JP2022179956A - Liquid composition for forming hydrophilic and oleophobic film and method for producing the same, hydrophilic and oleophobic film and hydrophilic and oleophobic nonwoven fabric - Google Patents
Liquid composition for forming hydrophilic and oleophobic film and method for producing the same, hydrophilic and oleophobic film and hydrophilic and oleophobic nonwoven fabric Download PDFInfo
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- JP2022179956A JP2022179956A JP2021086796A JP2021086796A JP2022179956A JP 2022179956 A JP2022179956 A JP 2022179956A JP 2021086796 A JP2021086796 A JP 2021086796A JP 2021086796 A JP2021086796 A JP 2021086796A JP 2022179956 A JP2022179956 A JP 2022179956A
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- 239000007788 liquid Substances 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000004745 nonwoven fabric Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 239000011737 fluorine Substances 0.000 claims abstract description 50
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 49
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 39
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 150000001298 alcohols Chemical class 0.000 claims abstract description 7
- 239000005871 repellent Substances 0.000 claims description 55
- 239000002270 dispersing agent Substances 0.000 claims description 27
- 150000002222 fluorine compounds Chemical class 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000003921 oil Substances 0.000 description 26
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 9
- -1 nitrogen-containing fluorine compound Chemical class 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 8
- 239000004584 polyacrylic acid Substances 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
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- 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
- C09D5/16—Antifouling paints; Underwater paints
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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Abstract
Description
本発明は、防汚機能を備えた親水撥油性膜形成用液組成物及びその製造方法に関する。またこの液組成物が硬化した成分を含む親水撥油性膜及びこの親水撥油性膜が繊維表面に形成された不織布に関する。 TECHNICAL FIELD The present invention relates to a hydrophilic oil-repellent film-forming liquid composition having an antifouling function and a method for producing the same. It also relates to a hydrophilic oil-repellent film containing a component obtained by curing the liquid composition and a non-woven fabric having the hydrophilic oil-repellent film formed on the fiber surface.
本発明者は、この種の親水撥油性膜形成用液組成物として、親水撥油剤と、造膜剤と、溶媒とを含む防汚性膜形成用液組成物を提案した（特許文献１（請求項１）参照。）。この液組成物は、親水撥油剤が両性型含窒素フッ素系化合物であり、造膜剤がポリアクリル酸であり、かつ溶媒が炭素数１～３の範囲にある１種又は２種以上のアルコール及び水であり、フッ素系化合物とポリアクリル酸とアルコールと水との質量比が、フッ素系化合物：ポリアクリル酸：アルコール：水＝（０．００１～０．１）：（０．１～４）：（２５～５５）：（４０～７５）であることを特徴とする。
特許文献１記載の発明によれば、塗膜を形成した場合に、膜表面が親水撥油性になって、防汚機能を膜に付与することができ、膜に虹色の干渉縞を発生せず、膜の外観が良好である。また水を含んだ布等により油で汚れた膜ごと除去できる。
The present inventor proposed a liquid composition for forming an antifouling film containing a hydrophilic oil-repellent agent, a film-forming agent, and a solvent as this type of liquid composition for forming a hydrophilic oil-repellent film (Patent Document 1 ( See claim 1).). In this liquid composition, the hydrophilic oil repellent is an amphoteric nitrogen-containing fluorine compound, the film-forming agent is polyacrylic acid, and the solvent is one or more alcohols having 1 to 3 carbon atoms. and water, and the mass ratio of the fluorine compound, polyacrylic acid, alcohol and water is fluorine compound: polyacrylic acid: alcohol: water = (0.001 to 0.1): (0.1 to 4 ):(25-55):(40-75).
According to the invention described in Patent Document 1, when a coating film is formed, the film surface becomes hydrophilic and oil-repellent, so that the film can be given an antifouling function, and rainbow-colored interference fringes are generated in the film. and the appearance of the film is good. Also, the oil-stained film can be removed with a cloth or the like containing water.
しかしながら、特許文献１に記載された防汚性膜形成用液組成物は、形成した膜が親水撥油性に優れるが、造膜剤であるポリアクリル酸が水に容易に溶けるため、水で膜を剥離し易い利点はあるものの、逆に、形成した膜の水への耐久性が低いことが課題でもあった。更に、ポリアクリル酸は、基材に塗布後、溶媒が無くなっても反応しないため、膜強度が高くなく、擦り耐久性が低い課題があった。 However, in the liquid composition for forming an antifouling film described in Patent Document 1, although the formed film is excellent in hydrophilic oil repellency, the polyacrylic acid used as the film forming agent is easily soluble in water. Although it has the advantage of being easy to peel off, there is also a problem that the durability of the formed film to water is low. In addition, polyacrylic acid does not react after being applied to a substrate even if the solvent disappears.
本発明の目的は、形成した膜が親水撥油性に優れ、水への耐久性と形成した膜を擦ったときの耐久性がそれぞれ高い親水撥油性膜形成用液組成物及びその製造方法を提供することにある。本発明の別の目的は、親水撥油性に優れ、水への耐久性と擦り耐久性がそれぞれ高い親水撥油性膜を提供することにある。本発明の更に別の目的は、親水撥油性に優れ、水への耐久性と擦り耐久性がそれぞれ高い親水撥油性膜が繊維表面に形成された親水撥油性不織布を提供することにある。 An object of the present invention is to provide a liquid composition for forming a hydrophilic oil-repellent film, which forms a film having excellent hydrophilic oil repellency, is highly resistant to water, and has high durability when the formed film is rubbed, and a method for producing the same. to do. Another object of the present invention is to provide a hydrophilic oil-repellent film which is excellent in hydrophilic oil-repellency and has high durability to water and durability to rubbing. Still another object of the present invention is to provide a hydrophilic oil-repellent nonwoven fabric having a hydrophilic oil-repellent film having excellent hydrophilic oil repellency, high durability to water and high resistance to rubbing, formed on the fiber surface.
本発明の第１の観点は、下記式（１）又は式（２）で表されるフッ素系化合物剤（Ａ）と、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）と、炭素数１～３の範囲にある１種又は２種以上のアルコール及び水である溶媒（Ｃ）とを含む親水撥油性膜形成用液組成物であって、前記フッ素系化合物剤（Ａ）と前記自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）との合計質量を１００質量％とするとき、前記フッ素系化合物（Ａ）を０．０４質量％～４０質量％含み、前記自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）を６０質量％～９９．９６質量％含むことを特徴とする親水撥油性膜形成用液組成物である。 A first aspect of the present invention is a fluorine compound agent (A) represented by the following formula (1) or formula (2), a self-reactive carboxyl group- and/or acetyl group-containing substance (B), A hydrophilic oil-repellent film-forming liquid composition containing one or more alcohols having 1 to 3 carbon atoms and a solvent (C) which is water, wherein the fluorine-based compound agent (A) and When the total mass of the self-reactive carboxyl group- and/or acetyl group-containing material (B) is 100% by mass, the fluorine-based compound (A) is contained in 0.04% by mass to 40% by mass, and the self- The hydrophilic oil-repellent film-forming liquid composition contains 60% by mass to 99.96% by mass of a reactive carboxyl group- and/or acetyl group-containing substance (B).
上記式（１）及び式（２）中、ｐ、ｑ及びｒは、それぞれ同一又は互いに異なる１～６の整数である。また上記式（１）及び式（２）中、Ｘは、炭素数２～１０の炭化水素基であって、エーテル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から選択される１種以上の結合を含んでいてもよい。また上記式（１）及び式（２）中、Ｙは、ベタイン構造である親水基である。 In formulas (1) and (2) above, p, q and r are the same or different integers of 1 to 6, respectively. In the above formulas (1) and (2), X is a hydrocarbon group having 2 to 10 carbon atoms and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. may contain one or more bonds that In formulas (1) and (2) above, Y is a hydrophilic group having a betaine structure.
本発明の第２の観点は、第１の観点に基づく発明であって、前記自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）が、エチレン－アクリル酸共重合体、エチレン－酢酸ビニル共重合体、又はエチレン－酢酸ビニル－アクリル酸共重合体である親水撥油性膜形成用液組成物である。 A second aspect of the present invention is an invention based on the first aspect, wherein the self-reactive carboxyl group- and/or acetyl group-containing material (B) is an ethylene-acrylic acid copolymer, ethylene-acetic acid It is a hydrophilic oil-repellent film-forming liquid composition that is a vinyl copolymer or an ethylene-vinyl acetate-acrylic acid copolymer.
本発明の第３の観点は、第１の観点に基づく発明であって、前記フッ素系化合物（Ａ）が、分散剤（Ｄ）を用いて水に分散され、前記フッ素系化合物（Ａ）に対する前記分散剤（Ｄ）の質量比（Ｄ）／（Ａ）が０．２～１０であって、前記分散剤（Ｄ）が、ジカルボン酸、トリカルボン酸又はヒドロキシカルボン酸或いはその水溶液である親水撥油性膜形成用液組成物である。 A third aspect of the present invention is an invention based on the first aspect, wherein the fluorine-based compound (A) is dispersed in water using a dispersant (D), and the fluorine-based compound (A) The dispersant (D) has a mass ratio (D)/(A) of 0.2 to 10, and the dispersant (D) is a dicarboxylic acid, a tricarboxylic acid, a hydroxycarboxylic acid, or an aqueous solution thereof. This is an oily film-forming liquid composition.
本発明の第４の観点は、第１の観点の式（１）又は式（２）で表されるフッ素系化合物（Ａ）を分散剤（Ｄ）を用いて水に分散する工程と、前記フッ素系化合物の水分散液と、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）と、炭素数１～３の範囲にある１種又は２種以上のアルコール及び水である溶媒（Ｃ）とを混合する工程とを含み、前記分散剤（Ｄ）が、ジカルボン酸、トリカルボン酸又はヒドロキシカルボン酸或いはその水溶液である親水撥油性膜形成用液組成物の製造方法である。 A fourth aspect of the present invention is a step of dispersing the fluorine-based compound (A) represented by formula (1) or formula (2) of the first aspect in water using a dispersant (D); An aqueous dispersion of a fluorine-based compound, a self-reactive carboxyl group- and/or acetyl group-containing material (B), and a solvent ( C), wherein the dispersant (D) is a dicarboxylic acid, tricarboxylic acid or hydroxycarboxylic acid or an aqueous solution thereof.
本発明の第５の観点は、第１ないし第３の観点のいずれかの観点の親水撥油性膜形成用液組成物が硬化した成分を含む親水撥油性膜である。 A fifth aspect of the present invention is a hydrophilic oil-repellent film containing a component obtained by curing the hydrophilic oil-repellent film-forming liquid composition according to any one of the first to third aspects.
本発明の第６の観点は、第５の観点の親水撥油性膜が不織布を構成する繊維表面に形成された不織布である。 A sixth aspect of the present invention is the nonwoven fabric according to the fifth aspect, in which the hydrophilic oil-repellent film is formed on the surface of the fibers constituting the nonwoven fabric.
本発明の第１の観点の親水撥油性膜形成用液組成物は、上記式（１）又は式（２）で表されるフッ素系化合物剤（Ａ）を所定量含むため、形成した膜が親水撥油性に優れる。また、カルボキシル基及び／又はアセチル基含有物（Ｂ）は、溶媒が無くなっても重合をしないポリアクリル酸とは異なり、自己反応型であるため、塗布後、溶媒が揮発し、溶媒が無くなると、カルボキシル基及び／又はアセチル基含有物同士が重合することで、重合度が上がり、水に溶解しにくい膜を形成する特性を有する。更に、上記液組成物は、カルボキシル基及び／又はアセチル基含有物（Ｂ）を所定量含むため、形成した膜の水への耐久性と擦り耐久性がそれぞれ高い。 Since the hydrophilic oil-repellent film-forming liquid composition of the first aspect of the present invention contains a predetermined amount of the fluorine compound agent (A) represented by the above formula (1) or (2), the formed film is Excellent hydrophilic oil repellency. In addition, unlike polyacrylic acid, which does not polymerize even when the solvent is gone, the carboxyl group- and/or acetyl group-containing material (B) is self-reactive, so after coating, the solvent evaporates, and when the solvent is gone, , carboxyl group- and/or acetyl group-containing substances polymerize with each other to increase the degree of polymerization and form a film that is difficult to dissolve in water. Furthermore, since the liquid composition contains a predetermined amount of the carboxyl group- and/or acetyl group-containing substance (B), the formed film has high resistance to water and high resistance to rubbing.
本発明の第２の観点の親水撥油性膜形成用液組成物は、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）が、エチレン－アクリル酸共重合体、エチレン－酢酸ビニル共重合体、又はエチレン－酢酸ビニル－アクリル酸共重合体であるため、このような共重合体がフッ素系化合物（Ａ）のバインダとして作用するとともに、液組成物を基材表面に成膜したときに、膜を基材表面に堅牢に結着させることができる。 In the hydrophilic oil-repellent film-forming liquid composition of the second aspect of the present invention, the self-reactive carboxyl group- and/or acetyl group-containing material (B) is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, Since it is a polymer or an ethylene-vinyl acetate-acrylic acid copolymer, such a copolymer acts as a binder for the fluorine-based compound (A), and when the liquid composition is formed on the substrate surface. Additionally, the membrane can be firmly attached to the substrate surface.
本発明の第３の観点の親水撥油性膜形成用液組成物は、水に溶解しにくいフッ素系化合物（Ａ）が、特定の分散剤（Ｄ）を特定の質量比（Ｄ）／（Ａ）で用いるため、水に良好に分散される。 In the hydrophilic oil-repellent film-forming liquid composition according to the third aspect of the present invention, a fluorine-based compound (A) that is difficult to dissolve in water contains a specific dispersant (D) at a specific mass ratio (D)/(A). ), it disperses well in water.
本発明の第４の観点の親水撥油性膜形成用液組成物の製造方法では、水に溶解しにくいフッ素系化合物（Ａ）を特定の分散剤（Ｄ）を用いて水に分散してフッ素系化合物（Ａ）の分散液を調製しておき、この水分散液と、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）と、炭素数１～３の範囲にある１種又は２種以上のアルコール及び水である溶媒（Ｃ）とを混合するため、フッ素系化合物（Ａ）が均一に分散した親水撥油性膜形成用液組成物を得ることができる。 In the method for producing a hydrophilic oil-repellent film-forming liquid composition according to the fourth aspect of the present invention, the fluorine-based compound (A), which is difficult to dissolve in water, is dispersed in water using a specific dispersant (D) to obtain fluorine. A dispersion of the system compound (A) is prepared, and this aqueous dispersion, a self-reactive carboxyl group- and/or acetyl group-containing substance (B), and one having 1 to 3 carbon atoms or Since two or more kinds of alcohols and the solvent (C), which is water, are mixed, a hydrophilic oil-repellent film-forming liquid composition in which the fluorine-based compound (A) is uniformly dispersed can be obtained.
本発明の第５の観点の親水撥油性膜は、親水撥油性に優れ、水への耐久性と擦り耐久性がそれぞれ高い特長がある。 The hydrophilic oil-repellent film of the fifth aspect of the present invention is characterized by excellent hydrophilic oil-repellent properties, high water resistance, and high abrasion resistance.
本発明の第６の観点の不織布は、親水撥油性に優れ、水への耐久性と擦り耐久性がそれぞれ高い親水撥油性膜が繊維表面に形成されるため、汚れ防止のために使用したときに、付着した汚れを、洗浄することで落とすことができ、高い擦り耐久性により複数回汚れ防止用に使用することができる。また油水分離のために使用したときには、油を弾いて水を通過させるため、油水分離フィルタとして使用することができる。 The nonwoven fabric of the sixth aspect of the present invention has excellent hydrophilic oil repellency, and a hydrophilic oil repellent film having high durability to water and high resistance to rubbing is formed on the fiber surface. In addition, attached dirt can be removed by washing, and it can be used for preventing dirt multiple times due to its high rubbing durability. Moreover, when used for oil-water separation, it repels oil and allows water to pass through, so it can be used as an oil-water separation filter.
次に本発明を実施するための形態を説明する。 Next, a mode for carrying out the present invention will be described.
〔親水撥油性膜形成用液組成物〕
本実施の形態の親水撥油性膜形成用液組成物（以下、単に液組成物ということもある。）は、上記式（１）又は式（２）に示されるフッ素系化合物（Ａ）と、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）と、炭素数１～３の範囲にある１種又は２種以上のアルコール及び水である溶媒（Ｃ）を混合して調製される。このフッ素系化合物は形成した膜に親水撥油性を付与するために用いられ、自己反応型のカルボキシル基及び／又はアセチル基含有物は上記液組成物で膜を形成するための造膜剤として用いられる。溶媒であるアルコールと水はフッ素系化合物及び自己反応型のカルボキシル基及び／又はアセチル基含有物をそれぞれ溶液化するために用いられる。
[Liquid composition for forming a hydrophilic oil-repellent film]
The hydrophilic oil-repellent film-forming liquid composition of the present embodiment (hereinafter sometimes simply referred to as the liquid composition) comprises a fluorine-based compound (A) represented by the above formula (1) or (2), Prepared by mixing a self-reactive carboxyl group- and/or acetyl group-containing material (B) with a solvent (C) that is one or more alcohols having 1 to 3 carbon atoms and water. . This fluorine-based compound is used to impart hydrophilic oil repellency to the formed film, and the self-reactive carboxyl group- and/or acetyl group-containing substance is used as a film-forming agent for forming a film from the liquid composition. be done. Alcohol and water as solvents are used to dissolve the fluorine-based compound and the self-reactive carboxyl group- and/or acetyl group-containing material, respectively.
上記液組成物の溶媒（Ｃ）を除いたときのフッ素系化合物（Ａ）と自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）の各含有割合は、フッ素系化合物剤（Ａ）と自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）との合計質量を１００質量％とするとき、フッ素系化合物（Ａ）を０．０４質量％～４０質量％含み、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）を６０質量％～９９．９６質量％含む。好ましい含有割合は、フッ素系化合物（Ａ）は０．２質量％～１０質量％であり、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）は９０質量％～９９．８質量％である。 Each content ratio of the fluorine compound (A) and the self-reactive carboxyl group- and/or acetyl group-containing substance (B) when excluding the solvent (C) of the liquid composition is the fluorine compound agent (A) When the total mass of the self-reactive carboxyl group- and/or acetyl group-containing material (B) is 100% by mass, the fluorine-based compound (A) is contained in an amount of 0.04% to 40% by mass, and the self-reactive 60% by mass to 99.96% by mass of the carboxyl group- and/or acetyl group-containing material (B). Preferred content ratios are 0.2% to 10% by mass for the fluorine compound (A) and 90% to 99.8% by mass for the self-reactive carboxyl group- and/or acetyl group-containing material (B). is.
上記液組成物におけるフッ素系化合物（Ａ）の含有量が下限値未満では形成した膜が親水撥油性に劣り、上限値を超えると液組成物を塗布する基材への濡れ性が悪く成膜性が悪くなる。また形成した膜からフッ素系化合物が脱落する。自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）の含有量が下限値未満では形成される膜の基材への密着性や強度に劣り、上限値を超えるとフッ素系化合物（Ａ）の含有量が相対的に小さくなり膜に撥油性を付与できない。 If the content of the fluorine-based compound (A) in the above liquid composition is less than the lower limit, the formed film is inferior in hydrophilic oil repellency. sexuality worsens. Moreover, the fluorine-based compound falls off from the formed film. If the content of the self-reactive carboxyl group- and/or acetyl group-containing substance (B) is less than the lower limit, the formed film will have poor adhesion and strength to the substrate, and if it exceeds the upper limit, the fluorine-based compound (A ) is relatively small, and oil repellency cannot be imparted to the film.
上記液組成物は、フッ素系化合物（Ａ）を水に分散させるための分散剤（Ｄ）を更に含むことが好ましい。前記フッ素系化合物（Ａ）に対する前記分散剤（Ｄ）の質量比（Ｄ）／（Ａ）が０．２～１０であることが好ましい。質量比が０．２未満でも、１０を超えてもフッ素系化合物の水分散液の安定性が悪化し易い。この質量比は０．３～５であることがより好ましい。 The liquid composition preferably further contains a dispersant (D) for dispersing the fluorine compound (A) in water. The mass ratio (D)/(A) of the dispersant (D) to the fluorine compound (A) is preferably 0.2-10. Even if the mass ratio is less than 0.2 or exceeds 10, the stability of the aqueous dispersion of the fluorine-based compound tends to deteriorate. More preferably, this mass ratio is 0.3-5.
〔フッ素系化合物（Ａ）〕
本実施の形態の親水撥油性膜形成用液組成物におけるフッ素系化合物（Ａ）の上記式（１）中のペルフルオロエーテル基としては、より具体的には、下記式（３）～（７）で示されるペルフルオロエーテル基を挙げることができる。
[Fluorine compound (A)]
More specifically, the perfluoroether group in the above formula (1) of the fluorine-based compound (A) in the hydrophilic oil-repellent film-forming liquid composition of the present embodiment includes the following formulas (3) to (7) A perfluoroether group represented by can be mentioned.
本実施の形態の親水撥油性膜形成用液組成物におけるフッ素系化合物（Ａ）の上記式（２）中のペルフルオロエーテル基としては、より具体的には、下記式（８）～（１１）で示されるペルフルオロエーテル基を挙げることができる。 More specifically, the perfluoroether group in the above formula (2) of the fluorine-based compound (A) in the hydrophilic oil-repellent film-forming liquid composition of the present embodiment includes the following formulas (8) to (11) A perfluoroether group represented by can be mentioned.
また、上記式（１）又は式（２）中のＸとしては、下記式（１２）～（１６）で示される構造を挙げることができる。なお、下記式（１２）はエーテル結合、下記式（１３）はエステル結合、下記式（１４）はアミド結合、下記式（１５）はウレタン結合、下記式（１６）はスルホンアミド結合を含む例を示している。 Further, examples of X in the above formula (1) or (2) include structures represented by the following formulas (12) to (16). In addition, the following formula (12) is an ether bond, the following formula (13) is an ester bond, the following formula (14) is an amide bond, the following formula (15) is an urethane bond, and the following formula (16) is an example containing a sulfonamide bond. is shown.
ここで、上記式（１２）～（１６）中、Ｒ2及びＲ3は炭素数が０から１０の炭化水素基、Ｒ4は水素原子または炭素数１から６の炭化水素基である。Ｒ2及びＲ3の炭化水素基の例とは、メチレン基、エチレン基等のアルキレン基が挙げられ、Ｒ4の炭化水素基の例とは、メチル基、エチル基等のアルキル基の他、フェニル基、ビニル基等も挙げられる。 In formulas (12) to (16) above, R 2 and R 3 are hydrocarbon groups having 0 to 10 carbon atoms, and R 4 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of hydrocarbon groups for R 2 and R 3 include alkylene groups such as methylene group and ethylene group, and examples of hydrocarbon groups for R 4 include alkyl groups such as methyl group and ethyl group, A phenyl group, a vinyl group, and the like are also included.
また、上記式（１）又は式（２）中のＹとしては、カルボキシベタイン型、スルホベタイン型、アミンオキシド型、フォスフォベタイン型等が挙げられる。 Y in the above formula (1) or formula (2) includes carboxybetaine type, sulfobetaine type, amine oxide type, phosphobetaine type and the like.
ここで、上記式（１）及び式（２）で表されるペルフルオロエーテル構造を有するフッ素系化合物の具体例としては、例えば、下記式（１７）～（２２）で表される構造が挙げられる。 Here, specific examples of the fluorine-based compound having a perfluoroether structure represented by the above formulas (1) and (2) include structures represented by the following formulas (17) to (22). .
〔自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）〕
自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）は、エチレン－アクリル酸共重合体、エチレン－酢酸ビニル共重合体、又はエチレン－酢酸ビニル－アクリル酸共重合体である。市販品として、エチレン－酢酸ビニル系のものとしては、セポルジョンＶＡ４０６Ｎ、セポルジョンＶＡ４０７Ｎ（いずれも住友精化社製）、スミカフレックスＳ－２０１ＨＱ、Ｓ－３５５ＨＱ、Ｓ－４０１Ｑ、Ｓ－４６５ＨＱ（いずれも住友化学社製）、アクアテックスＥＣ－１８００、ＥＣ－１２００（いずれもジャパンコーティングレジン社製が挙げられる。またエチレン－アクリル酸共重合体としては、ザイクセンＡ、ザイクセンＬ、ザイクセンＮ（いずれも住友精化社製）などが、エチレン－酢酸ビニル－アクリル酸系のものとしてはスミカフレックスＳ－９００ＨＬ（住友化学社製）などが挙げられる。また、エチレン－酢酸ビニル－塩化ビニル共重合体であるスミカフレックスＳ－８３０や、エチレン－酢酸ビニル－バーサチック酸ビニル共重合であるスミカフレックスＳ－９５０ＨＱ（いずれも住友化学社製）も挙げられる。更に、アクリル系のものとしてはＴＯＣＲＹＬ ＢＣＸ－１１６０Ｒ－２（トーヨーケム社製）が挙げられる。
[Self-reactive carboxyl group- and/or acetyl group-containing material (B)]
The self-reactive carboxyl group- and/or acetyl group-containing material (B) is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer. Commercially available ethylene-vinyl acetate products include Sepoljon VA406N, Sepoljon VA407N (both manufactured by Sumitomo Seika), Sumikaflex S-201HQ, S-355HQ, S-401Q, and S-465HQ (both Sumitomo Seika). Chemical Co.), Aquatex EC-1800, EC-1200 (both manufactured by Japan Coating Resin Co., Ltd.).Ethylene-acrylic acid copolymers include Zaixen A, Zaixen L, and Zaixen N (both Sumitomo Seiko Chemical Co., Ltd.), etc., and ethylene-vinyl acetate-acrylic acid type ones include Sumikaflex S-900HL (manufactured by Sumitomo Chemical Co., Ltd.), etc. Sumika is an ethylene-vinyl acetate-vinyl chloride copolymer. Flex S-830 and Sumikaflex S-950HQ (both manufactured by Sumitomo Chemical Co., Ltd.), which is an ethylene-vinyl acetate-vinyl versatate copolymer, may also be mentioned. manufactured by Toyochem).
〔溶媒（Ｃ）〕
本実施の形態の親水撥油性膜形成用液組成物における溶媒（Ｃ）の炭素数１～３の範囲にあるアルコールとしては、例えば、メタノール、エタノール、プロパノール（ｎ－プロパノール、イソプロパノール）が挙げられる。炭素数が４以上のアルコールを用いると、上記フッ素系化合物のアルコールへの溶解性が良好でなくなる。本実施の形態の水としては、イオン交換水、蒸留水などの純水、又は超純水が挙げられる。
[Solvent (C)]
Examples of the alcohol having 1 to 3 carbon atoms in the solvent (C) in the hydrophilic oil-repellent film-forming liquid composition of the present embodiment include methanol, ethanol, and propanol (n-propanol, isopropanol). . When an alcohol having 4 or more carbon atoms is used, the solubility of the fluorine-based compound in alcohol becomes poor. Water used in the present embodiment includes pure water such as ion-exchanged water and distilled water, or ultrapure water.
〔分散剤（Ｄ）〕
本実施の形態でフッ素系化合物（Ａ）を水に分散するための分散剤（Ｄ）は、ジカルボン酸、トリカルボン酸又はヒドロキシカルボン酸或いはその水溶液であることが好ましい。例えば、グリコール酸、フマル酸、マレイン酸、コハク酸、リンゴ酸、酒石酸、クエン酸及びグルコン酸が挙げられる。
[Dispersant (D)]
In the present embodiment, the dispersant (D) for dispersing the fluorine compound (A) in water is preferably a dicarboxylic acid, tricarboxylic acid or hydroxycarboxylic acid or an aqueous solution thereof. Examples include glycolic acid, fumaric acid, maleic acid, succinic acid, malic acid, tartaric acid, citric acid and gluconic acid.
〔親水撥油性膜形成用液組成物の製造方法〕
親水撥油性膜形成用液組成物は次の方法により、概略製造される。
図１に示すように、フッ素系化合物（Ａ）１１とアルコール１２とを混合してフッ素系化合物（Ａ）をアルコール１２に溶解してフッ素系化合物（Ａ）のアルコール溶液１３を調製する。一方、分散剤（Ｄ）１４と水１５とを混合してその混合液にフッ素系化合物（Ａ）のアルコール溶液１３を添加混合してフッ素系化合物（Ａ）の水分散液１６を調製する。フッ素系化合物（Ａ）に対する前記分散剤（Ｄ）の質量比（Ｄ）／（Ａ）が０．２～１０であることが好ましい。フッ素系化合物（Ａ）の水分散液１６と自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）１７と溶媒（Ｃ）１８とを混合することにより、親水撥油性膜形成用液組成物２０を調製する。フッ素系化合物剤（Ａ）と自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）との合計質量を１００質量％とするとき、フッ素系化合物（Ａ）を０．０４質量％～４０質量％含み、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）を６０質量％～９９．９６質量％含むように、液組成物２０中の溶媒（Ｃ）を除いたときのフッ素系化合物（Ａ）と自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）の各添加量が決められる。
[Method for producing hydrophilic oil-repellent film-forming liquid composition]
The hydrophilic oil-repellent film-forming liquid composition is roughly produced by the following method.
As shown in FIG. 1, a fluorine-based compound (A) 11 and an
〔親水撥油性膜の形成方法〕
本実施の形態の親水撥油性膜は、基材上に上記液組成物を塗布した後に、大気中で室温乾燥させて上記液組成物を硬化することにより形成される。この基材としては、特に限定されないが、ステンレス鋼（ＳＵＳ）、アルミニウム、鉄等の金属板、窓ガラス、鏡等のガラス、タイル、ポリ塩化ビニル（ＰＶＣ）等のプラスチック又はポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム等又は不織布が挙げられる。
[Method for forming hydrophilic oil-repellent film]
The hydrophilic oil-repellent film of the present embodiment is formed by coating the liquid composition on a substrate and then drying it in the atmosphere at room temperature to cure the liquid composition. The base material is not particularly limited, but may be stainless steel (SUS), metal plates such as aluminum and iron, glass such as window glass and mirrors, tiles, plastics such as polyvinyl chloride (PVC), or polyethylene terephthalate (PET). , polyester films such as polybutylene terephthalate and polyethylene naphthalate, and non-woven fabrics.
不織布は、限定されないが、通気度が０．１ｍｌ／ｍ2／ｓ～４５０ｍｌ／ｍ2／ｓの範囲にあって、ポリエチレンテレフタレート（ＰＥＴ）、ポリプロピレン（ＰＰ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ガラス、アルミナ、炭素、セルロース、パルプ、ナイロン及び金属からなる群より選ばれた１種又は２種以上の繊維により好ましくは構成される。例示すれば、セルロース混合エステル性のメンブレンフィルタ、ガラス繊維ろ紙、ポリエチレンテレフタレート繊維とガラス繊維を混用した不織布（安積濾紙社製、商品名：３４０又は３５６）が挙げられる。 本実施の形態の親水撥油性膜が不織布を構成する繊維表面に形成された不織布は、機械油を使用する工場、油が飛散する厨房、油蒸気が立ちこめるレンジフード、換気扇、冷蔵庫扉等において、油汚れを防止する分野並びに油水分離機能が求められる分野に用いられる。 The nonwoven fabric has air permeability ranging from, but not limited to, 0.1 ml/m 2 /s to 450 ml/m 2 /s, polyethylene terephthalate (PET), polypropylene (PP), polytetrafluoroethylene (PTFE), It is preferably composed of one or more fibers selected from the group consisting of glass, alumina, carbon, cellulose, pulp, nylon and metal. Examples include a cellulose-mixed ester membrane filter, glass fiber filter paper, and a non-woven fabric made of a mixture of polyethylene terephthalate fiber and glass fiber (manufactured by Azumi Filter Paper Co., Ltd., trade name: 340 or 356). The nonwoven fabric in which the hydrophilic oil-repellent film of the present embodiment is formed on the surface of the fibers constituting the nonwoven fabric can be used in factories using machine oil, kitchens where oil scatters, range hoods, ventilation fans, refrigerator doors, etc. It is used in fields that prevent oil stains and fields that require an oil-water separation function.
上記液組成物を不織布以外の基材に塗布する方法としては、スクリーン印刷法、バーコート法、ダイコート法、ドクターブレード、スピン法、刷毛塗り法等が挙げられる。
上記液組成物を不織布に塗布するには、親水撥油性膜形成用液組成物に不織布をディッピングして液組成物から引上げ、大気中、室温で不織布を水平な金網等の上に拡げて一定の液分量になるまで脱液する。別法として、引き上げた不織布を振り払って余分な液を除去するか、或いは引き上げた不織布をマングルロール（絞り機）に通して脱液する。脱液した不織布は、大気中、２５℃～１４０℃の温度で０．５時間～２４時間乾燥する。
Examples of the method for applying the liquid composition to a substrate other than the nonwoven fabric include a screen printing method, a bar coating method, a die coating method, a doctor blade method, a spin method, and a brush coating method.
In order to apply the above liquid composition to a nonwoven fabric, the nonwoven fabric is dipped in the hydrophilic oil-repellent film-forming liquid composition, pulled up from the liquid composition, and spread on a horizontal wire mesh or the like in the atmosphere at room temperature. Drain until the liquid volume is Alternatively, the pulled-up nonwoven fabric is shaken off to remove excess liquid, or the pulled-up nonwoven fabric is passed through a mangle roll (squeezing machine) to remove the liquid. The drained nonwoven fabric is dried in air at a temperature of 25° C. to 140° C. for 0.5 hour to 24 hours.
〔親水撥油性膜〕
上記方法で形成された親水撥油性膜は、親水撥油性に優れ、水への耐久性と擦り耐久性がそれぞれ高い特長がある。
[Hydrophilic oil-repellent film]
The hydrophilic oil-repellent film formed by the above method is characterized by excellent hydrophilic oil-repellency, high water resistance, and high abrasion resistance.
次に本発明の実施例を比較例とともに詳しく説明する。先ず、フッ素系化合物（Ａ）の水分散液を調製する製造例１～７及び比較製造例１、２を説明し、次いでこれらの製造例及び比較製造例を用いた親水撥油性膜形成用液組成物の調製に関する実施例１～７及び比較例１～３を説明する。 Next, examples of the present invention will be described in detail together with comparative examples. First, Production Examples 1 to 7 and Comparative Production Examples 1 and 2 for preparing an aqueous dispersion of the fluorine-based compound (A) will be described, and then the hydrophilic oil-repellent film-forming liquid using these Production Examples and Comparative Production Examples. Examples 1-7 and Comparative Examples 1-3 relating to the preparation of compositions are described.
＜製造例１＞
上述した式（１７）で表されるフッ素系化合物をエタノールに溶解して、５０質量％のエタノール溶液を得た。次に、５００ｍｌビーカーに、水１６３．６３ｇと、分散剤（Ｄ）としてマレイン酸１．３８ｇを入れて、撹拌機で混合した。混合した液を撹拌しながら、上記５０質量％のエタノール溶液５５．０ｇを滴下して、３０分間撹拌し、フッ素系化合物（Ａ）の水分散液を調製した。フッ素系化合物（Ａ）に対する分散剤（Ｄ）の質量比（Ｄ）／（Ａ）は５．０であった。
以下の表１に製造例１のフッ素系化合物（Ａ）の水分散液の調製条件を示す。
<Production Example 1>
A 50% by mass ethanol solution was obtained by dissolving the fluorine-based compound represented by the above formula (17) in ethanol. Next, 163.63 g of water and 1.38 g of maleic acid as a dispersant (D) were placed in a 500 ml beaker and mixed with a stirrer. While stirring the mixed liquid, 55.0 g of the 50% by mass ethanol solution was added dropwise, and the mixture was stirred for 30 minutes to prepare an aqueous dispersion of the fluorinated compound (A). The mass ratio (D)/(A) of the dispersant (D) to the fluorine compound (A) was 5.0.
Table 1 below shows the preparation conditions of the aqueous dispersion of the fluorine-based compound (A) of Production Example 1.
＜製造例２～７及び比較製造例１、２＞
製造例２～６及び比較製造例１、２では、分散剤（Ｄ）の種類を製造例１と異なる種類に変更し、フッ素系化合物（Ａ）を製造例１と異なる種類に変更し、フッ素系化合物（Ａ）に対する分散剤（Ｄ）の質量比（Ｄ）／（Ａ）を製造例１とは異なるように、５０質量％のエタノール溶液の秤量（５５．０ｇ）は変えずに、（分散剤（Ｄ）の秤量を変更した。それ以外は製造例１と同様にして、上記表１に示すように、製造例２～６及び比較製造例１、２の各フッ素系化合物（Ａ）の水分散液を調製した。表１中の式の番号は、上述したフッ素系化合物（Ａ）の式の番号を意味する。なお、製造例７では、分散剤（Ｄ）を用いなかった。また比較製造例１では、分散剤（Ｄ）として、重炭酸ナトリウムを用いた。
<Production Examples 2 to 7 and Comparative Production Examples 1 and 2>
In Production Examples 2 to 6 and Comparative Production Examples 1 and 2, the type of dispersant (D) was changed to a type different from that in Production Example 1, the fluorine compound (A) was changed to a type different from that in Production Example 1, and fluorine ( The weighing amount of the dispersant (D) was changed, and each fluorine-based compound (A) of Production Examples 2 to 6 and Comparative Production Examples 1 and 2 was prepared in the same manner as in Production Example 1, as shown in Table 1 above. The number of the formula in Table 1 means the number of the formula of the fluorine-based compound (A) described above.In Production Example 7, the dispersant (D) was not used. In Comparative Production Example 1, sodium bicarbonate was used as the dispersant (D).
〔親水撥油性膜形成用液組成物の調製のための実施例１～７、比較例１～３〕
＜実施例１＞
水７５．２７ｇと、自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）としてのスミカフレックス３５５ＨＱ１７．７３ｇと、製造例１で得られたフッ素系化合物（Ａ）の水分散液２．００ｇとを、５００ｍｌのビーカーにそれぞれ入れて、これらを混合したのち、工業アルコール（日本アルコール産業社製、ＡＰ－７）５．００ｇを添加混合して、親水撥油性膜形成用液組成物を調製した。この内容を以下の表２に示す。
[Examples 1 to 7 and Comparative Examples 1 to 3 for preparing a hydrophilic oil-repellent film-forming liquid composition]
<Example 1>
75.27 g of water, 17.73 g of Sumikaflex 355HQ as a self-reactive carboxyl group- and/or acetyl group-containing substance (B), and an aqueous dispersion of the fluorinated compound (A) obtained in Production Example 12. 00 g of each of them are placed in a 500 ml beaker and mixed, then 5.00 g of industrial alcohol (manufactured by Nippon Alcohol Sangyo Co., Ltd., AP-7) is added and mixed to obtain a hydrophilic oil repellent film forming liquid composition. prepared. The contents are shown in Table 2 below.
表２には、『溶媒を除く液組成物中の含有割合』としてのフッ素系化合物（Ａ）と自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）の各割合（質量％）も示す。なお、溶媒を除く液組成物中のフッ素系化合物（Ａ）の含有割合（％）は、[（Ａ）／[（Ａ）＋（Ｂ）]]の百分率であり、溶媒を除く液組成物中の自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）の含有割合（％）は、[（Ｂ）／[（Ａ）＋（Ｂ）]]の百分率である。 Table 2 also shows each ratio (% by mass) of the fluorine-based compound (A) and the self-reactive carboxyl group- and/or acetyl group-containing substance (B) as "the content ratio in the liquid composition excluding the solvent". show. The content ratio (%) of the fluorine-based compound (A) in the liquid composition excluding the solvent is the percentage of [(A)/[(A) + (B)]], and the liquid composition excluding the solvent The content (%) of the self-reactive carboxyl group- and/or acetyl group-containing substance (B) in the composition is a percentage of [(B)/[(A)+(B)]].
＜実施例２～７及び比較例１～３＞
表２に示すように、実施例２～７及び比較例１、２では、表１に示す製造例１～７又は比較製造例１、２で得られたフッ素系化合物（Ａ）の水分散液をそれぞれ用いて、それぞれの水分散液の秤量を決定した。また自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）の種類と秤量を実施例１と同一にするか又は変更した。溶媒（Ｃ）の種類は実施例１と同一にし、秤量は実施例１と同一にするか又は変更した。
<Examples 2 to 7 and Comparative Examples 1 to 3>
As shown in Table 2, in Examples 2 to 7 and Comparative Examples 1 and 2, aqueous dispersions of fluorine-based compounds (A) obtained in Production Examples 1 to 7 or Comparative Production Examples 1 and 2 shown in Table 1 was used to determine the weighing of each aqueous dispersion. Also, the type and weighing amount of the self-reactive carboxyl group- and/or acetyl group-containing material (B) were the same as in Example 1 or changed. The type of solvent (C) was the same as in Example 1, and the weighing was the same as in Example 1 or changed.
比較例３のフッ素系化合物（Ａ）の水分散液の欄で（注１）として示すように、比較例３のこの液は、フッ素系化合物（Ａ）の水分散液ではなく、式(２２)のフッ素系化合物の５０質量％エタノール溶液をエタノールで更に希釈した液を用いた。また比較例３の自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）の欄で（注２）として示すように、自己反応型のカルボキシル基及び／又はアセチル基含有物の代わりに、特許文献１に示されるポリアクリル酸の一種であるアクアリックＨＬ４１５（日本触媒社製）を用いた。
このようにして、実施例２～７及び比較例１～３の各親水撥油性膜形成用液組成物を調製した。
As indicated by (Note 1) in the column of the aqueous dispersion of the fluorine-based compound (A) in Comparative Example 3, this liquid of Comparative Example 3 is not the aqueous dispersion of the fluorine-based compound (A), but the formula (22 ) was prepared by further diluting the 50% by mass ethanol solution of the fluorine-based compound in ) with ethanol. In addition, as shown in (Note 2) in the column of self-reactive carboxyl group- and/or acetyl group-containing material (B) in Comparative Example 3, instead of the self-reactive carboxyl group- and/or acetyl group-containing material, Aqualic HL415 (manufactured by Nippon Shokubai Co., Ltd.), which is a type of polyacrylic acid disclosed in Patent Document 1, was used.
In this manner, the hydrophilic oil-repellent film-forming liquid compositions of Examples 2 to 7 and Comparative Examples 1 to 3 were prepared.
＜比較試験と評価＞
（1）サンプルの作製
ポリエチレンテレフタレート（ＰＥＴ）繊維とガラス繊維とを混用した、通気度が１０ｍｌ／ｍ2／ｓの安積濾紙社製の不織布（商品名：３５６）を基材とした。この不織布を上記実施例１～７及び比較例１～３で得られた１０種類の撥水撥油性膜形成用液組成物にそれぞれ別々にディッピングし、余分な液を振り払い、室温で２４時間乾燥させて、基材である不織布の繊維表面に親水撥油性膜を形成した１０種類のサンプルを得た。
<Comparative test and evaluation>
(1) Preparation of Sample A non-woven fabric (trade name: 356) manufactured by Azumi Roshi Co., Ltd., which is a mixture of polyethylene terephthalate (PET) fiber and glass fiber and has an air permeability of 10 ml/m 2 /s, was used as the base material. This nonwoven fabric was separately dipped in each of the 10 kinds of water- and oil-repellent film-forming liquid compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3, and the excess liquid was shaken off and left at room temperature for 24 hours. After drying, 10 types of samples were obtained in which a hydrophilic oil-repellent film was formed on the fiber surface of the nonwoven fabric as the substrate.
（2）サンプルの親水撥油性の評価
１０種類のサンプルに対して、２２℃±１℃のイオン交換水と２２℃±１℃のｎーヘキサデカンを用いて親水撥油性を評価した。具体的には、親水撥油性膜を形成した直後のサンプルに上記水とｎーヘキサデカンをそれぞれ滴下した後のサンプルの濡れ性と、水中にサンプルを３０分間浸漬し、乾燥した後のサンプルの濡れ性をそれぞれ評価した。またサンプルの表面を水を含ませたセルロース製不織布（旭化成社製、ペンコットＭ－３）により一定荷重で２０回擦った。擦った後に上記水とｎーヘキサデカンをサンプルにそれぞれ滴下した後のサンプルの濡れ性を評価した。これらの結果を以下の表３に示す。
表３において、サンプルに水が浸透する場合をサンプルに親水性があると判定し、『良好』とし、水が浸透しない場合をサンプルに親水性がないと判定し、『不良』とした。またサンプルがｎーヘキサデカンを弾く場合を撥油性があると判定し、『良好』とし、ｎーヘキサデカンを弾かない場合を撥油性がないと判定し、『不良』とした。
(2) Evaluation of hydrophilic oil repellency of samples Ten kinds of samples were evaluated for hydrophilic oil repellency using ion-exchanged water at 22°C ± 1°C and n-hexadecane at 22°C ± 1°C. Specifically, the wettability of the sample after dropping the water and n-hexadecane on the sample immediately after forming the hydrophilic oil-repellent film, and the wettability of the sample after immersing the sample in water for 30 minutes and drying. were evaluated respectively. The surface of the sample was rubbed 20 times under a constant load with a cellulose nonwoven fabric (Pencot M-3, manufactured by Asahi Kasei Co., Ltd.) soaked with water. The wettability of the sample was evaluated after the water and n-hexadecane were dropped on the sample after rubbing. These results are shown in Table 3 below.
In Table 3, when water permeated the sample, it was determined that the sample had hydrophilicity and was rated as "good", and when water did not permeate, the sample was determined as having no hydrophilicity and was rated as "bad". When the sample repelled n-hexadecane, it was judged to have oil repellency and was judged as "good".
表３から明らかなように、比較例１の液組成物では、分散剤（Ｄ）として、重炭酸ナトリウムを用いたため、得られたフッ素系化合物の水分散液は高粘度の凝集体であったけれども、液組成物は塗料化した。この液組成物により不織布の繊維表面に膜を形成したサンプルは、水とｎーヘキサデカンをそれぞれ滴下した後の評価、水を浸漬した後の評価及び擦り試験後の評価はいずれも、水を浸透せず親水性は『不良』であり、ｎ－ヘキサデカンを弾かず撥油性は『不良』であった。 As is clear from Table 3, in the liquid composition of Comparative Example 1, since sodium bicarbonate was used as the dispersant (D), the obtained aqueous dispersion of the fluorine-based compound was a highly viscous aggregate. However, the liquid composition was turned into a paint. A sample in which a film was formed on the fiber surface of the nonwoven fabric with this liquid composition was evaluated after dropping water and n-hexadecane, after being immersed in water, and after a rubbing test. The hydrophilicity was "poor" without repelling n-hexadecane, and the oil repellency was "poor".
比較例２の液組成物では、フッ素系化合物（Ａ）に対する分散剤（Ｄ）の質量比（Ｄ）／（Ａ）が１５と大き過ぎたため、得られたフッ素系化合物の水分散液はやや高粘度であったけれども、液組成物は塗料化した。この液組成物により不織布の繊維表面に膜を形成したサンプルは、水とｎーヘキサデカンをそれぞれ滴下した後の評価、水を浸漬した後の評価及び擦り試験後の評価はいずれも、水が浸透して親水性は『良好』であった。その一方、水とｎーヘキサデカンをそれぞれ滴下した後の評価、水を浸漬した後の評価及び擦り試験後の評価はいずれも、ｎ－ヘキサデカンを弾かず撥油性は『不良』であった。 In the liquid composition of Comparative Example 2, the mass ratio (D)/(A) of the dispersant (D) to the fluorine-based compound (A) was too large at 15, so the obtained aqueous dispersion of the fluorine-based compound was slightly Although the viscosity was high, the liquid composition turned into a paint. A sample in which a film was formed on the fiber surface of the nonwoven fabric with this liquid composition was evaluated after dropping water and n-hexadecane, after being immersed in water, and after a rubbing test. The hydrophilicity was "good". On the other hand, the evaluation after dripping water and n-hexadecane, the evaluation after immersion in water, and the evaluation after the rubbing test all showed that n-hexadecane was not repelled and the oil repellency was "poor".
比較例３の液組成物では、造膜剤として、特許文献１に示されるポリアクリル酸の一種であるアクアリックＨＬ４１５を用いて調製したため、この液組成物により不織布の繊維表面に膜を形成したサンプルは、水とｎーヘキサデカンをそれぞれ滴下した後の評価は、いずれも、水が浸透して親水性は『良好』であった。しかし、水を浸漬した後の評価は、親水性及び撥油性も『不良』であった。更に擦り試験後の評価は、親水性は『良好』であったが、撥油性については『不良』であった。 The liquid composition of Comparative Example 3 was prepared using Aqualic HL415, which is a type of polyacrylic acid disclosed in Patent Document 1, as a film-forming agent, so that this liquid composition formed a film on the fiber surface of the nonwoven fabric. The sample was evaluated as "favorable" in terms of water permeation and hydrophilicity after dropping water and n-hexadecane. However, in the evaluation after immersion in water, both hydrophilicity and oil repellency were "bad". Furthermore, the evaluation after the rubbing test was "good" in hydrophilicity, but "bad" in oil repellency.
これらに対して、表３から明らかなように、実施例１～７の液組成物により不織布の繊維表面に膜を形成したサンプルは、水とｎーヘキサデカンをそれぞれ滴下した後の評価、水を浸漬した後の評価及び擦り試験後の評価はいずれも、水が浸透して親水性が『良好』であり、ｎ－ヘキサデカンを弾いて撥油性が『良好』であった。 On the other hand, as is clear from Table 3, the samples in which films were formed on the fiber surfaces of the nonwoven fabrics using the liquid compositions of Examples 1 to 7 were evaluated after dropping water and n-hexadecane, respectively, and immersed in water. Both the evaluation after washing and the evaluation after the rubbing test showed that the hydrophilicity was "good" due to water permeation, and the oil repellency was "good" due to repelling n-hexadecane.
本発明の親水撥油性膜形成用液組成物は、機械油を使用する工場、油が飛散する厨房、油蒸気が立ちこめるレンジフード、換気扇、冷蔵庫扉等において、油汚れを防止する分野に用いられる。また本発明の親水撥油性膜が不織布を構成する繊維表面に形成された不織布は上記と同様の分野並びに油水分離機能が求められる分野に用いられる。 The hydrophilic oil-repellent film-forming liquid composition of the present invention is used in the field of preventing oil stains in factories using machine oil, kitchens where oil scatters, range hoods, ventilators, refrigerator doors, etc. where oil vapor is trapped. . The nonwoven fabric having the hydrophilic oil-repellent film of the present invention formed on the surface of the fibers constituting the nonwoven fabric can be used in the same fields as described above as well as in fields where an oil-water separation function is required.
１１ フッ素系化合物（Ａ）
１２ アルコール
１３ フッ素系化合物（Ａ）のアルコール溶液
１４ 分散剤（Ｄ）
１５ 水
１６ フッ素系化合物（Ａ）の水分散液
１７ 自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）
１８ 溶媒（Ｄ）
２０ 親水撥油性膜形成用液組成物
11 fluorine compound (A)
12
15
18 solvent (D)
20 Hydrophilic oil-repellent film-forming liquid composition
Claims (6)
前記フッ素系化合物剤（Ａ）と前記自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）との合計質量を１００質量％とするとき、前記フッ素系化合物（Ａ）を０．０４質量％～４０質量％含み、前記自己反応型のカルボキシル基及び／又はアセチル基含有物（Ｂ）を６０質量％～９９．９６質量％含むことを特徴とする親水撥油性膜形成用液組成物。
When the total mass of the fluorine compound agent (A) and the self-reactive carboxyl group- and/or acetyl group-containing material (B) is 100% by mass, the fluorine compound (A) is 0.04 mass%. % to 40% by mass, and 60% to 99.96% by mass of the self-reactive carboxyl group- and/or acetyl group-containing substance (B).
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