WO2020218619A1 - 組成物の製造方法、及び、組成物 - Google Patents
組成物の製造方法、及び、組成物 Download PDFInfo
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- WO2020218619A1 WO2020218619A1 PCT/JP2020/018041 JP2020018041W WO2020218619A1 WO 2020218619 A1 WO2020218619 A1 WO 2020218619A1 JP 2020018041 W JP2020018041 W JP 2020018041W WO 2020218619 A1 WO2020218619 A1 WO 2020218619A1
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- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 101150096839 Fcmr gene Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 101150032645 SPE1 gene Proteins 0.000 description 1
- 101100366397 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SPE3 gene Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 150000003672 ureas Chemical group 0.000 description 1
- 150000003673 urethanes Chemical group 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
- C08F16/26—Monomers containing oxygen atoms in addition to the ether oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F116/14—Monomers containing only one unsaturated aliphatic radical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/243—Dialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
- C08F216/1425—Monomers containing side chains of polyether groups
- C08F216/1441—Monomers containing side chains of polypropylene oxide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
-
- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/10—Homopolymers or copolymers of unsaturated ethers
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/34—Molecular weight or degree of polymerisation
Definitions
- the present disclosure relates to a method for producing a composition and the composition.
- fluoropolymers having a sulfonic acid group or a carboxyl group have been attracting attention as materials for electrolyte membranes for fuel cells, chemical sensors, etc., and are being studied.
- Patent Document 1 describes a method for producing a fluoropolymer dispersion, which comprises an acid treatment step of adding an acid to an aqueous dispersion containing a fluoropolymer precursor and performing ultrafiltration.
- the fluoropolymer precursors represent -SO 3 X 1 and / or -COOZ 1 (X 1 represents M 1 1 / L or NR 1 R 2 R 3 R 4 , R 1 , R 2 , R 3 and R 4 represents the same or different alkyl group having a hydrogen atom or 1 to 4 carbon atoms.
- Z 1 represents M 2 1 / L or NR 5 R 6 R 7 R 8 and represents R 5 , R 6 , R 7 and R 8 represent the same or different alkyl groups having a hydrogen atom or 1 to 4 carbon atoms.
- M 1 and M 2 represent the same or different L-valent metal, and the L-valent metal. Is a metal belonging to Group 1, Group 2, Group 4, Group 8, Group 11, Group 12, and Group 13 of the periodic table), and the acid treatment step is the same as -SO 3 X 1. the one that changes the -SO 3 H, and / or a fluoropolymer dispersion production method characterized by the -COOZ 1 is intended to vary the -COOH is described.
- the structural unit N3 is represented by a monomer derived from a monomer copolymerizable with the fluorine-containing monomer of the above formula (5-1)], the structural unit M3 is 55 to 100 mol%, and the structural unit N3 is 0 to 0 to Described is a coating composition for forming an antireflection film for an upper layer of a photoresist containing a fluoropolymer (A1) having a carboxyl group and containing 45
- the present disclosure provides a method for producing a composition capable of efficiently removing low molecular weight substances.
- a composition having a reduced low molecular weight is provided.
- the present disclosure includes step A of performing ultrafiltration, microfiltration or dialysis membrane treatment of a composition containing water and a fluoropolymer, or a combination thereof.
- Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- A is -COOM,-. SO 3 M, -OSO 3 M or -C (CF 3) 2 OM ( M is, -H, a metal atom, -NR 7 4, good imidazolium be substituted, substituted It is a pyridinium which may have a substituent or a phosphonium which may have a substituent, and R 7 is an H or an organic group), provided that at least one of X, Y and Z contains a fluorine atom.)
- This is a method for producing a composition, which is a polymer containing a structural unit M3 derived from a monomer represented by.
- the structural unit M3 is preferably a structural unit (1A) based on a monomer represented by the following general formula (1A).
- the structural unit M3 is preferably a structural unit (1a) based on the fluoroallyl ether compound represented by the following general formula (1a).
- CX 2 CFCF 2- O- (CF (CF 3 ) CF 2 O) n5- CF (CF 3 ) -A (1a) (In the equation, each X is the same and represents F or H. n5 represents 0 or an integer of 1 to 10, and A is the same as the above definition.)
- A is preferably ⁇ COOM. It is preferable that M is -H, -Na, -K, -Li or -NH 4 .
- the structural unit M3 is 5 to 100 mol% with respect to the total polymerization unit, and the structural unit N3 derived from a monomer copolymerizable with the monomer represented by the general formula (1).
- the structural unit N3 is preferably a structural unit derived from tetrafluoroethylene.
- the fluoropolymer preferably has a number average molecular weight of the polymer is 0.5 ⁇ 10 4 ⁇ 75.0 ⁇ 10 4.
- the fluoropolymer is preferably a polymer in which the ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms is 50% or more, and the polymer contains an ionic group and has an ion exchange rate of 53 or less. ..
- the fluoropolymer is preferably a water-soluble polymer in which the ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms is 50% or more.
- the present disclosure also refers to polymers in which water and hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms in an amount of 50% or more, and an ionic group is contained and an ion exchange rate is 53 or less.
- a method for producing a composition which comprises the step A1 of performing ultrafiltration, microfiltration, diafiltration, or a combination thereof for the composition to be contained.
- the polymer is preferably a polymer having a number average molecular weight of 0.5 ⁇ 10 4 to 75.0 ⁇ 10 4 .
- the polymer is preferably a water-soluble polymer.
- the present disclosure also comprises ultrafiltration, microfiltration or dialysis membrane treatment of compositions containing water and water-soluble polymers in which hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms in an amount of 50% or more.
- it is a method for producing a composition, which comprises a step A2 for carrying out a combination thereof.
- the ultrafiltration, microfiltration or dialysis membrane treatment is preferably performed at a temperature of 20 ° C. or higher.
- the ultrafiltration is preferably performed using an ultrafiltration membrane having a molecular weight cut-off of 1.5 ⁇ 10 4 Da or more.
- CX 2 CY (-CZ 2- O-Rf-A) (1)
- X is the same or different, -H or -F
- Y is -H, -F, an alkyl group or a fluorine-containing alkyl group
- Z is the same or different, -H,-.
- F an alkyl group or a fluoroalkyl group.
- Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- A is -COOM,-.
- M is, -H, a metal atom, -NR 7 4, good imidazolium be substituted, substituted It is a pyridinium which may have a substituent or a phosphonium which may have a substituent, and R 7 is an H or an organic group), provided that at least one of X, Y and Z contains a fluorine atom.
- a fluoropolymer which is a polymer containing the structural unit M3 derived from the monomer represented by The composition is characterized in that the content of a compound having a molecular weight of 700 or more and 3000 or less is 3.5% or less with respect to the fluoropolymer.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less with respect to the fluoropolymer.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the fluoropolymer.
- Rf is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having an ether bond and having 2 to 12 carbon atoms.
- the structural unit M3 is preferably a structural unit (1A) based on a monomer represented by the following general formula (1A).
- CH 2 CF (-CF 2- O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)
- the structural unit M3 is preferably a structural unit (1a) based on the fluoroallyl ether compound represented by the following general formula (1a).
- CX 2 CFCF 2- O- (CF (CF 3 ) CF 2 O) n5- CF (CF 3 ) -A (1a) (In the equation, each X is the same and represents F or H. n5 represents 0 or an integer of 1 to 10, and A is the same as the above definition.)
- A is preferably ⁇ COOM.
- M is -H, -Na, -K, -Li or -NH 4 .
- the structural unit M3 is 5 to 100 mol% with respect to the total polymerization unit, and the structural unit N3 derived from a monomer copolymerizable with the monomer represented by the general formula (1).
- the fluoropolymer preferably has a number average molecular weight of the polymer is 0.5 ⁇ 10 4 ⁇ 75.0 ⁇ 10 4.
- the fluoropolymer preferably has a hydrogen atom bonded to a carbon atom substituted with a fluorine atom in an amount of 50% or more, contains an ionic group, and has an ion exchange rate of 53 or less.
- the fluoropolymer is preferably a water-soluble polymer in which the ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms is 50% or more.
- the present disclosure also refers to polymers in which water and hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms in an amount of 50% or more, and an ionic group is contained and the ion exchange rate is 53 or less.
- the composition is characterized in that the content of a compound having a molecular weight of 700 or more and 3000 or less is 3.5% or less with respect to the polymer.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less with respect to the polymer.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the polymer.
- the polymer is preferably a polymer having a number average molecular weight of 0.5 ⁇ 10 4 to 75.0 ⁇ 10 4 .
- the polymer is preferably a water-soluble polymer.
- the present disclosure also includes water and a water-soluble polymer in which a hydrogen atom bonded to a carbon atom is replaced with a fluorine atom in an amount of 50% or more.
- the composition is characterized in that the content of the compound having a molecular weight of 700 or more and 3000 or less is 3.5% or less with respect to the water-soluble polymer.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less with respect to the water-soluble polymer.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the water-soluble polymer.
- CX 2 CY (-CZ 2- O-Rf-A) (1)
- X is the same or different, -H or -F
- Y is -H, -F, an alkyl group or a fluorine-containing alkyl group
- Z is the same or different, -H,-.
- F an alkyl group or a fluoroalkyl group.
- Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- A is -COOM,-.
- a fluoropolymer which is a polymer containing the structural unit M3 derived from the monomer represented by The composition is characterized in that the content of the monomer dimer and trimmer forming the structural unit constituting the fluoropolymer is 2.0% or less with respect to the fluoropolymer.
- the fluoropolymer is preferably a polymer in which the ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms is 50% or more, and the polymer contains an ionic group and has an ion exchange rate of 53 or less. ..
- the fluoropolymer is preferably a water-soluble polymer in which the ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms is 50% or more.
- the present disclosure also refers to polymers in which water and hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms in an amount of 50% or more, and an ionic group is contained and the ion exchange rate is 53 or less.
- the composition is characterized in that the content of the monomer dimer and trimmer forming the structural unit constituting the polymer is 2.0% or less with respect to the polymer.
- the polymer is preferably a water-soluble polymer.
- the present disclosure also includes water and a water-soluble polymer in which a hydrogen atom bonded to a carbon atom is replaced with a fluorine atom in an amount of 50% or more.
- the composition is characterized in that the content of the monomer dimer and trimmer forming the structural unit constituting the water-soluble polymer is 2.0% or less with respect to the water-soluble polymer.
- composition of the present disclosure is preferably a coating agent.
- the production method of the present disclosure can efficiently remove low molecular weight substances in the composition.
- the production method of the present disclosure includes step A of performing ultrafiltration, microfiltration, dialysis membrane treatment, or a combination thereof of a composition containing water and a fluoropolymer, and the fluoropolymer is a general formula ( 1):
- CX 2 CY (-CZ 2- O-Rf-A) (1)
- X is the same or different, -H or -F
- Y is -H, -F, an alkyl group or a fluorine-containing alkyl group
- Z is the same or different, -H,-.
- F an alkyl group or a fluoroalkyl group.
- Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- A is -COOM,-. SO 3 M, -OSO 3 M or -C (CF 3) 2 OM ( M is, -H, a metal atom, -NR 7 4, good imidazolium be substituted, substituted
- M is, a pyridinium which may have a substituent or a phosphonium which may have a substituent, and R 7 is an H or an organic group), provided that at least one of X, Y and Z contains a fluorine atom.
- It is a method for producing a composition (hereinafter, also referred to as "the first production method of the present disclosure”), which is a polymer containing a structural unit M3 derived from a monomer represented by.
- a fluoropolymer composition containing a low molecular weight substance in addition to the fluoropolymer can be obtained.
- ultrafiltration, precision filtration or dialysis membrane treatment is particularly effective for the composition containing the above-mentioned specific fluoropolymer, and a low molecular weight substance (for example, a molecular weight of 700 or more and 3000 or less) is particularly effective.
- the composition obtained by the first production method of the present disclosure may be an aqueous solution.
- X is ⁇ H or ⁇ F. Both of X may be -F, and at least one may be -H. For example, one may be -F and the other may be -H, or both may be -H.
- Y is an —H, —F, an alkyl group or a fluorine-containing alkyl group.
- the alkyl group may be an alkyl group containing no fluorine atom and may have 1 or more carbon atoms.
- the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less.
- the fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms.
- the fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less.
- Y, -H, -F or -CF 3 is preferable, and -F is more preferable.
- Z is the same or different, and is an —H, —F, alkyl group or fluoroalkyl group.
- the alkyl group may be an alkyl group containing no fluorine atom and may have 1 or more carbon atoms.
- the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less.
- the fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms.
- the fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less.
- -H, -F or -CF 3 is preferable, and -F is more preferable.
- At least one of the above X, Y and Z contains a fluorine atom.
- X may be -H and Y and Z may be -F.
- the Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- the fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is a terminal and contains an ether bond between carbon carbons.
- the fluorine-containing alkylene group preferably has 2 or more carbon atoms.
- the number of carbon atoms of the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.
- fluorinated alkylene group -CF 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 CH 2 -, - CF (CF 3) - , -CF (CF 3) CF 2 -, - CF (CF 3) CH 2 - and the like.
- the fluorine-containing alkylene group is preferably a perfluoroalkylene group.
- the fluorine-containing alkylene group having an ether bond preferably has 3 or more carbon atoms.
- the number of carbon atoms of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less.
- Examples of the fluorine-containing alkylene group having an ether bond include the following formula: (In the formula, Z 1 is F or CF 3 ; Z 2 and Z 3 are H or F, respectively; Z 4 is H, F or CF 3 ; p1 + q1 + r1 is an integer of 1 to 10; s1 is 0 or 1; t1 is 0. It is also preferable that it is a divalent group represented by (an integer of ⁇ 5).
- n is an integer of 1 to 10
- n is an integer of 1 to 10
- M is, -H, a metal atom, -NR 7 4, a substituent It is an imidazolium which may have, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, and R 7 is H or an organic group).
- R 7 an organic group of H or C 1-10 is preferable, an organic group of H or C 1-4 is more preferable, and an alkyl group of H or C 1-4 is further preferable.
- the metal atom examples include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li are preferable.
- M -H, preferably is a metal atom or -NR 7 4, -H, alkali metal (Group 1), alkaline earth metal (Group 2) or -NR 7 4, more preferably, -H, -Na , -K, -Li or -NH 4 are more preferable, -Na, preferably from -K or -NH 4 further particularly preferred -Na or -NH 4, -NH 4 is most preferred.
- -COOM or -SO 3 M is preferable, and -COOM is more preferable.
- CX 2 CFCF 2- O- (CF (CF 3 ) CF 2 O) n5- CF (CF 3 ) -A
- each X is the same and represents F or H.
- N5 represents 0 or an integer of 1 to 10, and A is the same as the above definition.
- the unit (1a) is exemplified as a suitable one.
- n5 is preferably 0 or an integer of 1 to 5 in that fluoropolymer particles having a small primary particle diameter can be obtained, and more preferably 0, 1 or 2. , 0 or 1, more preferably.
- the above-mentioned A is preferably ⁇ COOM in that appropriate water solubility and surface activity can be obtained, and the above-mentioned M is H or in that the heat resistance of the obtained molded product is improved because it does not easily remain as an impurity. It is preferably NH 4 .
- the structural unit M3 is preferably a structural unit (1A) based on a monomer represented by the following general formula (1A).
- CH 2 CF (-CF 2- O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)
- the monomer represented by the general formula (1A) has the following formula.
- Z 1 is F or CF 3 ;
- Z 2 and Z 3 are H or F, respectively;
- Z 4 is H, F or CF 3 ;
- p1 + q1 + r1 is an integer of 0 to 10;
- s1 is 0 or 1;
- t1 is 0.
- Etc. are preferably mentioned, among them
- examples of the monomer represented by the general formula (1) include a monomer represented by the following formula.
- the structural unit M3 is also preferably a structural unit (1') based on a monomer represented by the following general formula (1').
- CH 2 CFCF 2- ORf 10- COOH (1')
- Rf 10 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- the Rf 10 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- the fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is a terminal and contains an ether bond between carbon carbons.
- the fluorine-containing alkylene group preferably has 2 or more carbon atoms. Further, 30 or less is preferable, 20 or less is more preferable, and 10 or less is further preferable.
- fluorinated alkylene group -CF 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 CH 2 -, - CF (CF 3) - , -CF (CF 3) CF 2 -, - CF (CF 3) CH 2 - and the like.
- the fluorine-containing alkylene group is preferably a perfluoroalkylene group.
- the fluorine-containing alkylene group having an ether bond preferably has 3 or more carbon atoms.
- the number of carbon atoms of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less.
- Examples of the fluorine-containing alkylene group having an ether bond include the following formula: (In the formula, Z 1 is F or CF 3 ; Z 2 and Z 3 are H or F, respectively; Z 4 is H, F or CF 3 ; p1 + q1 + r1 is an integer of 1 to 10; s1 is 0 or 1; t1 is 0. It is also preferable that it is a divalent group represented by (an integer of ⁇ 5).
- n is an integer of 1 to 10
- n is an integer of 1 to 10
- the monomer represented by the general formula (1') is represented by the following formula.
- Z 1 is F or CF 3 ;
- Z 2 and Z 3 are H or F, respectively;
- Z 4 is H, F or CF 3 ;
- p1 + q1 + r1 is an integer of 0 to 10;
- s1 is 0 or 1;
- t1 is 0. Examples thereof include integers of to 5, but when Z 3 and Z 4 are both H, p1 + q1 + r1 + s1 is not 0). More specifically
- Etc. are preferably mentioned, among them
- n5 represents 0 or an integer of 1 to 10
- the fluoroallyl ether compound represented by is exemplified as a suitable one.
- the above n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1.
- the fluoropolymer may be a homopolymer composed of only the structural unit M3, or is derived from a monomer copolymerizable with the structural unit M3 and the monomer represented by the general formula (1). It may be a copolymer containing the structural unit N3. From the viewpoint of solubility in the polymerization medium, a homopolymer composed of only the structural unit M3 is preferable.
- the structural unit M3 may be the same or different at each appearance, and the fluoropolymer may contain two or more different monomer-derived structural units M3 represented by the general formula (1). Good.
- the structural unit N3 is preferably a structural unit derived from tetrafluoroethylene.
- the structural unit N3 may be the same or different at each appearance, and the fluoropolymer is derived from a monomer copolymerizable with two or more different monomers represented by the general formula (1).
- the structural unit N3 may be included.
- Rf 3 are monomers represented by a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms. ..
- Examples of the other monomer include the formula (n2-1):
- X 9 is H, F or CH 3 ;
- Rf 4 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms). Also mentioned is a monomer.
- e6 is an integer of 1 to 10.
- the content of the structural unit M3 of the fluoropolymer is preferably 1.0 mol% or more, more preferably 3.0 mol% or more, still more preferably 5.0 mol% or more, and 10 mol% or more, based on the total polymerization units.
- the above is even more preferable, 20 mol% or more is particularly preferable, and 30 mol% or more is particularly preferable. More preferably, it is 40 mol% or more, further preferably 60 mol% or more, even more preferably 80 mol% or more, particularly preferably 90 mol% or more, substantially 100 mol. % Is particularly preferable, and it is most preferably composed of only the structural unit M3.
- the content of the structural unit N3 is preferably 99.0 mol% or less, more preferably 97.0 mol% or less, further preferably 95.0 mol% or less, and 90 mol, based on the total polymerization units.
- % Or less is even more preferable, 80 mol% or less is particularly preferable, and 70 mol% or less is particularly preferable. More preferably, it is 60 mol% or less, further preferably 40 mol% or less, even more preferably 20 mol% or less, particularly preferably 10 mol% or less, and substantially 0 mol% is particularly important. It is particularly preferable that the structural unit N3 is not contained.
- the content of the structural unit derived from the fluoroallyl ether compound represented by the formula (1a) is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol% with respect to the total polymerization units.
- the above is even more preferable, 40 mol% or more is even more preferable, 60 mol% or more is particularly preferable, 80 mol% or more is particularly preferable, 90 mol% or more is particularly preferable, and substantially 100 mol% is particularly preferable. preferable.
- the content of the structural unit derived from tetrafluoroethylene is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and further preferably 60 mol% with respect to the total polymerization units.
- the following is even more preferable, 40 mol% or less is particularly preferable, 20 mol% or less is particularly more preferable, 10 mol% or less is particularly preferable, and substantially 0 mol% is particularly preferable.
- the number average molecular weight of the fluoropolymer is preferably from 0.1 ⁇ 10 4 or more, more preferably 0.2 ⁇ 10 4 or more, more preferably 0.3 ⁇ 10 4 or more, more is 0.4 ⁇ 10 4 or more by preferably, preferably in especially it is 0.5 ⁇ 10 4 or more, particularly preferably 1.0 ⁇ 10 4 or more, particularly preferably especially is 3.0 ⁇ 10 4 or more, 3.1 ⁇ 10 4 or more is most preferred. Further, preferably 75.0 ⁇ 10 4 or less, more preferably 50.0 ⁇ 10 4 or less, more preferably 40.0 ⁇ 10 4 or less, preferably in especially is 30.0 ⁇ 10 4 or less, 20.0 ⁇ 10 4 or less is particularly preferred.
- the number average molecular weight is too low, the dispersibility (property to stably disperse other components) is lowered, and there is a possibility that the product cannot be used as a dispersant. If the number average molecular weight is too high, the viscosity becomes high and handling may become complicated.
- the weight average molecular weight of the fluoropolymer is preferably from 0.2 ⁇ 10 4 or more, more preferably 0.4 ⁇ 10 4 or more, more preferably 0.6 ⁇ 10 4 or more, more is 0.8 ⁇ 10 4 or more the preferred, particularly preferred 1.0 ⁇ 10 4 or more, particularly preferably more is 5.0 ⁇ 10 4 or more, more particularly preferably 10.0 ⁇ 10 4 or more, preferably in especially is 15.0 ⁇ 10 4 or more, particularly preferred especially is 20.0 ⁇ 10 4 or more, and most preferably 25.0 ⁇ 10 4 or more. Further, preferably 150.0 ⁇ 10 4 or less, more preferably 100.0 ⁇ 10 4 or less, more preferably 60.0 ⁇ 10 4 or less, particularly preferably 50.0 ⁇ 10 4 or less, 40.0 ⁇ 10 4 or less is particularly preferable.
- the number average molecular weight and the weight average molecular weight are values for which the molecular weight is calculated by gel permeation chromatography (GPC) using monodisperse polyethylene oxide (PEO) and polyethylene glycol (PEG) manufactured by Tosoh and Agent as standards. If measurement by GPC is not possible, the number average molecular weight of the fluoropolymer can be obtained from the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. it can. The melt flow rate can be measured in accordance with JIS K 7210.
- the ratio of hydrogen atoms bonded to carbon atoms replaced with fluorine atoms is preferably 50% or more.
- the ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms is the number of fluorine atoms relative to the total number of hydrogen atoms bonded to carbon atoms and halogen atoms bonded to carbon atoms (including fluorine atoms). It is calculated as a ratio.
- the ratio of the hydrogen atom bonded to the carbon atom replaced with the fluorine atom in the above fluoropolymer is not particularly limited, but is more preferably 80% or more, further preferably 90% or more, particularly preferably 95% or more, most preferably. Is 100%.
- the fluoropolymer preferably contains an ionic group.
- the fluoropolymer preferably has an ion exchange rate (IXR) of 53 or less.
- the IXR is defined as the number of carbon atoms in the polymer backbone with respect to the ionic group.
- Precursor groups that become ionic by hydrolysis eg, -SO 2 F
- the IXR is preferably 0.5 or more, more preferably 1 or more, further preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and particularly preferably 8 or more.
- the IXR is preferably 43 or less, more preferably 33 or less, and even more preferably 23 or less.
- the ionic groups are typically distributed along the polymer backbone.
- the fluoropolymer preferably contains a polymer backbone along with a repeating side chain attached to the backbone, which side chain has an ionic group.
- the fluoropolymer preferably contains an ionic group having a pKa of less than 10, more preferably less than 7.
- the ionic group of the fluoropolymer is preferably selected from the group consisting of sulfonates, carboxylates, phosphonates, and phosphates.
- the term "sulfonate, carboxylate, phosphonate, and phosphate" is intended to refer to the respective salts, or the respective acids that can form the salts.
- the salt is preferably an alkali metal salt or an ammonium salt.
- a preferred ionic group is a sulfonate group.
- the fluoropolymer is preferably a water-soluble polymer.
- Water soluble means the property of being easily dissolved or dispersed in an aqueous medium.
- the particle size of a water-soluble polymer cannot be measured by, for example, dynamic light scattering (DLS).
- DLS dynamic light scattering
- the particle size of the water-insoluble polymer can be measured by, for example, a dynamic light scattering method (DLS).
- the fluoropolymer can be produced by a conventionally known method except that the above-mentioned monomer is used.
- the concentration of the fluoropolymer is not particularly limited and may be, for example, 0.1 to 20% by mass.
- the concentration of the fluoropolymer in the composition is preferably 18.0% by mass or less because the removal efficiency of the low molecular weight substance becomes more efficient. It is more preferably 15.0% by mass or less, further preferably 12.0% by mass or less, and particularly preferably 10.0% by mass or less.
- the concentration of the fluoropolymer is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 1.2% by mass or more, and particularly preferably 1.5% by mass or more.
- the composition containing water and the fluoropolymer may contain one single fluoropolymer, or may contain two or more different fluoropolymers.
- the pH of the composition containing water and the fluoropolymer is preferably 0 to 11, more preferably 0.5 to 8.0.
- the pH can be adjusted with a pH adjuster.
- the pH adjuster may be an acid or an alkali, and examples thereof include phosphate, sodium hydroxide, potassium hydroxide, aqueous ammonia and the like. It is also preferable that the first production method of the present disclosure includes a step of adjusting the pH of the composition containing water and the fluoropolymer to 1.0 to 7.0 before the step A.
- the composition containing water and the fluoropolymer may be obtained, for example, by polymerizing a monomer represented by the general formula (1).
- One of the preferred embodiments of the first production method of the present disclosure is to include a step of polymerizing the monomer represented by the general formula (1) (hereinafter, also referred to as “polymerization step”).
- the polymerization step is preferably carried out in an aqueous medium. That is, the first production method of the present disclosure includes a step of obtaining a composition containing water and a fluoropolymer by polymerizing the monomer represented by the general formula (1) in an aqueous medium. It is also preferable.
- the polymerization step is not limited as long as a composition containing water and a fluoropolymer can be obtained, and a known method can be adopted.
- the composition containing water and the above-mentioned fluoropolymer may be a polymerized composition obtained by polymerization, or may be a diluted or concentrated composition obtained by polymerization. Alternatively, it may be subjected to dispersion stabilization processing or the like. In order to facilitate ultrafiltration, microfiltration or dialysis membrane treatment, it is also preferable to adjust the viscosity of the composition containing the fluoropolymer by these treatments.
- the viscosity of the composition containing water and the fluoropolymer used in the step A is preferably 25 mPa ⁇ s or less because ultrafiltration, microfiltration or dialysis membrane treatment proceeds smoothly.
- the viscosity of the composition can be adjusted by, for example, a method of adjusting the number average molecular weight of the fluoropolymer, a method of adjusting the concentration of the fluoropolymer in the composition, a method of adjusting the temperature of the composition, and the like.
- low molecular weight substances can be removed by subjecting a composition containing water and a fluoropolymer to a treatment such as ultrafiltration.
- the composition containing water and the fluoropolymer used in the step A may contain a low molecular weight substance, for example, the content of the low molecular weight substance is preferably 5.0% with respect to the fluoropolymer. It is super, more preferably 5.5% or more, still more preferably 6.0% or more, or more than 2.0%.
- Examples of the low molecular weight dimer include a compound having a molecular weight of 700 or more and 3000 or less, a compound having a molecular weight of 400 or more and 3000 or less, a compound having a molecular weight of 700 or more and less than 10000, a monomer dimer and trimmer forming the structural unit M3, and a polymer described later. Examples thereof include monomeric dimers and trimmers forming structural units constituting ⁇ , and monomeric dimers and trimmers forming structural units constituting water-soluble polymers, which will be described later.
- the content of the low molecular weight substance is a value calculated from the peak area of GPC and / or a value calculated by measurement by liquid chromatography-mass spectrometry (LC / MS / MS).
- the ultrafiltration or microfiltration is not limited to the cross-flow method or the dead-end method, but the cross-flow method is preferable from the viewpoint of reducing clogging of the membrane.
- the ultrafiltration can be performed using an ultrafiltration membrane.
- the ultrafiltration can be performed using, for example, an ultrafiltration device having an ultrafiltration membrane, and a centrifugal ultrafiltration method, a batch type ultrafiltration method, a circulation type ultrafiltration method, or the like can be adopted.
- the molecular weight cut-off of the ultrafiltration membrane is usually about 0.1 ⁇ 10 4 to 30 ⁇ 10 4 Da.
- the lower limit of the molecular weight cutoff of the ultrafiltration membrane suppresses clogging of the membrane, because it can efficiently reduce the low molecular weight material, in order of preference, 0.3 ⁇ 10 4 Da or more, 0.5 ⁇ 10 4 Da or more, 1.0 ⁇ 10 4 Da or more, 1.5 ⁇ 10 4 Da or more, 2.0 ⁇ 10 4 Da or more, 3.0 ⁇ 10 4 Da or more, 5.0 ⁇ 10 4 Da or more, 8 It is 0.0 ⁇ 10 4 Da or more.
- the fractionated molecular weight is preferably 20 ⁇ 10 4 Da or less, more preferably 10 ⁇ 10 4 Da or less, from the viewpoint of reducing the low molecular weight body.
- the fractional molecular weight of the ultrafiltration membrane can be, for example, a molecular weight that can prevent 90% by passing polystyrene having a known weight average molecular weight through the membrane. Quantification of polystyrene can be performed using gel permeation chromatography.
- a compound having a molecular weight of 400 or more and 3000 or less in order to efficiently remove a compound having a molecular weight of 700 or more and 3000 or less, a compound having a molecular weight of 400 or more and 3000 or less, a compound having a molecular weight of 700 or more and less than 10000 from a composition containing a fluoropolymer, a composition containing a fluoropolymer It is preferable to carry out ultrafiltration.
- the fractional molecular weight of the ultrafiltration membrane used at this time is preferably 1.0 ⁇ 10 4 Da or more, more preferably 1.5 ⁇ 10 4 Da or more, and preferably 20.0 ⁇ 10 4 or more. It is Da or less, more preferably 10.0 ⁇ 10 4 Da or less.
- Examples of the shape of the ultrafiltration membrane include, but are not limited to, conventionally known ones, and examples thereof include a hollow fiber type, a flat membrane type, a spiral type, and a tubular type. From the viewpoint of preventing clogging, the hollow fiber type is preferable.
- the inner diameter of the hollow fiber type ultrafiltration membrane is not limited, but may be, for example, 0.1 to 2 mm. It is preferably 0.8 to 1.4 mm.
- the length of the hollow fiber type ultrafiltration membrane is not limited, but may be, for example, 0.05 to 3 m. It is preferably 0.05 to 2 m.
- the material of the extrafiltration membrane is not particularly limited, but is cellulose, cellulose ester, polysulfone, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, chlorinated polyethylene, polypropylene, polyolefin, polyvinyl alcohol. , Polymethylmethacrylate, polyacrylicnitrile, polyvinylidene fluoride, polytetrafluoroethylene and other organic materials, metals such as stainless steel, and inorganic materials such as ceramics.
- the material of the ultrafiltration membrane is preferably an organic material, more preferably chlorinated polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, acrylonitrile, polysulfone, or polyethersulfone, and polypolysulfone. Acrylonitrile or polyvinylidene fluoride is more preferred.
- ultrafiltration membrane DESAL's G-5 type, G-10 type, G-20 type, G-50 type, PW type, HWS UF type; KOCH's HFM-180, HFM- 183, HFM-251, HFM-300, HFM-116, HFM-183, HFM-300, HFK-131, HFK-328, MPT-U20, MPS-U20P, MPS-U20S; Synder's SPE1, SPE3, SPE5 , SPE10, SPE30, SPV5, SPV50, SOW30; Microza (registered trademark) UF series manufactured by Asahi Kasei Corporation; NTR7410 manufactured by Nitto Denko KK, etc.
- KOCH's HFM-180, HFM- 183, HFM-251, HFM-300, HFM-116, HFM-183, HFM-300, HFK-131, HFK-328, MPT-U20, MPS-U20P, MPS-U20S Synder'
- the ultrafiltration is preferably performed at a pressure of 0.01 MPa or more from the viewpoint of reducing low molecular weight substances. More preferably, it is 0.03 MPa or more, and even more preferably 0.05 MPa or more. From the viewpoint of pressure resistance, the pressure is preferably 0.5 MPa or less, more preferably 0.25 MPa or less, and even more preferably 0.2 MPa or less.
- the ultrafiltration is preferably performed at a flow rate of 10 mL / min or more, more preferably at a flow rate of 50 mL / min or more, and at a flow rate of 5000 mL / min or less. Is preferable, and the flow rate is more preferably 1000 mL / min or less.
- the microfiltration can be performed using a microfiltration membrane.
- Microfiltration membranes typically have an average pore diameter of 0.05-1.0 ⁇ m. Since the microfiltration membrane can efficiently reduce low molecular weight substances, it is preferable that the average pore diameter is 0.1 ⁇ m or more. It is more preferably 0.075 ⁇ m or more, and further preferably 0.1 ⁇ m or more. Moreover, it is preferable that the average pore diameter is 1.00 ⁇ m or less. More preferably, the average pore diameter is 0.50 ⁇ m or less, and even more preferably 0.25 ⁇ m or less.
- the average pore diameter of the microfiltration membrane can be measured according to ASTM F 316-03 (bubble point method).
- the shape of the microfiltration membrane is not limited to those conventionally known, and examples thereof include a hollow fiber type, a flat membrane type, a spiral type, and a tubular type. From the viewpoint of preventing clogging, the hollow fiber type is preferable.
- the inner diameter of the hollow fiber type ultrafiltration membrane is not limited, but may be, for example, 0.1 to 2 mm. It is preferably 0.8 to 1.4 mm.
- the length of the hollow fiber type ultrafiltration membrane is not limited, but may be, for example, 0.05 to 3 m. It is preferably 0.05 to 2 m.
- Examples of the material of the precision filter membrane include cellulose-based, aromatic polyamide, polyvinyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate, polytetrafluoroethylene, ceramics, and metal. Be done. Among them, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate, or polytetrafluoroethylene are preferable, and polyvinylidene nitrile or polyvinylidene fluoride is particularly preferable.
- NGK Insulator's Cefil Asahi Kasei's Microza U series, Microza P series; Sumitomo Electric's Poaflon SPMW, Poaflon OPMW, Poaflon PM; Toray's Trefil; Micro Examples thereof include NADIR MP005 and NADIR MV020 manufactured by Dyne Nadia; and X-flow manufactured by Norit.
- the microfiltration is preferably performed at a pressure of 0.01 MPa or more from the viewpoint of reducing low molecular weight substances. More preferably, it is 0.03 MPa or more, and even more preferably 0.05 MPa or more. From the viewpoint of pressure resistance, the pressure is preferably 0.5 MPa or less, more preferably 0.25 MPa or less, and even more preferably 0.2 MPa or less.
- the microfiltration is preferably performed at a flow rate of 10 mL / min or more, more preferably at a flow rate of 50 mL / min or more, and at a flow rate of 5000 mL / min or less. It is preferably carried out at a flow rate of 1000 mL / min or less.
- the dialysis membrane treatment is performed using a dialysis membrane.
- the dialysis membrane usually has a molecular weight cut-off of 0.05 ⁇ 10 4 to 100 ⁇ 10 4 Da.
- the dialysis membrane suppresses clogging of the membrane, because it can efficiently colored reduced, it is preferable fractional molecular weight of 0.3 ⁇ 10 4 Da or more.
- the molecular weight cut-off is more preferably 0.5 ⁇ 10 4 Da or more, further preferably 1.0 ⁇ 10 4 Da or more, even more preferably 1.5 ⁇ 10 4 Da or more, and 2.0 ⁇ 10 4 Da or more.
- the above is particularly preferable, 3.0 ⁇ 10 4 Da or more is particularly preferable, and 5.0 ⁇ 10 4 Da or more is most preferable.
- the molecular weight cut-off may be 8.0 ⁇ 10 4 Da or more.
- the molecular weight cut-off is preferably 20 ⁇ 10 4 Da or less, more preferably 10 ⁇ 10 4 Da or less, from the viewpoint of reducing coloration.
- the molecular weight cut-off of the dialysis membrane can be measured, for example, by the same method as that of the ultrafiltration membrane.
- a monomer dimer and trimmer forming the structural unit M3, a monomer dimer and trimmer forming the structural unit constituting the polymer ⁇ described later, and a structural unit constituting the water-soluble polymer described later are formed.
- a dialysis membrane treatment on the composition containing the fluoropolymer.
- the fractional molecular weight of the dialysis membrane used at this time is preferably 0.3 ⁇ 10 4 Da or more, more preferably 0.5 ⁇ 10 4 Da or more, and preferably 8.0 ⁇ 10 4 Da or less. It is more preferably 5.0 ⁇ 10 4 Da or less.
- the material of the dialysis membrane is not particularly limited, and examples thereof include polyethylene, cellulose, polyacrylonitrile, polymethylmethacrylate, ethylene vinyl alcohol copolymer, polysulfone, polyamide, and polyester polymer alloy.
- dialysis membrane examples include Spectra / Por (registered trademark) Float-A-Lyzer, Tube-A-Lyzer, Dialysis tubing, 6Dialysis tubing, and 7Dialysis tubing manufactured by Spectrum Laboratories.
- the ultrafiltration, microfiltration or dialysis membrane treatment is preferably performed at a temperature of 10 ° C. or higher. More preferably, it is 15 ° C. or higher, further preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher. By setting the temperature in the above range, the low molecular weight substance can be reduced more efficiently.
- the temperature is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, further preferably 70 ° C. or lower, and particularly preferably 60 ° C. or lower.
- the step A may include adding water to the composition containing water and the fluoropolymer, and the water may be added stepwise or continuously. Good. Further, a step of adding a pH adjuster to the composition containing water and the above-mentioned fluoropolymer may be included.
- ultrafiltration or microfiltration is preferable, and ultrafiltration is more preferable.
- the end point of the ultrafiltration, microfiltration or dialysis membrane treatment may be appropriately determined and is not limited.
- backwashing with water may be performed about once for about 1 to 24 hours during the filtration step.
- the first production method of the present disclosure it is possible to obtain a composition containing the above-mentioned fluoropolymer and having a reduced content of low molecular weight substances.
- the present disclosure also discloses a polymer in which water and a hydrogen atom bonded to a carbon atom are replaced with a fluorine atom in an amount of 50% or more, and an ionic group is contained, and an ion exchange rate is 53 or less.
- a method for producing a composition which comprises the step A1 of performing ultrafiltration, microfiltration, diafiltration, or a combination thereof for a composition containing (hereinafter, also referred to as “polymer ⁇ ”). Also referred to as “the second manufacturing method of the present disclosure”).
- the composition obtained by the second production method of the present disclosure may be an aqueous solution.
- the ratio of the hydrogen atom bonded to the carbon atom replaced with the fluorine atom is 50% or more, the ionic group is contained, and the ion exchange rate is 53. All of the same methods as those of the first production method of the present disclosure can be adopted except that the composition containing the polymer ⁇ described below is used.
- the "ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms" is the number of fluorine atoms relative to the total number of hydrogen atoms bonded to carbon atoms and halogen atoms bonded to carbon atoms (including fluorine atoms). It is calculated as a ratio of numbers.
- the polymer ⁇ is not particularly limited, and the ratio of hydrogen atoms bonded to carbon atoms replaced with fluorine atoms in the above-mentioned fluoropolymer is 50% or more, and an ionic group (anionic group) is used.
- a polymer containing the above-mentioned and having an ion exchange rate of 53 or less can be used, and the ratio of hydrogen atoms bonded to carbon atoms other than the above-mentioned fluoropolymer replaced with fluorine atoms is 50% or more, and A polymer containing an ionic group (anionic group) and having an ion exchange rate of 53 or less can also be used.
- Examples of the polymer ⁇ include a polymer containing a structural unit (I) based on a monomer represented by the general formula (I).
- the polymer ⁇ preferably contains two or more structural units (I).
- CX 1 X 3 CX 2 R-CZ 1 Z 2- A 0 (I)
- X 1 and X 3 are independently F, Cl, H or CF 3 , respectively;
- X 2 is an H, F, alkyl group or fluorine-containing alkyl group;
- a 0 is an anion. It is a sex group;
- R is a linking group;
- Z 1 and Z 2 are independently H, F, alkyl groups or fluorine-containing alkyl groups).
- As X 2 , F, Cl, H or CF 3 is preferable.
- Z 1 and Z 2 F or CF 3 is preferable, and one is F and the other is CF 3 .
- the anionic groups, sulfate groups, carboxylate groups, phosphate groups, phosphonate groups, sulfonate groups, or,, -C (CF 3) in 2 OM (wherein, M represents, -H, a metal atom, -NR 7 4, Imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, and R 7 is H or an organic group) is preferable. ..
- the polymer ⁇ may contain only the structural unit (I) based on one kind of monomer represented by the general formula (I), or two or more kinds represented by the general formula (I). It may contain the structural unit (I) based on the monomer of.
- R is a linking group.
- linking group refers to a divalent linking group.
- the linking group may be a single bond and preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, or 8 or more. It may be 10 or more, and may be 20 or more. The upper limit is not limited, but may be 100 or less, and may be 50 or less, for example.
- the linking group may be chain or branched chain, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and optionally one or more selected from the group consisting of sulfur, oxygen, and nitrogen. It may contain a heteroatom and optionally contain one or more functional groups selected from the group consisting of esters, amides, sulfonamides, carbonyls, carbonates, urethanes, ureas and carbamate.
- the linking group does not contain a carbon atom and may be a catenary heteroatom such as oxygen, sulfur or nitrogen.
- R is preferably, for example, a catenary heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.
- R When R is a divalent organic group, the hydrogen atom bonded to the carbon atom may be replaced with a halogen other than fluorine, for example, chlorine, and may or may not contain a double bond. Further, R may be either chain-shaped or branched-chain-shaped, and may be either cyclic or acyclic. Further, R may contain a functional group (for example, ester, ether, ketone, amine, halide, etc.).
- R may also be a non-fluorinated divalent organic group or a partially fluorinated or perfluorinated divalent organic group.
- R for example, a hydrocarbon group in which a fluorine atom is not bonded to a carbon atom, a hydrocarbon group in which a part of hydrogen atoms bonded to a carbon atom is replaced with a fluorine atom, or a hydrogen atom bonded to a carbon atom. All of may be hydrocarbon groups substituted with fluorine atoms, which may contain oxygen atoms, double bonds, or functional groups.
- R is preferably a hydrocarbon group having 1 to 100 carbon atoms which may contain an ether bond, and the hydrocarbon group has some or all of the hydrogen atoms bonded to the carbon atoms substituted with fluorine. You may.
- R preferably- (CH 2 ) a -,-(CF 2 ) a- , -O- (CF 2 ) a -,-(CF 2 ) a- O- (CF 2 ) b-, -O ( CF 2 ) a- O- (CF 2 ) b -,-(CF 2 ) a- [O- (CF 2 ) b ] c- , -O (CF 2 ) a- [O- (CF 2 ) b ] c -,-[(CF 2 ) a- O] b -[(CF 2 ) c- O] d- , -O [(CF 2 ) a- O] b -[(CF 2 ) c- O] d- , -O [(CF 2 ) a- O] b -[(CF 2 ) c- O] d -, -O [CF 2 ) a- O] b -
- a, b, c and d are independently at least one or more.
- a, b, c and d may be independently 2 or more, 3 or more, 4 or more, 10 or more, and 20 or more.
- the upper limit of a, b, c and d is, for example, 100.
- the general formula (r1) -CF 2 -O- (CX 6 2) e - ⁇ O-CF (CF 3) ⁇ f - (O) g - (r1)
- X 6 is H, F or CF 3 , respectively, e is an integer of 0 to 3, f is an integer of 0 to 3, and g is 0 or 1).
- a divalent group is preferred, and the general formula (r2): -CF 2- O- (CX 7 2 ) e- (O) g- (r2)
- a divalent group represented by in the formula, X 7 is independently H, F or CF 3 , e is an integer of 0 to 3, and g is 0 or 1) is more preferred.
- R represents may contain an oxygen atom, a perfluoroalkylene group is preferred, and specifically, -CF 2 -O -, - CF 2 -O-CF 2 -, - CF 2 -O-CF 2 CF 2 -, - CF 2 -O -CF (CF 3) -, - CF 2 -O-CF (CF 3) CF 2 -, or, -CF 2 -O-CF (CF 3) CF 2 -O- Is preferable.
- the general formula (I) -R-CZ 1 Z 2- the general formula (s1): -CF 2 -O- (CX 6 2) e - ⁇ O-CF (CF 3) ⁇ f - (O) g -CZ 1 Z 2 - (s1)
- X 6 are independently H, F or CF 3
- e is an integer of 0 to 3
- f is an integer of 0 to 3
- g is 0 or 1
- Z 1 And Z 2 are each independently represented by H, F, an alkyl group or a fluorine-containing alkyl group)
- Z 1 and Z 2 are F or CF 3. More preferably, one is F and the other is CF 3 .
- -R-CZ 1 Z 2 - as the general formula (s2): -CF 2- O- (CX 7 2 ) e- (O) g -CZ 1 Z 2- (s2)
- X 7 is independently H, F or CF 3
- e is an integer from 0 to 3
- g is 0 or 1
- Z 1 and Z 2 are independent, respectively. It is preferably represented by H, F, an alkyl group or a fluorine-containing alkyl group)
- Z 1 and Z 2 are more preferably F or CF 3 , one is F and the other is CF. It is more preferably 3 .
- the polymer ⁇ is highly fluorinated.
- Polymers except for anionic groups (A 0 ) such as, for example, phosphate group moieties (eg, CH 2 OP (O) (OM) 2 ) and sulfate group moieties (eg, CH 2 OS (O) 2 OM).
- a 0 anionic groups
- phosphate group moieties eg, CH 2 OP (O) (OM) 2
- sulfate group moieties eg, CH 2 OS (O) 2 OM
- 80% or more, 90% or more, 95% or more, or 100% of the CH bond in ⁇ is substituted with the CF bond.
- the ratio of the hydrogen atom bonded to the carbon atom replaced with the fluorine atom in the polymer ⁇ is 50% or more, and is not particularly limited, but is preferably 80% or more, more preferably 90% or more, still more preferably 95. % Or more, particularly preferably 100%.
- the polymer ⁇ has a CF bond and does not have a CH bond, except for the anionic group (A 0 ). That is, in the general formula (I), all of X 1 , X 2 , and X 3 are F, and R is preferably a perfluoroalkylene group having 1 or more carbon atoms, and the perfluoroalkylene group is It may be chained or branched chained, cyclic or acyclic, and may contain at least one catenary heteroatom. The number of carbon atoms of the perfluoroalkylene group may be 2 to 20, and may be 4 to 18.
- the polymer ⁇ may be partially fluorinated. That is, it is also preferable that the polymer ⁇ has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom, except for the anionic group (A 0 ).
- the anionic group (A 0 ) is -SO 3 M, -OSO 3 M, -COOM, -SO 2 NR'CH 2 COOM, -CH 2 OP (O) (OM) 2 , [-CH 2 O] 2.
- M is, H, a metal atom, NR 7 4, which may imidazolium substituted, a good phosphonium also have a pyridinium which may have a substituent or substituents, R 7 Is an H or an organic group.
- Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li are preferable.
- the M, -H preferably a metal atom or NR 7 4, -H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 7 4, more preferably, -H, -Na, -K , more preferably -Li or NH 4, -Na, preferably from -K or NH 4 further particularly preferred -Na, or NH 4, -NH 4 is most preferred.
- each structural unit (I) may have a different anionic group or may have the same anionic group.
- the polymer ⁇ is also preferably a polymer containing a structural unit (Ia) based on the monomer represented by the general formula (Ia).
- CF 2 CF-O-Rf 0- A 0 (Ia)
- a 0 is an anionic group and Rf 0 is hyperfluorinated, even if it is chain or branched chain, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted.
- Rf 0 is hyperfluorinated, even if it is chain or branched chain, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted.
- it is a perfluorinated divalent linking group that optionally additionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.
- the polymer ⁇ is also preferably a polymer containing a structural unit (Ib) based on the monomer represented by the general formula (Ib).
- CH 2 CH-O-Rf 0- A 0 (Ib) (In the formula, A 0 is an anionic group and Rf 0 is a perfluorinated divalent linking group as defined by formula Ia.)
- the polymer ⁇ is also preferably a polymer containing a structural unit (Ic) based on the monomer represented by the general formula (Ic).
- CH 2 CF-O-Rf 0- A 0 (Ic) (In the formula, A 0 is an anionic group and Rf 0 is a perfluorinated divalent linking group as defined by formula Ia.)
- a 0 is one of the preferred forms being a sulfate group.
- a 0 is, for example, -CH 2 OSO 3 M, -CH 2 CH 2 OSO 3 M, or -SO 2 NR'CH 2 CH 2 OSO 3 M, in which R'is H or the number of carbon atoms. It is an alkyl group of 1 to 4, and M is the same as above.
- a 0 is a sulfonate group.
- a 0 is, for example, -SO 3 M, and in the formula, M is the same as above.
- M is the same as above.
- a 0 is a carboxylate group.
- a 0 is, for example, COOM or SO 2 NR'CH 2 COOM, in which R'is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.
- a 0 is a phosphate group.
- a 0 for example, -CH 2 OP (O) (OM) 2 , [-CH 2 O] 2 P (O) (OM), -CH 2 CH 2 OP (O) (OM) 2 , [-CH 2 O CH 2 CH 2 O] 2 P (O) (OM), [-SO 2 NR'CH 2 CH 2 O] 2 P (O) (OM) or SO 2 NR'CH 2 CH 2 OP (O) (OM) ) 2
- R' is an alkyl group having 1 to 4 carbon atoms
- M is the same as above.
- a 0 is also one of preferred embodiments it is a phosphonate group.
- CF 2 CF (OCF 2 CF 2 P (O) (OM) 2 )
- CF 2 CF (O (O (O))
- M is, -H, a metal atom, -NR 7 4, good imidazolium be substituted, substituted It is a pyridinium which may have a substituent or a phosphonium which may have a substituent, and R 7 is an H or an organic group), provided that at least one of X, Y and Z contains a fluorine atom).
- Examples thereof include polymers containing the structural unit M3 derived from the above-mentioned monomers.
- the structural unit M3 contained in the polymer ⁇ is the same as the structural unit M3 contained in the fluoropolymer described above, and the preferred configuration is also the same.
- the polymer ⁇ is also preferably a polymer containing the structural unit (2) based on the monomer represented by the general formula (2).
- CX 2 CY (-O-Rf-A) (2)
- X is the same or different, —H or F
- Y is —H, —F, an alkyl group or a fluorine-containing alkyl group
- Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms.
- it is a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- A is the same as described above.
- X is ⁇ H or F. Both of X may be -F, and at least one may be -H. For example, one may be -F and the other may be -H, or both may be -H.
- Y is an —H, —F, an alkyl group or a fluorine-containing alkyl group.
- the alkyl group is an alkyl group that does not contain a fluorine atom and may have 1 or more carbon atoms.
- the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less.
- the fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms.
- the fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less.
- Y, -H, -F or CF 3 is preferable, and -F is more preferable.
- X and Y contains a fluorine atom.
- X may be -H and Y and Z may be -F.
- the Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- the fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is a terminal and contains an ether bond between carbon carbons.
- the fluorine-containing alkylene group of Rf preferably has 2 or more carbon atoms. Further, 30 or less is preferable, 20 or less is more preferable, and 10 or less is further preferable. Examples of the fluorine-containing alkylene group, -CF 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 CH 2 -, - CF (CF 3) -, -CF (CF 3) CF 2 - , - CF (CF 3) CH 2 - and the like.
- the fluorine-containing alkylene group is preferably a perfluoroalkylene group.
- the monomer represented by the general formula (2) is at least selected from the group consisting of the monomers represented by the general formulas (2a), (2b), (2c), (2d) and (2e).
- One type is preferable.
- CF 2 CF-O- (CF 2 ) n1- A (2a) (In the formula, n1 represents an integer from 1 to 10, and A is the same as above.)
- CF 2 CF-O- (CF 2 C (CF 3 ) F) n2- A (2b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as the above definition.)
- CF 2 CF-O- (CFX 1 ) n3- A (2c) (In the formula, X 1 represents F or CF 3 , n 3 represents an integer of 1 to 10, and A is the same as the above definition.)
- CF 2 CF-O- (CF 2 CFX 1 O) n4- (CF 2 ) n6- A (2d) (In the formula
- n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less.
- 2 COMM M is the same as the above definition in the formula).
- n2 is preferably an integer of 3 or less in terms of water solubility.
- n3 is preferably 5 or less integer in terms of water-soluble, the A is preferably -COOM, the M is preferably H or NH 4 ..
- X 1 is preferably ⁇ CF 3 in terms of water solubility
- n4 is preferably an integer of 5 or less in terms of water solubility
- A is ⁇ COMM. It is preferable that M is H or NH 4 .
- n5 is preferably an integer of 5 or less in terms of water-soluble, A is preferably a -COOM, M is preferably H or NH 4.
- the polymer ⁇ is also preferably a polymer containing the structural unit (3) based on the monomer represented by the general formula (3).
- CX 2 CY (-Rf-A) (3)
- X is the same or different, —H or F
- Y is —H, —F, an alkyl group or a fluorine-containing alkyl group
- Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms.
- it is a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- A is the same as described above.
- the fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is a terminal and contains an ether bond between carbon carbons.
- Rf is preferably a fluorine-containing alkylene group having 1 to 40 carbon atoms. In the general formula (3), it is preferable that at least one of X and Y contains a fluorine atom.
- the monomer represented by the above definition, and the general formula (3b): CF 2 CF- (CF 2 C (CF 3 ) F) n2- A (3b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as the above definition.) At least one selected from the group consisting of monomers represented by the above is preferable.
- A is, -SO 3 M or COOM is preferably, M, H, a metal atom, NR 7 4, good imidazolium be substituted, substituted Pyridinium which may have a group or phosphonium which may have a substituent is preferable.
- R 7 represents H or an organic group.
- n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less.
- A is preferably -COOM, M is preferably H or NH 4.
- n2 is in terms of water-soluble, preferably 3 or less an integer, A is preferably a -COOM, M is preferably H or NH 4.
- the polymer ⁇ at least one selected from the group consisting of a polymer containing the structural unit M3, a polymer containing the structural unit (2), and a polymer containing the structural unit (3) is preferable, and the structure is preferable.
- a polymer containing the unit M3 is more preferable.
- a polymer ⁇ containing a structural unit (II) based on a monomer represented by the general formula (II) can also be mentioned.
- the polymer ⁇ preferably contains two or more structural units (II).
- CX 1 X 3 CX 2 R II (-CZ 1 Z 2- A 0 ) nII (II) (In the formula, X 1 , X 2 , X 3 , A 0 , Z 1 and Z 2 are the same as the above definitions, R II is a (nII + 1) valence linking group, and n II is an integer of 2 or more)
- nII is an integer of 2 or more, preferably 2.
- Z 1 , Z 2 and A 0 may be the same or different.
- Examples of the monomer represented by the general formula (II) include a monomer represented by the general formula (1-II) and a monomer represented by the general formula (2-II).
- CF 2 CF-CF 2- O-Q F1 -CF (-Q F2- CZ 1 Z 2- A) 2 (1-II) (In the formula, Z 1 , Z 2 and A are the same as the above definitions, and Q F1 and Q F 2 are the same or different, and may contain a single bond, an ether bond between carbon carbons, and a fluorine-containing alkylene group or carbon.
- CF 2 CF-O-Q F1 -CF (-Q F2- CZ 1 Z 2- A) 2 (2-II) (In the formula, Z 1 , Z 2 , A, Q F1 and Q F 2 are the same as the above definitions)
- the polymer ⁇ includes trifluoroethylene, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), vinyl fluoride (VF), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), hexafluoroisobutylene, and the like.
- the polymer ⁇ may also contain structural units based on non-fluorine-containing monomers.
- the non-fluorinated monomer may be a monomer having a radically polymerizable ethylenically unsaturated bond.
- non-fluorine-containing monomer at least one selected from the group consisting of acrylic acid esters, methacrylic acid esters, unsaturated carboxylic acids, and hydrolyzable silyl group-containing monomers is preferable. Further, as the non-fluorine-containing monomer, it is selected from the group consisting of at least one monomer selected from the group consisting of acrylic acid ester and methacrylic acid ester, unsaturated carboxylic acids, and hydrolyzable silyl group-containing monomer. At least one type is more preferable. In addition, a monomer having a radically polymerizable ethylenically unsaturated bond may be used in combination.
- acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms or a methacrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms is preferable.
- acrylic acid alkyl esters and methacrylate alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, n-propyl methacrylate, ethyl methacrylate, n-butyl methacrylate and isopropyl.
- acrylic acid alkyl esters such as methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate.
- the above-mentioned acrylic acid alkyl ester or methacrylic acid alkyl ester includes 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and methacrylic acid.
- It may be a hydroxyl group-containing acrylic monomer having a hydroxyl group and a (meth) acryloyl group in a molecule such as 4-hydroxybutyl acid.
- acrylic acid esters or methacrylic acid esters may be used alone or in combination of two or more, and are preferably n-butyl acrylate and methyl methacrylate.
- At least one (meth) acrylic acid alkyl ester selected from the group consisting of methyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate is preferable. ..
- the acrylic acid ester or methacrylic acid ester does not contain a hydrolyzable silyl group.
- acrylic acid ester or methacrylic acid ester a combination of n-butyl acrylate and methyl methacrylate or a combination of n-butyl acrylate, methyl methacrylate and 2-ethylhexyl methacrylate is more preferable, and n-butyl acrylate and methyl methacrylate are used.
- a combination with 2-ethylhexyl methacrylate is particularly preferred.
- unsaturated carboxylic acids include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, and itaconic acid.
- unsaturated carboxylic acids include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, and itaconic acid.
- itaconic acid monoester maleic acid, maleic acid monoester, maleic acid anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, and undecylene acid.
- acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, maleic acid monoester because of its low homopolymerizability and difficulty in forming homopolymers and easy control of the introduction of carboxyl groups.
- At least one selected from the group consisting of fumaric acid, fumaric acid monoester, 3-allyloxypropionic acid, and undecyleneic acid is preferable.
- CH 2 CHCOO (CH 2 ) 3 Si (OCH 3 ) 3
- CH 2 CHCOO (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2
- CH 2 CHCOO (CH 2 ) 3 Si (OC 2 H 5 ) 3
- CH 2 CHCOO (CH 2 ) 3 Si (CH 3 ) (OC 2 H 5 ) 2
- CH 2 CHCOO (CH 2 ) 3 Si (CH 3 ) (OC 2 H 5 ) 2
- CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3
- CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2
- CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OC 2 H 5 ) 3
- CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OC 2 H 5 ) 3
- CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OC 2
- hydrolyzable silyl group-containing monomers ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, and ⁇ -methacryloxypropyl At least one selected from the group consisting of methyldiethoxysilane is preferable, and ⁇ -methacryloxypropyltriethoxysilane is more preferable.
- hydroxyl group-containing alkyl vinyl ethers examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 4-hydroxy-2.
- examples thereof include -methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.
- At least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is preferable because of its excellent polymerization reactivity.
- vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatic acid, vinyl laurate, vinyl stearate, vinyl cyclohexyl carboxylate, and benzoate.
- vinyl acid acid parat-butyl vinyl benzoate and the like.
- ⁇ -olefins examples include ethylene, propylene, n-butene, isobutene and styrene.
- the content of the structural unit (I) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass. % Or more is particularly preferable, 95% by mass or more is particularly preferable, and 99% by mass or more is most preferable.
- the content of the structural unit M3 is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass.
- the above is particularly preferable, 95% by mass or more is particularly preferable, and 99% by mass or more is most preferable.
- the total content of the structural unit based on the fluorine-containing monomer and the structural unit based on the non-fluorine-containing monomer is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less. , 20% by mass or less is even more preferable, 10% by mass or less is particularly preferable, 5% by mass or less is particularly preferable, and 1% by mass or less is most preferable.
- the number average molecular weight of the polymer ⁇ is preferably is 0.1 ⁇ 10 4 or more, more preferably 0.2 ⁇ 10 4 or more, more preferably 0.3 ⁇ 10 4 or more, 0.4 ⁇ 10 4 or more Even more preferably, preferably in especially it is 0.5 ⁇ 10 4 or more, particularly preferably 1.0 ⁇ 10 4 or more, particularly preferably especially is 3.0 ⁇ 10 4 or more, 3.1 ⁇ 10 4 or more is most preferred. Further, preferably 75.0 ⁇ 10 4 or less, more preferably 50.0 ⁇ 10 4 or less, more preferably 40.0 ⁇ 10 4 or less, preferably in especially is 30.0 ⁇ 10 4 or less, 20.0 ⁇ 10 4 or less is particularly preferred. If the number average molecular weight is too low, the dispersibility is lowered and it may not be possible to use it as a dispersant. If the number average molecular weight is too high, the viscosity becomes high and handling may become complicated.
- the weight average molecular weight of the polymer ⁇ is preferably is 0.2 ⁇ 10 4 or more, more preferably 0.4 ⁇ 10 4 or more, more preferably 0.6 ⁇ 10 4 or more, 0.8 ⁇ 10 4 or more Even more preferably, particularly preferably 1.0 ⁇ 10 4 or more, particularly preferably more it is 5.0 ⁇ 10 4 or more, more particularly preferably 10.0 ⁇ 10 4 or more, preferably in especially is 15.0 ⁇ 10 4 or more , particularly preferred especially is 20.0 ⁇ 10 4 or more, and most preferably 25.0 ⁇ 10 4 or more. Further, preferably 150.0 ⁇ 10 4 or less, more preferably 100.0 ⁇ 10 4 or less, more preferably 60.0 ⁇ 10 4 or less, particularly preferably 50.0 ⁇ 10 4 or less, 40.0 ⁇ 10 4 or less is particularly preferable.
- the number average molecular weight and the weight average molecular weight are values for which the molecular weight is calculated by gel permeation chromatography (GPC) using monodisperse polyethylene oxide (PEO) and polyethylene glycol (PEG) manufactured by Tosoh and Agent as standards. If measurement by GPC is not possible, the number average molecular weight of the polymer ⁇ should be obtained from the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. Can be done. The melt flow rate can be measured in accordance with JIS K 7210.
- the polymer ⁇ is preferably a water-soluble polymer.
- the polymer ⁇ has an ion exchange rate (IXR) of 53 or less.
- the IXR is preferably 0.5 or more, more preferably 1 or more, further preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and particularly preferably 8 or more. Further, the IXR is preferably 43 or less, more preferably 33 or less, and even more preferably 23 or less.
- the ionic groups anionic groups
- the polymer ⁇ contains a polymer main chain together with a repeating side chain bonded to the main chain, and the side chain has an ionic group.
- the polymer ⁇ preferably contains an ionic group (anionic group) having a pKa of less than 10, more preferably less than 7.
- the ionic group of the polymer ⁇ is preferably selected from the group consisting of sulfonates, carboxylates, phosphonates, phosphates, and mixtures thereof.
- the term "sulfonate, carboxylate, phosphonate, and phosphate" is intended to refer to the respective salts, or the respective acids that can form the salts.
- the salt is preferably an alkali metal salt or an ammonium salt.
- a preferred ionic group is a sulfonate group.
- the concentration of the polymer ⁇ is not particularly limited, and may be, for example, 0.1 to 20% by mass. Since the removal efficiency of the low molecular weight polymer becomes more efficient, the concentration of the polymer ⁇ is preferably 18.0% by mass or less. It is more preferably 15.0% by mass or less, further preferably 12.0% by mass or less, and particularly preferably 10.0% by mass or less. By setting the concentration of the polymer ⁇ in the above range, the low molecular weight substance can be removed more efficiently.
- the concentration of the polymer ⁇ is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 1.2% by mass or more, and particularly preferably 1.5% by mass or more.
- the composition containing the polymer ⁇ may contain one kind of single polymer ⁇ , or may contain two or more different kinds of polymer ⁇ .
- the composition containing the polymer ⁇ preferably has a pH of 0 to 11, more preferably 0.5 to 8.0.
- the pH can be adjusted with a pH adjuster.
- the pH adjuster may be an acid or an alkali, and examples thereof include phosphate, sodium hydroxide, potassium hydroxide, aqueous ammonia and the like. It is also preferable that the second production method of the present disclosure includes a step of adjusting the pH of the composition containing the polymer ⁇ to 1.0 to 7.0 before the step A1.
- the composition containing the above-mentioned polymer ⁇ can be obtained by a known polymerization method for obtaining the above-mentioned polymer ⁇ .
- One of the preferred embodiments of the second production method of the present disclosure is to include a step of polymerizing a monomer to obtain a polymer ⁇ .
- the above-mentioned monomer may be appropriately selected from the above-mentioned monomers constituting the polymer ⁇ .
- the step of obtaining the polymer ⁇ is preferably carried out in an aqueous medium. That is, it is also preferable that the second production method of the present disclosure includes a step of obtaining a composition containing the polymer ⁇ by polymerizing the monomer represented by the general formula (I) in an aqueous medium. ..
- the composition containing the polymer ⁇ may be a composition after polymerization obtained by polymerization, or may be a diluted or concentrated composition obtained after polymerization obtained by polymerization. It may have been subjected to dispersion stabilization processing or the like. In order to smoothly proceed with ultrafiltration, microfiltration or dialysis membrane treatment, it is also preferable to adjust the viscosity of the composition containing the polymer ⁇ by these treatments.
- the viscosity of the composition containing the polymer ⁇ used in the step A1 is preferably 25 mPa ⁇ s or less because ultrafiltration, microfiltration or dialysis membrane treatment proceeds smoothly.
- the viscosity of the composition can be adjusted by, for example, a method of adjusting the number average molecular weight of the polymer ⁇ , a method of adjusting the concentration of the polymer ⁇ in the composition, a method of adjusting the temperature of the composition, and the like. ..
- the above polymerization usually produces a low molecular weight product as a by-product.
- the low molecular weight substance can be removed by subjecting the composition containing the polymer ⁇ to a treatment such as ultrafiltration.
- the composition containing the polymer ⁇ used in the step A1 may contain a low molecular weight substance, and for example, the content of the low molecular weight substance is preferably more than 5.0% with respect to the polymer ⁇ . , More preferably 5.5% or more, still more preferably 6.0% or more, or more than 2.0%.
- Examples of the low molecular weight dimer include a compound having a molecular weight of 700 or more and 3000 or less, a compound having a molecular weight of 400 or more and 3000 or less, a compound having a molecular weight of 700 or more and less than 10000, a monomer dimer and trimmer forming the structural unit M3, and a polymer described later. Examples thereof include monomeric dimers and trimmers forming structural units constituting ⁇ , and monomeric dimers and trimmers forming structural units constituting water-soluble polymers, which will be described later.
- the content of the low molecular weight substance is a value calculated from the peak area of GPC and / or a value calculated by measurement by liquid chromatography-mass spectrometry (LC / MS / MS).
- a dimer and trimmer of a monomer represented by the general formula (I) (hereinafter, may be referred to as a monomer (I)) are preferable.
- the dimer and trimmer may be a polymer formed from one kind of monomer (I) as the monomer (I) represented by the general formula (I), or two or more kinds having different structures. It may be a copolymer formed from the monomer (I) of.
- examples of the dimer and trimmer include the above-mentioned monomeric dimer and trimmer as a monomer forming a suitable structural unit constituting the polymer ⁇ .
- composition containing the polymer ⁇ can be produced, for example, by polymerizing the monomer (I).
- the composition obtained by polymerizing the monomer (I) has a total of 1. as a polymer of the monomer (I), with respect to the mass of the polymer of the monomer (I). Includes over 0% dimers and trimmers.
- the content of the dimer and trimmer in the polymer of the monomer (I) may be, for example, 2.0% or more, or 3.0%, with respect to the polymer of the monomer (I). It may be more than that, 30.0% or less, or 20.0% or less.
- the content of dimer and trimmer in the composition is the ratio of the peak area of dimer and trimmer to the total area of each peak of the chromatogram obtained by gel permeation chromatography (GPC) analysis of the composition. It can be specified by calculating (area percentage).
- the polymerization of the monomer (I) produces a dimer and a trimmer of the monomer (I), and as a result, the dimer and the trimmer of the monomer (I) are contained in the polymer ⁇ .
- the mechanism by which the dimer and trimmer of the monomer (I) are generated is not always clear, but in particular, the polymerization reaction in the polymerization system in which the monomer (I) accounts for the majority of the monomers present in the polymerization system. Therefore, it is presumed that the dimerization and trimerization of the monomer (I) occur at a non-negligible frequency.
- the presence of the monomer (I) dimer and trimmer in the polymer ⁇ is clarified for the first time, and the dimer and trimmer of the monomer (I) in the polymer ⁇ are subjected to ultrafiltration, precision filtration and For the first time, it has been found that polymer ⁇ is removed with high efficiency by at least one means selected from the group consisting of diafiltration membrane treatment.
- the unreacted monomer (I) is usually removed from the composition at the same time.
- the content of the dimer and trimmer in the composition obtained by the second production method of the present disclosure is preferably 1.0% or less, more preferably 0.1% or less, based on the polymer ⁇ . It is more preferably 0.01% or less, particularly preferably 0.001% or less, and most preferably 0.0001% or less.
- the content of dimer and trimmer in the composition is the ratio of the peak area of dimer and trimmer to the total area of each peak of the chromatogram obtained by gel permeation chromatography (GPC) analysis of the composition. It can be specified by calculating (area percentage).
- the content of the dimer and trimmer in the composition is less than 0.5% with respect to the polymer ⁇ , it is specified by measurement by liquid chromatography-mass spectrometry (LC / MS / MS). be able to. Specifically, a composition having a content of 5 levels or more of the monomer (I) was prepared, LC / MS / MS analysis of each content was performed, and the content and the area area with respect to the content ( The relationship with the integrated value of the peak) is plotted to create a calibration curve of the monomer (I). Further, a calibration curve of the dimer and the trimmer of the monomer (I) is prepared from the calibration curve of the monomer (I).
- LC / MS / MS liquid chromatography-mass spectrometry
- Methanol is added to the polymer ⁇ to prepare a mixture, and the extract (supernatant) is recovered from the mixture by centrifugation, and the obtained extract is analyzed by LC / MS / MS. Then, using the calibration curve, the area area (integral value of peaks) of the chromatogram of the dimer and trimmer of the monomer (I) can be converted into the content of the dimer and the trimmer.
- the present disclosure also includes ultrafiltration, microfiltration or dialysis membrane treatment of compositions containing water and water-soluble polymers in which hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms in an amount of 50% or more.
- the present invention also relates to a method for producing a composition (hereinafter, also referred to as “the third production method of the present disclosure”), which comprises a step A2 for carrying out a combination thereof.
- the composition obtained by the third production method of the present disclosure may be an aqueous solution.
- the step A2 uses water and a composition containing a water-soluble polymer in which the ratio of hydrogen atoms bonded to carbon atoms replaced with fluorine atoms is 50% or more. Except for this, all the same methods as the first manufacturing method of the present disclosure can be adopted.
- the ultrafiltration, microfiltration or dialysis membrane treatment is preferably performed at a temperature of 10 ° C. or higher. More preferably, it is 15 ° C. or higher, further preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher. By setting the temperature in the above range, the low molecular weight substance can be reduced more efficiently.
- the temperature is preferably 90 ° C.
- the ultrafiltration is preferably performed using an ultrafiltration membrane having a molecular weight cut-off of 1.5 ⁇ 10 4 Da or more.
- the water-soluble polymer is not particularly limited, and for example, a water-soluble polymer in which a hydrogen atom bonded to a carbon atom is replaced with a fluorine atom in the above-mentioned fluoropolymer is 50% or more. It is possible to use a water-soluble polymer in which the ratio of hydrogen atoms bonded to carbon atoms replaced with fluorine atoms in the above-mentioned polymer ⁇ is 50% or more.
- CX 2 CY (-CZ 2- O-Rf-A) (1)
- X is the same or different, -H or -F
- Y is -H, -F, an alkyl group or a fluorine-containing alkyl group
- Z is the same or different, -H,-.
- F an alkyl group or a fluoroalkyl group.
- Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- A is -COOM,-.
- the first composition of the present disclosure may be an aqueous solution.
- the content of the compound having a molecular weight of 400 or more and 3000 or less in the first composition of the present disclosure is preferably 3.7% or less with respect to the fluoropolymer.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the fluoropolymer.
- the first composition of the present disclosure can improve dispersibility (property to disperse other components) when used as a dispersant in a polymer dispersion by reducing low molecular weight substances. it can.
- the coating agent obtained from the first composition of the present disclosure is excellent in transparency, water repellency, and antireflection property.
- the first composition of the present disclosure can be preferably produced by the first production method of the present disclosure.
- the first composition of the present disclosure comprises water.
- the content of water is not limited, and it is preferable that the fluoropolymer can be dispersed or dissolved.
- Examples of the fluoropolymer in the first composition of the present disclosure include those described in the first production method of the present disclosure. Moreover, all suitable embodiments can be adopted.
- at least one X may be ⁇ H, or both may be ⁇ H.
- the Rf is preferably a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having an ether bond and having 2 to 12 carbon atoms.
- A is preferably -COOM, and M is preferably -H, -Na, -K, -Li or -NH 4 .
- CX 2 CFCF 2- O- (CF (CF 3 ) CF 2 O) n5- CF (CF 3 ) -A (1a)
- each X is the same and represents F or H.
- N5 represents an integer of 0 or 1 to 10, and A is the same as the above definition.
- the unit (1a) is preferable, and the structural unit (1A) based on the monomer represented by the following general formula (1A) is also preferable.
- CH 2 CF (-CF 2- O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)
- the ratio of hydrogen atoms bonded to carbon atoms replaced with fluorine atoms is preferably 50% or more.
- the fluoropolymer preferably contains an ionic group and preferably has an ion exchange rate of 53 or less.
- the ratio of hydrogen atoms bonded to carbon atoms replaced with fluorine atoms is preferably 50% or more.
- the fluoropolymer is preferably a water-soluble polymer.
- the content (concentration) of the fluoropolymer is not particularly limited, but may be, for example, 0.1 to 10.0% by mass with respect to the composition.
- the first composition of the present disclosure may be a diluted or concentrated composition obtained by the first production method of the present disclosure described above.
- the first composition of the present disclosure may contain one single fluoropolymer or may contain two or more different fluoropolymers.
- the content of the compound having a molecular weight of 700 or more and 3000 or less is 3.5% or less with respect to the fluoropolymer. Dispersibility is excellent by setting the content of the compound having a molecular weight of 700 or more and 3000 or less in the above range. It is preferably 3.0% or less, more preferably 2.5% or less, still more preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0. It is less than 0.6%.
- the lower limit of the content of the compound having a molecular weight of 700 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and 3000 or less is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and 3000 or less is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less with respect to the fluoropolymer.
- the dispersibility is further improved. It is preferably 3.2% or less, more preferably 2.7% or less, still more preferably 1.7% or less, particularly preferably 1.2% or less, and particularly preferably. It is 1.0% or less, and most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 400 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 400 or more and 3000 or less is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the fluoropolymer.
- the dispersibility is further improved. It is preferably 4.0% or less, more preferably 2.0% or less, further preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0. It is 6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 10,000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and less than 10,000 is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 3000 is preferably 3.5% or less, more preferably 3.0, with respect to the fluoropolymer from the viewpoint of dispersibility. % Or less, more preferably 2.5% or less, still more preferably 2.0% or less, particularly still more preferably 1.5% or less, and particularly preferably 1.0% or less. Yes, most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 3000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 3000 is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and less than 3000 is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 5000 is preferably 4.0% or less, more preferably 3.5, with respect to the fluoropolymer from the viewpoint of dispersibility. % Or less, more preferably 3.0% or less, still more preferably 2.0% or less, particularly still more preferably 1.5% or less, and particularly preferably 1.0% or less. Yes, most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 5000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 5000 is a value calculated from the peak area of GPC.
- the compound having the molecular weight of 700 or more and less than 5000 is not limited, and any compound having the molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 20000 is preferably 11.0% or less, more preferably 10.0, with respect to the fluoropolymer from the viewpoint of dispersibility. % Or less, more preferably 9.0% or less, and particularly preferably 7.8% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 20000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 20000 is a value calculated from the peak area of GPC.
- the compound having the molecular weight of 700 or more and less than 20000 is not limited, and any compound having the molecular weight is included.
- the composition may be used as it is, or may be diluted or concentrated before use.
- the fluoropolymer may be used separately from the first composition of the present disclosure.
- the fluoropolymer can be separated and used as a dispersant.
- the dispersant can be used, for example, when polymerizing the polymer, or can be used as a dispersant to be added after the polymer is polymerized.
- the fluoromonomer can be polymerized in the presence of the fluoropolymer obtained from the first composition of the present disclosure to produce a fluoropolymer other than the above fluoropolymer.
- the fluoromonomer is not particularly limited as long as it is a monomer having at least one fluorine or a fluoroalkyl group, and for example, trifluoroethylene, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and fluoride.
- VF Vinyl
- CFE chlorotrifluoroethylene
- HFP hexafluoropropylene
- FVE perfluoroalkylethylene
- FVE fluorovinyl ether
- CH 2 CFCF 3
- CHF CHCF 3 (E form)
- fluoropolymers examples include polytetrafluoroethylene (PTFE), TFE, and other monomers copolymerizable with TFE (vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like. Copolymers with fluoropolymers, hydrocarbon olefins such as ethylene, propylene and isobutene, alkyl vinyl ethers, etc.
- Fluororesin such as ethylene-tetrafluoroethylene copolymer (ETFE), polyfluorovinylidene (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene-chlorotrifluoroethylene (ECTFE), vinylidene fluoride-hexafluoro Examples thereof include fluororubbers such as vinylidene fluoride-based rubbers (FKM) such as propylene copolymers, tetrafluoroethylene-propylene rubbers (FEPM), fluororubbers such as tetrafluoroethylene-perfluoromethylvinyl ether rubbers (FFKM), and fluoropolymers.
- FKM vinylidene fluoride-based rubbers
- FKM propylene copolymers
- FEPM tetrafluoroethylene-propylene rubbers
- FFKM tetrafluoroethylene-perfluoromethylvinyl ether rubbers
- the above-mentioned PTFE may be a homopolymer of TFE, or may be a modified PTFE containing 99.0% by mass or more of TFE and 1.0% by mass or less of a modified monomer.
- the other fluoropolymer is selected from the group consisting of melt-workable fluororesins containing PTFE and 60.0-98.0% by weight of TFE units and 2.0-40.0% by weight of other monomers. At least one type is preferable, and PTFE is particularly preferable.
- the first composition of the present disclosure can be used as a coating agent. Since the first composition of the present disclosure has a reduced content of a compound having a molecular weight of 700 or more and 3000 or less, it is excellent in dispersibility (property to disperse other components).
- the composition may contain the above-mentioned other fluoropolymer, water and the like.
- the present disclosure also discloses a polymer in which water and a hydrogen atom bonded to a carbon atom are replaced with a fluorine atom in an amount of 50% or more, and an ionic group is contained, and an ion exchange rate is 53 or less.
- a composition containing hereinafter, also referred to as "polymer ⁇ " and having a content of a compound having a molecular weight of 700 or more and 3000 or less of 3.5% or less with respect to the polymer ⁇ (hereinafter, "the present disclosure”). Also referred to as "second composition").
- the second composition of the present disclosure may be an aqueous solution.
- the content of the compound having a molecular weight of 400 or more and 3000 or less in the second composition of the present disclosure is preferably 3.7% or less with respect to the polymer ⁇ .
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the polymer ⁇ .
- the second composition of the present disclosure can improve dispersibility (property to disperse other components) when used as a dispersant in a polymer dispersion by reducing low molecular weight substances. it can.
- the coating agent obtained from the second composition of the present disclosure is excellent in transparency, water repellency, and antireflection property.
- the second composition of the present disclosure can be preferably produced by the second production method of the present disclosure.
- the second composition of the present disclosure comprises water.
- the content of water is not limited, and it is preferable that the fluoropolymer can be dispersed or dissolved.
- Examples of the polymer ⁇ in the second composition of the present disclosure include those described in the second production method of the present disclosure. Moreover, all suitable embodiments can be adopted.
- the polymer ⁇ is preferably a water-soluble polymer.
- the content of the polymer ⁇ is not particularly limited, but may be, for example, 0.1 to 10.0% by mass with respect to the composition.
- the second composition of the present disclosure may be a diluted or concentrated composition obtained by the second production method of the present disclosure described above.
- the second composition of the present disclosure may contain one single polymer ⁇ , or may contain two or more different polymers ⁇ .
- the content of the compound having a molecular weight of 700 or more and 3000 or less is 3.5% or less with respect to the polymer ⁇ . Dispersibility is excellent by setting the content of the compound having a molecular weight of 700 or more and 3000 or less in the above range. It is preferably 3.0% or less, more preferably 2.5% or less, still more preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0. It is less than 0.6%.
- the lower limit of the content of the compound having a molecular weight of 700 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and 3000 or less is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and 3000 or less is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less with respect to the polymer ⁇ .
- the dispersibility is further improved. It is preferably 3.2% or less, more preferably 2.7% or less, still more preferably 1.7% or less, particularly preferably 1.2% or less, and particularly preferably. It is 1.0% or less, and most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 400 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 400 or more and 3000 or less is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the polymer ⁇ . Dispersibility is further improved by setting the content of the compound having a molecular weight of 700 or more and less than 10,000 within the above range. It is preferably 4.0% or less, more preferably 2.0% or less, further preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0. It is 6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 10,000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and less than 10,000 is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 3000 is preferably 3.5% or less, more preferably 3.5% or less, based on the polymer ⁇ , from the viewpoint of dispersibility. It is 0% or less, more preferably 2.5% or less, still more preferably 2.0% or less, particularly preferably 1.5% or less, and particularly preferably 1.0% or less. Most preferably, it is 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 3000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 3000 is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and less than 3000 is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 5000 is preferably 4.0% or less with respect to the polymer ⁇ from the viewpoint of dispersibility, and more preferably 3. It is 5% or less, more preferably 3.0% or less, still more preferably 2.0% or less, particularly preferably 1.5% or less, and particularly preferably 1.0% or less. Most preferably, it is 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 5000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 5000 is a value calculated from the peak area of GPC.
- the compound having the molecular weight of 700 or more and less than 5000 is not limited, and any compound having the molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 20000 is preferably 11.0% or less, more preferably 10.1% or less, based on the polymer ⁇ from the viewpoint of dispersibility. It is 0% or less, more preferably 9.0% or less, and even more preferably 7.8% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 20000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 20000 is a value calculated from the peak area of GPC.
- the compound having the molecular weight of 700 or more and less than 20000 is not limited, and any compound having the molecular weight is included.
- the composition may be used as it is, or may be diluted or concentrated before use.
- the polymer ⁇ may be separated and used from the second composition of the present disclosure.
- the polymer ⁇ can be separated and used as a dispersant.
- the dispersant can be used, for example, when polymerizing the polymer, or can be used as a dispersant to be added after the polymer is polymerized.
- the fluoromonomer can be polymerized in the presence of the polymer ⁇ obtained from the second composition of the present disclosure to produce a polymer other than the above-mentioned polymer ⁇ .
- the fluoromonomer is not particularly limited as long as it is a monomer having at least one fluorine or a fluoroalkyl group, and for example, trifluoroethylene, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and fluoride.
- VF Vinyl
- CFE chlorotrifluoroethylene
- HFP hexafluoropropylene
- FVE fluorovinyl ether
- CH 2 CFCF 3
- CHF CHCF 3 (E form)
- Examples of the other polymers include polytetrafluoroethylene (PTFE), TFE, and other monomers copolymerizable with TFE (vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like. Copolymers with fluorine-containing monomers, hydrocarbon olefins such as ethylene, propylene and isobutene, alkyl vinyl ethers, etc.
- PTFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- other monomers copolymerizable with TFE vinylene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like.
- Copolymers with fluorine-containing monomers such as ethylene, propylene and isobutene, alkyl vinyl ether
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- PFA tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer
- ETFE ethylene-tetrafluoroethylene copolymer
- PVDF polyvinylidene fluoride
- PCTFE polychlorotrifluoroethylene
- ECTFE ethylene-chlorotrifluoroethylene
- ECTFE vinylidene fluoride-hexafluoro
- FKM vinylidene fluoride-based rubber
- FKM such as propylene copolymer
- fluororubber such as tetrafluoroethylene-propylene rubber (FEPM)
- FFKM tetrafluoroethylene-perfluoromethylvinyl ether rubber
- the above-mentioned PTFE may be a homopolymer of TFE, or may be a modified PTFE containing 99.0% by mass or more of TFE and 1.0% by mass or less of a modified monomer.
- the other polymer is selected from the group consisting of a melt-processable fluororesin containing PTFE and 60.0 to 98.0% by mass of TFE units and 2.0 to 40.0% by mass of other monomers. At least one type is preferable, and PTFE is particularly preferable.
- the second composition of the present disclosure can be used as a coating agent. Since the second composition of the present disclosure has a reduced content of a compound having a molecular weight of 700 or more and 3000 or less, it is excellent in dispersibility (property to disperse other components).
- the composition may contain the above-mentioned other polymer, water and the like.
- the present disclosure also includes water and a water-soluble polymer in which a hydrogen atom bonded to a carbon atom is replaced with a fluorine atom in an amount of 50% or more, and the content of a compound having a molecular weight of 700 or more and 3000 or less is the water-soluble. It also relates to a composition characterized by having a molecular weight of 3.5% or less based on the sex polymer (hereinafter, also referred to as “the third composition of the present disclosure”).
- the third composition of the present disclosure may be an aqueous solution.
- the content of the compound having a molecular weight of 400 or more and 3000 or less in the third composition of the present disclosure is preferably 3.7% or less with respect to the water-soluble polymer.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the water-soluble polymer.
- the third composition of the present disclosure can improve dispersibility (property to disperse other components) when used as a dispersant in a polymer dispersion by reducing low molecular weight substances. it can.
- the coating agent obtained from the third composition of the present disclosure is excellent in transparency, water repellency, and antireflection property.
- the third composition of the present disclosure can be preferably produced by the third production method of the present disclosure.
- the third composition of the present disclosure comprises water.
- the content of water is not limited, and it is preferable that the water-soluble polymer can be dispersed or dissolved, and the amount of the water-soluble polymer can be dissolved.
- Examples of the water-soluble polymer in the third composition of the present disclosure include those described in the third production method of the present disclosure. Moreover, all suitable embodiments can be adopted.
- the content of the water-soluble polymer is not particularly limited, but may be, for example, 0.1 to 10.0% by mass with respect to the composition.
- the third composition of the present disclosure may be a diluted or concentrated composition obtained by the third production method of the present disclosure described above.
- the third composition of the present disclosure may contain one single water-soluble polymer, or may contain two or more different water-soluble polymers.
- the content of the water-soluble polymer is not particularly limited, but may be, for example, 0.1 to 10.0% by mass with respect to the composition.
- the third composition of the present disclosure may be a diluted or concentrated composition obtained by the third production method of the present disclosure described above.
- the third composition of the present disclosure may contain one single water-soluble polymer, or may contain two or more different water-soluble polymers.
- the content of the compound having a molecular weight of 700 or more and 3000 or less is 3.5% or less with respect to the water-soluble polymer. Dispersibility is excellent by setting the content of the compound having a molecular weight of 700 or more and 3000 or less in the above range. It is preferably 3.0% or less, more preferably 2.5% or less, still more preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0. It is less than 0.6%.
- the lower limit of the content of the compound having a molecular weight of 700 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and 3000 or less is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and 3000 or less is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less with respect to the water-soluble polymer.
- the dispersibility is further improved. It is preferably 3.2% or less, and more preferably 2.7% or less. It is more preferably 1.7% or less, still more preferably 1.2% or less, particularly preferably 1.0% or less, and most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 400 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 400 or more and 3000 or less is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is preferably 5.0% or less with respect to the water-soluble polymer.
- the dispersibility is further improved. It is preferably 4.0% or less, more preferably 2.0% or less, further preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0. It is 6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 10,000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 10,000 is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and less than 10,000 is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 3000 is preferably 3.5% or less, more preferably 3) with respect to the water-soluble polymer from the viewpoint of dispersibility. It is 0.0% or less, more preferably 2.5% or less, still more preferably 2.0% or less, particularly preferably 1.5% or less, and particularly preferably 1.0%. It is less than or equal to, and most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 3000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 3000 is a value calculated from the peak area of GPC.
- the compound having the above molecular weight of 700 or more and less than 3000 is not limited, and any compound having the above molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 5000 is preferably 4.0% or less, more preferably 3) with respect to the water-soluble polymer from the viewpoint of dispersibility. It is 5.5% or less, more preferably 3.0% or less, still more preferably 2.0% or less, particularly preferably 1.5% or less, and particularly preferably 1.0%. It is less than or equal to, and most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 5000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 5000 is a value calculated from the peak area of GPC.
- the compound having the molecular weight of 700 or more and less than 5000 is not limited, and any compound having the molecular weight is included.
- the content of the compound having a molecular weight of 700 or more and less than 20000 is preferably 11.0% or less, more preferably 10 with respect to the water-soluble polymer from the viewpoint of dispersibility. It is 0.0% or less, more preferably 9.0% or less, and particularly preferably 7.8% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 20000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and less than 20000 is a value calculated from the peak area of GPC.
- the compound having the molecular weight of 700 or more and less than 20000 is not limited, and any compound having the molecular weight is included.
- the composition may be used as it is, or may be diluted or concentrated before use.
- the water-soluble polymer may be separated and used from the third composition of the present disclosure.
- the water-soluble polymer can be separated and used as a dispersant.
- the dispersant can be used, for example, when polymerizing the polymer, or can be used as a dispersant to be added after the polymer is polymerized.
- the fluoromonomer can be polymerized in the presence of the water-soluble polymer obtained from the third composition of the present disclosure to produce a polymer other than the above-mentioned water-soluble polymer.
- the fluoromonomer is not particularly limited as long as it is a monomer having at least one fluorine or a fluoroalkyl group, and for example, trifluoroethylene, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and fluoride.
- VF Vinyl
- CFE chlorotrifluoroethylene
- HFP hexafluoropropylene
- FVE fluorovinyl ether
- CH 2 CFCF 3
- CHF CHCF 3 (E form)
- Examples of the other polymers include polytetrafluoroethylene (PTFE), TFE, and other monomers copolymerizable with TFE (vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like. Copolymers with fluorine-containing monomers, hydrocarbon olefins such as ethylene, propylene and isobutene, alkyl vinyl ethers, etc.
- PTFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- other monomers copolymerizable with TFE vinylene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like.
- Copolymers with fluorine-containing monomers such as ethylene, propylene and isobutene, alkyl vinyl ether
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- PFA tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer
- ETFE ethylene-tetrafluoroethylene copolymer
- PVDF polyvinylidene fluoride
- PCTFE polychlorotrifluoroethylene
- ECTFE ethylene-chlorotrifluoroethylene
- ECTFE vinylidene fluoride-hexafluoro
- FKM vinylidene fluoride-based rubber
- FKM such as propylene copolymer
- fluororubber such as tetrafluoroethylene-propylene rubber (FEPM)
- FFKM tetrafluoroethylene-perfluoromethylvinyl ether rubber
- the above-mentioned PTFE may be a homopolymer of TFE, or may be a modified PTFE containing 99.0% by mass or more of TFE and 1.0% by mass or less of a modified monomer.
- the other polymer is selected from the group consisting of a melt-processable fluororesin containing PTFE and 60.0 to 98.0% by mass of TFE units and 2.0 to 40.0% by mass of other monomers. At least one type is preferable, and PTFE is particularly preferable.
- the third composition of the present disclosure can be used as a coating agent. Since the third composition of the present disclosure has a reduced content of a compound having a molecular weight of 700 or more and 3000 or less, it is excellent in dispersibility (property to disperse other components).
- the composition may contain the above-mentioned other polymer, water and the like.
- CX 2 CY (-CZ 2- O-Rf-A) (1)
- X is the same or different, -H or -F
- Y is -H, -F, an alkyl group or a fluorine-containing alkyl group
- Z is the same or different, -H,-.
- F an alkyl group or a fluoroalkyl group.
- Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
- A is -COOM,-.
- M is, -H, a metal atom, -NR 7 4, good imidazolium be substituted, substituted It is a pyridinium which may have a substituent or a phosphonium which may have a substituent, and R 7 is an H or an organic group), provided that at least one of X, Y and Z contains a fluorine atom).
- the content of the dimer and trimmer of the monomer which contains the fluoropolymer which is a polymer containing the structural unit M3 derived from the monomer and forms the structural unit constituting the fluoropolymer is higher than that of the fluoropolymer. It also relates to a composition characterized by being 0% or less (hereinafter, also referred to as “fourth composition of the present disclosure”).
- the fourth composition of the present disclosure may be an aqueous solution. Since the fourth composition of the present disclosure has a reduced content of the dimer and trimmer, the fourth composition of the present disclosure can be used to polymerize the monomers in an aqueous medium to obtain the dimer and trimmer. A polymer having a reduced content can be obtained.
- the fourth composition of the present disclosure can be preferably produced by the first production method of the present disclosure.
- the ratio of hydrogen atoms bonded to carbon atoms replaced with fluorine atoms is preferably 50% or more.
- the fluoropolymer preferably contains an ionic group and preferably has an ion exchange rate of 53 or less.
- the ratio of hydrogen atoms bonded to carbon atoms replaced with fluorine atoms is preferably 50% or more.
- the fluoropolymer is preferably a water-soluble polymer.
- the fourth composition of the present disclosure comprises water.
- the content of water is not limited as long as the fluoropolymer can be dispersed or dissolved.
- Examples of the fluoropolymer in the fourth composition of the present disclosure include those described in the first production method of the present disclosure. Moreover, all suitable embodiments can be adopted.
- the content of the fluoropolymer is not particularly limited, but may be, for example, 0.1 to 10.0% with respect to the composition.
- the fourth composition of the present disclosure may be a diluted or concentrated composition obtained by the first production method of the present disclosure described above.
- the fourth composition of the present disclosure may contain one single fluoropolymer or may contain two or more different fluoropolymers.
- a dimer and trimmer of a monomer represented by the general formula (I) (hereinafter, may be referred to as a monomer (I)) are preferable.
- the dimer and trimmer may be formed from one kind of monomer (I) as the monomer (I) represented by the general formula (I), or two or more kinds having different structures. It may be formed from the monomer (I).
- examples of the monomer forming a suitable structural unit constituting the fluoropolymer include the above-mentioned monomer dimer and trimmer.
- the contents of the dimer and the trimmer in the fourth composition of the present disclosure are 2.0% or less, 1.5% or less, 1.0% or less, and 0. It is 1% or less, 0.01% or less, 0.001% or less, 0.0001% or less.
- the method for measuring the content of dimer and trimer in the composition is as described above.
- the content of the compound having a molecular weight of 700 or more and less than 1000 is preferably 2.0% or less, more preferably 1.5% or less, still more preferably, with respect to the fluoropolymer. Is 1.0% or less, and even more preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 1000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and 3000 or less is preferably 3.5% or less, more preferably 3.0% or less, and further, with respect to the fluoropolymer. It is preferably 2.5% or less, still more preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less, more preferably 3.2% or less, and further, with respect to the fluoropolymer. It is preferably 2.7% or less, still more preferably 1.7% or less, particularly preferably 1.2% or less, particularly preferably 1.0% or less, and most preferably 0. It is 6% or less.
- the lower limit of the content of the compound having a molecular weight of 400 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the contents of the compound having a molecular weight of 700 or more and less than 1000, the compound having a molecular weight of 700 or more and 3000 or less, and the compound having a molecular weight of 400 or more and 3000 or less are values calculated from the peak area of GPC.
- Compounds having a molecular weight of 700 or more and less than 1000, compounds having a molecular weight of 700 or more and 3000 or less, and compounds having a molecular weight of 400 or more and 3000 or less are not limited, and all compounds having the above molecular weight are included.
- a fluoropolymer can be polymerized in the presence of the fluoropolymer obtained from the fourth composition of the present disclosure to produce a polymer other than the above-mentioned fluoropolymer.
- the fluoromonomer is not particularly limited as long as it is a monomer having at least one fluorine or a fluoroalkyl group, and for example, trifluoroethylene, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and fluoride.
- VF Vinyl
- CFE chlorotrifluoroethylene
- HFP hexafluoropropylene
- FVE fluorovinyl ether
- CH 2 CFCF 3
- CHF CHCF 3 (E form)
- Examples of the other polymers include polytetrafluoroethylene (PTFE), TFE, and other monomers copolymerizable with TFE (vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like. Copolymers with fluorine-containing monomers, hydrocarbon olefins such as ethylene, propylene and isobutene, alkyl vinyl ethers, etc.
- PTFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- other monomers copolymerizable with TFE vinylene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like.
- Copolymers with fluorine-containing monomers such as ethylene, propylene and isobutene, alkyl vinyl ether
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- PFA tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer
- ETFE ethylene-tetrafluoroethylene copolymer
- PVDF polyvinylidene fluoride
- PCTFE polychlorotrifluoroethylene
- ECTFE ethylene-chlorotrifluoroethylene
- ECTFE vinylidene fluoride-hexafluoro
- FKM vinylidene fluoride-based rubber
- FKM such as propylene copolymer
- fluororubber such as tetrafluoroethylene-propylene rubber (FEPM)
- FFKM tetrafluoroethylene-perfluoromethylvinyl ether rubber
- the above-mentioned PTFE may be a homopolymer of TFE, or may be a modified PTFE containing 99.0% by mass or more of TFE and 1.0% by mass or less of a modified monomer.
- the other polymer is selected from the group consisting of a melt-processable fluororesin containing PTFE and 60.0 to 98.0% by mass of TFE units and 2.0 to 40.0% by mass of other monomers. At least one type is preferable, and PTFE is particularly preferable.
- the fourth composition of the present disclosure can be used as a coating agent.
- the composition may contain the above-mentioned other polymer, water and the like.
- the present disclosure also comprises a polymer ⁇ in which the hydrogen atom bonded to the carbon atom is replaced with a fluorine atom in an amount of 50% or more and contains an ionic group and an ion exchange rate of 53 or less.
- a composition characterized in that the content of the monomer dimer and trimmer forming the structural unit constituting the polymer ⁇ is 2.0% or less with respect to the polymer ⁇ hereinafter, “the first of the present disclosure”). Also referred to as "composition of 5").
- the fifth composition of the present disclosure may be an aqueous solution. Since the fifth composition of the present disclosure has a reduced content of the dimer and trimmer, the fifth composition of the present disclosure can be used to polymerize the monomers in an aqueous medium to obtain the dimer and trimmer. A polymer having a reduced content can be obtained.
- the fifth composition of the present disclosure can be preferably produced by the second production method of the present disclosure.
- the fifth composition of the present disclosure comprises water.
- the content of water is not limited as long as the polymer ⁇ can be dispersed or dissolved.
- Examples of the polymer ⁇ in the fifth composition of the present disclosure include those described in the second production method of the present disclosure. Moreover, all suitable embodiments can be adopted.
- the polymer ⁇ is preferably a water-soluble polymer.
- the content of the polymer ⁇ is not particularly limited, but may be, for example, 0.1 to 10.0% by mass with respect to the composition.
- the fifth composition of the present disclosure may be a diluted or concentrated composition obtained by the second production method of the present disclosure described above.
- the fifth composition of the present disclosure may contain one single polymer ⁇ , or may contain two or more different polymers ⁇ .
- a dimer and trimmer of a monomer represented by the general formula (I) (hereinafter, may be referred to as a monomer (I)) are preferable.
- the dimer and trimmer may be formed from one kind of monomer (I) as the monomer (I) represented by the general formula (I), or two or more kinds having different structures. It may be formed from the monomer (I).
- examples of the dimer and trimmer include the above-mentioned monomeric dimer and trimmer as a monomer forming a suitable structural unit constituting the polymer ⁇ .
- the contents of the dimer and the trimmer in the fifth composition of the present disclosure are 2.0% or less, 1.5% or less, 1.0% or less, and 0 in the order of preference with respect to the polymer ⁇ . .1% or less, 0.01% or less, 0.001% or less, 0.0001% or less.
- the method for measuring the content of dimer and trimer in the composition is as described above.
- the content of the compound having a molecular weight of 700 or more and less than 1000 is preferably 2.0% or less, more preferably 1.5% or less, based on the polymer ⁇ . It is more preferably 1.0% or less, and even more preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 1000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and 3000 or less is preferably 3.5% or less, more preferably 3.0% or less, based on the polymer ⁇ . It is more preferably 2.5% or less, still more preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less, more preferably 3.2% or less, based on the polymer ⁇ . It is more preferably 2.7% or less, still more preferably 1.7% or less, particularly still more preferably 1.2% or less, particularly preferably 1.0% or less, and most preferably 0. It is less than 0.6%.
- the lower limit of the content of the compound having a molecular weight of 400 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the contents of the compound having a molecular weight of 700 or more and less than 1000, the compound having a molecular weight of 700 or more and 3000 or less, and the compound having a molecular weight of 400 or more and 3000 or less are values calculated from the peak area of GPC.
- Compounds having a molecular weight of 700 or more and less than 1000, compounds having a molecular weight of 700 or more and 3000 or less, and compounds having a molecular weight of 400 or more and 3000 or less are not limited, and all compounds having the above molecular weight are included.
- the fluoromonomer can be polymerized in the presence of the polymer ⁇ obtained from the fifth composition of the present disclosure to produce a polymer other than the above-mentioned polymer ⁇ .
- the fluoromonomer is not particularly limited as long as it is a monomer having at least one fluorine or a fluoroalkyl group, and for example, trifluoroethylene, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and fluoride.
- VF Vinyl
- CFE chlorotrifluoroethylene
- HFP hexafluoropropylene
- FVE fluorovinyl ether
- CH 2 CFCF 3
- CHF CHCF 3 (E form)
- Examples of the other polymers include polytetrafluoroethylene (PTFE), TFE, and other monomers copolymerizable with TFE (vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like. Copolymers with fluorine-containing monomers, hydrocarbon olefins such as ethylene, propylene and isobutene, alkyl vinyl ethers, etc.
- PTFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- other monomers copolymerizable with TFE vinylene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like.
- Copolymers with fluorine-containing monomers such as ethylene, propylene and isobutene, alkyl vinyl ether
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- PFA tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer
- ETFE ethylene-tetrafluoroethylene copolymer
- PVDF polyvinylidene fluoride
- PCTFE polychlorotrifluoroethylene
- ECTFE ethylene-chlorotrifluoroethylene
- ECTFE vinylidene fluoride-hexafluoro
- FKM vinylidene fluoride-based rubber
- FKM such as propylene copolymer
- fluororubber such as tetrafluoroethylene-propylene rubber (FEPM)
- FFKM tetrafluoroethylene-perfluoromethylvinyl ether rubber
- the above-mentioned PTFE may be a homopolymer of TFE, or may be a modified PTFE containing 99.0% by mass or more of TFE and 1.0% by mass or less of a modified monomer.
- the other polymer is selected from the group consisting of a melt-processable fluororesin containing PTFE and 60.0 to 98.0% by mass of TFE units and 2.0 to 40.0% by mass of other monomers. At least one type is preferable, and PTFE is particularly preferable.
- the fifth composition of the present disclosure can be used as a coating agent.
- the composition may contain the above-mentioned other polymer, water and the like.
- the present disclosure also comprises water and a water-soluble polymer in which a hydrogen atom bonded to a carbon atom is replaced with a fluorine atom in an amount of 50% or more, and forms a structural unit constituting the water-soluble polymer. Also in the composition characterized by the content of the monomer dimer and the trimmer being 2.0% or less with respect to the water-soluble polymer (hereinafter, also referred to as “the sixth composition of the present disclosure”). Related.
- the sixth composition of the present disclosure may be an aqueous solution. Since the sixth composition of the present disclosure has a reduced content of the dimer and the trimmer, the sixth composition of the present disclosure can be used to polymerize the monomers in an aqueous medium to obtain the dimer and the trimmer. A polymer having a reduced content can be obtained.
- the sixth composition of the present disclosure can be preferably produced by the third production method of the present disclosure.
- the sixth composition of the present disclosure comprises water.
- the content of water is not limited, and is preferably an amount in which the water-soluble polymer can be dispersed or dissolved, and preferably an amount in which the water-soluble polymer can be dissolved.
- water-soluble polymer in the sixth composition of the present disclosure examples include those described in the third production method of the present disclosure. Moreover, all suitable embodiments can be adopted.
- the content of the water-soluble polymer is not particularly limited, but may be, for example, 0.1 to 10.0% by mass with respect to the composition.
- the sixth composition of the present disclosure may be a diluted or concentrated composition obtained by the third production method of the present disclosure described above.
- the sixth composition of the present disclosure may contain one single water-soluble polymer, or may contain two or more different water-soluble polymers.
- a dimer and trimmer of a monomer represented by the general formula (I) (hereinafter, may be referred to as a monomer (I)) are preferable.
- the dimer and trimmer may be formed from one kind of monomer (I) as the monomer (I) represented by the general formula (I), or two or more kinds having different structures. It may be formed from the monomer (I).
- examples of the monomer forming a suitable structural unit constituting the water-soluble polymer include the above-mentioned monomer dimer and trimmer.
- the contents of the dimer and the trimmer in the sixth composition of the present disclosure are, in order of preference, 2.0% or less, 1.5% or less, 1.0% or less, based on the water-soluble polymer. It is 0.1% or less, 0.01% or less, 0.001% or less, 0.0001% or less.
- the method for measuring the content of dimer and trimer in the composition is as described above.
- the content of the compound having a molecular weight of 700 or more and less than 1000 is preferably 2.0% or less, more preferably 1.5% or less, based on the water-soluble polymer. , More preferably 1.0% or less, and even more preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and less than 1000 is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 700 or more and 3000 or less is preferably 3.5% or less, more preferably 3.0% or less, based on the water-soluble polymer. It is more preferably 2.5% or less, further preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 700 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the content of the compound having a molecular weight of 400 or more and 3000 or less is preferably 3.7% or less, more preferably 3.2% or less, based on the water-soluble polymer. , More preferably 2.7% or less, even more preferably 1.7% or less, particularly still more preferably 1.2% or less, particularly preferably 1.0% or less, and most preferably. It is 0.6% or less.
- the lower limit of the content of the compound having a molecular weight of 400 or more and 3000 or less is not limited, but is, for example, 0.01%.
- the contents of the compound having a molecular weight of 700 or more and less than 1000, the compound having a molecular weight of 700 or more and 3000 or less, and the compound having a molecular weight of 400 or more and 3000 or less are values calculated from the peak area of GPC.
- Compounds having a molecular weight of 700 or more and less than 1000, compounds having a molecular weight of 700 or more and 3000 or less, and compounds having a molecular weight of 400 or more and 3000 or less are not limited, and all compounds having the above molecular weight are included.
- the fluoromonomer can be polymerized in the presence of the water-soluble polymer obtained from the sixth composition of the present disclosure to produce a polymer other than the above-mentioned water-soluble polymer.
- the fluoromonomer is not particularly limited as long as it is a monomer having at least one fluorine or a fluoroalkyl group, and for example, trifluoroethylene, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and fluoride.
- VF Vinyl
- CFE chlorotrifluoroethylene
- HFP hexafluoropropylene
- FVE fluorovinyl ether
- CH 2 CFCF 3
- CHF CHCF 3 (E form)
- Examples of the other polymers include polytetrafluoroethylene (PTFE), TFE, and other monomers copolymerizable with TFE (vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like. Copolymers with fluorine-containing monomers, hydrocarbon olefins such as ethylene, propylene and isobutene, alkyl vinyl ethers, etc.
- PTFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- TFE polytetrafluoroethylene
- other monomers copolymerizable with TFE vinylene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and the like.
- Copolymers with fluorine-containing monomers such as ethylene, propylene and isobutene, alkyl vinyl ether
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- PFA tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer
- ETFE ethylene-tetrafluoroethylene copolymer
- PVDF polyvinylidene fluoride
- PCTFE polychlorotrifluoroethylene
- ECTFE ethylene-chlorotrifluoroethylene
- ECTFE vinylidene fluoride-hexafluoro
- FKM vinylidene fluoride-based rubber
- FKM such as propylene copolymer
- fluororubber such as tetrafluoroethylene-propylene rubber (FEPM)
- FFKM tetrafluoroethylene-perfluoromethylvinyl ether rubber
- the above-mentioned PTFE may be a homopolymer of TFE, or may be a modified PTFE containing 99.0% by mass or more of TFE and 1.0% by mass or less of a modified monomer.
- the other polymer is selected from the group consisting of a melt-processable fluororesin containing PTFE and 60.0 to 98.0% by mass of TFE units and 2.0 to 40.0% by mass of other monomers. At least one type is preferable, and PTFE is particularly preferable.
- the sixth composition of the present disclosure can be used as a coating agent.
- the composition may contain the above-mentioned other polymer, water and the like.
- the contents of Mw, Mn and low molecular weight substances having a molecular weight of 700 or more and less than 10,000 of the polymer (water-soluble polymer) are determined by gel permeation chromatography (GPC) using monodisperse polyethylene oxide (PEO) manufactured by Toso and Agent. The molecular weight was calculated and determined using polyethylene glycol (PEG) as a standard.
- the extract was analyzed using a liquid chromatograph mass spectrometer (Waters, LC-MS ACQUITY UPLC / TQD) to obtain a chromatogram of the extract.
- the content of the monomeric dimer and trimmer contained in the extract is the integral value of the peaks derived from the monomeric dimer and trimmer appearing in the chromatogram of the extract, using a calibration curve. It was determined by converting to the content of dimer and trimmer.
- the quantification limit in this measuring instrument configuration is 1 ng / mL.
- aqueous polymer solution (solid content concentration) Approximately 1 g of the polymer aqueous solution was dried in a vacuum dryer at 60 ° C. for 60 minutes, the mass of the heating residue was measured, and the ratio of the mass of the heating residue to the mass (1 g) of the polymer aqueous solution was determined. The value expressed as a percentage was adopted.
- the content of the low molecular weight substance having a molecular weight of 700 or more and 3000 or less was 3.7% with respect to the fluoropolymer.
- the content of the low molecular weight compound having a molecular weight of 400 or more and 3000 or less was 3.9% with respect to the fluoropolymer.
- Example 1 Water was added to the fluoropolymer aqueous solution A-1 to adjust the concentration of the fluoropolymer to 2.0% by mass, and then ultrafiltration was performed using an ultrafiltration membrane (molecular weight cut off of 50,000 Da). Ultrafiltration was performed while injecting water as appropriate.
- the content of the fluoropolymer Mw 360,000, Mn 140,000, and the low molecular weight substance having a molecular weight of 700 or more and less than 10,000 was 0.7% with respect to the fluoropolymer. From the above, it was found that this method was effective in removing low molecular weight substances.
- the content of the low molecular weight substance having a molecular weight of 700 or more and 3000 or less was 0.6% or less with respect to the fluoropolymer. Further, the content of the low molecular weight substance having a molecular weight of 400 or more and 3000 or less was 0.6% or less with respect to the fluoropolymer.
- Example 2 50 g of 10% hydrochloric acid was added to an aqueous solution (solid content 35 g) having a fluoropolymer concentration of 2.0% by mass prepared by adding water to the fluoropolymer aqueous solution A-1 to precipitate the fluoropolymer, and the precipitated fluoropolymer was prepared. The solution dissolved in acetone was poured into n-hexane, separated and vacuum dried to obtain 34.7 g of a colorless and transparent polymer.
- the content of the fluoropolymer Mw 350,000, Mn 130,000, and the low molecular weight polymer having a molecular weight of 700 or more and less than 10,000 was 6.8% by mass with respect to the fluoropolymer.
- the content of the low molecular weight substance having a molecular weight of 700 or more and 3000 or less was 3.6% with respect to the fluoropolymer.
- the content of the low molecular weight substance having a molecular weight of 400 or more and 3000 or less was 3.8% with respect to the fluoropolymer. From the above, it was found that the low molecular weight substance could hardly be removed by the conventional method of precipitating and recovering the fluoropolymer from the aqueous solution.
- CF 2 CFOCF 2 CF 2
- monomer E represented by COOH
- 30 g of water, and APS 6.0 mol% with respect to monomer E
- APS 6.0 mol% with respect to monomer E
- the polymer E was Mw 7,000 and Mn 5,000.
- the content of the low molecular weight compound having a molecular weight of 700 or more and 3000 or less was 4.6% with respect to the fluoropolymer.
- the content of the low molecular weight substance having a molecular weight of 400 or more and 3000 or less was 4.6% with respect to the fluoropolymer.
- Example 3 Water was added to the obtained polymer E aqueous solution E-1 and brought into contact with a dialysis membrane (molecular weight cut off of 35,000 Da, made of polyethylene) at 30 ° C. and filtered to obtain a polymer E aqueous solution E-2.
- a dialysis membrane molecular weight cut off of 35,000 Da, made of polyethylene
- the content of the polymer E was Mw 7,000, Mn 6,000, dimer, and trimmer with respect to the polymer E. It was less than 1 mass ppm.
- the concentration of the obtained polymer E aqueous solution E-2 was 3.6% by mass.
- the content of the low molecular weight substance having a molecular weight of 700 or more and 3000 or less was 0.05% or less with respect to the fluoropolymer. Further, the content of the low molecular weight substance having a molecular weight of 400 or more and 3000 or less was 0.05% or less with respect to the fluoropolymer.
- the content of the low molecular weight substance having a molecular weight of 700 or more and 3000 or less was 4.5% with respect to the fluoropolymer. Moreover, the content of the low molecular weight substance having a molecular weight of 400 or more and 3000 or less was 4.6% with respect to the fluoropolymer.
- Example 4 The obtained polymer F aqueous solution F-1 was brought into contact with a dialysis membrane (molecular weight cut-off 35000 Da, made of polyethylene) at 30 ° C. and filtered to obtain a polymer F aqueous solution F-2.
- a dialysis membrane molecular weight cut-off 35000 Da, made of polyethylene
- the content of the polymer F was Mw 0.99, Mn 6,000, dimer, and trimmer with respect to the polymer F. It was less than 1 mass ppm.
- the concentration of the obtained polymer F aqueous solution F-2 was 2.0% by mass.
- the content of the low molecular weight substance having a molecular weight of 700 or more and 3000 or less was 0.05% or less with respect to the fluoropolymer. Further, the content of the low molecular weight substance having a molecular weight of 400 or more and 3000 or less was 0.05% or less with respect to the fluoropolymer.
- CF 2 CFOCF 2 CF 2
- monomer E represented by COOH
- 30 g of water, and APS 2.5 mol% divided with respect to monomer E
- APS 2.5 mol% divided with respect to monomer E
- the polymer E was Mw 13,000 and Mn 88,000.
- the content of the low molecular weight compound having a molecular weight of 700 or more and 3000 or less was 3.9% with respect to the fluoropolymer. Moreover, the content of the low molecular weight substance having a molecular weight of 400 or more and 3000 or less was 4.0% with respect to the fluoropolymer.
- Example 5 Water was added to the obtained polymer E aqueous solution E-1 and brought into contact with a dialysis membrane (molecular weight cut off of 35,000 Da, made of polyethylene) at 30 ° C. and filtered to obtain a polymer E aqueous solution E-2.
- a dialysis membrane molecular weight cut off of 35,000 Da, made of polyethylene
- the content of the polymer E was 13,000 Mw, 11,000 Mn, dimer, and trimmer, as compared with the polymer E. It was less than 1 mass ppm.
- the concentration of the obtained polymer E aqueous solution E-2 was 3.5% by mass.
- the content of the low molecular weight substance having a molecular weight of 700 or more and 3000 or less was 0.05% or less with respect to the fluoropolymer. Further, the content of the low molecular weight substance having a molecular weight of 400 or more and 3000 or less was 0.05% or less with respect to the fluoropolymer.
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Abstract
Description
前記含フッ素ポリマー前駆体は、-SO3X1及び/又は-COOZ1(X1は、M1 1/L又はNR1R2R3R4を表し、R1、R2、R3及びR4は、同一又は異なって、水素原子若しくは炭素数1~4のアルキル基を表す。Z1は、M2 1/L又はNR5R6R7R8を表し、R5、R6、R7及びR8は、同一又は異なって、水素原子若しくは炭素数1~4のアルキル基を表す。M1及びM2は、同一又は異なって、L価の金属を表し、前記L価の金属は、周期表の1族、2族、4族、8族、11族、12族、13族に属する金属である。)を有するものであり、前記酸処理工程は、前記-SO3X1を-SO3Hに変化させるもの、及び/又は、前記-COOZ1を-COOHに変化させるものであることを特徴とする含フッ素ポリマー分散体製造方法が記載されている。
-(M3)-(N3)- (M-3)
[式中、構造単位M3は式(5-1):
CH2=CFCF2-ORf10-COOH (5-1)
(式中、Rf10は炭素数1~40の2価の含フッ素アルキレン基または炭素数2~100のエーテル結合を有する2価の含フッ素アルキレン基)で表わされる単量体由来の構造単位;構造単位N3は前記式(5-1)の含フッ素単量体と共重合可能な単量体由来の構造単位]で示され、構造単位M3を55~100モル%、構造単位N3を0~45モル%含み、数平均分子量が3.1×104~75.0×104であるカルボキシル基を有する含フッ素重合体(A1)を含むフォトレジスト上層反射防止膜形成用コーティング組成物が記載されている。
前記フルオロポリマーは、一般式(1):
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)
で表わされる単量体由来の構造単位M3を含む重合体である
ことを特徴とする組成物の製造方法である。
一般式(1)中、Xの両方が-Hであることが好ましい。
一般式(1)中、Rfが炭素数1~10の含フッ素アルキレン基、又は、エーテル結合を有する炭素数2~12の含フッ素アルキレン基であることが好ましい。
構造単位M3は、下記一般式(1A)で表される単量体に基づく構造単位(1A)であることが好ましい。
CH2=CF(-CF2-O-Rf-A) (1A)
(式中、Rf及びAは前記と同じ。)
構造単位M3は、下記一般式(1a)で表されるフルオロアリルエーテル化合物に基づく構造単位(1a)であることが好ましい。
CX2=CFCF2-O-(CF(CF3)CF2O)n5-CF(CF3)-A (1a)
(式中、各Xは、同一であり、F又はHを表す。n5は0又は1~10の整数を表し、Aは、前記定義と同じ。)
Aは、-COOMであることが好ましい。
Mが-H、-Na、-K、-Li又は-NH4であることが好ましい。
前記フルオロポリマーは、前記構造単位M3が全重合単位に対して5~100モル%であり、前記一般式(1)で表される単量体と共重合可能な単量体由来の構造単位N3が全重合単位に対して0~95モル%である重合体であることが好ましい。
前記構造単位N3は、テトラフルオロエチレン由来の構造単位であることが好ましい。
前記フルオロポリマーは、数平均分子量が0.5×104~75.0×104である重合体であることが好ましい。
前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下である重合体であることが好ましい。
前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体であることが好ましい。
前記重合体は、水溶性重合体であることが好ましい。
前記限外濾過は、分画分子量が1.5×104Da以上の限外濾過膜を用いて行うことが好ましい。
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)
で表わされる単量体由来の構造単位M3を含む重合体であるフルオロポリマーを含み、
分子量700以上3000以下の化合物の含有量が前記フルオロポリマーに対して3.5%以下である
ことを特徴とする組成物である。
分子量700以上10000未満の化合物の含有量が前記フルオロポリマーに対して5.0%以下であることが好ましい。
一般式(1)中、Xの少なくとも1つが-Hであることが好ましい。
一般式(1)中、Xの両方が-Hであることが好ましい。
一般式(1)中、Rfが炭素数1~10の含フッ素アルキレン基、又は、エーテル結合を有する炭素数2~12の含フッ素アルキレン基であることが好ましい。
構造単位M3は、下記一般式(1A)で表される単量体に基づく構造単位(1A)であることが好ましい。
CH2=CF(-CF2-O-Rf-A) (1A)
(式中、Rf及びAは前記と同じ。)
構造単位M3は、下記一般式(1a)で表されるフルオロアリルエーテル化合物に基づく構造単位(1a)であることが好ましい。
CX2=CFCF2-O-(CF(CF3)CF2O)n5-CF(CF3)-A (1a)
(式中、各Xは、同一であり、F又はHを表す。n5は0又は1~10の整数を表し、Aは、前記定義と同じ。)
Aは、-COOMであることが好ましい。
Mが-H、-Na、-K、-Li又は-NH4であることが好ましい。
前記フルオロポリマーは、前記構造単位M3が全重合単位に対して5~100モル%であり、前記一般式(1)で表される単量体と共重合可能な単量体由来の構造単位N3が全重合単位に対して0~95モル%である重合体であることが好ましい。
前記フルオロポリマーは、数平均分子量が0.5×104~75.0×104である重合体であることが好ましい。
前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下であることが好ましい。
前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体であることが好ましい。
分子量700以上3000以下の化合物の含有量が前記重合体に対して3.5%以下である
ことを特徴とする組成物である。
分子量700以上10000未満の化合物の含有量が前記重合体に対して5.0%以下であることが好ましい。
前記重合体は、数平均分子量が0.5×104~75.0×104である重合体であることが好ましい。
前記重合体は、水溶性重合体であることが好ましい。
分子量700以上3000以下の化合物の含有量が前記水溶性重合体に対して3.5%以下である
ことを特徴とする組成物である。
分子量700以上10000未満の化合物の含有量が前記水溶性重合体に対して5.0%以下であることが好ましい。
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)
で表わされる単量体由来の構造単位M3を含む重合体であるフルオロポリマーを含み、
前記フルオロポリマーを構成する構造単位を形成する単量体のダイマーおよびトリマーの含有量が前記フルオロポリマーに対して2.0%以下であることを特徴とする組成物である。
前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体であることが好ましい。
前記重合体を構成する構造単位を形成する単量体のダイマーおよびトリマーの含有量が前記重合体に対して2.0%以下であることを特徴とする組成物である。
前記水溶性重合体を構成する構造単位を形成する単量体のダイマーおよびトリマーの含有量が前記水溶性重合体に対して2.0%以下であることを特徴とする組成物である。
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)
で表わされる単量体由来の構造単位M3を含む重合体であることを特徴とする組成物の製造方法(以下「本開示の第1の製造方法」ともいう)である。
本開示の第1の製造方法により得られる組成物は、水溶液であってよい。
上記アルキル基は、フッ素原子を含有しないアルキル基であり、炭素数は1以上であればよい。上記アルキル基の炭素数は6以下が好ましく、4以下がより好ましく、3以下が更に好ましい。
上記含フッ素アルキル基は、フッ素原子を少なくとも1つ含有するアルキル基であり、炭素数は1以上であればよい。上記含フッ素アルキル基の炭素数は6以下が好ましく、4以下がより好ましく、3以下が更に好ましい。
上記Yとしては、-H、-F又は-CF3が好ましく、-Fがより好ましい。
上記アルキル基は、フッ素原子を含有しないアルキル基であり、炭素数は1以上であればよい。上記アルキル基の炭素数は6以下が好ましく、4以下がより好ましく、3以下が更に好ましい。
上記含フッ素アルキル基は、フッ素原子を少なくとも1つ含有するアルキル基であり、炭素数は1以上であればよい。上記含フッ素アルキル基の炭素数は6以下が好ましく、4以下がより好ましく、3以下が更に好ましい。
上記Zとしては、-H、-F又は-CF3が好ましく、-Fがより好ましい。
上記含フッ素アルキレン基の炭素数は2以上が好ましい。また、上記含フッ素アルキレン基の炭素数は、30以下が好ましく、20以下がより好ましく、10以下が更に好ましい。上記含フッ素アルキレン基としては、-CF2-、-CH2CF2-、-CF2CF2-、-CF2CH2-、-CF2CF2CH2-、-CF(CF3)-、-CF(CF3)CF2-、-CF(CF3)CH2-等が挙げられる。上記含フッ素アルキレン基は、パーフルオロアルキレン基であることが好ましい。
上記エーテル結合を有する含フッ素アルキレン基としては、例えば、下記式:
R7としては、H又はC1-10の有機基が好ましく、H又はC1-4の有機基がより好ましく、H又はC1-4のアルキル基が更に好ましい。
上記金属原子としては、アルカリ金属(1族)、アルカリ土類金属(2族)等が挙げられ、Na、K又はLiが好ましい。
上記Mとしては、-H、金属原子又は-NR7 4が好ましく、-H、アルカリ金属(1族)、アルカリ土類金属(2族)又は-NR7 4がより好ましく、-H、-Na、-K、-Li又は-NH4が更に好ましく、-Na、-K又は-NH4が更により好ましく、-Na又は-NH4が特に好ましく、-NH4が最も好ましい。
上記Aとしては、-COOM又は-SO3Mが好ましく、-COOMがより好ましい。
CX2=CFCF2-O-(CF(CF3)CF2O)n5-CF(CF3)-A (1a)
(式中、各Xは、同一であり、F又はHを表す。n5は0又は1~10の整数を表し、Aは、上記定義と同じ。)で表されるフルオロアリルエーテル化合物に基づく構造単位(1a)が好適なものとして例示される。
上記一般式(1a)において、上記n5は一次粒子径が小さいフルオロポリマー粒子を得ることができる点で0又は1~5の整数であることが好ましく、0、1又は2であることがより好ましく、0又は1であることが更に好ましい。上記Aは、適度な水溶性と界面活性が得られる点で-COOMであることが好ましく、上記Mは、不純物として残留しにくく、得られた成形体の耐熱性が向上する点で、H又はNH4であることが好ましい。
CH2=CF(-CF2-O-Rf-A) (1A)
(式中、Rf及びAは前記と同じ。)
(式中、Rf及びAは上記と同じ)
CH2=CFCF2-ORf10-COOH (1’)
(式中、Rf10は、炭素数1~40の含フッ素アルキレン基または炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。)
上記含フッ素アルキレン基の炭素数は2以上が好ましい。また、30以下が好ましく、20以下がより好ましく、10以下が更に好ましい。上記含フッ素アルキレン基としては、-CF2-、-CH2CF2-、-CF2CF2-、-CF2CH2-、-CF2CF2CH2-、-CF(CF3)-、-CF(CF3)CF2-、-CF(CF3)CH2-等が挙げられる。上記含フッ素アルキレン基は、パーフルオロアルキレン基であることが好ましい。
上記エーテル結合を有する含フッ素アルキレン基としては、例えば、下記式:
上記エーテル結合を有する含フッ素アルキレン基として具体的には、-CF(CF3)CF2-O-CF(CF3)-、-(CF(CF3)CF2-O)n-CF(CF3)-(式中、nは1~10の整数)、-CF(CF3)CF2-O-CF(CF3)CH2-、-(CF(CF3)CF2-O)n-CF(CF3)CH2-(式中、nは1~10の整数)、-CH2CF2CF2O-CH2CF2CH2-、-CF2CF2CF2O-CF2CF2-、-CF2CF2CF2O-CF2CF2CH2-、-CF2CF2O-CF2-、-CF2CF2O-CF2CH2-等が挙げられる。上記エーテル結合を有する含フッ素アルキレン基は、パーフルオロアルキレン基であることが好ましい。
CH2=CFCF2-O-(CF(CF3)CF2O)n5-CF(CF3)-COOH
(1a’)
(式中、n5は0又は1~10の整数を表す。)で表されるフルオロアリルエーテル化合物が好適なものとして例示される。
上記式(1a’)において、上記n5は0又は1~5の整数であることが好ましく、0、1又は2であることがより好ましく、0又は1であることが更に好ましい。
なかでも、共重合性が良好である点で、テトラフルオロエチレン(CF2=CF2)、クロロトリフルオロエチレン(CF2=CFCl)及びフッ化ビニリデン(CH2=CF2)からなる群より選択される少なくとも1種が好ましく、テトラフルオロエチレンがより好ましい。従って、上記構造単位N3は、テトラフルオロエチレン由来の構造単位であることが好ましい。上記構造単位N3は、各出現において、同一または異なっていてもよく、上記フルオロポリマーは、2種以上の異なる一般式(1)で表される単量体と共重合可能な単量体由来の構造単位N3を含んでいてもよい。
CH2=CHO-Rf5 (n2-2)
(式中、Rf5は炭素数1~40の含フッ素アルキル基または炭素数2~100のエーテル結合を有する含フッ素アルキル基)で表される含フッ素ビニルエーテルも挙げられる。
CH2=CHCH2O-Rf6 (n2-3)
(式中、Rf6は炭素数1~40の含フッ素アルキル基または炭素数2~100のエーテル結合を有する含フッ素アルキル基)で表される含フッ素アリルエーテル、式(n2-4):
CH2=CH-Rf7 (n2-4)
(式中、Rf7は炭素数1~40の含フッ素アルキル基または炭素数2~100のエーテル結合を有する含フッ素アルキル基)で表される含フッ素ビニル単量体等も挙げられる。
CH2=CFCF2-O-(CF(CF3)CF2O)n5-CF(CF3)-COOH (1a)
(式中、n5は0又は1~10の整数を表す。)で表されるフルオロアリルエーテル化合物由来の構造単位であり、構造単位N3はテトラフルオロエチレン由来の構造単位であることが特に好ましい態様の一つである。
数平均分子量が低すぎると、分散性(他の成分を安定に分散させる性質)が低下し、分散剤として使用できないおそれがある。数平均分子量が高すぎると、粘度が高くなってしまい、ハンドリングが煩雑になるおそれがある。
上記フルオロポリマーは、イオン性基を含むことが好ましい。
上記フルオロポリマーは、53以下のイオン交換率(IXR)を有することが好ましい。上記IXRは、イオン性基に対するポリマー主鎖中の炭素原子数と定義される。加水分解によりイオン性となる前駆体基(例えば、-SO2F)は、IXRを決定する目的ではイオン性基と見なされない。
上記IXRは、0.5以上が好ましく、1以上がより好ましく、3以上が更に好ましく、4以上が更により好ましく、5以上が殊更に好ましく、8以上が特に好ましい。また、IXRは43以下が好ましく、33以下がより好ましく、23以下が更に好ましい。
上記フルオロポリマーにおいて、イオン性基は、典型的に、ポリマー主鎖に沿って分布している。上記フルオロポリマーは、ポリマー主鎖を、この主鎖に結合された繰り返し側鎖とともに含み、この側鎖はイオン性基を有することが好ましい。
フルオロポリマーは、10未満、より好ましくは7未満のpKaを有するイオン性基を含むことが好ましい。フルオロポリマーのイオン性基は、好ましくは、スルホナート、カルボキシラート、ホスホナート、及び、ホスファートからなる群から選択される。
用語「スルホナート、カルボキシラート、ホスホナート、およびホスファート」は、それぞれの塩、または塩を形成し得るそれぞれの酸をいうことが意図される。塩が用いられる場合、好ましくは、その塩はアルカリ金属塩またはアンモニウム塩である。好ましいイオン性基は、スルホナート基である。
上記フルオロポリマーは、水溶性重合体であることが好ましい。「水溶性」とは、容易に水性媒体に溶解又は分散する性質を意味する。水溶性を有する重合体は、例えば、動的光散乱法(DLS)によって、粒子径を測定できない。一方、非水溶性を有する重合体は、例えば、動的光散乱法(DLS)によって、粒子径を測定することができる。
低分子量体の除去効率がより効率的になることから、組成物における上記フルオロポリマーの濃度は18.0質量%以下であることが好ましい。より好ましくは15.0質量%以下であり、更に好ましくは12.0質量%以下であり、特に好ましくは10.0質量%以下である。上記フルオロポリマーの濃度を上記範囲にすることでより効率的に低分子量体を除去することができる。上記フルオロポリマーの濃度は、0.5質量%以上が好ましく、1.0質量%以上がより好ましく、1.2質量%以上が更に好ましく、1.5質量%以上が特に好ましい。
水、及び、上記フルオロポリマーを含む組成物は、1種の単一のフルオロポリマーを含んでいてもよいし、2種以上の異なるフルオロポリマーを含んでいてもよい。
本開示の第1の製造方法は、工程Aの前に、水、及び、フルオロポリマーを含む組成物のpHを1.0~7.0にする工程を含むことも好ましい。
上記重合工程は、水、及び、フルオロポリマーを含む組成物が得られるものであれば限定されず、公知の方法を採用することができる。
工程Aにおいて用いる、水、及び、フルオロポリマーを含む組成物の粘度は、限外濾過、精密濾過又は透析膜処理が円滑に進むことから、25mPa・s以下が好ましい。組成物の粘度は、たとえば、フルオロポリマーの数平均分子量を調整する方法、組成物中のフルオロポリマーの濃度を調整する方法、組成物の温度を調整する方法などにより、調整することができる。
工程Aにおいて用いる、水、及び、上記フルオロポリマーを含む組成物は、低分子量体を含むものであってよく、例えば、低分子量体の含有量がフルオロポリマーに対して、好ましくは5.0%超であり、より好ましくは5.5%以上であり、さらに好ましくは6.0%以上であり、あるいは2.0%超である。
低分子量体としては、例えば、分子量700以上3000以下の化合物、分子量400以上3000以下の化合物、分子量700以上10000未満の化合物、構造単位M3を形成する単量体のダイマーおよびトリマー、後述する重合体αを構成する構造単位を形成する単量体のダイマーおよびトリマー、後述する水溶性重合体を構成する構造単位を形成する単量体のダイマーおよびトリマーなどが挙げられる。
上記低分子量体の含有量は、GPCのピーク面積より算出した値および/または液体クロマトグラフィ-質量分析法(LC/MS/MS)による測定により算出した値である。
また、上記分画分子量は、低分子量体低減の観点から、20×104Da以下が好ましく、10×104Da以下がより好ましい。
上記限外濾過膜の分画分子量は、例えば、重量平均分子量が既知のポリスチレンを膜に通水し、90%阻止できる分子量を分画分子量とすることができる。ポリスチレンの定量は、ゲル透過クロマトグラフィを用いて行うことができる。
中空糸型限外濾過膜の内径は限定されないが、例えば、0.1~2mmであってよい。好ましくは、0.8~1.4mmである。
中空糸型限外濾過膜の長さは限定されないが、例えば、0.05~3mであってよい。好ましくは、0.05~2mである。
限外濾過膜の材質は、有機材料であることが好ましく、塩素化ポリエチレン、ポリプロピレン、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリアクリルニトリル、ポリスルホン、又は、ポリエーテルスルホンであることがより好ましく、ポリアクリルニトリル又はポリフッ化ビニリデンが更に好ましい。
上記精密濾過膜は、効率的に低分子量体低減できることから、平均細孔径が0.1μm以上であることが好ましい。より好ましくは0.075μm以上であり、更に好ましくは0.1μm以上である。また、平均細孔径が1.00μm以下であることが好ましい。より好ましくは平均細孔径が0.50μm以下であり、更に好ましくは0.25μm以下である。
上記精密濾過膜の平均細孔径は、ASTM F 316-03(バブルポイント法)に準拠して測定することが可能である。
中空糸型限外濾過膜の内径は限定されないが、例えば、0.1~2mmであってよい。好ましくは、0.8~1.4mmである。
中空糸型限外濾過膜の長さは限定されないが、例えば、0.05~3mであってよい。好ましくは、0.05~2mである。
上記透析膜は、膜の目詰まりを抑制し、効率的に着色低減をできることから、分画分子量が0.3×104Da以上であることが好ましい。上記分画分子量は、0.5×104Da以上がより好ましく、1.0×104Da以上が更に好ましく、1.5×104Da以上が更により好ましく、2.0×104Da以上が殊更に好ましく、3.0×104Da以上が特に好ましく、5.0×104Da以上が最も好ましい。上記分画分子量は8.0×104Da以上であってもよい。
また、上記分画分子量は、着色低減の観点から、20×104Da以下が好ましく、10×104Da以下がより好ましい。
上記透析膜の分画分子量は、例えば、限外濾過膜と同じ方法で測定することができる。
従って、上記工程Aは、水、及び、上記フルオロポリマーを含む組成物に水を追加する工程を含んでもよく、上記水は、段階的に追加してもよいし、連続的に添加してもよい。また、水、及び、上記フルオロポリマーを含む組成物にpH調整剤を添加する工程を含んでもよい。
上記限外濾過、精密濾過又は透析膜処理の終点は、適宜決定すればよく限定されない。
また、上記限外濾過、精密濾過又は透析膜処理は、濾過膜の耐久性向上のため、濾過工程時において1~24時間を目安に一回程度水で逆洗浄してもよい。
本開示の第2の製造方法において、上記工程A1は、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下である重合体αを含む組成物を用いること以外は、本開示の第1の製造方法と同じ方法を全て採用できる。
なお、「炭素原子に結合した水素原子がフッ素原子に置換された割合」は、炭素原子に結合する水素原子と、炭素原子に結合するハロゲン原子(フッ素原子を含む)との合計数に対するフッ素原子数の割合として求められる。
CX1X3=CX2R-CZ1Z2-A0 (I)
(式中、X1およびX3は、それぞれ独立して、F、Cl、HまたはCF3であり;X2は、H、F、アルキル基または含フッ素アルキル基であり;A0は、アニオン性基であり;Rは連結基であり;Z1およびZ2は、それぞれ独立して、H、F、アルキル基または含フッ素アルキル基である)
X2としては、F、Cl、H又はCF3が好ましい。また、Z1及びZ2としては、FまたはCF3が好ましく、一方がFで他方がCF3であることがさらに好ましい。
式中、a、b、cおよびdは独立して少なくとも1以上である。a、b、cおよびdは独立して、2以上であってよく、3以上であってよく、4以上であってよく、10以上であってよく、20以上であってよい。a、b、cおよびdの上限は、たとえば、100である。
-CF2-O-(CX6 2)e-{O-CF(CF3)}f-(O)g- (r1)
(式中、X6はそれぞれ独立してH、FまたはCF3であり、eは0~3の整数であり、fは0~3の整数であり、gは0または1である)で表される2価の基が好ましく、一般式(r2):
-CF2-O-(CX7 2)e-(O)g- (r2)
(式中、X7はそれぞれ独立してH、FまたはCF3であり、eは0~3の整数であり、gは0または1である)で表される2価の基がより好ましい。
-CF2-O-(CX6 2)e-{O-CF(CF3)}f-(O)g-CZ1Z2- (s1)
(式中、X6はそれぞれ独立してH、FまたはCF3であり、eは0~3の整数であり、fは0~3の整数であり、gは0または1であり、Z1およびZ2は、それぞれ独立して、H、F、アルキル基または含フッ素アルキル基である)で表されるものが好ましく、式(s1)において、Z1およびZ2は、FまたはCF3がより好ましく、一方がFで他方がCF3であることがさらに好ましい。
-CF2-O-(CX7 2)e-(O)g-CZ1Z2- (s2)
(式中、X7はそれぞれ独立してH、FまたはCF3であり、eは0~3の整数であり、gは0または1であり、Z1およびZ2は、それぞれ独立して、H、F、アルキル基または含フッ素アルキル基である)で表されるものが好ましく、式(s2)において、Z1およびZ2は、FまたはCF3がより好ましく、一方がFで他方がCF3であることがさらに好ましい。
CF2=CF-O-Rf0-A0 (Ia)
(式中、A0はアニオン性基であり、Rf0は、過フッ素化されており、鎖状または分岐鎖状、環状または非環状構造、飽和または不飽和、置換または非置換であってもよく、硫黄、酸素、および窒素からなる群から選択される1つ以上のヘテロ原子を任意追加的に含有する過フッ素化二価連結基である。)
CH2=CH-O-Rf0-A0 (Ib)
(式中、A0はアニオン性基であり、Rf0は式Iaで定義される過フッ素化二価連結基である。)
CH2=CF-O-Rf0-A0 (Ic)
(式中、A0はアニオン性基であり、Rf0は式Iaで定義される過フッ素化二価連結基である。)
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)で表わされる単量体由来の構造単位M3を含む重合体が挙げられる。
CX2=CY(-O-Rf-A) (2)
(式中、Xは、同一または異なって、-HまたはFであり、Yは-H、-F、アルキル基または含フッ素アルキル基であり、Rfは炭素数1~40の含フッ素アルキレン基、または、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、前記と同じである。)
CF2=CF-O-(CF2)n1-A (2a)
(式中、n1は、1~10の整数を表し、Aは前記と同じ。)
CF2=CF-O-(CF2C(CF3)F)n2-A (2b)
(式中、n2は、1~5の整数を表し、Aは、前記定義と同じ。)
CF2=CF-O-(CFX1)n3-A (2c)
(式中、X1は、FまたはCF3を表し、n3は、1~10の整数を表し、Aは、前記定義と同じ。)
CF2=CF-O-(CF2CFX1O)n4-(CF2)n6-A (2d)
(式中、n4は、1~10の整数を表し、n6は、1~3の整数を表し、AおよびX1は、前記定義と同じ。)
CF2=CF-O-(CF2CF2CFX1O)n5-CF2CF2CF2-A (2e)
(式中、n5は、1~10の整数を表し、AおよびX1は、前記定義と同じ。)
CX2=CY(-Rf-A) (3)
(式中、Xは、同一または異なって、-HまたはFであり、Yは-H、-F、アルキル基または含フッ素アルキル基であり、Rfは炭素数1~40の含フッ素アルキレン基、または、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、前記と同じである。)
CF2=CF-(CF2)n1-A (3a)
(式中、n1は、1~10の整数を表し、Aは、前記定義と同じ。)で表される単量体、および、一般式(3b):
CF2=CF-(CF2C(CF3)F)n2-A (3b)
(式中、n2は、1~5の整数を表し、Aは、前記定義と同じ。)で表される単量体からなる群より選択される少なくとも1種が好ましい。
CX1X3=CX2RII(-CZ1Z2-A0)nII (II)
(式中、X1、X2、X3、A0、Z1およびZ2は上記定義と同じ、RIIは(nII+1)価連結基であり、nIIは2以上の整数である)
CF2=CF-CF2-O-QF1-CF(-QF2-CZ1Z2-A)2 (1-II)
(式中、Z1、Z2およびAは上記定義と同じ、QF1およびQF2は、同一又は異なって、単結合、炭素炭素間にエーテル結合を含んでいてもよい含フッ素アルキレン基または炭素炭素間にエーテル結合を含んでいてもよい含フッ素オキシアルキレン基である)
CF2=CF-O-QF1-CF(-QF2-CZ1Z2-A)2 (2-II)
(式中、Z1、Z2、A、QF1およびQF2は上記定義と同じ)
また、非含フッ素モノマーとして、アクリル酸エステル及びメタクリル酸エステルからなる群より選択される少なくとも一種の単量体、不飽和カルボン酸類、並びに、加水分解性シリル基含有単量体からなる群より選択される少なくとも1種がより好ましい。
そのほか、ラジカル重合性のエチレン性不飽和結合をもつ単量体を併用してもよい。
これらのアクリル酸エステルまたはメタクリル酸エステルは、単独で用いてもよいし、2種以上を併用してもよく、n-ブチルアクリレート、及び、メチルメタクリレートであることが好ましい。
CH2=CHCOO(CH2)3Si(OCH3)3、
CH2=CHCOO(CH2)3Si(CH3)(OCH3)2、
CH2=CHCOO(CH2)3Si(OC2H5)3、
CH2=CHCOO(CH2)3Si(CH3)(OC2H5)2、
CH2=C(CH3)COO(CH2)3Si(OCH3)3、
CH2=C(CH3)COO(CH2)3Si(CH3)(OCH3)2、
CH2=C(CH3)COO(CH2)3Si(OC2H5)3、
CH2=C(CH3)COO(CH2)3Si(CH3)(OC2H5)2、
CH2=C(CH3)COO(CH2)2O(CH2)3Si(OCH3)3、
CH2=C(CH3)COO(CH2)2(CH2)3Si(CH3)(OCH3)2、CH2=C(CH3)COO(CH2)11Si(OCH3)3、
CH2=C(CH3)COO(CH2)11Si(CH3)(OCH3)2、
などがあげられる。これらの加水分解性シリル基含有単量体は、単独で用いてもよいし、2種以上を併用してもよい。
数平均分子量が低すぎると、分散性が低下し、分散剤として使用できないおそれがある。数平均分子量が高すぎると、粘度が高くなってしまい、ハンドリングが煩雑になるおそれがある。
上記重合体αは、53以下のイオン交換率(IXR)を有する。上記IXRは、0.5以上が好ましく、1以上がより好ましく、3以上が更に好ましく、4以上が更により好ましく、5以上が殊更に好ましく、8以上が特に好ましい。また、IXRは43以下が好ましく、33以下がより好ましく、23以下が更に好ましい。上記重合体αにおいて、イオン性基(アニオン性基)は、典型的に、ポリマー主鎖に沿って分布している。上記重合体αは、ポリマー主鎖を、この主鎖に結合された繰り返し側鎖とともに含み、この側鎖はイオン性基を有することが好ましい。
重合体αは、10未満、より好ましくは7未満のpKaを有するイオン性基(アニオン性基)を含むことが好ましい。重合体αのイオン性基は、好ましくは、スルホナート、カルボキシラート、ホスホナート、ホスファート、及びそれらの混合物からなる群から選択される。
用語「スルホナート、カルボキシラート、ホスホナート、およびホスファート」は、それぞれの塩、または塩を形成し得るそれぞれの酸をいうことが意図される。塩が用いられる場合、好ましくは、その塩はアルカリ金属塩またはアンモニウム塩である。好ましいイオン性基は、スルホナート基である。
低分子量体の除去効率がより効率的になることから、上記重合体αの濃度18.0質量%以下であることが好ましい。より好ましくは15.0質量%以下であり、更に好ましくは12.0質量%以下であり、特に好ましくは10.0質量%以下である。上記重合体αの濃度を上記範囲にすることでより効率的に低分子量体を除去することができる。上記重合体αの濃度は、0.5質量%以上が好ましく、1.0質量%以上がより好ましく、1.2質量%以上が更に好ましく、1.5質量%以上が特に好ましい。
上記重合体αを含む組成物は、1種の単一の重合体αを含んでいてもよいし、2種以上の異なる重合体αを含んでいてもよい。
本開示の第2の製造方法は、工程A1の前に、重合体αを含む組成物のpHを1.0~7.0にする工程を含むことも好ましい。
工程A1において用いる上記重合体αを含む組成物は、低分子量体を含むものであってよく、例えば、低分子量体の含有量が重合体αに対して、好ましくは5.0%超であり、より好ましくは5.5%以上であり、さらに好ましくは6.0%以上であり、あるいは2.0%超である。
上記低分子量体の含有量は、GPCのピーク面積より算出した値および/または液体クロマトグラフィ-質量分析法(LC/MS/MS)による測定により算出した値である。
具体的には、単量体(I)の5水準以上の含有量の組成物を作成し、それぞれの含有量のLC/MS/MS分析を行ない、含有量と、その含有量に対するエリア面積(ピークの積分値)との関係をプロットし、単量体(I)の検量線を作成する。さらに、単量体(I)の検量線から、単量体(I)のダイマーおよびトリマーの検量線を作成する。
重合体αにメタノールを加えて混合物を調製し、遠心分離により混合物から抽出液(上澄み液)を回収し、得られた抽出液をLC/MS/MS分析する。
そして、検量線を用いて、単量体(I)のダイマーおよびトリマーのクロマトグラムのエリア面積(ピークの積分値)を、ダイマーおよびトリマーの含有量に換算することができる。
本開示の第3の製造方法により得られる組成物は、水溶液であってよい。
上記工程A2において、上記限外濾過、精密濾過又は透析膜処理は、10℃以上の温度で行うことが好ましい。より好ましくは、15℃以上であり、更に好ましくは、20℃以上であり、特に好ましくは、30℃以上である。温度を上記範囲にすることでより効率的に低分子量体を低減することができる。上記温度は、90℃以下が好ましく、80℃以下がより好ましく、70℃以下が更に好ましく、60℃以下が特に好ましい。
限外濾過は、分画分子量が1.5×104Da以上の限外濾過膜を用いて行うことが好ましい。
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)
で表わされる単量体由来の構造単位M3を含む重合体であるフルオロポリマーを含み、分子量700以上3000以下の化合物の含有量が上記フルオロポリマーに対して3.5%以下であることを特徴とする組成物(以下「本開示の第1の組成物」ともいう)にも関する。
本開示の第1の組成物は、分子量400以上3000以下の化合物の含有量が前記フルオロポリマーに対して3.7%以下であることが好ましい。
また、本開示の第1の組成物は、分子量700以上10000未満の化合物の含有量が前記フルオロポリマーに対して5.0%以下であることが好ましい。
本開示の第1の組成物は、低分子量体が低減されていることによって、ポリマー分散体への分散剤として用いた場合に、分散性(他の成分を分散させる性質)を向上させることができる。
また、本開示の第1の組成物から得られたコーティング剤は、透明性、撥水性、反射防止性に優れる。
本開示の第1の組成物は、好適には本開示の第1の製造方法により、製造することができる。
例えば、上記一般式(1)において、Xは少なくとも1つが-Hであってよいし、両方が-Hであってもよい。上記Rfは炭素数1~10の含フッ素アルキレン基、又は、エーテル結合を有する炭素数2~12の含フッ素アルキレン基であることが好ましい。Aは、-COOMが好ましく、Mは、-H、-Na、-K、-Li又は-NH4が好ましい。
上記構造単位M3としては、例えば、下記一般式(1a):
CX2=CFCF2-O-(CF(CF3)CF2O)n5-CF(CF3)-A (1a)
(式中、各Xは、同一であり、F又はHを表す。n5は0又は1~10の整数を表し、Aは、上記定義と同じ。)で表されるフルオロアリルエーテル化合物に基づく構造単位(1a)が好ましく、下記一般式(1A)で表される単量体に基づく構造単位(1A)であることも好ましい。
CH2=CF(-CF2-O-Rf-A) (1A)
(式中、Rf及びAは前記と同じ。)
上記フルオロポリマーは、イオン性基を含むことが好ましく、イオン交換率が53以下であることが好ましい。
上記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であることが好ましい。
上記フルオロポリマーは、水溶性重合体であることが好ましい。
本開示の第1の組成物は、上述した本開示の第1の製造方法で得られた組成物を希釈又は濃縮したものであってもよい。
本開示の第1の組成物は、1種の単一のフルオロポリマーを含んでいてもよいし、2種以上の異なるフルオロポリマーを含んでいてもよい。
上記分子量が700以上3000以下の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が400以上3000以下の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が400以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上10000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上10000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上3000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上3000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上5000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上5000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上20000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
また、本開示の第1の組成物からフルオロポリマーを分離して使用してもよい。例えば、上記フルオロポリマーを分離して分散剤として使用することができる。分散剤は、例えば、ポリマーを重合する際に使用することができるし、ポリマーを重合した後に添加する分散剤として使用することもできる。
上記フルオロモノマーとしては、少なくとも1つのフッ素またはフルオロアルキル基を有するモノマーであれば特に限定されるものではなく、例えば、トリフルオロエチレン、テトラフルオロエチレン(TFE)、フッ化ビニリデン(VdF)、フッ化ビニル(VF)、クロロトリフルオロエチレン(CTFE)、ヘキサフルオロプロピレン(HFP)、ヘキサフルオロイソブチレン、パーフルオロアルキルエチレン、フルオロビニルエーテル(FVE)、CH2=CFCF3、CHF=CHCF3(E体)、CHF=CHCF3(Z体)等を含んでよい。
上記他のフルオロポリマーとしては、PTFE及び60.0~98.0質量%のTFE単位および2.0~40.0質量%の他のモノマーを含む溶融加工性フッ素樹脂からなる群より選択される少なくとも1種が好ましく、特にPTFEが好ましい。
本開示の第2の組成物は、分子量400以上3000以下の化合物の含有量が重合体αに対して3.7%以下であることが好ましい。
また、本開示の第2の組成物は、分子量700以上10000未満の化合物の含有量が重合体αに対して5.0%以下であることが好ましい。
本開示の第2の組成物は、低分子量体が低減されていることによって、ポリマー分散体への分散剤として用いた場合に、分散性(他の成分を分散させる性質)を向上させることができる。
本開示の第2の組成物は、好適には本開示の第2の製造方法により、製造することができる。
本開示の第2の組成物は水を含む。水の含有量は限定されず、フルオロポリマーが分散又は溶解できる量であることが好ましい。
本開示の第2の組成物における重合体αとしては、本開示の第2の製造方法で記載したものが挙げられる。また、好適な態様を全て採用できる。
上記重合体αは、水溶性重合体であることが好ましい。
本開示の第2の組成物は、上述した本開示の第2の製造方法で得られた組成物を希釈又は濃縮したものであってもよい。
本開示の第2の組成物は、1種の単一の重合体αを含んでいてもよいし、2種以上の異なる重合体αを含んでいてもよい。
上記分子量が700以上3000以下の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が400以上3000以下の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が400以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上10000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上10000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上3000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上3000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上5000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上5000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上20000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上20000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
また、本開示の第2の組成物から重合体αを分離して使用してもよい。例えば、上記重合体αを分離して分散剤として使用することができる。分散剤は、例えば、ポリマーを重合する際に使用することができるし、ポリマーを重合した後に添加する分散剤として使用することもできる。
上記フルオロモノマーとしては、少なくとも1つのフッ素またはフルオロアルキル基を有するモノマーであれば特に限定されるものではなく、例えば、トリフルオロエチレン、テトラフルオロエチレン(TFE)、フッ化ビニリデン(VdF)、フッ化ビニル(VF)、クロロトリフルオロエチレン(CTFE)、ヘキサフルオロプロピレン(HFP)、ヘキサフルオロイソブチレン、パーフルオロアルキルエチレン、およびフルオロビニルエーテル(FVE)、CH2=CFCF3、CHF=CHCF3(E体)、CHF=CHCF3(Z体)等を含んでよい。
上記他の重合体としては、PTFE及び60.0~98.0質量%のTFE単位および2.0~40.0質量%の他のモノマーを含む溶融加工性フッ素樹脂からなる群より選択される少なくとも1種が好ましく、特にPTFEが好ましい。
本開示の第3の組成物は、分子量400以上3000以下の化合物の含有量が水溶性重合体に対して3.7%以下であることが好ましい。
分子量700以上10000未満の化合物の含有量が水溶性重合体に対して5.0%以下であることが好ましい。
本開示の第3の組成物は、低分子量体が低減されていることによって、ポリマー分散体への分散剤として用いた場合に、分散性(他の成分を分散させる性質)を向上させることができる。
本開示の第3の組成物は、好適には本開示の第3の製造方法により、製造することができる。
本開示の第3の組成物は水を含む。水の含有量は限定されず、水溶性重合体が分散又は溶解できる量であることが好ましく、水溶性重合体が溶解できる量であることが好ましい。
本開示の第3の組成物における水溶性重合体としては、本開示の第3の製造方法で記載したものが挙げられる。また、好適な態様を全て採用できる。
本開示の第3の組成物は、上述した本開示の第3の製造方法で得られた組成物を希釈又は濃縮したものであってもよい。
本開示の第3の組成物は、1種の単一の水溶性重合体を含んでいてもよいし、2種以上の異なる水溶性重合体を含んでいてもよい。
本開示の第3の組成物は、上述した本開示の第3の製造方法で得られた組成物を希釈又は濃縮したものであってもよい。
本開示の第3の組成物は、1種の単一の水溶性重合体を含んでいてもよいし、2種以上の異なる水溶性重合体を含んでいてもよい。
上記分子量が700以上3000以下の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が400以上3000以下の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が400以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上10000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上10000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上3000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上3000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上5000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上5000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記分子量が700以上20000未満の化合物の含有量はGPCのピーク面積により算出した値である。
上記分子量が700以上20000未満の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
また、本開示の第3の組成物から水溶性重合体を分離して使用してもよい。例えば、上記水溶性重合体を分離して分散剤として使用することができる。分散剤は、例えば、ポリマーを重合する際に使用することができるし、ポリマーを重合した後に添加する分散剤として使用することもできる。
上記フルオロモノマーとしては、少なくとも1つのフッ素またはフルオロアルキル基を有するモノマーであれば特に限定されるものではなく、例えば、トリフルオロエチレン、テトラフルオロエチレン(TFE)、フッ化ビニリデン(VdF)、フッ化ビニル(VF)、クロロトリフルオロエチレン(CTFE)、ヘキサフルオロプロピレン(HFP)、ヘキサフルオロイソブチレン、パーフルオロアルキルエチレン、およびフルオロビニルエーテル(FVE)、CH2=CFCF3、CHF=CHCF3(E体)、CHF=CHCF3(Z体)等を含んでよい。
上記他の重合体としては、PTFE及び60.0~98.0質量%のTFE単位および2.0~40.0質量%の他のモノマーを含む溶融加工性フッ素樹脂からなる群より選択される少なくとも1種が好ましく、特にPTFEが好ましい。
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)で表わされる単量体由来の構造単位M3を含む重合体であるフルオロポリマーを含み、前記フルオロポリマーを構成する構造単位を形成する単量体のダイマーおよびトリマーの含有量が前記フルオロポリマーに対して2.0%以下であることを特徴とする組成物(以下「本開示の第4の組成物」ともいう)にも関する。
本開示の第4の組成物は、ダイマーおよびトリマーの含有量が低減されていることから、本開示の第4の組成物を水性媒体中でのモノマーの重合に用いることによって、ダイマーおよびトリマーの含有量が低減されたポリマーを得ることができる。
本開示の第4の組成物は、好適には本開示の第1の製造方法により、製造することができる。
上記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であることが好ましい。
上記フルオロポリマーは、イオン性基を含むことが好ましく、イオン交換率が53以下であることが好ましい。
上記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であることが好ましい。
上記フルオロポリマーは、水溶性重合体であることが好ましい。
本開示の第4の組成物は、上述した本開示の第1の製造方法で得られた組成物を希釈又は濃縮したものであってもよい。
本開示の第4の組成物は、1種の単一のフルオロポリマーを含んでいてもよいし、2種以上の異なるフルオロポリマーを含んでいてもよい。
分子量が700以上1000未満の化合物、分子量が700以上3000以下の化合物および分子量が400以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記フルオロモノマーとしては、少なくとも1つのフッ素またはフルオロアルキル基を有するモノマーであれば特に限定されるものではなく、例えば、トリフルオロエチレン、テトラフルオロエチレン(TFE)、フッ化ビニリデン(VdF)、フッ化ビニル(VF)、クロロトリフルオロエチレン(CTFE)、ヘキサフルオロプロピレン(HFP)、ヘキサフルオロイソブチレン、パーフルオロアルキルエチレン、およびフルオロビニルエーテル(FVE)、CH2=CFCF3、CHF=CHCF3(E体)、CHF=CHCF3(Z体)等を含んでよい。
上記他の重合体としては、PTFE及び60.0~98.0質量%のTFE単位および2.0~40.0質量%の他のモノマーを含む溶融加工性フッ素樹脂からなる群より選択される少なくとも1種が好ましく、特にPTFEが好ましい。
本開示の第5の組成物は、ダイマーおよびトリマーの含有量が低減されていることから、本開示の第5の組成物を水性媒体中でのモノマーの重合に用いることによって、ダイマーおよびトリマーの含有量が低減されたポリマーを得ることができる。
本開示の第5の組成物は、好適には本開示の第2の製造方法により、製造することができる。
上記重合体αは、水溶性重合体であることが好ましい。
本開示の第5の組成物は、上述した本開示の第2の製造方法で得られた組成物を希釈又は濃縮したものであってもよい。
本開示の第5の組成物は、1種の単一の重合体αを含んでいてもよいし、2種以上の異なる重合体αを含んでいてもよい。
分子量が700以上1000未満の化合物、分子量が700以上3000以下の化合物および分子量が400以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記フルオロモノマーとしては、少なくとも1つのフッ素またはフルオロアルキル基を有するモノマーであれば特に限定されるものではなく、例えば、トリフルオロエチレン、テトラフルオロエチレン(TFE)、フッ化ビニリデン(VdF)、フッ化ビニル(VF)、クロロトリフルオロエチレン(CTFE)、ヘキサフルオロプロピレン(HFP)、ヘキサフルオロイソブチレン、パーフルオロアルキルエチレン、およびフルオロビニルエーテル(FVE)、CH2=CFCF3、CHF=CHCF3(E体)、CHF=CHCF3(Z体)等を含んでよい。
上記他の重合体としては、PTFE及び60.0~98.0質量%のTFE単位および2.0~40.0質量%の他のモノマーを含む溶融加工性フッ素樹脂からなる群より選択される少なくとも1種が好ましく、特にPTFEが好ましい。
本開示の第6の組成物は、ダイマーおよびトリマーの含有量が低減されていることから、本開示の第6の組成物を水性媒体中でのモノマーの重合に用いることによって、ダイマーおよびトリマーの含有量が低減されたポリマーを得ることができる。
本開示の第6の組成物は、好適には本開示の第3の製造方法により、製造することができる。
本開示の第6の組成物は、上述した本開示の第3の製造方法で得られた組成物を希釈又は濃縮したものであってもよい。
本開示の第6の組成物は、1種の単一の水溶性重合体を含んでいてもよいし、2種以上の異なる水溶性重合体を含んでいてもよい。
分子量が700以上1000未満の化合物、分子量が700以上3000以下の化合物および分子量が400以上3000以下の化合物は限定されず、上記分子量を有する化合物であれば全て含まれる。
上記フルオロモノマーとしては、少なくとも1つのフッ素またはフルオロアルキル基を有するモノマーであれば特に限定されるものではなく、例えば、トリフルオロエチレン、テトラフルオロエチレン(TFE)、フッ化ビニリデン(VdF)、フッ化ビニル(VF)、クロロトリフルオロエチレン(CTFE)、ヘキサフルオロプロピレン(HFP)、ヘキサフルオロイソブチレン、パーフルオロアルキルエチレン、およびフルオロビニルエーテル(FVE)、CH2=CFCF3、CHF=CHCF3(E体)、CHF=CHCF3(Z体)等を含んでよい。
上記他の重合体としては、PTFE及び60.0~98.0質量%のTFE単位および2.0~40.0質量%の他のモノマーを含む溶融加工性フッ素樹脂からなる群より選択される少なくとも1種が好ましく、特にPTFEが好ましい。
フルオロポリマー(水溶性重合体)のMw、Mn及び分子量700以上10000未満の低分子量体の含有量は、ゲルパーミエーションクロマトグラフィ(GPC)により、東ソー社製およびAgilent社製単分散ポリエチレンオキサイド(PEO)、ポリエチレングリコール(PEG)を標準として分子量を算出して求めた。
(1)水溶液からの抽出
重合体の水溶液の濃度を測定し、重合体の固形分0.2gに相当する量の水溶液を秤量した。その後、水溶液中に含まれている水と合わせ、水とメタノールとの体積比が50/50(体積%)となるように、水とメタノールを加え、重合体ならびに水およびメタノールを含有する混合液を得た。その後、得られた混合液を用いて、4000rpmで1時間遠心分離を行い、重合体を含む上澄み液を抽出液として回収した。
液体クロマトグラフ質量分析計(Waters, LC-MS ACQUITY UPLC/TQD)を用いて、抽出液の分析を行い、抽出液のクロマトグラムを得た。
抽出液に含まれる単量体のダイマーおよびトリマーの含有量は、抽出液のクロマトグラムに現れる単量体のダイマーおよびトリマーに由来するピークの積分値を、検量線を用いて、単量体のダイマーおよびトリマーの含有量に換算することにより求めた。
1ng/mL~100ng/mLの含有量既知の単量体のメタノール標準溶液を5水準調製し、液体クロマトグラフ質量分析計(Waters, LC-MS ACQUITY UPLC/TQD)を用いて測定を行った。それぞれの単量体の含有量と、その含有量に対するピークの積分値との関係をプロットし、各単量体の検量線(一次近似)を作成した。次に、各単量体の検量線(一次近似)を用いて、各単量体のダイマーおよびトリマーの検量線を作成した。
重合体水溶液約1gを、減圧乾燥機中で60℃、60分の条件で乾燥し、加熱残分の質量を測定し、重合体水溶液の質量(1g)に対する、加熱残分の質量の割合を百分率で表した値を採用した。
CH2=CFCF2OCF(CF3)COOHで表される単量体140g、水260g、APS(0.5mol%)を加え、窒素雰囲気下にて60℃で17時間加熱撹拌し、CH2=CFCF2OCF(CF3)COOHの単独重合体であるフルオロポリマーを含むフルオロポリマー水溶液A-1を得た。GPC分析した結果、フルオロポリマーのMw32万、Mn10万、分子量700以上10000未満の低分子量体の含有量が、フルオロポリマーに対して7.1%であった。また、分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して3.7%であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して3.9%であった。
フルオロポリマー水溶液A-1に水を加えて、フルオロポリマーの濃度を2.0質量%に調整したのちに、限外ろ過膜(分画分子量50000Da)を用いて限外濾過を実施した。適宜注水を行いながら限外濾過を実施した。限外濾過後の水溶液をGPC分析した結果、フルオロポリマーのMw36万、Mn14万、分子量700以上10000未満の低分子量体の含有量が、フルオロポリマーに対して0.7%であった。以上より低分子量体の除去は本方法が有効であったことが分かった。また、分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して0.6%以下であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して0.6%以下であった。
フルオロポリマー水溶液A-1に水を加えて調製した、フルオロポリマーの濃度が2.0質量%の水溶液(固形分35g)に10%塩酸を50g加え、フルオロポリマーを析出させ、析出したフルオロポリマーをアセトンに溶解させたものをn-ヘキサンに注ぎ、分離、真空乾燥させ、無色透明な重合体34.7gを得た。得た重合体をGPC分析した結果、フルオロポリマーのMw35万、Mn13万、分子量700以上10000未満の低分子量体の含有量が、フルオロポリマーに対して6.8質量%であった。また、分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して3.6%であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して3.8%であった。
以上より、水溶液からフルオロポリマーを析出して回収する従来の方法では、低分子量体をほとんど除去できないことが分かった。
CF2=CFOCF2CF2COOHで表される単量体E10g、水30g、APS(単量体Eに対して6.0mol%)を反応器に加え、窒素雰囲気下にて80℃で23時間加熱撹拌し、CF2=CFOCF2CF2COOHの単独重合体である重合体Eを含む重合体E水溶液E-1を得た。得られた重合体E水溶液E-1をGPC分析した結果、重合体Eは、Mw0.7万、Mn0.5万であった。分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して4.6%であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して4.6%であった。
得られた重合体E水溶液E-1に水を加えて、透析膜(分画分子量35000Da、ポリエチレン製)に、30℃で接触させ濾過を実施し、重合体E水溶液E-2を得た。得られた重合体E水溶液E-2をGPC分析およびLC-MS分析した結果、重合体Eは、Mw0.7万、Mn0.6万、ダイマー、及びトリマーの含有量が、重合体Eに対して1質量ppm未満であった。得られた重合体E水溶液E-2の濃度は、3.6質量%であった。分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して0.05%以下であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して0.05%以下であった。
CF2=CFOCF2CF(CF3)OCF2COOHで表される単量体F4.1gとCF2=CF25.2g、APS(単量体Fに対して8.8mol%)を加え、窒素雰囲気下にて80℃で7時間加熱撹拌し、CF2=CFOCF2CF(CF3)OCF2COOHで表される単量体FとCF2=CF2の共重合体(重合体F)を含む重合体F水溶液F-1を得た。得られた重合体F水溶液F-1をGPC分析した結果、重合体Fは、Mw0.7万、Mn0.4万であった。分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して4.5%であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して4.6%であった。
得られた重合体F水溶液F-1に、透析膜(分画分子量35000Da、ポリエチレン製)に、30℃で接触させ濾過を実施し、重合体F水溶液F-2を得た。得られた重合体F水溶液F-2をGPC分析およびLC-MS分析した結果、重合体Fは、Mw0.9万、Mn0.6万、ダイマー、及びトリマーの含有量が、重合体Fに対して1質量ppm未満であった。得られた重合体F水溶液F-2の濃度は、2.0質量%であった。分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して0.05%以下であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して0.05%以下であった。
CF2=CFOCF2CF2COOHで表される単量体E10g、水30g、APS(単量体Eに対して2.5mol%分割)を反応器に加え、窒素雰囲気下にて50℃で76時間加熱撹拌し、CF2=CFOCF2CF2COOHの単独重合体である重合体Eを含む重合体E水溶液E-1を得た。得られた重合体E水溶液E-1をGPC分析およびLC-MS分析した結果、重合体Eは、Mw1.3万、Mn0.8万であった。分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して3.9%であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して4.0%であった。
得られた重合体E水溶液E-1に水を加えて、透析膜(分画分子量35000Da、ポリエチレン製)に、30℃で接触させ濾過を実施し、重合体E水溶液E-2を得た。得られた重合体E水溶液E-2をGPC分析およびLC-MS分析した結果、重合体Eは、Mw1.3万、Mn1.0万、ダイマー、及びトリマーの含有量が、重合体Eに対して1質量ppm未満であった。得られた重合体E水溶液E-2の濃度は、3.5質量%であった。分子量700以上3000以下の低分子量体の含有量が、フルオロポリマーに対して0.05%以下であった。また、分子量400以上3000以下の低分子量体の含有量が、フルオロポリマーに対して0.05%以下であった。
Claims (48)
- 水、及び、フルオロポリマーを含む組成物を限外濾過、精密濾過又は透析膜処理、若しくは、それらの組合せを実施する工程Aを含み、
前記フルオロポリマーは、一般式(1):
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)
で表わされる単量体由来の構造単位M3を含む重合体である
ことを特徴とする組成物の製造方法。 - 一般式(1)中、Xの少なくとも1つが-Hである請求項1記載の製造方法。
- 一般式(1)中、Xの両方が-Hである請求項1又は2記載の製造方法。
- 一般式(1)中、Rfが炭素数1~10の含フッ素アルキレン基、又は、エーテル結合を有する炭素数2~12の含フッ素アルキレン基である請求項1~3のいずれかに記載の製造方法。
- 構造単位M3は、下記一般式(1A)で表される単量体に基づく構造単位(1A)である請求項1~4のいずれかに記載の製造方法。
CH2=CF(-CF2-O-Rf-A) (1A)
(式中、Rf及びAは前記と同じ。) - 構造単位M3は、下記一般式(1a)で表されるフルオロアリルエーテル化合物に基づく構造単位(1a)である請求項1~5のいずれかに記載の製造方法。
CX2=CFCF2-O-(CF(CF3)CF2O)n5-CF(CF3)-A (1a)
(式中、各Xは、同一であり、F又はHを表す。n5は0又は1~10の整数を表し、Aは、前記定義と同じ。) - Aは、-COOMである請求項1~6のいずれかに記載の製造方法。
- Mが-H、-Na、-K、-Li又は-NH4である請求項1~7のいずれかに記載の製造方法。
- 前記フルオロポリマーは、前記構造単位M3が全重合単位に対して5~100モル%であり、前記一般式(1)で表される単量体と共重合可能な単量体由来の構造単位N3が全重合単位に対して0~95モル%である重合体である請求項1~8のいずれかに記載の製造方法。
- 前記構造単位N3は、テトラフルオロエチレン由来の構造単位である請求項9記載の製造方法。
- 前記フルオロポリマーは、数平均分子量が0.5×104~75.0×104である重合体である請求項1~10のいずれかに記載の製造方法。
- 前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下である重合体である請求項1~11のいずれかに記載の製造方法。
- 前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体である請求項1~12のいずれかに記載の製造方法。
- 水、及び、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下である重合体を含む組成物を限外濾過、精密濾過又は透析膜処理、若しくは、それらの組合せを実施する工程A1を含むことを特徴とする組成物の製造方法。
- 前記重合体は、数平均分子量が0.5×104~75.0×104である重合体である請求項14記載の製造方法。
- 前記重合体は、水溶性重合体である請求項14又は15記載の製造方法。
- 水、及び、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体を含む組成物を限外濾過、精密濾過又は透析膜処理、若しくは、それらの組合せを実施する工程A2を含むことを特徴とする組成物の製造方法。
- 前記限外濾過、精密濾過又は透析膜処理は、20℃以上の温度で行う請求項1~17のいずれかに記載の製造方法。
- 前記限外濾過は、分画分子量が1.5×104Da以上の限外濾過膜を用いて行う請求項1~18のいずれかに記載の製造方法。
- 水、及び、一般式(1):
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)
で表わされる単量体由来の構造単位M3を含む重合体であるフルオロポリマーを含み、
分子量700以上3000以下の化合物の含有量が前記フルオロポリマーに対して3.5%以下である
ことを特徴とする組成物。 - 分子量400以上3000以下の化合物の含有量が前記フルオロポリマーに対して3.7%以下である請求項20に記載の組成物。
- 分子量700以上10000未満の化合物の含有量が前記フルオロポリマーに対して5.0%以下である請求項20に記載の組成物。
- 一般式(1)中、Xの少なくとも1つが-Hである請求項20~22のいずれか記載の組成物。
- 一般式(1)中、Xの両方が-Hである請求項20~23のいずれか記載の組成物。
- 一般式(1)中、Rfが炭素数1~10の含フッ素アルキレン基、又は、エーテル結合を有する炭素数2~12の含フッ素アルキレン基である請求項20~24のいずれかに記載の組成物。
- 構造単位M3は、下記一般式(1A)で表される単量体に基づく構造単位(1A)である請求項20~25のいずれかに記載の組成物。
CH2=CF(-CF2-O-Rf-A) (1A)
(式中、Rf及びAは前記と同じ。) - 構造単位M3は、下記一般式(1a)で表されるフルオロアリルエーテル化合物に基づく構造単位(1a)である請求項20~26のいずれかに記載の組成物。
CX2=CFCF2-O-(CF(CF3)CF2O)n5-CF(CF3)-A (1a)
(式中、各Xは、同一であり、F又はHを表す。n5は0又は1~10の整数を表し、Aは、前記定義と同じ。) - Aは、-COOMである請求項20~27のいずれかに記載の組成物。
- Mが-H、-Na、-K、-Li又は-NH4である請求項20~28のいずれかに記載の組成物。
- 前記フルオロポリマーは、前記構造単位M3が全重合単位に対して5~100モル%であり、前記一般式(1)で表される単量体と共重合可能な単量体由来の構造単位N3が全重合単位に対して0~95モル%である重合体である請求項20~29のいずれかに記載の組成物。
- 前記フルオロポリマーは、数平均分子量が0.5×104~75.0×104である重合体である請求項20~30のいずれかに記載の組成物。
- 前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下である請求項20~31のいずれかに記載の組成物。
- 前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体である請求項20~32のいずれかに記載の組成物。
- 水、及び、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下である重合体を含み、
分子量700以上3000以下の化合物の含有量が前記重合体に対して3.5%以下である
ことを特徴とする組成物。 - 分子量400以上3000以下の化合物の含有量が前記重合体に対して3.7%以下である請求項34に記載の組成物。
- 分子量700以上10000未満の化合物の含有量が前記重合体に対して5.0%以下である請求項34に記載の組成物。
- 前記重合体は、数平均分子量が0.5×104~75.0×104である重合体である請求項34~36のいずれかに記載の組成物。
- 前記重合体は、水溶性重合体である請求項34~37のいずれか記載の組成物。
- 水、及び、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体を含み、
分子量700以上3000以下の化合物の含有量が前記水溶性重合体に対して3.5%以下である
ことを特徴とする組成物。 - 分子量400以上3000以下の化合物の含有量が前記水溶性重合体に対して3.7%以下である請求項39に記載の組成物。
- 分子量700以上10000未満の化合物の含有量が前記水溶性重合体に対して5.0%以下である請求項39に記載の組成物。
- 水、及び、一般式(1):
CX2=CY(-CZ2-O-Rf-A) (1)
(式中、Xは、同一又は異なって、-H又は-Fであり、Yは-H、-F、アルキル基又は含フッ素アルキル基であり、Zは、同一又は異なって、-H、-F、アルキル基又はフルオロアルキル基である。Rfは炭素数1~40の含フッ素アルキレン基、又は、炭素数2~100のエーテル結合を有する含フッ素アルキレン基である。Aは、-COOM、-SO3M、-OSO3M又は-C(CF3)2OM(Mは、-H、金属原子、-NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基)である。但し、X、Y及びZの少なくとも1つはフッ素原子を含む。)
で表わされる単量体由来の構造単位M3を含む重合体であるフルオロポリマーを含み、
前記フルオロポリマーを構成する構造単位を形成する単量体のダイマーおよびトリマーの含有量が前記フルオロポリマーに対して2.0%以下であることを特徴とする組成物。 - 前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下である重合体である請求項42記載の組成物。
- 前記フルオロポリマーは、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体である請求項42又は43記載の組成物。
- 水、及び、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上であり、かつ、イオン性基を含み、イオン交換率が53以下である重合体を含み、
前記重合体を構成する構造単位を形成する単量体のダイマーおよびトリマーの含有量が前記重合体に対して2.0%以下であることを特徴とする組成物。 - 前記重合体は、水溶性重合体である請求項45記載の組成物。
- 水、及び、炭素原子に結合した水素原子がフッ素原子に置換された割合が50%以上である水溶性重合体を含み、
前記水溶性重合体を構成する構造単位を形成する単量体のダイマーおよびトリマーの含有量が前記水溶性重合体に対して2.0%以下であることを特徴とする組成物。 - コーティング剤である請求項20~47のいずれかに記載の組成物。
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WO2022107894A1 (ja) * | 2020-11-19 | 2022-05-27 | ダイキン工業株式会社 | ポリテトラフルオロエチレンの製造方法およびポリテトラフルオロエチレンを含有する組成物 |
WO2022107889A1 (ja) * | 2020-11-19 | 2022-05-27 | ダイキン工業株式会社 | フルオロポリマーおよびその製造方法 |
WO2022107888A1 (ja) * | 2020-11-19 | 2022-05-27 | ダイキン工業株式会社 | フルオロポリマーおよびその製造方法 |
CN116406351A (zh) * | 2020-11-19 | 2023-07-07 | 大金工业株式会社 | 含氟聚合物及其制造方法 |
EP4249467A4 (en) * | 2020-11-19 | 2024-10-02 | Daikin Ind Ltd | FLUOROPOLYMER AND PROCESS FOR MANUFACTURING THE SAME |
EP4249524A4 (en) * | 2020-11-19 | 2024-10-16 | Daikin Ind Ltd | FLUOROPOLYMER AND METHOD FOR PRODUCING SAME |
WO2022244785A1 (ja) * | 2021-05-19 | 2022-11-24 | ダイキン工業株式会社 | フルオロポリマー、水溶液およびコーティング組成物 |
WO2023182228A1 (ja) * | 2022-03-23 | 2023-09-28 | ダイキン工業株式会社 | フルオロポリマー、水溶液、コーティング組成物およびフルオロポリマーの製造方法 |
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JP7557152B2 (ja) | 2024-09-27 |
EP3960775A1 (en) | 2022-03-02 |
CN113748135A (zh) | 2021-12-03 |
JP7295456B2 (ja) | 2023-06-21 |
JP2023106602A (ja) | 2023-08-01 |
US20220195080A1 (en) | 2022-06-23 |
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EP3960775A4 (en) | 2023-01-25 |
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