composition, surface treatment agent, coating liquid, article, and method for producing article | |
| WO2024038866A1 (en) | Compound, composition, surface treatment agent, coating liquid, article, and method for producing article | |
| CN117500863A (en) | Fluorine-containing ether compound, fluorine-containing ether mixture, coating agent, article, and method for producing article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |