JPS63273668A - Hydrophilic film-forming composition, hydrophilic film thereof and production of said hydrophilic film - Google Patents
Hydrophilic film-forming composition, hydrophilic film thereof and production of said hydrophilic filmInfo
- Publication number
- JPS63273668A JPS63273668A JP10817087A JP10817087A JPS63273668A JP S63273668 A JPS63273668 A JP S63273668A JP 10817087 A JP10817087 A JP 10817087A JP 10817087 A JP10817087 A JP 10817087A JP S63273668 A JPS63273668 A JP S63273668A
- Authority
- JP
- Japan
- Prior art keywords
- hydrophilic
- group
- film
- groups
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 90
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- 238000010894 electron beam technology Methods 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 12
- 125000003368 amide group Chemical group 0.000 claims abstract description 12
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims description 48
- 238000004132 cross linking Methods 0.000 claims description 42
- 239000004094 surface-active agent Substances 0.000 claims description 33
- -1 methacryloyl groups Chemical group 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 28
- 125000000524 functional group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 125000005462 imide group Chemical group 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 8
- 230000007774 longterm Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 125000002743 phosphorus functional group Chemical group 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 2
- 150000003863 ammonium salts Chemical class 0.000 abstract 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 229920001002 functional polymer Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BLYOHBPLFYXHQA-UHFFFAOYSA-N n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound C=CCN(CC=C)C(=O)C=C BLYOHBPLFYXHQA-UHFFFAOYSA-N 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZCUBIPKXZDFIFT-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C=C ZCUBIPKXZDFIFT-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- DZNJSBHVDXLTIK-UHFFFAOYSA-N 1-(hydroxymethyl)imidazolidine-2,4-dione Chemical compound OCN1CC(=O)NC1=O DZNJSBHVDXLTIK-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- QJUCCGSXGKTYBT-UHFFFAOYSA-N 2,4,4-trimethylpent-2-enamide Chemical compound NC(=O)C(C)=CC(C)(C)C QJUCCGSXGKTYBT-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 description 1
- JNDVNJWCRZQGFQ-UHFFFAOYSA-N 2-methyl-N,N-bis(methylamino)hex-2-enamide Chemical compound CCCC=C(C)C(=O)N(NC)NC JNDVNJWCRZQGFQ-UHFFFAOYSA-N 0.000 description 1
- WEAQXVDSAUMZHI-UHFFFAOYSA-M 2-methylprop-2-enamide;trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CC(=C)C(N)=O.CCC[N+](C)(C)C WEAQXVDSAUMZHI-UHFFFAOYSA-M 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SDIXRDNYIMOKSG-UHFFFAOYSA-L disodium methyl arsenate Chemical compound [Na+].[Na+].C[As]([O-])([O-])=O SDIXRDNYIMOKSG-UHFFFAOYSA-L 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
- XOYONZYDWNTDAL-UHFFFAOYSA-N n-butoxyprop-2-enamide Chemical compound CCCCONC(=O)C=C XOYONZYDWNTDAL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229940079938 nitrocellulose Drugs 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は防曇性を有する親水性膜、それを形成するため
の組成物及び親水性膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydrophilic film having antifogging properties, a composition for forming the same, and a method for producing the hydrophilic film.
[従来の技術]
浴室用鏡、サングラス、眼鏡レンズ、腕時計のカバーガ
ラス、スキー用ゴーグル等は湿気にふれることが多いの
で曇りやすく、これらの曇りを防止するために従来種々
の試−みがなされた。[Prior Art] Bathroom mirrors, sunglasses, eyeglass lenses, watch cover glasses, ski goggles, etc. are prone to fogging because they are often exposed to moisture, and various attempts have been made to prevent these from fogging. Ta.
特開昭55−69678号は親水性基を含有する光硬化
性エチレン性不飽和化合物と、親水性基を含有しない光
硬化性エチレン性不飽和化合物と、光硬化開始剤とから
なる防曇剤を開示している。しかしながらこの防曇剤で
は親水性基が選択的に表面に存在するわけではないので
防曇性が低い上に、光硬化開始剤を含有しているので耐
光性に劣る。JP-A-55-69678 discloses an antifogging agent comprising a photocurable ethylenically unsaturated compound containing a hydrophilic group, a photocurable ethylenically unsaturated compound not containing a hydrophilic group, and a photocuring initiator. is disclosed. However, in this antifogging agent, hydrophilic groups are not selectively present on the surface, so the antifogging property is low, and since it contains a photocuring initiator, the light resistance is poor.
特開昭57−163568号は紫外線吸収剤を多量に含
有する紫外線じゃへい性ポリ塩化ビニル系樹脂フィルム
の少なくとも一部をカチオン重合系のエネルギー線硬化
性樹脂組成物で被覆したことを特徴とする防曇性を有す
る農業用フィルムを開示している。カチオン重合系エネ
ルギー線硬化性樹脂組成物はエネルギー線(紫外線)の
照射により高分子化又は架橋して塗膜を形成するカチオ
ン重合性樹脂組成物で、例えばエポキシ系樹脂、環状エ
ーテル類、ラクトン類、ビニル化合物等である。JP-A No. 57-163568 is characterized in that at least a portion of an ultraviolet-resistant polyvinyl chloride resin film containing a large amount of ultraviolet absorber is coated with a cationically polymerized energy ray-curable resin composition. Discloses an agricultural film having antifogging properties. Cationic polymerizable energy ray curable resin compositions are cationic polymerizable resin compositions that are polymerized or crosslinked to form a coating film by irradiation with energy rays (ultraviolet rays), such as epoxy resins, cyclic ethers, and lactones. , vinyl compounds, etc.
しかしながら、これは表面にカチオン重合系エネルギー
線硬化性樹脂組成物の塗膜を形成することにより、ポリ
塩化ビニル系樹脂フィルム中の界面活性剤等の表面移行
及び流出飛散を防止又は抑制したものであるので、防曇
性に関しては必ずしも満足ではなかった。However, this method prevents or suppresses surface migration and outflow scattering of surfactants, etc. in polyvinyl chloride resin films by forming a coating film of a cationically polymerized energy ray-curable resin composition on the surface. Therefore, I was not necessarily satisfied with the anti-fog properties.
特開昭58−103533号は防曇フィルムの片面に紫
外線硬化型塗料を塗布し、紫外線照射により硬化させ、
フィルムの防曇持続性を改良することを特徴とする方法
を開示している。この塗料の塗膜は紫外線照射により架
橋されるため、防曇フィルムからの防暑剤の滲出を防止
することができる。しかし塗膜自体に親水性基を有さな
いために特に初期防曇性に劣る他、紫外線硬化型である
ために増感剤を含有しており、日光や蛍光灯の光線中の
紫外線による劣化が著しいという問題がある。JP-A-58-103533 discloses a method in which an ultraviolet curable paint is applied to one side of an anti-fog film and cured by ultraviolet irradiation.
Disclosed is a method characterized in improving the anti-fog persistence of a film. Since the coating film of this paint is crosslinked by ultraviolet irradiation, it is possible to prevent the heat protectant from oozing out from the antifogging film. However, since the coating film itself does not have a hydrophilic group, its initial antifogging properties are particularly poor, and since it is an ultraviolet curing type, it contains a sensitizer, so it deteriorates due to sunlight and ultraviolet rays from fluorescent lamps. The problem is that there is a significant
その他特開昭80−100914号及び60−1010
42号は透明性の高い合成樹脂フィルムまたはシートか
らなる基材に透明アセチルセルロース系フィルムをS熱
性接着剤で接合し、しかる後表面をNa OH水溶液等
で親水化処理することを特徴とする防暑性合成樹脂シー
ト状物の製造方法を開示している。Other JP-A-80-100914 and 60-1010
No. 42 is a heat protection product that is characterized by bonding a transparent acetyl cellulose film to a base material made of a highly transparent synthetic resin film or sheet using an S heat adhesive, and then treating the surface to make it hydrophilic with an aqueous NaOH solution or the like. Discloses a method for manufacturing a synthetic resin sheet.
しかしながらこのシート状物は架橋されていないので強
度的に不十分であり、かつ界面活性剤がフィルム内部か
ら徐々に滲゛出することによる防曇効果を期待すること
はできない。その上この親水化処理工程自体全工程を複
雑にしているので、実用的でない。However, since this sheet-like material is not crosslinked, its strength is insufficient, and the antifogging effect due to the surfactant gradually seeping out from inside the film cannot be expected. Moreover, this hydrophilic treatment process itself complicates the entire process, making it impractical.
なお従来からある界面活性剤を樹脂に練込む方法では、
界面活性剤の滲出が著しいので、防曇性持続性が劣る。In addition, with the conventional method of kneading surfactants into resin,
Since the leaching of the surfactant is significant, the durability of the antifogging property is poor.
[発明が解決しようとする問題点1
以上の通りいまだ十分な防曇性を有するとともに耐久性
(防曇持続性)、耐劣化性、機械的強度等に優れたもの
は提案されていない。[Problem to be Solved by the Invention 1] As mentioned above, no material has yet been proposed that has sufficient anti-fog properties and is excellent in durability (anti-fog durability), deterioration resistance, mechanical strength, etc.
従って本発明の目的は十分な防曇性を有するとともに耐
久性、耐劣化性、機械的強度等に優れた新規な親水性膜
を提供することである。Therefore, an object of the present invention is to provide a novel hydrophilic film that has sufficient antifogging properties and is excellent in durability, deterioration resistance, mechanical strength, etc.
本発明のもう1つの目的はかかる親水性膜を形成するた
めの組成物を提供することである。Another object of the invention is to provide a composition for forming such a hydrophilic membrane.
本発明のさらにもう1つの目的はかかる親水性膜を製造
する方法を提供することである。Yet another object of the invention is to provide a method for manufacturing such hydrophilic membranes.
[問題点を解決するための手段]
以上の目的に鑑み鋭意研究の結果、本発明者等は骨格と
なるポリマーと親水性モノマー及び親水性架橋性モノマ
ーとの混合物の塗膜に電子線を照射すると架橋反応によ
り両者が結合し、かつ親水性膜ツマ−が表面に浮き上が
ることにより親水基が表面に多く存在する膜が青られる
ことを発見し、本発明に想到した。[Means for solving the problem] In view of the above objectives, as a result of intensive research, the present inventors irradiated a coating film of a mixture of a polymer skeleton, a hydrophilic monomer, and a hydrophilic crosslinking monomer with an electron beam. Then, they discovered that the two bonded together through a crosslinking reaction, and the hydrophilic membrane particles floated to the surface, thereby turning the membrane with many hydrophilic groups on the surface blue, and they came up with the present invention.
すなわち、本発明の電子線照射により親水性膜を形成す
る親水性膜形成組成物はポリマーと親水性モノマーと親
水性架橋性モノマーとを含有することを特徴とする。本
発明の組成物は界面活性剤を含有してもよく、さらに必
要に応じ溶剤を含有してもよい。That is, the hydrophilic film-forming composition of the present invention, which forms a hydrophilic film by electron beam irradiation, is characterized by containing a polymer, a hydrophilic monomer, and a hydrophilic crosslinkable monomer. The composition of the present invention may contain a surfactant and may further contain a solvent if necessary.
また本発明の親水性膜はポリマーと親水性モノマーと親
水性架橋性モノマーとを含有する混合物の膜状物に電子
線を照射してなり、前記ポリマーが前記親水性モノマー
及び前記親水性架橋性モノマーと架橋していることを特
徴とする。同様に本発明の親水性膜は界面活性剤を含有
してもよい。Further, the hydrophilic film of the present invention is obtained by irradiating a film-like material of a mixture containing a polymer, a hydrophilic monomer, and a hydrophilic crosslinkable monomer with an electron beam, and the hydrophilic monomer and the hydrophilic crosslinkable monomer are It is characterized by being crosslinked with a monomer. Similarly, the hydrophilic membrane of the present invention may contain a surfactant.
さらに本発明の親水性膜の製造方法はポリマーと親水性
モノマーと親水性架橋性モノマーとを混合し、膜状に塗
布した上で0.5〜2”OMradの電子線を照射する
ことを特徴とする。本方法においても、界面活性剤を混
合物に添加してよい。Furthermore, the method for producing a hydrophilic film of the present invention is characterized in that a polymer, a hydrophilic monomer, and a hydrophilic crosslinking monomer are mixed, coated in a film form, and then irradiated with an electron beam of 0.5 to 2" OMrad. Also in this method, a surfactant may be added to the mixture.
本発明に使用するポリマーは親水性膜の骨格となるもの
であるので、造膿性を有する必要がある。Since the polymer used in the present invention forms the skeleton of the hydrophilic membrane, it must have purulent properties.
また親水性膜が十分な野命(耐用性)を有するためには
良好な耐水性を有する必要があり、そのためにはポリマ
ーは疎水性を有するのが望ましい。In addition, in order for a hydrophilic film to have sufficient longevity (durability), it must have good water resistance, and for this purpose, it is desirable that the polymer have hydrophobicity.
上記ポリマーは無官能ポリマーと官能ポリマーのいずれ
でもよい。The above polymer may be either a non-functional polymer or a functional polymer.
無官能ポリマーとしては、ポリアクリル酸アルキルエス
テル、ポリメタクリル酸アルキルエステル、ポリウレタ
ン、ポリエステル、ポリアミド、ポリ酢酸ビニル、ポリ
塩化ビニル、ポリスチレン、ポリアクリロニトリル、ポ
リビニルピロリドン等を使用することができる。As the non-functional polymer, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, polyurethane, polyester, polyamide, polyvinyl acetate, polyvinyl chloride, polystyrene, polyacrylonitrile, polyvinylpyrrolidone, etc. can be used.
さらに親水性モノマーとの相溶性を良好にするために無
官能ポリマーに親水性基をあらかじめ導入してもよい。Furthermore, in order to improve compatibility with hydrophilic monomers, a hydrophilic group may be introduced into the non-functional polymer in advance.
これには後述の親水性基を有するモノマー(親水性モノ
マー)との共重合体とする。For this purpose, a copolymer with a monomer having a hydrophilic group (hydrophilic monomer), which will be described later, is used.
親水性モノマーの無官能ポリマーに対する割合は50モ
ル%以下であり、これを超えると得られる膜の耐水性が
低下する。The ratio of the hydrophilic monomer to the non-functional polymer is 50 mol% or less, and if it exceeds this, the water resistance of the resulting membrane will decrease.
さらに部分ケン化ポリビニルアルコール、ポリビニルブ
チラール、ポリビニルアセクール等のポリビニルアルコ
ールの誘導体や、ニトロセルロース、セルロースアセテ
ート、セルロースアセテートブチレート、セルロースア
セテートプロピオネート、ヒドロキシプロピルセルロー
ス等のセルロース誘導体も使用することができる。Furthermore, derivatives of polyvinyl alcohol such as partially saponified polyvinyl alcohol, polyvinyl butyral, and polyvinyl acecool, and cellulose derivatives such as nitrocellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and hydroxypropyl cellulose can also be used. can.
一方、官能ポリマーは紫外線により架橋反応を起す官能
基を有するポリマーであり、官能基の例として以下のも
のがある。On the other hand, a functional polymer is a polymer having a functional group that causes a crosslinking reaction by ultraviolet rays, and examples of the functional group include the following.
アクリロイル基 −0C−〇−CH2
!1
CH3
メタクリロイル基 −QC−C=CH2ア リ ル
基 −CH−CH=CH2官能基はポリマーの分
子量300〜i ooooに1つの割合であるのが望ま
しく、分子量10000当り1つ未満の?J合だと官能
基による架橋効果はほとんどなく、分子量300当り1
つを超える割合だと架橋密度が高くなりすぎる。Acryloyl group -0C-〇-CH2! 1 CH3 Methacryloyl group -QC-C=CH2 Allyl group -CH-CH=CH2 Functional group is desirably present at a ratio of one per molecular weight of 300 to ioooo of the polymer, and less than one per 10,000 molecular weight? In the case of J coupling, there is almost no crosslinking effect due to the functional group, and 1/300 molecular weight.
If the ratio exceeds one, the crosslinking density will become too high.
官能ポリマーとしてはウレタンアクリレート、ポリエス
テルアクリレート、エポキシアクリレ−ト等や、アクリ
ル酸アルキルエステルとアクリル酸−2−ヒドロキシエ
チルとの共重合体の水酸基にアクリル酸クロリド又はア
クリル酸−2−ヒドロキシエチルとジイソシアナートの
1:1付加体を付加することによりアクリロイル基を導
入した共重合体や、アクリル酸アルキルエステルとアク
リル酸の共重合体のカルボキシル基にグリシジルメタク
リレートを付加した共重合体や、ポリビニルブチラール
の残存水酸基にアクリル酸クロリド又はアクリル酸−2
−ヒドロキシエチルとジイソシアナートの1:1付加体
を付加したもの等を使用することができる。Examples of functional polymers include urethane acrylate, polyester acrylate, epoxy acrylate, etc., and acrylic acid chloride or 2-hydroxyethyl acrylate on the hydroxyl group of a copolymer of acrylic acid alkyl ester and 2-hydroxyethyl acrylate. Copolymers with acryloyl groups introduced by adding a 1:1 adduct of diisocyanate, copolymers with glycidyl methacrylate added to the carboxyl group of a copolymer of acrylic acid alkyl ester and acrylic acid, and polyvinyl Acrylic acid chloride or acrylic acid-2 is added to the remaining hydroxyl group of butyral.
-A 1:1 adduct of hydroxyethyl and diisocyanate can be used.
なお上記ポリマーはオリゴマー状でもよいが、造膜性の
観点から分子量は1000〜30万(重量平均)である
のが好ましい。The above-mentioned polymer may be in the form of an oligomer, but from the viewpoint of film-forming properties, the molecular weight is preferably from 1,000 to 300,000 (weight average).
親水性モノマーは水酸基、カルボキシル基(金属塩)、
アミド基、イミド基、スルホン基、アンモニウム塩基、
リン酸基等の親水性基を含有するモノマーであり、例え
ばアクリル酸2−ヒドロキシエチル、メタクリル111
2−ヒドロキシエチル、アクリル酸2−ヒドロキシプロ
ピル、メタクリル酸2−ヒドロキシプロピル、アクリル
酸、メタクリル酸、アクリル酸金属塩、メタクリル酸金
lI塩、アクリルアミド、メタクリルアミド、ジメチル
アミノプロピルアクリルアミド、ジメチルアミノプロピ
ルメタクリルアミド、N−アクリロイルモルフォリン、
N−メタクリロイルモルフォリン、N−メチロールアク
リルアミドニーN−メチロールメタクリルアミド、t−
ブチルアクリルアミド、t−プチルメタクリルアミド、
N−メトキシメチルアクリルアミド、N−エトキシメチ
ルアクリルアミド、N−n−ブトキシアクリルアミド、
N、 N−ジメチルアクリルアミド、N、N−ジメチル
アミノプロピルアクリルアミド、N、N−ジメチルアミ
ノプロピルメタクリルアミド、ポリエチレングリコール
モノメタクリレート、ポリプロピレングリコールモノメ
タクリレート、グリセロールモノメタクリレート、2−
アクリルアミド2−メチルプロパンスルホン酸、メタア
クリルアミドプロピルトリメチルアンモニウムクロライ
ド、メタクリロイルオキシエチルトリメチルアンモニウ
ムクロライド、モノ(2−メタクロイロキシエチル)ア
シッドホスフェート等が挙げられる。Hydrophilic monomers include hydroxyl groups, carboxyl groups (metal salts),
Amide group, imide group, sulfone group, ammonium base,
A monomer containing a hydrophilic group such as a phosphoric acid group, such as 2-hydroxyethyl acrylate, methacryl 111
2-hydroxyethyl, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, metal acrylate, gold lI methacrylate salt, acrylamide, methacrylamide, dimethylaminopropylacrylamide, dimethylaminopropyl methacrylate amide, N-acryloylmorpholine,
N-methacryloylmorpholine, N-methylol acrylamide, N-methylol methacrylamide, t-
Butylacrylamide, t-butylmethacrylamide,
N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-n-butoxyacrylamide,
N,N-dimethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, glycerol monomethacrylate, 2-
Examples include acrylamide 2-methylpropanesulfonic acid, methacrylamide propyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, and mono(2-methacryloyloxyethyl) acid phosphate.
親水性架橋性モノマーは水酸基、カルボキシル基(金属
塩)、アミド基、イミド基、スルホン酸基(金属塩)、
アンモニウム塩基、リン酸基等の親水性基と、アクリル
ロイル基、メタクリロイル基、アリル基、エポキシ基等
電子線照射によって容易にラジカルとなる2つ以上の架
橋性官能基を 有するモノマーである。Hydrophilic crosslinking monomers include hydroxyl groups, carboxyl groups (metal salts), amide groups, imide groups, sulfonic acid groups (metal salts),
A monomer that has a hydrophilic group such as an ammonium base or a phosphate group, and two or more crosslinkable functional groups that easily become radicals when irradiated with electron beams, such as an acryloyl group, a methacryloyl group, an allyl group, or an epoxy group.
このような親水性架橋性モノマーとしては例えば、グリ
セロールジ(メタ)アクリレート、グリセロールメタク
リレートアクリレート等の水酸基を有するもの、エチレ
ングリコール・ジグリシジルエーテルジ(メタ)アクリ
レート、ポリエチレングリコール・ジグリシジルエーテ
ルジ(メタ)アクリレート、ポリプロピレングリコール
・ジグリシジルエーテルジ(メタ)アクリレート、ネオ
ペンチルグリコール・ジグリシジルエーテルジ(メタ)
アクリレート、グリセリンジグリシジル工−テルジ(メ
タ)アクリレート、ビスフエーノルAジグリシジルエー
テルジ(メタ)アクリレート、トリメチロールプロパン
トリグリシジルエーテルジ(メタ)アクリレート等のジ
オール・ジグリシジルエーテルとアクリル酸との1:2
付加物、ペンタエリスリトールモノ(メタ)アクリレー
ト、ペンタエリスリトールジ(メタ)アクリレート、ペ
ンタエリスリトールトリ(メタ)アクリレート、ジペン
タエリスリトールモノ(メタ)アクリレート、ジペンタ
エリスリトールジ(メタ)アクリレート、ジペンタエリ
スリトールテトラ
クリレート、ジペンタエリスリトールテトラ(メタ)ア
クリレート、ジペンタエリスリトールペンタ(メタ)ア
クリレート等のペンタエリスリトール誘導体、メチレン
ビス(メタ)アクリルアミド、アクリルアミド・グリオ
キサール付加体、アクリルアミド・メチロエチレン尿素
縮合物、1,3゜5−トリアクリロイルへキサヒドロs
−トリアジ・ ン、N、N−ジアリルアクリルアミド、
アクリルアミド・メチロールメラミン縮合物、アクリル
アミド・メチロールトリアゾン縮合物、アクリルアミド
・メチロールヒダントイン縮合物、アクリルアミド・メ
チロール尿素、N、N−ジアリルアクリルアミド等のア
クリルアミド誘導体等がある。Examples of such hydrophilic crosslinking monomers include those having a hydroxyl group such as glycerol di(meth)acrylate and glycerol methacrylate acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, and polyethylene glycol diglycidyl ether di(meth)acrylate. ) acrylate, polypropylene glycol diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)
1:2 of diol/diglycidyl ether such as acrylate, glycerin diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane triglycidyl ether di(meth)acrylate and acrylic acid.
Adducts, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tetracrylate pentaerythritol derivatives such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, methylene bis(meth)acrylamide, acrylamide/glyoxal adduct, acrylamide/methyloethylene urea condensate, 1,3゜5- triacryloyl hexahydro s
-triazine, N,N-diallylacrylamide,
Examples include acrylamide derivatives such as acrylamide/methylolmelamine condensate, acrylamide/methyloltriazone condensate, acrylamide/methylolhydantoin condensate, acrylamide/methylolurea, and N,N-diallylacrylamide.
本発明の親水性膜形成組成物はまた界面活性剤を含有す
ることができる。界面活性剤は親水性膜から徐々に表面
に滲出することにより防曇性を付与する作用を有する。The hydrophilic film-forming composition of the present invention can also contain a surfactant. The surfactant has the effect of imparting antifogging properties by gradually exuding from the hydrophilic film to the surface.
親水性膜形成組成物との相溶性が良ければ陰イオン性、
非イオン性及び陽イオン性のいずれの界面活性剤も使用
することができる。If the compatibility with the hydrophilic film-forming composition is good, it is anionic;
Both nonionic and cationic surfactants can be used.
陰イオン性界面活性剤としては脂肪酸塩、アルキル1i
ilエステル塩、アルキルベンゼンスルホン酸塩、アル
キルナフタレンスルホン酸塩、ジアルキルスルホコハク
酸エステル塩、アルキルリン酸エステル塩、ナフタレン
スルホン酸−ホルマリン縮合物、ポリオキシエチレンア
ルキル硫酸エステル塩等があり、非イオン性界面活性剤
としてはポリオキシエチレンアルキルエーテル、ポリオ
キシエチレンアルキルフェノールエーテル、ポリオキシ
エチレン脂肪酸エステル、ソルビタン脂肪酸エステル、
ポリオキシエチレンソルビタン脂肪酸エステル、ポリオ
キシエチレンアルキルアミン、グリセリン脂肪酸エステ
ル、オキシエチレンーオキシプロピレンプロックボリマ
ー等があり、陽イオン性界面活性剤としてはアルキルア
ミン、4級アンモニウム塩等がある。As anionic surfactants, fatty acid salts, alkyl 1i
il ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate ester salt, alkyl phosphate ester salt, naphthalene sulfonic acid-formalin condensate, polyoxyethylene alkyl sulfate ester salt, etc. Examples of activators include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester,
Examples include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene-oxypropylene block polymer, and examples of cationic surfactants include alkylamines and quaternary ammonium salts.
本発明の組成物は必要に応じ溶剤を含有してもよい。溶
剤は単に組成物の流動性を調節するだけでなく、塗膜の
表面に親水性モノマーを浮き上がらせる作用も有するの
で、本発明の親水膜を形成するのに好ましい。使用し得
る溶剤としては、メタノール、エタノール、イソプロパ
ツール、メチルセルソルブ、エチルセルソルブ等のアル
コール類、テトラヒドロフラン等のエーテル類、メチル
エチルケトン、アセトン、メチルイソブチルケトン等の
ケトン類、酢酸エチル、酢酸ブチル等のエステル類、ト
ルエン、キシレン等の芳香族炭化水素類等、又はこれら
の混合溶剤がある。The composition of the present invention may contain a solvent if necessary. The solvent not only adjusts the fluidity of the composition but also has the effect of lifting the hydrophilic monomer onto the surface of the coating film, and is therefore preferred for forming the hydrophilic film of the present invention. Usable solvents include alcohols such as methanol, ethanol, isopropanol, methyl cellosolve, and ethyl cellosolve, ethers such as tetrahydrofuran, ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, ethyl acetate, and butyl acetate. and aromatic hydrocarbons such as toluene and xylene, and mixed solvents thereof.
本発明の親水性膜形成組成物においては、ポリマー10
0重量部当り、親水性モノマーは5〜200重量部であ
る。5重量部未満だと十分な親水性が付与されず、逆に
200重量部を超えると膜の耐水性が低下する。好まし
い親水性モノマーの含有量は20〜150重量部である
。In the hydrophilic film-forming composition of the present invention, polymer 10
0 parts by weight, the hydrophilic monomer is 5 to 200 parts by weight. If it is less than 5 parts by weight, sufficient hydrophilicity will not be imparted, and if it exceeds 200 parts by weight, the water resistance of the membrane will decrease. The preferred content of hydrophilic monomer is 20 to 150 parts by weight.
親水性架橋性モノマーはポリマー100重量部当り1〜
300垂働部である。1重量部未満だと十分な親水性及
び架橋性が付与されず、逆に300重量部を超えると膜
の耐水性が低下するとともに架橋密度が高くなりすぎる
。好嫌しい親水性架橋性モノマーの含有量は1〜100
重吊部である。The hydrophilic crosslinking monomer is 1 to 100 parts by weight of the polymer.
It is a 300 turbulent part. If it is less than 1 part by weight, sufficient hydrophilicity and crosslinking properties will not be imparted, whereas if it exceeds 300 parts by weight, the water resistance of the membrane will decrease and the crosslinking density will become too high. The content of unfavorable hydrophilic crosslinking monomers is 1 to 100
This is a heavy lifting section.
界面活性剤を添加する場合、ポリマー100重量部当り
100重量部以下である。100重量部を超えると界面
活性剤の滲出が多過ぎるようになる。好ましい含有量は
1〜50重量部である。When a surfactant is added, the amount is 100 parts by weight or less per 100 parts by weight of the polymer. If it exceeds 100 parts by weight, too much surfactant leaches out. The preferred content is 1 to 50 parts by weight.
溶剤の添加量は膜の形成方法により異るが、塗布により
塗膜を形成する場合、組成物中の固形分が5〜sow
m%、好ましくは5〜30重最%重量るようにする。一
般的には溶剤添加量はポリマー100重量部当り600
0重量部以下とする。The amount of solvent added varies depending on the film formation method, but when forming a coating film by coating, the solid content in the composition is 5 to sow.
m%, preferably 5 to 30% by weight. Generally, the amount of solvent added is 600 parts per 100 parts by weight of polymer.
The amount shall be 0 parts by weight or less.
上記本発明の組成物を用い、以下の方法により親水性膜
を形成することができる。A hydrophilic film can be formed by the following method using the composition of the present invention.
まず適当な粘度に調整した組成物を、グラビアリバース
法、三本リバース法、グラビアダイレクト法、四本リバ
ース法等のロールコート方式により、塗布する。用途に
応じ、塗布をベースフィルム等の支持体上に行うのが好
ましい。ベースフィルムとしては一般に透明なプラスチ
ックを使用するが、装飾等の目的で着色フィルムや不透
明フィルムを使用することもできる。また塗膜との接着
性を向上させるため、易接肴処理をしたフィルムを用い
ることもできる。ベースフィルムの材質としてはポリエ
ステル、ポリエチレン、ポリプロピレン、ポリカーボネ
ート、ポリアクリレート、ポリスチレン、ポリアミド、
ポリイミド、ポリ塩化ビニル等を使用することができる
。First, a composition adjusted to an appropriate viscosity is applied by a roll coating method such as a gravure reverse method, a three-line reverse method, a gravure direct method, or a four-line reverse method. Depending on the application, the coating is preferably carried out on a support such as a base film. Transparent plastic is generally used as the base film, but colored or opaque films can also be used for decorative purposes. Furthermore, in order to improve adhesion to the coating film, a film that has been subjected to easy-to-apply treatment can also be used. Base film materials include polyester, polyethylene, polypropylene, polycarbonate, polyacrylate, polystyrene, polyamide,
Polyimide, polyvinyl chloride, etc. can be used.
ベースフィルム等の上に形成した組成、?0の塗膜は溶
剤を蒸発除去するため、ドライヤー等で加熱しながら乾
燥する。加熱温度が高すぎるとモノマー類も蒸発してし
まうので、最高140℃程度とする。The composition formed on the base film etc.? The coating film of No. 0 is dried while being heated with a dryer etc. in order to remove the solvent by evaporation. If the heating temperature is too high, the monomers will also evaporate, so the maximum heating temperature is about 140°C.
以上のようにして形成した本発明の組成物の塗膜におい
ては、モノマーが表面に浮き上がり、モノマー・リッチ
相とポリマー・リッチ相とからなる傾向があることがわ
かった。これは本発明の重要な特徴である。すなわち、
このような「配向」のため親水性基が表面に相対的に多
く存在し、耐水性、機械的強度等を有するポリマー骨格
部分に支持された親水性膜構造が得られる。It has been found that in the coating film of the composition of the present invention formed as described above, the monomer tends to float to the surface and consists of a monomer-rich phase and a polymer-rich phase. This is an important feature of the invention. That is,
Due to such "orientation", a relatively large number of hydrophilic groups are present on the surface, and a hydrophilic membrane structure supported by a polymer skeleton having water resistance, mechanical strength, etc. can be obtained.
次に、この塗膜に電子線の照射を行う。照射方法として
はエレクトロンカーテン方式、ビームスキャニング方式
等任意の方法を用いることができる。電子線の照射によ
り、ポリマーは官能基の有無にかかわらず架橋可能とな
り、親水性モノマー及び親水性架橋性モノマーがグラフ
ト重合又はブロック重合の形式でポリマーに架橋する。Next, this coating film is irradiated with an electron beam. As the irradiation method, any method such as an electron curtain method or a beam scanning method can be used. Irradiation with electron beams makes the polymer crosslinkable with or without functional groups, and hydrophilic monomers and hydrophilic crosslinkable monomers crosslink to the polymer in the form of graft or block polymerization.
この点が紫外線照射による架橋と著しい相違点である。This point is markedly different from crosslinking by ultraviolet irradiation.
照射する電子線のエネルギーは150〜200kcV程
度であり、照!11量は組成物の組成及び所望する架橋
密度の程度等により異なる。ポリマーに官能基がある程
照射量は少なくてすみ、また架橋密度を高くする程照射
量を多くする必要がある。特に界面活性剤を含有する場
合、架橋密度が高すぎるとその滲出が不十分となり、防
曇作用が低下するので、照射量の制錘は重要である。以
上のことがら一般に照射量は5〜20Mradであり、
0.5M rad未満であると未反応モノマーが残留す
ることがあり、20M radを超えると架橋密度が高
くなりすぎる。The energy of the irradiated electron beam is about 150 to 200kcV, and it is very bright! The amount of 11 varies depending on the composition of the composition, the desired degree of crosslinking density, etc. The more functional groups there are in the polymer, the smaller the irradiation dose is required, and the higher the crosslinking density, the more the irradiation dose needs to be increased. In particular, when a surfactant is contained, controlling the irradiation amount is important because if the crosslinking density is too high, the leaching of the surfactant will be insufficient and the antifogging effect will be reduced. Considering the above, the irradiation dose is generally 5 to 20 Mrad,
If it is less than 0.5 M rad, unreacted monomers may remain, and if it exceeds 20 M rad, the crosslink density becomes too high.
特に個々の組成のものについて言えば、(a)無官能ポ
リマー十親水性モノマーの場合0.5〜15Mradが
好ましく、(b)官能ポリマー士親水性七ツマー十親水
性架橋性モノマーの場合0.5〜15M radが好ま
しく、(C)無官能ポリマー十親水性モノマー十親水性
架橋性モノマー十界面活性剤の場合0.5〜10M r
adが好嫌しく、(d)官能ポリマー+親水性モノマー
十親水性架橋性モノマー十界面活性剤の場合0.5〜I
OM radが好ましい。In particular, regarding the individual compositions, (a) 0.5 to 15 Mrad is preferable in the case of a non-functional polymer and a hydrophilic monomer, and (b) 0.5 to 15 Mrad is preferable in the case of a functional polymer and a hydrophilic monomer and a hydrophilic crosslinkable monomer. 5 to 15 M rad is preferable, and in the case of (C) non-functional polymer + hydrophilic monomer + hydrophilic crosslinking monomer + surfactant, 0.5 to 10 M r
ad is preferable or unfavorable, and in the case of (d) functional polymer + hydrophilic monomer + hydrophilic crosslinking monomer + surfactant, 0.5 to I
OM rad is preferred.
このようにして作成した親水性膜は、ポリマー骨格に親
水性モノマー及び親水性架橋性七ツマ−が架橋している
とともに、膜表面に親水性モノマ及び親水性架橋性モノ
マー−の親水基が集中しているという独特のII4造を
有する。また膜全体は架橋しているので、十分な硬度及
び強度を有する。The hydrophilic membrane thus prepared has a polymer skeleton crosslinked with a hydrophilic monomer and a hydrophilic crosslinking monomer, and the hydrophilic groups of the hydrophilic monomer and hydrophilic crosslinking monomer are concentrated on the membrane surface. It has a unique II4 structure. Furthermore, since the entire film is crosslinked, it has sufficient hardness and strength.
特に本発明においては親水性モノマーと親水性架橋性モ
ノマーとの相溶性が良く、得られた親水性膜の防曇性は
非常に良好である。In particular, in the present invention, the hydrophilic monomer and the hydrophilic crosslinking monomer have good compatibility, and the resulting hydrophilic film has very good antifogging properties.
このように表面に存在する親水性基のために、特に水蒸
気が短期間当たるような用途において優れた防曇性を有
する。従って、そのような用途に使用するものには界面
活性剤を含有する必要は特にない。Because of the hydrophilic groups present on the surface, it has excellent antifogging properties, especially in applications where it is exposed to water vapor for a short period of time. Therefore, it is not particularly necessary to contain a surfactant in those used for such purposes.
これに対して、長期間水蒸気に曝される用途に使用する
ものについては、界面活性剤を含有する必要がある。こ
の場合、表面の親水性基が初期防曇性を発揮し、膜中に
存在する界面活性剤は膜表面に付着した水分により表面
に滲出してきて長期防曇性を発揮する。ここで本発明の
親水性膜は架橋しているので、界面活性剤の滲出は徐々
であり、非常に長期間にわたって防曇性を維持すること
ができる。また電子線の照射条件を変えることにより架
橋密度を調節して、界面活性剤の滲出速度をコントロー
ルすることができる。On the other hand, for those used in applications that are exposed to water vapor for a long period of time, it is necessary to contain a surfactant. In this case, the hydrophilic groups on the surface exhibit initial antifogging properties, and the surfactant present in the film oozes out to the surface due to moisture adhering to the membrane surface, thereby exhibiting long-term antifogging properties. Here, since the hydrophilic film of the present invention is crosslinked, the surfactant leaches out gradually, and the antifogging property can be maintained for a very long period of time. Furthermore, by changing the electron beam irradiation conditions, the crosslinking density can be adjusted to control the exudation rate of the surfactant.
本発明の親水性膜はベースフィルム上に塗膜として形成
することができるので、ベースフィルムに接着剤を塗布
することにより、鏡や窓等所望の所に貼着することがで
きる。また可撓性とすることもできるので、メガネやゴ
ーグル等の曲面状のものにも貼着できる。Since the hydrophilic film of the present invention can be formed as a coating film on a base film, it can be attached to a desired location such as a mirror or window by applying an adhesive to the base film. Furthermore, since it can be made flexible, it can be attached to curved objects such as glasses and goggles.
なお本発明の親水性膜はベースフィルム上の塗膜として
形成する場合、0.1〜30μmの厚さを有するように
する。0.1μm未満だと膜強度が弱いのみならず防曇
性が長続きせず、また30μmを超える厚さとしても効
果の一層の向上はほとんど期待できない。In addition, when the hydrophilic film of the present invention is formed as a coating film on a base film, it has a thickness of 0.1 to 30 μm. If the thickness is less than 0.1 μm, not only will the film strength be weak, but the antifogging property will not last long, and even if the thickness exceeds 30 μm, further improvement in effectiveness cannot be expected.
[実 施 例] 本発明を以下の実施例によりさらに詳細に説明する。[Example] The present invention will be explained in further detail by the following examples.
実施例 1
アクリルポリマー溶液300重量部と、親水性モノマー
として2−ヒドロキシエチルメタクリレート1001f
i部と、親水性架橋性モノマーとしてペンタエリスリト
ールトリアクリレート10重伍部と、界面活性剤として
エマルゲン106(花王(株)製)5重量部と、溶剤と
してメチルセルソルブ300重量部とを均一に混合し、
本発明の組成物をa製した。Example 1 300 parts by weight of acrylic polymer solution and 1001f of 2-hydroxyethyl methacrylate as a hydrophilic monomer
Part i, 10 parts by weight of pentaerythritol triacrylate as a hydrophilic crosslinking monomer, 5 parts by weight of Emulgen 106 (manufactured by Kao Corporation) as a surfactant, and 300 parts by weight of Methyl Celsolve as a solvent were uniformly added. mix,
The composition of the present invention was prepared in a.
なおアクリルポリマー溶液の調製は以下の手順で行った
。すなわち、メチルメタクリレート700重量部と、2
−ヒドロキシエチルメタクリレート390重量部と、ア
ゾビスイソブチロニトリル1.5重量部とメチルセルソ
ルブ2210重量部とを、31!流管及び撹拌器を具備
し、窒素置換したセパラブルフラスコに入れ、N2気流
中で85℃で5時間反応させた。その後さらにアゾビス
イソブチロニトリルを1.5重量部添加し、3時間反応
させた。生成したアクリルポリマー澄液は33重量%の
濃度であり、ゲル透過クロマトグラフィー(GPC)に
より測定したところ、重l平均分子1 (MW )は7
.5x10’であった。またモノマーのピークは認めら
れなかった。Note that the acrylic polymer solution was prepared according to the following procedure. That is, 700 parts by weight of methyl methacrylate and 2
-390 parts by weight of hydroxyethyl methacrylate, 1.5 parts by weight of azobisisobutyronitrile, and 2210 parts by weight of methyl cellosolve, 31! The mixture was placed in a separable flask equipped with a flow tube and a stirrer and purged with nitrogen, and reacted at 85°C for 5 hours in a N2 stream. Thereafter, 1.5 parts by weight of azobisisobutyronitrile was further added, and the mixture was reacted for 3 hours. The resulting acrylic polymer clear liquid had a concentration of 33% by weight, and as measured by gel permeation chromatography (GPC), the average molecular weight (MW) was 7.
.. It was 5x10'. Moreover, no monomer peak was observed.
上記組成物をロールコータ−により厚さ50μmのポリ
エステルフィルム(ルミラーTタイプ)に5μmの厚み
で均一に塗布し、ドライヤーで乾燥後、エレクトロンカ
ーテン型EB装置(ES 1社製)により175keV
の電子線を5 M rad照射し、塗膜を硬化させた。The above composition was uniformly coated to a thickness of 5 μm on a polyester film (Lumirror T type) with a thickness of 50 μm using a roll coater, and after drying with a dryer, it was heated at 175 keV using an electron curtain type EB device (manufactured by ES 1).
The coating film was cured by irradiating with an electron beam of 5 M rad.
得られた親水性フィルムの防曇性評価は下記テストによ
り行った。The antifogging property of the obtained hydrophilic film was evaluated by the following test.
(1)水の接触角テスト。(1) Water contact angle test.
(2)呼気テスト(呼気により曇りが発生するか、否か
を調べる)。テスト評価 O:曇らず、×:曇り発生
(3)氷水呼気テスト(氷水入りのビーカーにフィルム
を貼り、1分後に呼気をかけて曇りが発生するか否かを
調べる)。(2) Breath test (to check whether cloudiness occurs with exhaled breath). Test evaluation O: No clouding, ×: Cloudy occurrence (3) Ice water breath test (A film is pasted on a beaker containing ice water, and 1 minute later, exhalation is applied to check whether or not clouding occurs).
(4) 60℃湯気テスト(60℃の湯気にフィルム
を当てて曇りが発生するか否かを調べる)。(4) 60°C steam test (examine whether clouding occurs by exposing the film to steam at 60°C).
(5)、96℃湯気テスト(96℃の湯気にフィルムを
当てて曇りが発生するか否かを調べる)。(5) 96°C steam test (examine whether clouding occurs by exposing the film to steam at 96°C).
上記(4)〜(5)のテストにおいて、結果を下記の第
1表に示す。In the tests (4) to (5) above, the results are shown in Table 1 below.
友1且−1二ヱ
第1表に示す各組成の組成物を用いて、実施例1と同様
の方法で親水性フィルムを作成し、同じテストを行った
。結果を同じく第1表に示す。Friend 1 and -12 Using the compositions shown in Table 1, hydrophilic films were prepared in the same manner as in Example 1, and the same tests were conducted. The results are also shown in Table 1.
大1Ulヱ
官能ポリマーとしてウレタンアクリレート100重量部
と、親水性モノマーとしてN、N−ジメチルアクリルア
ミド50重量部と、親水性架橋性モノマーとしてグリセ
リンジグリシジルエーテルジアクリレートと、界面活性
剤として[レオドールTW−01064(花王(株)製
)5重量部と、溶剤としてメチルエチルケトン500重
量部とを混合し、本発明の親水性膜形成用組成物をa製
した。100 parts by weight of urethane acrylate as a large 1U1 functional polymer, 50 parts by weight of N,N-dimethylacrylamide as a hydrophilic monomer, glycerin diglycidyl ether diacrylate as a hydrophilic crosslinking monomer, and [Rheodol TW-] as a surfactant. 5 parts by weight of 01064 (manufactured by Kao Corporation) and 500 parts by weight of methyl ethyl ketone as a solvent were mixed to prepare a composition for forming a hydrophilic film of the present invention.
なおウレタンアクリレートのm’thは以下の通り行っ
た。すなわち、実施例1と同じ装置を用い、その中にブ
チレンアジペート(「ニラボランN−45フ04日本ポ
リウレタン(株)製)650gと、メチルエチルケトン
300qと、イソホロンジイソシアネート444qとを
入れ、60℃で攪、拌しながら、ジプチル錫ジラウレー
ト1qをメチルエチルケトン10gに溶かしたものを滴
下した。Note that m'th of urethane acrylate was determined as follows. That is, using the same apparatus as in Example 1, 650 g of butylene adipate ("Niraboran N-45 F04 manufactured by Nippon Polyurethane Co., Ltd."), 300 q of methyl ethyl ketone, and 444 q of isophorone diisocyanate were placed therein, and stirred at 60 ° C. While stirring, 1 q of diptyltin dilaurate dissolved in 10 g of methyl ethyl ketone was added dropwise.
5時間窒素気流中で攪拌しながら2−ヒドロキシエチル
アクリレート232qを滴下し、滴下終了後さらに70
℃で3時間攪拌を継続した。赤外線吸収スペクトルによ
り−NGO基のピークが消失したのを確認して、反応を
終了した。得られたポリマーの重量平均分子量(Mw)
はGPCにより1700であった。232q of 2-hydroxyethyl acrylate was added dropwise with stirring in a nitrogen stream for 5 hours, and after the completion of the addition, an additional 70
Stirring was continued for 3 hours at °C. The reaction was terminated when it was confirmed by infrared absorption spectrum that the peak of the -NGO group had disappeared. Weight average molecular weight (Mw) of the obtained polymer
was 1700 by GPC.
上記組成物を実施例1と同様の方法で易接着性ポリエス
テルフィルム(東洋紡@製K −1522>上に塗布し
、乾燥後同じ電子線照射条件で硬化させた。得られた親
水性!膜の防曇性について、実施例1と同じテストを行
った。結果を第2表に示す。The above composition was applied onto an easily adhesive polyester film (Toyobo K-1522) in the same manner as in Example 1, and after drying, it was cured under the same electron beam irradiation conditions. Regarding antifogging properties, the same test as in Example 1 was conducted.The results are shown in Table 2.
K1鼠旦ニュユ
実施例11と同様にして、第2表に示す組成の組成物か
ら親水性塗膜のフィルムを形成し、各親水性フィルムに
ついて同じ防曇性のテストを行った。結果を第2表に示
す。K1 Rat Nuyu In the same manner as in Example 11, hydrophilic coating films were formed from the compositions shown in Table 2, and the same antifogging test was conducted for each hydrophilic film. The results are shown in Table 2.
実施例13
実施例1において調製した組成物において゛、界面活性
剤の最を0〜30ilfi部の間で種々に変化させた。Example 13 In the composition prepared in Example 1, the amount of surfactant was varied from 0 to 30 parts.
得られた各組成物について、実施例1と同じテストを行
うとともに、長期防曇性を評価するために耐水浸漬テス
トをおこなった。なお耐水浸漬テストは25℃の水にフ
ィルムを24時間浸漬し、水から取り出した後で60℃
湯気テストを行い、防曇性を維持しているか否か調べる
ことからなり、60℃の湯気にさらして1分間曇らなけ
れば(防曇性を維持していれば)○、そうでなければ×
とした。結果を第3表に示す。Each of the obtained compositions was subjected to the same test as in Example 1, and also to a water immersion test to evaluate long-term antifogging properties. The water resistance immersion test was conducted by immersing the film in water at 25°C for 24 hours, and after taking it out from the water at 60°C.
A steam test is conducted to determine whether the product maintains its anti-fogging properties.If it does not fog up after being exposed to steam at 60℃ for 1 minute (if it maintains its anti-fogging properties), it is ○, otherwise it is ×.
And so. The results are shown in Table 3.
衷ILL生
実施例1におけるのと同じ組成物を用いて、同様の方法
で5μmの厚さに塗布を行い、ドライヤーで乾燥させた
。得られた塗膜の種々の照射量で175keVの電子線
を照射し、種々の架ta密度の親水性塗膜を得た。得ら
れた親水性塗膜の防曇性を測定した。結果を電子線照射
量とともに第4表に示す。Using the same composition as in Example 1, coating was carried out in the same manner to a thickness of 5 μm and dried with a dryer. The obtained coating films were irradiated with an electron beam of 175 keV at various doses to obtain hydrophilic coating films with various cross-ta densities. The antifogging property of the obtained hydrophilic coating film was measured. The results are shown in Table 4 along with the electron beam irradiation amount.
衷1」LLユ
実施例2に示す組成の組成物に対して実施例14と同じ
実験を行った。結果を第5表に示す。The same experiment as in Example 14 was conducted on the composition shown in Example 2. The results are shown in Table 5.
比較例1
実施例3において親水性モノマーとしてのグリセロール
モノメタクリレートを使用しない以外全く同じようにし
て、塗膜を形成し、得られた塗膜の防曇性を評価した。Comparative Example 1 A coating film was formed in exactly the same manner as in Example 3 except that glycerol monomethacrylate as the hydrophilic monomer was not used, and the antifogging properties of the resulting coating film were evaluated.
結果を第6表に示す。The results are shown in Table 6.
比較例2
実施例3において親水性架橋性モノマーとしてのジペン
タエリスリトールペンタアクリレートを使用しない以外
全く同じようにして、塗膜を形成し、得られた塗膜の防
曇性を評価した。結果を第6表に示す。Comparative Example 2 A coating film was formed in exactly the same manner as in Example 3 except that dipentaerythritol pentaacrylate as the hydrophilic crosslinking monomer was not used, and the antifogging properties of the resulting coating film were evaluated. The results are shown in Table 6.
第6表に示す結果から親水性モノマーと親水性架橋性モ
ノマーとは相乗効果を発揮することがわかり、いずれが
欠けても本発明の防曇効果が得られない。The results shown in Table 6 show that the hydrophilic monomer and the hydrophilic crosslinking monomer exhibit a synergistic effect, and if either one is lacking, the antifogging effect of the present invention cannot be obtained.
比較例3
実施例1に示す組成の組成物を塗布後、l”usi o
nDR8−120LIVli[t (ソマール製)を
用いて紫外線の照射を10分間行った。しかしながら硬
化反応は起きなかった。このことから、本発明の組成物
は電子線によりはじめて架橋(硬化)することがわかる
。Comparative Example 3 After applying the composition shown in Example 1, l”usi o
Ultraviolet irradiation was performed for 10 minutes using nDR8-120LIVli[t (manufactured by Somar). However, no curing reaction occurred. This shows that the composition of the present invention is crosslinked (cured) only by electron beams.
[発明の効果]
以上の通り本発明の親水性“膜形成組成物は親水性モノ
マー及び親水性架橋性モノマーを表面に析出させて硬化
する性質を有するため、初期防曇性を有する親水性膜を
提供することができる。また電子線により架橋するもの
であるので、熱硬化と比較して架橋密度を自由に調整す
ることができる。[Effects of the Invention] As described above, the hydrophilic film-forming composition of the present invention has the property of curing by precipitating hydrophilic monomers and hydrophilic crosslinking monomers on the surface, so that it can form a hydrophilic film with initial antifogging properties. Furthermore, since crosslinking is performed by electron beams, the crosslinking density can be adjusted more freely than in the case of thermosetting.
そのため界面活性剤(長期防曇性付与剤)の滲出を制御
することができる。また加熱せずに硬化(架橋)できる
ので、熱に弱い素材にも防曇性を付与できる。さらに紫
外線による架橋のように珊感剤を用いないので、耐候性
が良好であり、長期の使用によっても劣化が少ない。Therefore, leaching of the surfactant (long-term antifogging agent) can be controlled. Furthermore, since it can be cured (crosslinked) without heating, anti-fog properties can be imparted to heat-sensitive materials. Furthermore, since no sensitizing agent is used as in crosslinking with ultraviolet rays, weather resistance is good and there is little deterioration even after long-term use.
またこのような組成物から形成される本発明の親水性膜
は表面の親水基により初期防曇性を有し、かつ界面活性
剤を含有する場合には、架橋した構造を通して徐々に滲
出することにより長期にわたり防曇性を維持することが
できる。また架橋しているので十分な機械的強度及び硬
度を有する。その上高温下での防曇特性が優れていると
いう利点も有する。In addition, the hydrophilic film of the present invention formed from such a composition has initial antifogging properties due to the hydrophilic groups on the surface, and when it contains a surfactant, it gradually oozes out through the crosslinked structure. As a result, anti-fog properties can be maintained for a long period of time. Furthermore, since it is crosslinked, it has sufficient mechanical strength and hardness. Furthermore, it also has the advantage of having excellent antifogging properties at high temperatures.
さらに本発明の製造方法は組成物の塗膜に所望量の電子
線を照射するので、親水性膜の硬化度(架橋密度)を適
当に調節することができ、それによりとくに長期防曇性
をコントロールすることができる。Furthermore, since the production method of the present invention irradiates the coating film of the composition with a desired amount of electron beams, the degree of curing (crosslinking density) of the hydrophilic film can be adjusted appropriately, thereby improving long-term antifogging properties. can be controlled.
Claims (47)
いて、ポリマーと、親水性モノマーと親水性架橋性モノ
マーとを含有することを特徴とする親水性膜形成組成物
。(1) A composition for forming a hydrophilic film by electron beam irradiation, characterized by containing a polymer, a hydrophilic monomer, and a hydrophilic crosslinkable monomer.
物において、前記ポリマーが官能基を実質的に有さない
ことを特徴とする親水性膜形成組成物。(2) The hydrophilic film-forming composition according to claim 1, wherein the polymer has substantially no functional group.
物において、前記ポリマーが官能基を有することを特徴
とする親水性膜形成組成物。(3) The hydrophilic film-forming composition according to claim 1, wherein the polymer has a functional group.
物において、前記ポリマーの官能基がアクリロイル基、
メタクリロイル基、アリル基及びエポキシ基のいずれか
1種又は2種以上であることを特徴とする親水性膜形成
組成物。(4) In the hydrophilic film-forming composition according to claim 3, the functional group of the polymer is an acryloyl group,
A hydrophilic film-forming composition comprising one or more of methacryloyl groups, allyl groups, and epoxy groups.
載の親水性膜形成組成物において、前記親水性モノマー
は水酸基、カルボキシル基及びその金属塩、アミド基、
イミド基、スルホン酸基、アンモニウム塩基及びリン酸
基のいずれか1種又は2種以上を含有することを特徴と
する親水性膜形成組成物。(5) In the hydrophilic film-forming composition according to any one of claims 1 to 4, the hydrophilic monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group,
A hydrophilic film-forming composition characterized by containing one or more of an imide group, a sulfonic acid group, an ammonium base, and a phosphoric acid group.
載の親水性膜形成組成物において、前記親水性架橋性モ
ノマーは水酸基、カルボキシル基及びその金属塩、アミ
ド基、イミド基、スルホン酸基及びその金属塩、アンモ
ニウム塩基及びリン酸基のいずれか1種又は2種以上の
親水性基とアクリロイル基、メタクリロイル基、アリル
基及びエポキシ基のいずれか1種又は2種以上の架橋性
官能基とを含有することを特徴とする親水性膜形成組成
物。(6) In the hydrophilic film-forming composition according to any one of claims 1 to 5, the hydrophilic crosslinkable monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, Crosslinking of one or more hydrophilic groups of sulfonic acid groups and their metal salts, ammonium bases, and phosphoric acid groups with one or more of acryloyl groups, methacryloyl groups, allyl groups, and epoxy groups. 1. A hydrophilic film-forming composition characterized by containing a functional group.
載の親水性膜形成組成物において、前記ポリマー100
重量部に対して前記親水性モノマーは5〜200重量部
であり、前記親水性架橋性モノマーは1〜300重量部
であることを特徴とする親水性膜形成組成物。(7) In the hydrophilic film-forming composition according to any one of claims 1 to 6, the polymer 100
A hydrophilic film-forming composition, wherein the hydrophilic monomer is 5 to 200 parts by weight, and the hydrophilic crosslinking monomer is 1 to 300 parts by weight.
載の親水性膜形成組成物において、さらに溶剤を含有す
ることを特徴とする親水性膜形成組成物。(8) The hydrophilic film-forming composition according to any one of claims 1 to 9, further comprising a solvent.
いて、前記溶剤は前記ポリマー100重量部に対して6
000重量部以下であることを特徴とする親水性膜形成
組成物。(9) In the hydrophilic film formation according to claim 8, the solvent is 6 parts by weight based on 100 parts by weight of the polymer.
1,000 parts by weight or less of a hydrophilic film-forming composition.
おいて、ポリマーと、親水性モノマーと、親水性架橋性
モノマーと界面活性剤とを含有することを特徴とする親
水性膜形成組成物。(10) A composition for forming a hydrophilic film by electron beam irradiation, which contains a polymer, a hydrophilic monomer, a hydrophilic crosslinking monomer, and a surfactant.
組成物において、前記ポリマーが官能基を実質的に有さ
ないことを特徴とする親水性膜形成組成物。(11) The hydrophilic film-forming composition according to claim 10, wherein the polymer has substantially no functional group.
組成物において、前記ポリマーが官能基を有することを
特徴とする親水性膜形成組成物。(12) The hydrophilic film-forming composition according to claim 10, wherein the polymer has a functional group.
組成物において、前記ポリマーの官能基がアクリロイル
基、メタクリロイル基、アリル基及びエポキシ基のいず
れか1種又は2種以上であることを特徴とする親水性膜
形成組成物。(13) In the hydrophilic film-forming composition according to claim 12, the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. A hydrophilic film-forming composition characterized by:
かに記載の親水性膜形成組成物において、前記親水性モ
ノマーは水酸基、カルボキシル基及びその金属塩、アミ
ド基、イミド基、スルホン酸基及びその金属塩、アンモ
ニウム塩基及びリン酸基のいずれか1種又は2種以上を
含有することを特徴とする親水性膜形成組成物。(14) In the hydrophilic film-forming composition according to any one of claims 10 to 13, the hydrophilic monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, and a sulfonic acid group. A hydrophilic film-forming composition characterized by containing one or more of a group and a metal salt thereof, an ammonium base, and a phosphoric acid group.
かに記載の親水性膜形成組成物において、前記親水性架
橋性モノマーは水酸基、カルボキシル基及びその金属塩
、アミド基、イミド基、スルホン酸基及びその金属塩、
アンモニウム塩基及びリン酸基のいずれか1種又は2種
以上の親水性基と、アクリロイル基、メタクリロイル基
、アリル基及びエポキシ基のいずれか1種又は2種以上
の架橋性官能基とを含有することを特徴とする親水性膜
形成組成物。(15) In the hydrophilic film-forming composition according to any one of claims 10 to 14, the hydrophilic crosslinkable monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, sulfonic acid group and its metal salt,
Contains one or more hydrophilic groups selected from ammonium bases and phosphoric acid groups, and one or more crosslinkable functional groups selected from acryloyl groups, methacryloyl groups, allyl groups, and epoxy groups. A hydrophilic film-forming composition characterized by:
かに記載の親水性膜形成組成物において、前記ポリマー
100重量部に対して前記親水性モノマーは5〜200
重量部であり、前記親水性架橋性モノマーは1〜300
重量部であることを特徴とする親水性膜形成組成物。(16) In the hydrophilic film-forming composition according to any one of claims 10 to 15, the hydrophilic monomer is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer.
The hydrophilic crosslinking monomer is 1 to 300 parts by weight.
A hydrophilic film-forming composition characterized in that parts by weight.
親水性膜形成組成物において、前記界面活性剤は前記ポ
リマー100重量部に対して100重量部以下であるこ
とを特徴とする親水性膜形成組成物。(17) The hydrophilic film-forming composition according to claims 10 to 16, wherein the surfactant is present in an amount of 100 parts by weight or less based on 100 parts by weight of the polymer. Film-forming composition.
組成物において、前記界面活性剤は1〜50重量部であ
ることを特徴とする親水性膜形成組成物。(18) The hydrophilic film-forming composition according to claim 17, wherein the surfactant is contained in an amount of 1 to 50 parts by weight.
かに記載の親水性膜形成組成物において、さらに溶剤を
含有することを特徴とする親水性膜形成組成物。(19) The hydrophilic film-forming composition according to any one of claims 10 to 18, further comprising a solvent.
組成物において、前記溶剤は前記ポリマー100重量部
に対して6000重量部以下であることを特徴とする親
水性膜形成組成物。(20) The hydrophilic film-forming composition according to claim 19, wherein the amount of the solvent is 6000 parts by weight or less based on 100 parts by weight of the polymer.
モノマーとを含有する混合物の膜状物に電子線を照射し
てなり、前記ポリマーが前記親水性モノマー及び前記親
水性架橋性モノマーと架橋していることを特徴とする親
水性膜。(21) A film-like material of a mixture containing a polymer, a hydrophilic monomer, and a hydrophilic crosslinkable monomer is irradiated with an electron beam, and the polymer crosslinks with the hydrophilic monomer and the hydrophilic crosslinkable monomer. A hydrophilic membrane characterized by:
いて、前記ポリマーが官能基を実質的に有さないことを
特徴とする親水性膜。(22) The hydrophilic membrane according to claim 21, wherein the polymer has substantially no functional groups.
いて、前記ポリマーが官能基を有することを特徴とする
親水性膜。(23) The hydrophilic membrane according to claim 21, wherein the polymer has a functional group.
いて、前記ポリマーの官能基がアクリロイル基、メタク
リロイル基、アリル基及びエポキシ基のいずれか1種又
は2種以上であることを特徴とする親水性膜。(24) The hydrophilic membrane according to claim 23, wherein the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. hydrophilic membrane.
かに記載の親水性膜において、前記親水性モノマーは水
酸基、カルボキシル基及びその金属塩、アミド基、イミ
ド基、スルホン酸基及びその金属塩、アンモニウム塩基
及びリン酸基のいずれか1種又は2種以上を含有するこ
とを特徴とする親水性膜。(25) In the hydrophilic membrane according to any one of claims 21 to 24, the hydrophilic monomer includes hydroxyl groups, carboxyl groups, metal salts thereof, amide groups, imide groups, sulfonic acid groups, and A hydrophilic membrane characterized by containing one or more of a metal salt, an ammonium base, and a phosphoric acid group.
かに記載の親水性膜において、前記親水性架橋性モノマ
ーは水酸基、カルボキシル基及びその金属塩、アミド基
、イミド基、スルホン酸基及びその金属塩、アンモニウ
ム塩基及びリン酸基のいずれか1種又は2種以上の親水
性基と、アクリロイル基、メタクリロイル基、アリル基
及びエポキシ基のいずれか1種又は2種以上の架橋性官
能基とを含有することを特徴とする親水性膜。(26) In the hydrophilic membrane according to any one of claims 21 to 25, the hydrophilic crosslinking monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, and a sulfonic acid group. and a metal salt thereof, one or more hydrophilic groups of an ammonium base and a phosphoric acid group, and one or more crosslinkable functionalities of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. A hydrophilic membrane characterized by containing a group.
かに記載の親水性膜において、前記ポリマー100重量
部に対して前記親水性モノマーは5〜200重量部であ
り、前記親水性架橋性モノマーは1〜300重量部ある
ことを特徴とする親水性膜。(27) In the hydrophilic membrane according to any one of claims 21 to 26, the hydrophilic monomer is present in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer, and the hydrophilic crosslinking 1. A hydrophilic membrane characterized in that the content of the hydrophilic monomer is 1 to 300 parts by weight.
かに記載の親水性膜において、前記混合物がさらに溶剤
を含有することを特徴とする親水性膜。(28) The hydrophilic membrane according to any one of claims 21 to 27, wherein the mixture further contains a solvent.
いて、前記溶剤は前記ポリマー100重量部に対して6
000重量部以下であることを特徴とする親水性膜。(29) In the hydrophilic membrane according to claim 28, the solvent is 6 parts by weight based on 100 parts by weight of the polymer.
1,000 parts by weight or less.
かに記載の親水性膜において、前記親水性基が表面に多
く存在することを特徴とする親水性膜。(30) The hydrophilic membrane according to any one of claims 21 to 29, characterized in that many of the hydrophilic groups are present on the surface.
かに記載の親水性膜において、前記膜状物が支持体上に
塗布された塗膜であることを特徴とする親水性膜。(31) The hydrophilic membrane according to any one of claims 21 to 30, characterized in that the membrane-like material is a coating coated on a support.
いて、膜厚が0.1〜30μmであることを特徴とする
親水性膜。(32) The hydrophilic membrane according to claim 31, wherein the hydrophilic membrane has a thickness of 0.1 to 30 μm.
モノマーと、界面活性剤とを含有する混合物の膜状物に
電子線を照射してなり、前記ポリマーが前記親水性モノ
マー及び前記親水性架橋性モノマーと架橋していること
を特徴とする親水性膜。(33) A film-like material of a mixture containing a polymer, a hydrophilic monomer, a hydrophilic crosslinkable monomer, and a surfactant is irradiated with an electron beam, and the polymer is A hydrophilic membrane characterized by being crosslinked with a crosslinking monomer.
いて、前記ポリマーが官能基を実質的に有さないことを
特徴とする親水性膜。(34) The hydrophilic membrane according to claim 33, wherein the polymer has substantially no functional groups.
いて、前記ポリマーが官能基を有することを特徴とする
親水性膜。(35) The hydrophilic membrane according to claim 33, wherein the polymer has a functional group.
いて、前記ポリマーの官能基がアクリロイル基、メタク
リロイル基、アリル基及びエポキシ基のいずれか1種又
は2種以上であることを特徴とする親水性膜。(36) The hydrophilic membrane according to claim 35, wherein the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. hydrophilic membrane.
かに記載の親水性膜において、前記親水性モノマーは水
酸基、カルボキシル基及びその金属塩、アミド基、イミ
ド基、スルホン酸基及びその金属塩、アンモニウム塩基
及びリン酸基のいずれか1種又は2種以上を含有するこ
とを特徴とする親水性膜。(37) In the hydrophilic membrane according to any one of claims 33 to 36, the hydrophilic monomer includes hydroxyl groups, carboxyl groups, metal salts thereof, amide groups, imide groups, sulfonic acid groups, and A hydrophilic membrane characterized by containing one or more of a metal salt, an ammonium base, and a phosphoric acid group.
かに記載の親水性膜において、前記親水性架橋性モノマ
ーは水酸基、カリボキシル基及びその金属塩、アミド基
、イミド基、スルホンサン基及びその金属塩、アンモニ
ウム塩基及びリンサン基のいずれか1種又は2種以上の
親水性基と、アクリルロイ基、メタクリロイル基、アリ
ル基及びエポキシ基のいずれか1種又は2種以上の架橋
性官能基とを含有することを特徴とする親水性膜。(38) In the hydrophilic membrane according to any one of claims 33 and 37, the hydrophilic crosslinking monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, and a sulfone group. and a metal salt thereof, one or more hydrophilic groups selected from ammonium bases and phosphorus groups, and one or more crosslinkable functionalities selected from acrylloyl groups, methacryloyl groups, allyl groups, and epoxy groups. A hydrophilic membrane characterized by containing a group.
かに記載の親水性膜において、前記ポリマー100重量
部に対して前記親水性モノマーは5〜200重量部であ
り、前記親水性架橋性モノマーは1〜300重量部であ
ることを特徴とする親水性膜。(39) In the hydrophilic membrane according to any one of claims 33 to 38, the hydrophilic monomer is present in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer, and the hydrophilic crosslinking 1. A hydrophilic membrane characterized in that the content of the hydrophilic monomer is 1 to 300 parts by weight.
親水性膜において、前記界面活性剤は前記ポリマー10
0重量部に対して100重量部以下であることを特徴と
する親水性膜。(40) In the hydrophilic membrane according to claims 33 to 39, the surfactant is
A hydrophilic membrane characterized in that the amount is 100 parts by weight or less relative to 0 parts by weight.
いて、前記界面活性剤は1〜50重量部であることを特
徴とする親水性膜。(41) The hydrophilic membrane according to claim 40, wherein the surfactant is contained in an amount of 1 to 50 parts by weight.
か記載の親水性膜において、前記親水性基が表面に多く
存在することを特徴とする親水性膜。(42) The hydrophilic membrane according to any one of claims 33 to 41, characterized in that many of the hydrophilic groups are present on the surface.
かに記載の親水性膜において、表面に存在する前記親水
性基が初期防曇性を発揮し、膜中から滲出する前記界面
活性剤が長期防曇性を発揮することを特徴とする親水性
膜。(43) In the hydrophilic film according to any one of claims 33 to 42, the hydrophilic group present on the surface exhibits initial antifogging properties, and the surfactant exudes from within the film. A hydrophilic film characterized by a long-term antifogging agent.
かに記載の親水性膜において、前記膜状物が支持体上に
塗布された塗膜であることを特徴とする親水性膜。(44) The hydrophilic membrane according to any one of claims 33 to 43, wherein the film-like material is a coating film applied on a support.
かに記載の親水性膜において、膜厚が0.1〜30μm
であることを特徴とする親水性膜。(45) In the hydrophilic film according to any one of claims 33 to 44, the film thickness is 0.1 to 30 μm.
A hydrophilic membrane characterized by:
マーとを混合し、膜状に塗布した上で0.5〜20Mr
adの電子線を照射することを特徴とする親水性膜の製
造方法。(46) Mix a polymer, a hydrophilic monomer, and a hydrophilic crosslinking monomer, apply it in a film, and apply 0.5 to 20 Mr.
A method for producing a hydrophilic film, the method comprising irradiating an ad electron beam.
マー界面活性剤とを混合し、膜状に塗布した上で0.5
〜20Mradの電子線を照射することを特徴とする親
水性膜の製造方法。(47) Mix a polymer, a hydrophilic monomer, and a hydrophilic crosslinking monomer surfactant, apply it in a film form, and
A method for producing a hydrophilic membrane, comprising irradiating with an electron beam of ~20 Mrad.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10817087A JPS63273668A (en) | 1987-04-30 | 1987-04-30 | Hydrophilic film-forming composition, hydrophilic film thereof and production of said hydrophilic film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10817087A JPS63273668A (en) | 1987-04-30 | 1987-04-30 | Hydrophilic film-forming composition, hydrophilic film thereof and production of said hydrophilic film |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63273668A true JPS63273668A (en) | 1988-11-10 |
Family
ID=14477758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10817087A Pending JPS63273668A (en) | 1987-04-30 | 1987-04-30 | Hydrophilic film-forming composition, hydrophilic film thereof and production of said hydrophilic film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63273668A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02269777A (en) * | 1989-02-17 | 1990-11-05 | Swedlow Inc | Radiation-curable coating composition which forms transparent, abrasion resistant coloring coating |
US20090191373A1 (en) * | 2005-12-02 | 2009-07-30 | Mitsui Chemicals ,Inc. | Single Layer Film and Hydrophilic Material Comprising the Same |
WO2015029878A1 (en) * | 2013-08-30 | 2015-03-05 | Dicグラフィックス株式会社 | Aqueous ultraviolet radiation-curable overprint varnish composition |
JP2016044244A (en) * | 2014-08-23 | 2016-04-04 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent composition |
CN106823856A (en) * | 2017-03-21 | 2017-06-13 | 亚美滤膜(南通)有限公司 | Hydrophilic porous polyolefine material and its hydrophilically modified processing method |
JP2018090685A (en) * | 2016-12-01 | 2018-06-14 | Dic株式会社 | Active energy ray curable antifogging composition and cured article using the same |
WO2019058498A1 (en) * | 2017-09-22 | 2019-03-28 | ナトコ株式会社 | Coating composition, coating material, cured film, article including cured film, and production method for article including cured film |
-
1987
- 1987-04-30 JP JP10817087A patent/JPS63273668A/en active Pending
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02269777A (en) * | 1989-02-17 | 1990-11-05 | Swedlow Inc | Radiation-curable coating composition which forms transparent, abrasion resistant coloring coating |
US20090191373A1 (en) * | 2005-12-02 | 2009-07-30 | Mitsui Chemicals ,Inc. | Single Layer Film and Hydrophilic Material Comprising the Same |
US8617711B2 (en) * | 2005-12-02 | 2013-12-31 | Mitsui Chemicals, Inc. | Single layer film and hydrophilic material comprising the same |
WO2015029878A1 (en) * | 2013-08-30 | 2015-03-05 | Dicグラフィックス株式会社 | Aqueous ultraviolet radiation-curable overprint varnish composition |
JP2016044244A (en) * | 2014-08-23 | 2016-04-04 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent composition |
JP2018090685A (en) * | 2016-12-01 | 2018-06-14 | Dic株式会社 | Active energy ray curable antifogging composition and cured article using the same |
CN106823856A (en) * | 2017-03-21 | 2017-06-13 | 亚美滤膜(南通)有限公司 | Hydrophilic porous polyolefine material and its hydrophilically modified processing method |
CN106823856B (en) * | 2017-03-21 | 2020-10-30 | 亚美滤膜(南通)有限公司 | Hydrophilic porous polyolefin material and hydrophilic modification treatment method thereof |
WO2019058498A1 (en) * | 2017-09-22 | 2019-03-28 | ナトコ株式会社 | Coating composition, coating material, cured film, article including cured film, and production method for article including cured film |
JPWO2019058498A1 (en) * | 2017-09-22 | 2020-10-01 | ナトコ株式会社 | A method for manufacturing a coating composition, a coating material, a cured film, an article having a cured film, and an article having a cured film. |
US10876014B2 (en) | 2017-09-22 | 2020-12-29 | Natoco Co., Ltd. | Coating composition, coating material, cured film, article having cured film, and method for producing article having cured film |
EP3686255A4 (en) * | 2017-09-22 | 2021-04-14 | Natoco Co., Ltd. | Coating composition, coating material, cured film, article including cured film, and production method for article including cured film |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5180760A (en) | Anti-fogging resin film-forming composition | |
EP2599799A1 (en) | Single-layer film and hydrophilic material comprising same | |
US4018939A (en) | Method of rendering surfaces nonfogging | |
CA1057997A (en) | Radiation curable composition containing prepolymer with bonded hydroxyalkyl ester and halo substituted anhydride | |
JPS63273668A (en) | Hydrophilic film-forming composition, hydrophilic film thereof and production of said hydrophilic film | |
JP2649799B2 (en) | Hydrophilic film-forming composition, hydrophilic film thereof and method for producing the same | |
US5273812A (en) | Non-fogging sheet and its production | |
US3963806A (en) | Reaction product of polyalkylene imine and epoxy, halo, ethylenic substituted difunctional compounds | |
EP0339909B1 (en) | Anti-fogging resin film-forming composition | |
JPH0686581B2 (en) | Paint composition | |
JPH02255854A (en) | Composition for forming antifogging resin coating | |
EP0473780B1 (en) | Antifog sheet and method of its production | |
JPS63258904A (en) | Hydrophilic film-forming composition and hydrophilic film and production process thereof | |
JPH08269387A (en) | Thermosetting coating composition | |
JP2545241B2 (en) | Method for improving antifogging property of hydrophilic film | |
JPS63258905A (en) | Hydrophilic film-forming composition and hydrophilic film and production process thereof | |
JP2632848B2 (en) | Anti-fog sheet | |
JPH1143614A (en) | Antifogging film and its production | |
JP2007021010A (en) | Zwitterion coating | |
JP2525651B2 (en) | Anti-fog sheet and method for producing the same | |
JPH05186620A (en) | Coated molded product and its production | |
JPH0632997A (en) | Ultraviolet-curable coating composition | |
JP2711857B2 (en) | Anti-fog insulation sheet | |
JP2851420B2 (en) | Anti-fog sheet and method for producing the same | |
JPS63137933A (en) | Coating composition and molded resin article having excellent surface characteristics and produced by coating said composition |