WO2022203060A1 - 二種のパーフルオロポリエーテルを含有する硬化性組成物 - Google Patents
二種のパーフルオロポリエーテルを含有する硬化性組成物 Download PDFInfo
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- WO2022203060A1 WO2022203060A1 PCT/JP2022/014564 JP2022014564W WO2022203060A1 WO 2022203060 A1 WO2022203060 A1 WO 2022203060A1 JP 2022014564 W JP2022014564 W JP 2022014564W WO 2022203060 A1 WO2022203060 A1 WO 2022203060A1
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- perfluoropolyether
- active energy
- energy ray
- curable composition
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- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
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- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- GBSGXZBOFKJGMG-UHFFFAOYSA-N 3-propan-2-yloxypropan-1-ol Chemical compound CC(C)OCCCO GBSGXZBOFKJGMG-UHFFFAOYSA-N 0.000 description 1
- IXAUCVOJRVFRBJ-UHFFFAOYSA-N 4-(trichloromethyl)triazine Chemical class ClC(Cl)(Cl)C1=CC=NN=N1 IXAUCVOJRVFRBJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- NPHBJTOCGLOQOT-UHFFFAOYSA-N CC(C)(C(C1=CC=C(CC(C=C2)=CC=C2C(C(C)(C(C2=CC=CC=C2)=O)O)=O)C=C1)=O)O Chemical class CC(C)(C(C1=CC=C(CC(C=C2)=CC=C2C(C(C)(C(C2=CC=CC=C2)=O)O)=O)C=C1)=O)O NPHBJTOCGLOQOT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 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
- RABVYVVNRHVXPJ-UHFFFAOYSA-N [3-(hydroxymethyl)-1-adamantyl]methanol Chemical compound C1C(C2)CC3CC1(CO)CC2(CO)C3 RABVYVVNRHVXPJ-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- NNVDGGDSRRQJMV-UHFFFAOYSA-L [dioctyl(2,2,5,5-tetramethylhexanoyloxy)stannyl] 2,2,5,5-tetramethylhexanoate Chemical compound CCCCCCCC[Sn](OC(=O)C(C)(C)CCC(C)(C)C)(OC(=O)C(C)(C)CCC(C)(C)C)CCCCCCCC NNVDGGDSRRQJMV-UHFFFAOYSA-L 0.000 description 1
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- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
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- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- PJWNIOJGDLTZPK-UHFFFAOYSA-N cyclohexanone;methanol Chemical compound OC.O=C1CCCCC1 PJWNIOJGDLTZPK-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
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- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000000123 paper 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
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
Definitions
- the present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display elements, and capable of forming a hard coat layer excellent in slipperiness, scratch resistance, abrasion resistance and water repellency. , relates to homogeneous curable compositions free of suspensions and sediments.
- perfluoropolyether used in the present invention refers to one having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group.
- the "poly(oxyperfluoroalkylene) group A compound having an active energy ray-polymerizable group at the end of a molecular chain containing a fluoroalkylene) group is referred to as a “perfluoropolyether”.
- touch panels have been introduced into various devices such as portable information terminal devices such as mobile phones and tablet computers, laptop computers, home appliances, and automobile interior and exterior parts. is often operated by touching with a finger or a pen.
- the surface of the touch panel is required to be water and oil repellent in order to facilitate the removal of fingerprints, and the water and oil repellency is maintained even after repeated finger rubbing.
- Abrasion resistance is required.
- the surface of the touch panel is operated with a finger or a pen, the surface is required to have smoothness from the viewpoint of the touch feeling of the finger or the pen.
- the surface of the touch panel is required to have scratch resistance in order to prevent scratches.
- a surface coat layer such as a hard coat layer is provided.
- Fluorine-containing compounds exhibit high lubricity and water and oil repellency, and are therefore used as materials for forming hard coat layers. method is used. Fluorine-based surface modifiers are known to segregate on the surface of the hard coat layer due to the low surface energy of fluorine atoms.
- a method in which a high-density crosslinked structure is formed to increase the surface hardness of the hard coat layer and provide resistance to external force.
- a material for forming such a hard coat layer at present, polyfunctional acrylate materials that are three-dimensionally crosslinked by radicals generated by irradiation with active energy rays are most used.
- the fluorine-based surface modifier added to the coating liquid for forming the hard coat layer is generally a material having an active energy ray-polymerizable group in order to impart scratch resistance and wear resistance to the hard coat layer.
- Patent Document 1 From the viewpoint of scratch resistance and wear resistance, a low-molecular-weight material capable of forming a high-density crosslinked structure and having many active energy ray-polymerizable groups and having a so-called small acrylic equivalent is preferred.
- Patent Document 2 in order to obtain durability properties such as scratch resistance and wear resistance in the hard coat layer, for example, when a fluorine-based surface modifier having a crosslinkable group is used, fluorine atoms are added. The molecular chains contained therein are immobilized, and the slipperiness of the hard coat layer is reduced. In other words, there is a trade-off relationship between durability properties such as scratch resistance and wear resistance, and slipperiness, and it is difficult to achieve both high levels of properties.
- Patent Document 3 discloses a fluorine-containing polyether that becomes aggregates when obtaining a hard coating agent composition and causes cloudiness of the composition, and the composition. have reported the combined use of a fluorine-containing block copolymer with excellent compatibility with
- Patent Document 4 a linear polymer having a fluoropolyether in the main chain and having an acrylic group at one or both ends of the molecular chain and having a fluorine content of 48% by mass to 62% by mass, and a fluoropolyether as the main chain
- a linear polymer having a siloxane skeleton with a fluorine content of 25% by mass or more and less than 45% by mass having a plurality of acrylic groups at both ends of the molecular chain the fluorine content is 48% by mass. % to 62% by mass of the straight-chain polymer improves the solubility in the composition, resulting in a hard coat layer with excellent water repellency and slipperiness.
- paragraph [0006] of Patent Document 4 describes "wear resistance typified by slipperiness", and wear resistance is indirectly evaluated by slipperiness. Therefore, there are no specific examples regarding scratch resistance and abrasion resistance.
- An object of the present invention is to provide a homogeneous curable composition free of suspended solids and sediments, capable of forming a hard coat layer having both durability and lubricity, which are in a trade-off relationship, at a high level of properties. do. In addition to these, it is necessary for the hard coat layer to have high liquid repellency in consideration of actual use.
- the present invention provides (a) an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule, (b) a perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500 (however, (c) perfluoropolyether described later) excluding fluoropolyethers), (c) a perfluoropolyether having the active energy ray polymerizable group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500; and (d) active A curable composition containing a polymerization initiator that generates radicals by energy rays.
- the (c) perfluoropolyether has the active energy ray-polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1,550 to 3,500.
- the (c) perfluoropolyether has an active energy ray-polymerizable group via a urethane bond.
- the (c) perfluoropolyether has a fluorine atom content of 35% by mass to 65% by mass.
- the poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has repeating units -(CF 2 O)- and/or repeating units -(CF 2 CF 2 O)-, and both repeating units is a group formed by combining these repeating units by block bonding, random bonding, or block bonding and random bonding.
- the molecular chain containing the poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has a structure represented by the following formula [1].
- m is the number of repeating units -(CF 2 CF 2 O)-
- n is the number of repeating units -(CF 2 O)-
- m and n each independently represent an integer of 0 or more
- q is the number of oxyethylene groups and represents an integer of 0 to 20.
- n each independently represent an integer of 1 or more.
- the (c) perfluoropolyether is a compound represented by the following formula [2].
- m, n and q have the same definitions as in the above formula [1]
- A represents the terminal group having the active energy ray-polymerizable group.
- the terminal group A is a group represented by the following formula [A1] or [A2].
- R 1 and R 2 each independently represent a hydrogen atom or a methyl group
- * is a bond with the urethane bond of the compound represented by the above formula [2] represents.
- the (b) perfluoropolyether has the active energy ray-polymerizable groups at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.
- the molecular chain containing the poly(oxyperfluoroalkylene) group of the (b) perfluoropolyether has a structure represented by the following formula [3].
- r is the number of repeating units -(CF 2 CF 2 O)-
- s is the number of repeating units -(CF 2 O)-
- r and s each independently represent an integer of 0 or more, and when both repeating units are present, these repeating units are block-bonded, random-bonded, or block-bonded and random-bonded. .
- r and s each independently represent an integer of 1 or more.
- the (b) perfluoropolyether is a compound represented by the following formula [4].
- r and s have the same definitions as in the above formula [3]
- A represents the terminal group having the active energy ray-polymerizable group.
- the terminal group A is a group represented by the following formula [A1] or [A2].
- R 1 and R 2 each independently represent a hydrogen atom or a methyl group
- * is a bond with the urethane bond of the compound represented by the above formula [4] represents.
- the curable composition of the present invention further comprises (e) a solvent.
- a cured film obtained from the curable composition is a cured film obtained from the curable composition.
- a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film.
- the film substrate has a lower layer of the hard coat layer between the surface of the film substrate and the hard coat layer, and the film substrate is a resin film.
- the hard coat layer has a thickness of 1 ⁇ m to 20 ⁇ m.
- a method for producing a hard coat film comprising the steps of coating the curable composition on a film substrate to form a coating film, and irradiating the coating film with an active energy ray to cure it to form a hard coat layer.
- a step of applying the curable composition on a film substrate to form a coating film, a step of removing the solvent from the coating film by heating, and a hard coating by irradiating the coating film with an active energy ray and curing it A method for producing a hard coat film, comprising a step of forming layers.
- Forming a hard coat film further comprising the step of forming a lower layer of the hard coat layer on the surface of the film substrate, wherein the film substrate is a resin film and a coating film is formed on the lower layer of the hard coat layer. Production method.
- a surface modifier comprising a perfluoropolyether (B) which is a reaction product of a compound having a functional group and the active energy ray-polymerizable group.
- the perfluoropolyether (B) has the active energy ray-polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1,550 to 3,500.
- the perfluoropolyether (B) has a fluorine atom content of 35% by mass to 65% by mass.
- the perfluoropolyether (A) has the active energy ray-polymerizable group at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.
- the molecular chain containing the poly(oxyperfluoroalkylene) group of the perfluoropolyether (A) has a structure represented by the following formula [3]
- the poly(oxyperfluoroalkylene) of the perfluoropolyether (B) alkylene) group has a structure represented by the following formula [1].
- m is the number of repeating units -(CF 2 CF 2 O)-
- n is the number of repeating units -(CF 2 O)-
- m and n each independently represent an integer of 0 or more
- q represents the number of oxyethylene groups and represents an integer of 0 to 20
- r represents a repeating unit -(CF 2 CF 2 O)- number and s are the number of repeating units -(CF 2 O)-, satisfying 5 ⁇ (r+s) ⁇ 40
- r and s each independently represent an integer of 0 or more
- the repeating unit -(CF 2 CF 2 O)- and repeating unit -(CF 2 O)-, these repeating units are combined by block bond, random bond, or block bond and random bond .
- n and n each independently represent an integer of 1 or more
- r and s each independently represent an integer of 1 or more.
- the perfluoropolyether (A) is a compound represented by the following formula [4]
- the perfluoropolyether (B) is a compound represented by the following formula [2].
- m, n and q have the same definitions as in the above formula [1]
- r and s have the same definitions as in the above formula [3]
- A is the above represents a terminal group having an active energy ray-polymerizable group
- the terminal group A is a group represented by the following formula [A1] or [A2].
- R 1 and R 2 each independently represent a hydrogen atom or a methyl group
- * is the urethane of the compound represented by the above formula [2] or formula [4] Represents a bond with a bond.
- a curable composition useful for forming a cured film and a hard coat layer having both excellent scratch resistance/wear resistance and excellent slipperiness even in a thin film having a thickness of 1 ⁇ m to 20 ⁇ m. can provide.
- a curable composition useful for forming a cured film and a hard coat layer imparting high water repellency in addition to achieving both of the above properties, and a hard coat layer excellent in these properties are provided.
- a hard coat film can be provided.
- the active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule is an active It refers to a monomer that undergoes a polymerization reaction and cures when irradiated with energy rays.
- Preferred (a) polyfunctional monomers in the curable composition of the present invention are selected from the group consisting of monomers selected from the group consisting of polyfunctional (meth)acrylate compounds and polyfunctional urethane (meth)acrylate compounds described later. Monomers selected from the group consisting of monomers and lactone-modified polyfunctional (meth)acrylate compounds can be mentioned.
- the polyfunctional monomer (a) one of the above polyfunctional (meth)acrylate compounds can be used alone, or two or more of them can be used in combination.
- the (meth)acrylate compound includes both an acrylate compound and a methacrylate compound.
- (meth)acrylic acid includes acrylic acid and methacrylic acid.
- the (a) polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene-modified monomer include oxymethylene-modified, oxyethylene-modified, and oxypropylene-modified.
- examples of the oxyalkylene-modified polyfunctional monomer include oxyalkylene-modified compounds of the polyfunctional (meth)acrylate compound or polyfunctional urethane (meth)acrylate compound.
- the oxyalkylene-modified polyfunctional monomers may also be used singly or in combination of two or more.
- polyfunctional monomers preferable in the present invention include polyfunctional monomers having at least 3 (meth)acryloyl groups per molecule, for example, at least 4 per molecule.
- polyfunctional monomers include monomers selected from the group consisting of oxyalkylene-modified polyfunctional (meth)acrylate compounds having at least three (meth)acryloyl groups in one molecule. .
- Examples of the polyfunctional (meth)acrylate compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth) Acrylates, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin
- preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. can be mentioned.
- Examples of the oxyalkylene-modified polyfunctional (meth)acrylate compound include oxyalkylene-modified polyol (meth)acrylate compounds.
- Examples of the polyols include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
- polyfunctional urethane (meth)acrylate compound for example, a compound obtained by reacting a polyfunctional isocyanate and a (meth)acrylate having a hydroxy group, and a compound obtained by reacting a polyfunctional isocyanate and a (meth)acrylate having a hydroxy group with a polyol
- examples include compounds obtained by reaction, but the polyfunctional urethane (meth)acrylate compounds that can be used in the present invention are not limited to these examples.
- polyfunctional isocyanates examples include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
- (meth)acrylates having a hydroxy group examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , and tripentaerythritol hepta(meth)acrylate.
- polystyrene resin examples include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol; these diols and succinic acid and maleic acid.
- polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as adipic acid; polyether polyols; and polycarbonate diols.
- the polyfunctional monomer may be a lactone-modified polyfunctional (meth)acrylate compound, and the lactone to be modified is preferably ⁇ -caprolactone.
- the lactone-modified polyfunctional (meth)acrylate compound include ⁇ -caprolactone-modified pentaerythritol tri(meth)acrylate, ⁇ -caprolactone-modified pentaerythritol tetra(meth)acrylate, and ⁇ -caprolactone-modified dipentaerythritol penta(meth)acrylate. , and ⁇ -caprolactone-modified dipentaerythritol hexa(meth)acrylate.
- (b) Perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500 The perfluoropolyether having an active energy ray-polymerizable group at the end of the molecular chain containing the (b) component poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 is hereinafter simply referred to as "(b ) perfluoropolyether”.
- (b) Perfluoropolyether excludes (c) perfluoropolyether described later.
- the (b) perfluoropolyether which is preferable in the curable composition of the present invention, has an active energy ray-polymerizable group via a urethane bond at the end of the molecular chain containing the poly(oxyperfluoroalkylene) group.
- the ends of the molecular chain containing the poly(oxyperfluoroalkylene) group may be all or part of the ends of the molecular chain.
- all terminals and part of the molecular chain are both terminals and one terminal of the linear molecular chain, respectively.
- linking group between the poly(oxyperfluoroalkylene) group and the urethane bond examples include a hydrocarbon group having an ether bond, and in the hydrocarbon group, at least one hydrogen atom is substituted with a fluorine atom. may have been Also, preferred (b) perfluoropolyethers do not have silicon atoms in their chemical structure.
- (b) Perfluoropolyether serves as a surface modifier in the hard coat layer formed from the curable composition of the present invention.
- component (c) described below serves as a surface modifier in the hard coat layer formed from the curable composition of the present invention.
- the (b) perfluoropolyether has excellent compatibility with the (a) polyfunctional monomer, clouding is suppressed and it is possible to form a hard coat layer exhibiting a transparent appearance.
- poly(oxyperfluoroalkylene) group -[CF 2 O]-(oxyperfluoromethylene group) and -[CF 2 CF 2 O]- from the viewpoint of obtaining a cured film having good scratch resistance.
- a group having both (oxyperfluoroethylene groups) as repeating units is preferred. In that case, the bonding of these oxyperfluoroalkylene groups may be either block bonding or random bonding.
- Perfluoropolyether is not limited to those having one active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and two or more active energy ray-polymerizable groups may have Examples of the active energy ray-polymerizable group include (meth)acryloyl groups and vinyl groups. group. Among these terminal groups, a group having two active energy ray-polymerizable groups and represented by the formula [A2] is preferable.
- the perfluoropolyether has active energy ray-polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group from the viewpoint of obtaining a cured film with good scratch resistance. More preferably, the number of the active energy ray-polymerizable groups in one molecule is large. The number of the polymerizable groups is preferably 2 or more, more preferably 3 or more, at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.
- Perfluoropolyether having a weight average molecular weight of 1,400 to 3,500 can provide a hard coat layer with excellent scratch resistance, abrasion resistance, and slipperiness.
- the content of (b) perfluoropolyether in the curable composition of the present invention is, for example, 0.05 parts by mass to 10 parts by mass, 0.05 parts by mass with respect to 100 parts by mass of the (a) polyfunctional monomer parts to 5 parts by mass, or 0.05 to 3 parts by mass, preferably 0.1 to 3 parts by mass, more preferably 0.1 to 1 part by mass.
- the perfluoropolyether content is 0.05 parts by mass or more, so that the hard coat layer can be provided with sufficient scratch resistance, and (b) the perfluoropolyether content is When it is 3 parts by mass or less, it is sufficiently compatible with (a) the polyfunctional monomer, and a hard coat layer with little cloudiness can be obtained.
- Perfluoropolyethers can be used singly or in combination of two or more. When two or more types are combined, one end (one end) of the molecular chain containing the poly(oxyperfluoroalkylene) group has an active energy ray-polymerizable group via a urethane bond, and other than the molecular chain A perfluoropolyether having a hydroxy group at one end (the other end) may be included.
- Perfluoropolyether is, for example, a raw material perfluoropolyether having a hydroxy group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group and having a number average molecular weight of 1200 to 3000, and the hydroxy It is obtained by reacting a group-reactive functional group and a compound having the active energy ray-polymerizable group.
- the functional group that reacts with the hydroxy group include a hydroxy group, a carboxy group and an isocyanate group.
- a fluorine atom-containing group more preferably a trifluoromethoxy group, at one end opposite to the one end having a hydroxyl group of the raw material perfluoropolyether.
- the active energy ray polymerization The (c) perfluoropolyether having a fluorine atom-containing group at one end opposite to the one end having a functional group can sufficiently migrate to the surface of the hard coat layer, and exhibits excellent water repellency and It can express slipperiness.”
- Perfluoropolyether is not limited to those having one active energy ray-polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and two or more active energy ray-polymerized It may have a sexual group.
- the active energy ray-polymerizable group include (meth)acryloyl groups and vinyl groups. group.
- these terminal groups a group having two active energy ray-polymerizable groups and represented by the formula [A2] is preferable.
- the (c) perfluoropolyether together with the (b) perfluoropolyether, functions as a surface modifier in the hard coat layer formed from the curable composition of the present invention.
- (c) perfluoropolyether has excellent compatibility with (b) perfluoropolyether, it is possible to form a hard coat layer that suppresses white turbidity and presents a transparent appearance.
- (c) perfluoropolyether preferably has a poly(oxyalkylene) group from the viewpoint of compatibility with (a) the polyfunctional monomer.
- a poly(oxyethylene) group is preferred as the poly(oxyalkylene) group.
- the (c) perfluoropolyether preferable in the curable composition of the present invention has an active energy ray-polymerizable group via a urethane bond only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group.
- the poly(oxyperfluoroalkylene) group -[CF 2 O]-(oxyperfluoromethylene group) and -[CF 2 CF 2 O]- from the viewpoint of obtaining a cured film having good scratch resistance.
- a group having both (oxyperfluoroethylene groups) as repeating units is preferred. In that case, the bonding of these oxyperfluoroalkylene groups may be either block bonding or random bonding.
- Perfluoropolyether has a fluorine atom content of, for example, 35% by mass or more and 65% by mass or less, preferably 40% by mass or more and 65% by mass, more preferably 45% by mass or more and 65% by mass. is.
- a hard coat layer having excellent water repellency and slipperiness can be obtained. There is a possibility that sufficient characteristics cannot be obtained.
- the perfluoropolyether has a weight average molecular weight of 1,550 to 3,500, preferably 1,600 to 3,500, and more preferably 1,700 to 3,500.
- (c) perfluoropolyether tends to stay on the surface of the hard coat layer obtained from the curable composition of the present invention, and the layer surface Since the shear stress is sufficiently reduced, a hard coat layer with excellent slipperiness can be obtained.
- the weight-average molecular weight of (c) the perfluoropolyether is within the above range, the hardness of the layer surface is appropriately adjusted, and a hard coat layer having excellent durability such as scratch resistance can be obtained. . That is, when the weight-average molecular weight of (c) the perfluoropolyether is within the above range, both lubricity and durability can be achieved.
- the content of (c) perfluoropolyether in the curable composition of the present invention is, for example, 0.05 parts by mass to 10 parts by mass, 0.05 parts by mass with respect to 100 parts by mass of the (a) polyfunctional monomer parts to 5 parts by mass, or 0.05 parts to 3 parts by mass.
- the content of (c) perfluoropolyether is 0.05 parts by mass or more, (c) perfluoropolyether is sufficiently present on the surface of the hard coat layer obtained from the curable composition of the present invention. Therefore, a hard coat layer having excellent lubricity can be obtained.
- the content of (c) perfluoropolyether is 3 parts by mass or less, it is sufficiently compatible with (b) perfluoropolyether, and a hard coat layer with little cloudiness can be obtained.
- the content of (c) perfluoropolyether is, for example, 10 to 800 parts by mass, more preferably 10 to 500 parts by mass with respect to 100 parts by mass of (b) perfluoropolyether, More preferably, it is 10 to 400 parts by mass.
- Perfluoropolyethers can be used singly or in combination of two or more.
- the (d) polymerization initiator that is preferable in the curable composition of the present invention is a polymerization initiator that generates radicals upon exposure to active energy rays such as electron beams, ultraviolet rays, and X-rays, particularly ultraviolet irradiation.
- polymerization initiators such as benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones , biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts.
- polymerization initiators may be used alone or in combination of two or more.
- alkylphenones As the polymerization initiator (d), it is preferable to use alkylphenones as the polymerization initiator (d). By using alkylphenones, a cured film with improved scratch resistance can be obtained.
- alkylphenones examples include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)- ⁇ -hydroxyalkyl such as 2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one Phenones; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, etc. 2,2-dimethoxy-1,2-diphenylethan-1-one; and methyl phenylglyoxylate.
- the content of the polymerization initiator (d) in the curable composition of the present invention is, for example, 0.5 parts by mass to 20 parts by mass, preferably 1 part by mass to 100 parts by mass of the polyfunctional monomer (a). 20 parts by mass, more preferably 2 to 10 parts by mass.
- the curable composition of the present invention may contain (e) a solvent as an optional component, ie, it may be in the form of a varnish.
- a solvent As the solvent, the solubility and dispersibility of the components (a) to (d), and the workability during coating of the curable composition for forming a cured film (hard coat layer) described later, It may be appropriately selected in consideration of the drying properties before and after curing.
- the (e) solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits and cyclohexane; Halides such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve Esters or ester ethers such as acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4
- amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP); and sulfoxides such as dimethylsulfoxide (DMSO), and solvents obtained by mixing two or more of these solvents.
- DMF N,N-dimethylformamide
- DMAc N,N-dimethylacetamide
- NMP N-methyl-2-pyrrolidone
- sulfoxides such as dimethylsulfoxide (DMSO), and solvents obtained by mixing two or more of these solvents.
- the content of (e) the solvent in the curable composition of the present invention is not particularly limited. It is the concentration that becomes mass %.
- the solid content concentration also referred to as non-volatile content concentration refers to the solid content ( excluding the solvent component from all components) content.
- the curable composition of the present invention may generally contain additives, such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, which are generally added as necessary, as long as they do not impair the effects of the present invention.
- additives such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, which are generally added as necessary, as long as they do not impair the effects of the present invention.
- Agents, adhesion imparting agents, plasticizers, ultraviolet absorbers, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc. may be used singly or in combination of two or more thereof.
- the curable composition of the present invention can form a cured film by coating (coating) a substrate to form a coating film, and irradiating the coating film with an active energy ray to polymerize (cure) it,
- the cured film is also an object of the present invention.
- the hard coat layer in the hard coat film to be described later the cured film can be used.
- the base material examples include various resins (polyesters such as polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPU), polyolefins, polyamides, polyimides, epoxy resins, , melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin), metal, wood, paper, glass, slate can be done.
- the shape of these substrates may be plate-like, film-like or three-dimensional molded body.
- a primer layer an ultraviolet absorbing layer, an infrared absorbing layer, a near-infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather resistant layer, an antireflection layer, and an antistatic layer may be added to the surface of the base material.
- a layer, an anti-discoloration layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer, etc. may be formed as a lower layer of the hard coat layer, and a plurality of lower layers of the hard coat layer may be laminated.
- the layer formed on the surface of the substrate is not particularly limited as long as it does not impair the effects of the present invention.
- the coating method on the substrate includes cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, spray coating method, bar coating method, die coating method, inkjet method, printing method (letterpress printing method , Intaglio printing method, lithographic printing method, screen printing method, etc.) can be appropriately selected, among which roll-to-roll method can be used, and from the viewpoint of thin film coating, letterpress printing method In particular, it is desirable to use the gravure coating method. It is preferable that the curable composition of the present invention is filtered in advance using a filter having a pore size of about 0.2 ⁇ m, and then applied. When applying, a solvent may be added to the curable composition, if necessary. Examples of the solvent in this case include various solvents listed in the above [(e) solvent].
- the coating film is pre-dried with a heating means such as a hot plate or an oven to remove the solvent (solvent removal step).
- a heating means such as a hot plate or an oven to remove the solvent (solvent removal step).
- the heat drying conditions are preferably, for example, 40° C. to 120° C. and about 30 seconds to 10 minutes.
- the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Active energy rays include, for example, ultraviolet rays, electron beams and X-rays, and ultraviolet rays are particularly preferred.
- the polymerization may be completed by performing post-baking, specifically by heating using a heating means such as a hot plate or an oven.
- the thickness of the cured film formed is usually 0.1 ⁇ m to 20 ⁇ m, preferably 0.5 ⁇ m to 10 ⁇ m after drying and curing.
- a hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced using the curable composition of the present invention.
- the hard coat film is also an object of the present invention, and the hard coat film is suitably used for protecting the surface of various display elements such as touch panels and liquid crystal displays.
- the hard coat layer in the hard coat film of the present invention comprises the steps of applying the curable composition of the present invention onto a film substrate to form a coating film, optionally removing the solvent by heating, and It can be formed by a method including a step of irradiating the film with an active energy ray such as ultraviolet rays to cure the coating film.
- the present invention also includes a method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, including these steps.
- polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrenes, polyolefins, Films such as polyamide, polyimide, and triacetyl cellulose (TAC) can be used.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- TPU thermoplastic polyurethanes
- TPU thermoplastic polyurethanes
- Films such as polyamide, polyimide, and triacetyl cellulose (TAC) can be used.
- the film substrate may be formed by laminating a plurality of layers.
- a primer layer an ultraviolet absorption layer, an infrared absorption layer, a near-infrared absorption layer, an electromagnetic wave absorption layer, a color correction layer, a refractive index adjustment layer, a weather resistant layer, an antireflection layer, and an antistatic layer may be added to the surface of the resin film.
- a discoloration prevention layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer, and the like, which are different from the resin film may be laminated as a lower layer of the hard coat layer, and the hard coat layer may be under the A plurality of layers may be laminated.
- the layer laminated on the surface of the resin film is not particularly limited as long as it does not impair the effects of the present invention.
- the method of applying the curable composition of the present invention on the film substrate (coating film forming step) and the method of irradiating the active energy ray to the coating film (curing step) are listed in the above-mentioned ⁇ cured film>.
- method can be used.
- the curable composition of the present invention contains a solvent (in the form of a varnish)
- a step of drying the coating film to remove the solvent can be included after the coating film forming step, if necessary.
- the method of drying the coating film (solvent removal step) mentioned in the above ⁇ Cured film> can be used.
- the layer thickness (film thickness) of the hard coat layer thus obtained is, for example, 1 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 10 ⁇ m.
- the present invention also includes a surface modifier containing a perfluoropolyether (B) which is a reaction product with a compound having a reactive functional group and an active energy ray-polymerizable group.
- perfluoropolyether (A) is the same as the above-mentioned (b) perfluoropolyether
- perfluoropolyether (B) is the same as the above-mentioned (c) perfluoropolyether.
- Coating device by bar coater PM-9050MC manufactured by SMT Co., Ltd.
- Bar A-Bar OSP-15 manufactured by OSG System Products Co., Ltd.
- Film thickness measurement device F20 film thickness measurement system manufactured by Filmetrics Co., Ltd.
- Oven device Two-layer clean oven (upper and lower type) PO- manufactured by Sanki Keiso Co., Ltd. 250-45-D
- UV curing device CV-110QC-G manufactured by Heraeus Co., Ltd.
- Lamp Electrodeless lamp H-bulb manufactured by Heraeus Co., Ltd.
- Scratch resistance test and abrasion resistance test Apparatus Reciprocating abrasion tester TRIBOGEAR TYPE: 30S manufactured by Shinto Kagaku Co., Ltd. Scanning speed: 3200 mm/min Scanning distance: 50 mm (6)
- Contact angle measurement device DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measurement temperature: 23°C (7)
- Probe 0.6mmR sapphire pin Load: 200g Scanning speed: 2 mm/sec Scanning distance: 10 mm (8) Total light transmittance, haze measurement device: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
- Polyfunctional acrylate PA1 dipentaerythritol pentaacrylate/hexaacrylate mixture [Aronix (registered trademark) M-403 manufactured by Toagosei Co., Ltd.]
- Multifunctional acrylate PA2 Oxyethylene-modified multifunctional acrylate [Daiichi Kogyo Seiyaku Co., Ltd.
- PFPE2 A perfluoropolyether of the following structure having one hydroxy group at one end without a poly(oxyalkylene) group [manufactured by Solvay Specialty Polymers, Inc., calculated from the analysis results by X 19 F-NMR and 1 H-NMR.
- PFPE3 A perfluoropolyether of the following structure having one hydroxy group via a poly(oxyethylene) group only at one end [Fomblin (registered trademark) 4102X 19 F-NMR and 1 H-NMR manufactured by Solvay Specialty Polymers Co., Ltd.
- PFPE4 A perfluoropolyether having the following structure having one hydroxy group only at one end without a poly(oxyalkylene) group [FO2 manufactured by Apollo Scientific, molecular weight 978.15]
- PFPE5 A perfluoropolyether having the following structure having one hydroxy group at only one end without a poly(oxyalkylene) group (1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol ) [C10GOL manufactured by Exfluor Research, molecular weight 548.1]
- PFPE6 A perfluoropolyether having the following structure having one hydroxy group at only one end without a poly(oxyalkylene) group (1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol ) [C10GOL manufactured by Exfluor Research, molecular weight 548.1]
- PFPE6 A perfluoropolyether having the following structure having one hydroxy group at only one end without a poly
- N1 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Kalenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.]
- N2 2-acryloyloxyethyl isocyanate [Karenzu (registered trademark) AOI manufactured by Showa Denko K.K.]
- SMA6 Perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group [Optool (registered trademark) DAC
- Neostan (registered trademark) U-830]
- MEK methyl ethyl ketone
- PGME propylene glycol monomethyl ether
- PGMEA propylene glycol monomethyl ether acetate
- MeOH methanol
- O2959 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one
- IGM Resins OMNIRAD registered trademark 2959
- AN1 PEDOT-PSS aqueous dispersion [Sigma-Aldrich PEDOT-PSS 3.0% by mass to 4.0% by mass aqueous dispersion high conductive grade product number 655201]
- the weight average molecular weight Mw of the obtained SMA3 measured in terms of polystyrene by GPC was 1908, and the degree of dispersion Mw/Mn was 1.0. Further, the content of fluorine atoms in SMA3 calculated by combustion ion chromatography was 47% by mass.
- the weight average molecular weight Mw of the obtained SMA4 measured in terms of polystyrene by GPC was 1299, and the degree of dispersion Mw/Mn was 1.0.
- the fluorine atom content in SMA4 calculated by combustion ion chromatography is 51% by mass, which is about the same as the fluorine atom content of 51% by mass theoretically calculated from the structure of SMA4. rice field.
- the weight average molecular weight Mw of the obtained SMA5 measured in terms of polystyrene by GPC was 1029, and the degree of dispersion Mw/Mn was 1.0.
- the fluorine atom content in SMA5 calculated by combustion ion chromatography is 46% by mass, which is about the same as the fluorine atom content of 47% by mass theoretically calculated from the structure of SMA5. rice field.
- the weight average molecular weight Mw of the obtained SMA8 measured in terms of polystyrene by GPC was 1609, and the degree of dispersion Mw/Mn was 1.0. Further, the content of fluorine atoms in SMA8 calculated by combustion ion chromatography was 54% by mass.
- Examples 1 to 9, Comparative Examples 1 to 13 Each component shown in Table 1 was mixed to prepare a curable composition having a solid concentration shown in Table 1.
- the solid content refers to components other than the solvent.
- [parts] represents [parts by mass]
- [%] represents [% by mass].
- the polyfunctional acrylate and the surface modifier in Table 1 each represent the solid content.
- curable compositions are applied to an A4 size PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., thickness 100 ⁇ m] having a primer layer formed on both sides by a bar coater. to obtain a coating film.
- the coating film was dried in an oven at 60° C. for 8 minutes to remove the solvent.
- a hard coat film having a hard coat layer (cured film) was produced by exposing the obtained film to UV light at an exposure dose of 300 mJ/cm 2 in a nitrogen atmosphere.
- Examples 10 to 11, Comparative Examples 14 to 15 Each component shown in Table 2 was mixed to prepare a curable composition having a solid concentration shown in Table 2.
- the solid content refers to components other than the solvent.
- [parts] represents [parts by mass]
- [%] represents [% by mass].
- the polyfunctional acrylate and the surface modifier in Table 2 each represent the solid content.
- curable compositions are applied to an A4 size PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., thickness 100 ⁇ m] having a primer layer formed on both sides by a bar coater. to obtain a coating film.
- the coating was dried in an oven at 65°C for 3 minutes to remove the solvent.
- a hard coat film having a hard coat layer (cured film) was produced by exposing the obtained film to UV light at an exposure dose of 300 mJ/cm 2 in a nitrogen atmosphere.
- the surface of the hard coat layer of the obtained hard coat film was subjected to 5,000 reciprocations at a stroke of 50 mm with a steel wool [BONSTAR (registered trademark) #0000 (ultrafine)] attached to a reciprocating abrasion tester under a load of 1 kg. rubbed. After that, visually check the degree of scratches in the area excluding the range of 5 mm width at both ends of the stroke of 50 mm, and confirm that the scratches are on the surface of the hard coat layer with a microscope (Keyence Corporation). Evaluated according to Criteria A, B and C.
- A No scratches (0 scratches)
- B Scratches (1 to 4 scratches with a length of 1 mm to 9 mm)
- C Scratches (5 or more scratches with a length of 1 mm to 9 mm, or 1 or more scratches with a length of 1 cm or more) [Water repellency] 1 ⁇ L of water was applied to the surface of the hard coat layer, and after 5 seconds, the contact angle ⁇ was measured 5 times, and the average value was evaluated according to the following criteria.
- the contact angle was measured 5 seconds after the water was applied, because the contact angle measured immediately after the water was applied was high and unstable.
- the surface of the hard coat layer was rubbed back and forth 2,500 times with a load of 1 kg using a cylindrical eraser [RUBBER STICK manufactured by Minoan, ⁇ 6.0 mm] attached to a reciprocating abrasion tester. 1 ⁇ L of water was applied to the rubbed portion, and the contact angle ⁇ after 5 seconds was measured at 5 points. Assuming actual use as a hard coat layer, at least B is required, and A is desirable.
- the curable compositions of Examples 1 to 8 had polyfunctional acrylates PA1 to PA4 and poly(oxyperfluoroalkylene) groups at both ends of the molecular chain, respectively.
- a molecular chain piece containing a perfluoropolyether SMA1 having a functional group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further containing a poly(oxyperfluoroalkylene) group A weight average molecular weight of 1710 obtained by reacting a perfluoropolyether compound PFPE2 or PFPE3 having a number average molecular weight of 1750 to 1950 having one hydroxy group only at the end with the isocyanate compound N1 having the active energy ray polymerizable group.
- the curable compositions of Examples 1 to 8 exhibited excellent homogeneity, and the hard coat films provided with the hard coat layers obtained from the curable compositions exhibited excellent It exhibited slipperiness, scratch resistance, water repellency and abrasion resistance.
- the curable composition of Example 9 has an active energy ray-polymerizable group at the end of a molecular chain containing a polyfunctional acrylate PA1, a poly(oxyperfluoroalkylene) group, and a weight average It contains a perfluoropolyether SMA6 having a molecular weight of 1521 and a fluorine atom content of 35% by mass, and has one hydroxy group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group.
- the curable composition of Example 9 contains SMA2 having a weight average molecular weight of 1710 obtained by reacting a perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 with the isocyanate compound N1 having the active energy ray polymerizable group. Then, as shown in Table 3, the curable composition of Example 9 exhibited excellent homogeneity, and the hard coat film provided with the hard coat layer obtained from the curable composition exhibited excellent lubricity and repellency. It showed water resistance and abrasion resistance.
- the hard coat film comprising the hard coat layer obtained from the curable composition of Example 9 has a hard coat layer comprising the hard coat layer obtained from the curable composition of Examples 1 to 8 in terms of scratch resistance.
- the other items shown in Table 2 showed excellent property levels, albeit slightly worse than the films.
- the curable composition of Comparative Example 1 has an active energy ray-polymerizable group at each end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group.
- perfluoropolyether SMA1 having a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and a hydroxy at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group
- the hard coat film provided with the hard coat layer obtained from the curable composition is superior to that of Examples 1 to 3.
- the hard coat film obtained from the curable composition of Example 9 it showed inferior results in slipperiness and scratch resistance. From this result, even if a perfluoropolyether having an active energy ray-polymerizable group only at one end of a molecular chain containing a (oxyperfluoroalkylene) group with a high fluorine atom content is used, slipperiness and scratch resistance can be improved. It was shown that the weight-average molecular weight of the perfluoropolyether is important for slipperiness and scratch resistance.
- the curable composition of Comparative Example 2 has an active energy ray-polymerizable group at both ends of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA1 having a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and a hydroxy at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group
- the curable compositions of Comparative Examples 3 and 4 had one hydroxyl group only at one end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group.
- a perfluoropolyether having a number average molecular weight of 1750 to 1950 which contains SMA4 with a weight average molecular weight of 1299 or SMA5 with a weight average molecular weight of 1029, and which has a hydroxy group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group. It contains SMA2 having a weight average molecular weight of 1710 obtained by reacting the compound PFPE2 with the isocyanate compound N1 having the active energy ray-polymerizable group.
- the curable compositions of Comparative Examples 3 and 4 were inferior in homogeneity, and the hard coat films provided with the hard coat layers obtained from the curable compositions had slipperiness and resistance. It showed inferior results in scratch resistance and abrasion resistance. It is believed that this is because the weight average molecular weights of SMA4 and SMA5 are too small to destroy the aggregation structure of SMA2, thereby failing to assist the solubility in the coating solution. As a result, SMA2 agglomerated in the coating liquid, and SMA2 was not sufficiently segregated on the surface of the hard coat layer.
- the curable composition of Comparative Example 5 has active energy ray-polymerizable groups at both ends of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group.
- the weight average molecular weight is 3973, and the content of fluorine atoms is 29% by mass.
- SMA2 having a weight average molecular weight of 1710 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 having one.
- the curable composition of Comparative Example 5 exhibits excellent homogeneity and exhibits excellent lubricity, but a hard coat film comprising a hard coat layer obtained from the curable composition. showed inferior results in scratch resistance and abrasion resistance. This result indicates that good slipperiness does not necessarily lead to good scratch resistance and abrasion resistance.
- the hard coat film comprising the hard coat layer obtained from the curable composition of Comparative Example 5 is more durable than the hard coat film comprising the hard coat layer obtained from the curable compositions of Examples 1 to 9.
- the reason for the inferior scratch resistance and wear resistance is considered to be that the weight average molecular weight of SMA7 is larger than that of SMA1 and SMA6, and the fixing ability in the film is lowered.
- the content of fluorine atoms in SMA7 is smaller than that of SMA1 and SMA6, and the compatibility between SMA2 and SMA7 is poor, resulting in phase separation between SMA2 and SMA7 on the hard coat layer surface. Conceivable.
- the curable composition of Comparative Example 6 has one hydroxy group only at one end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. It contains SMA2 having a weight average molecular weight of 1710 obtained by reacting a perfluoropolyether compound PFPE2 having a molecular weight of 1750 to 1950 with the isocyanate compound N1 having the active energy ray-polymerizable group. Then, as shown in Table 3, the curable composition of Comparative Example 6 was inferior in homogeneity to the curable composition of Example 1, in which SMA1 was added to the curable composition of Comparative Example 6.
- the hard coat film comprising the hard coat layer obtained from the curable composition of Example 6 has better slipperiness and resistance than the hard coat film comprising the hard coat layer obtained from the curable composition of Example 1. All of the scratch resistance, water repellency and abrasion resistance were inferior.
- This is a perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500, which acts as a solubilizer for SMA2. This is probably because SMA2 agglomerates in the coating liquid because it does not contain
- the curable composition of Comparative Example 7 has one hydroxy group only at one end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. It contains SMA3 having a weight average molecular weight of 1908 obtained by reacting a perfluoropolyether compound PFPE3 having a molecular weight of 1900 with the isocyanate compound N1 having the active energy ray-polymerizable group. Then, as shown in Table 3, although the curable composition of Comparative Example 7 is excellent in homogeneity, the hard coat film provided with the hard coat layer obtained from the curable composition has the curability of Comparative Example 7.
- the scratch resistance and water repellency were inferior. This is because the single use of SMA3 has a strong cohesive force and makes it easy to aggregate inside the film, and SMA3 cannot be sufficiently segregated on the surface of the hard coat layer, and SMA3 is active only at one end. This is probably because the immobilization ability in the membrane is low due to the presence of the energy ray-polymerizable group.
- the curable composition of Comparative Example 8 has a molecular weight of 978 having one hydroxy group only at one end of a molecular chain containing a polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group.
- SMA4 having a weight average molecular weight of 1299 obtained by reacting the perfluoropolyether compound PFPE4 of No. 15 with the isocyanate compound N1 having the active energy ray-polymerizable group.
- the curable composition obtained from the curable composition of Comparative Example 8 was inferior in homogeneity compared to the curable composition of Comparative Example 1 in which SMA1 was added to the curable composition of Comparative Example 8.
- the hard coat film provided with the hard coat layer showed inferior results in all of slipperiness, scratch resistance, and wear resistance. This is probably because SMA4 aggregates inside the film and cannot be sufficiently segregated on the surface of the hard coat layer, and the molecular chain containing the poly(oxyperfluoroalkylene) group of SMA4 is short.
- the curable composition of Comparative Example 9 has a molecular weight of 548 having one hydroxy group only at one end of a molecular chain containing a polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. It contains SMA5 having a weight average molecular weight of 1029 obtained by reacting the perfluoropolyether compound PFPE5 of No. 1 with the isocyanate compound N1 having the active energy ray-polymerizable group.
- the hard coat film provided with the hard coat layer obtained from the curable composition is poly(oxyperfluoroalkylene ) group is short, it shows inferior results in all of slipperiness, water repellency, scratch resistance, and abrasion resistance.
- the curable composition of Comparative Example 10 has an active energy ray-polymerizable group at each end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA1 having a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass.
- the curable composition of Comparative Example 10 is excellent in homogeneity, and the hard coat film provided with the hard coat layer obtained from the curable composition has water repellency, scratch resistance, and Although it has excellent wear resistance, it does not contain SMA2 compared to the hard coat film provided with the hard coat layer obtained from the curable composition of Example 1 in which SMA2 was added to the curable composition of Comparative Example 10. Therefore, it showed inferior results in slipperiness. This is because SMA1 has eight acrylic groups in one molecule, and thus has a high immobilization ability in the film, so that it has excellent scratch resistance and abrasion resistance. It is considered that the mobility is low and the slipperiness is poor.
- the curable composition of Comparative Example 12 has active energy ray-polymerizable groups at both ends of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA7 having a weight average molecular weight of 3973 and a fluorine atom content of 29% by mass.
- the curable composition of Comparative Example 12 is excellent in homogeneity, but the hard coat film provided with the hard coat layer obtained from the curable composition is cured in Comparative Example 12.
- the curable composition of Comparative Example 13 has an active energy ray-polymerizable group at each end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA1 having a weight-average molecular weight of 2494 and a fluorine atom content of 42% by mass, and further comprising a poly(oxyperfluoroalkylene) group, a hydroxy group at each of both ends of the molecular chain
- a weight average molecular weight of 1609 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with a perfluoropolyether compound PFPE6 having a number average molecular weight of 1550 and having a fluorine atom content is 54% by mass of SMA8.
- the curable composition of Comparative Example 13 exhibited excellent homogeneity, and the hard coat film comprising the hard coat layer obtained from the curable composition had water repellency and scratch resistance.
- the slip properties and wear resistance were inferior. From these results, a hard coat film obtained from a curable composition containing a perfluoropolyether having an active energy ray-polymerizable group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group as a surface modifier.
- the curable compositions of Examples 10 to 11 had polyfunctional acrylates PA1 or PA2 and poly(oxyperfluoroalkylene) groups at both ends of the molecular chain, respectively.
- a molecular chain piece containing a perfluoropolyether SMA1 having a functional group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further containing a poly(oxyperfluoroalkylene) group SMA3 having a weight average molecular weight of 1908 obtained by reacting a perfluoropolyether compound PFPE3 having a number average molecular weight of 1900 having one hydroxy group only at the terminal with the isocyanate compound N1 having the active energy ray polymerizable group.
- the curable compositions of Examples 10 to 11 exhibited excellent homogeneity, and the hard coat films provided with the hard coat layers obtained from the curable compositions exhibited excellent It exhibited slipperiness, scratch resistance, water repellency and abrasion resistance.
- the curable composition of Comparative Example 14 has an active energy ray-polymerizable group at each end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA1 having a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and an antistatic agent AN1.
- the curable composition of Comparative Example 14 is excellent in homogeneity, and the hard coat film provided with the hard coat layer obtained from the curable composition has water repellency, scratch resistance, and Although it has excellent wear resistance, it does not contain SMA3 compared to the hardcoat film comprising the hardcoat layer obtained from the curable composition of Example 10, which is the curable composition of Comparative Example 14 with SMA3 added. Therefore, it showed inferior results in slipperiness. This is because SMA1 has eight acrylic groups in one molecule, and thus has a high fixing ability in the film. it is conceivable that.
- the curable composition of Comparative Example 15 has one hydroxy group only at one end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. It contains SMA3 with a weight average molecular weight of 1908 obtained by reacting a perfluoropolyether compound PFPE3 with a molecular weight of 1900 with the isocyanate compound N1 having the active energy ray-polymerizable group, and further contains an antistatic agent AN1. Then, as shown in Table 4, although the curable composition of Comparative Example 15 is excellent in homogeneity, the hard coat film provided with the hard coat layer obtained from the curable composition has the curability of Comparative Example 15.
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Abstract
Description
なお、本発明に使用する「パーフルオロポリエーテル」は、ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有するものを云う。ここで、前記ポリ(オキシパーフルオロアルキレン)基を含む分子鎖又は活性エネルギー線重合性基が、その炭化水素基等の水素原子の全てをフッ素原子に置き換えていない場合でも、「ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有するもの」は、「パーフルオロポリエーテル」と称する。
特許文献4には、滑り性に関し、上記フッ素含有率が48質量%乃至62質量%の直鎖ポリマーにおいて、分子鎖の片末端にアクリル基を有する場合と、分子鎖の両末端にアクリル基を有する場合とで、同等の滑り性である結果が記載されている。そのため、滑り性に関し十分な特性水準にないことが想定できる。
本発明では、トレードオフ関係にある耐久特性と滑り性とを高い特性水準で両立するハードコート層が形成可能な、浮遊物及び沈降物のない均質な硬化性組成物を提供することを課題とする。これらに加え、実使用を想定する上で、ハードコート層が高い撥液特性を兼ね備えることが必要となる。
(b)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(但し、後述する(c)パーフルオロポリエーテルを除く)、
(c)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500のパーフルオロポリエーテル、及び
(d)活性エネルギー線によりラジカルを発生する重合開始剤を含む、硬化性組成物。
(b)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(但し、後述する(c)パーフルオロポリエーテルを除く)0.05質量部乃至3質量部、
(c)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500のパーフルオロポリエーテル0.05質量部乃至3質量部、及び
(d)活性エネルギー線によりラジカルを発生する重合開始剤0.5質量部乃至20質量部を含む、硬化性組成物。
(b)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル0.05質量部乃至3質量部(但し、後述する(c)パーフルオロポリエーテルを除く)、
(c)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみにヒドロキシ基を有する数平均分子量が1200乃至3000の原料パーフルオロポリエーテルと、該ヒドロキシ基と反応する官能基及び前記活性エネルギー線重合性基を有する化合物との反応生成物であるパーフルオロポリエーテル0.05質量部乃至3質量部、及び
(d)活性エネルギー線によりラジカルを発生する重合開始剤0.5質量部乃至20質量部を含む、硬化性組成物。
本発明の硬化性組成物の各成分について、以下に説明する。
(a)成分の(メタ)アクリロイル基を1分子中に2個以上有する活性エネルギー線硬化性多官能モノマー(以下、単に「(a)多官能モノマー」とも称する。)とは、紫外線等の活性エネルギー線を照射することで重合反応が進行し、硬化するモノマーを指す。
(b)成分のポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテルを以下、単に「(b)パーフルオロポリエーテル」とも称する。(b)パーフルオロポリエーテルは、後述する(c)パーフルオロポリエーテルを除くものである。本発明の硬化性組成物において好ましい(b)パーフルオロポリエーテルは、ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に、ウレタン結合を介して活性エネルギー線重合性基を有する。前記ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端は、該分子鎖の全ての末端及び一部の末端、いずれでもよい。前記分子鎖が直鎖状である場合、該分子鎖の全ての末端及び一部の末端は、それぞれ該直鎖状の分子鎖の両末端及び片末端である。前記ポリ(オキシパーフルオロアルキレン)基と前記ウレタン結合との間の連結基として、例えば、エーテル結合を有する炭化水素基が挙げられ、該炭化水素基は、水素原子の少なくとも1つがフッ素原子で置換されていてもよい。また、好ましい(b)パーフルオロポリエーテルは、その化学構造中にケイ素原子を有さない。
(c)成分のポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに、前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500のパーフルオロポリエーテルを以下、単に「(c)パーフルオロポリエーテル」とも称する。(c)パーフルオロポリエーテルは、例えば、前記ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみにヒドロキシ基を有する数平均分子量が1200乃至3000の原料パーフルオロポリエーテルと、該ヒドロキシ基と反応する官能基及び前記活性エネルギー線重合性基を有する化合物とを反応させて得られる。前記ヒドロキシ基と反応する官能基として、例えば、ヒドロキシ基、カルボキシ基及びイソシアネート基が挙げられる。
「また、原料パーフルオロポリエーテルのヒドロキシ基を有する片末端とは反対側の片末端に、フッ素原子を含む基を有することが好ましく、より好ましくはトリフルオロメトキシ基を有する。前記活性エネルギー線重合性基を有する片末端とは反対側の片末端に該フッ素原子を含む基を有する(c)パーフルオロポリエーテルは、ハードコート層の表面に十分に移行することができ、優れた撥水性及び滑り性を発現することができる。」
本発明の硬化性組成物において好ましい(d)重合開始剤は、例えば、電子線、紫外線、X線等の活性エネルギー線により、特に紫外線照射によりラジカルを発生する重合開始剤である。
本発明の硬化性組成物は、任意成分として(e)溶媒を含有してもよく、すなわちワニスの形態としてもよい。(e)溶媒としては、前記(a)成分乃至(d)成分の溶解・分散性、また、後述する硬化膜(ハードコート層)の形成に係る硬化性組成物の塗工時の作業性、硬化前後の乾燥性等を考慮して適宜選択すればよい。
また、本発明の硬化性組成物には、本発明の効果を損なわない限り、必要に応じて一般的に添加される添加剤、例えば、重合禁止剤、光増感剤、レベリング剤、界面活性剤、密着性付与剤、可塑剤、紫外線吸収剤、貯蔵安定剤、帯電防止剤、無機充填剤、顔料、染料等のうち一種を単独で、或いは二種以上を組み合わせて適宜配合してよい。
本発明の硬化性組成物は、基材上に塗布(コーティング)して塗膜を形成し、該塗膜に活性エネルギー線を照射して重合(硬化)させることにより、硬化膜を形成でき、該硬化膜も本発明の対象である。また後述するハードコートフィルムにおけるハードコート層として、上記硬化膜からなるものを用いることができる。
本発明の硬化性組成物を用いて、フィルム基材の少なくとも一方の面(表面)にハードコート層を備えるハードコートフィルムを製造することができる。該ハードコートフィルムも本発明の対象であり、該ハードコートフィルムは、例えば、タッチパネル、液晶ディスプレイ等の各種表示素子の表面を保護するために好適に用いられる。
ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(A)(但し、後述するパーフルオロポリエーテル(B)を除く)、及びポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500のパーフルオロポリエーテル(B)を含む表面改質剤も、本発明の対象である。
さらに、ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(A)(但し、後述するパーフルオロポリエーテル(B)を除く)、及びポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみにヒドロキシ基を有する数平均分子量が1200乃至3000の原料パーフルオロポリエーテルと、該ヒドロキシ基と反応する官能基及び前記活性エネルギー線重合性基を有する化合物との反応生成物であるパーフルオロポリエーテル(B)を含む表面改質剤も本発明に含まれる。
なお、「パーフルオロポリエーテル(A)」は、前述した(b)パーフルオロポリエーテルと同一であり、「パーフルオロポリエーテル(B)」は前述した(c)パーフルオロポリエーテルと同一である。
装置:(株)エスエムテー製 PM-9050MC
バー:オーエスジーシステムプロダクツ(株)製 A-Bar OSP-15 最大ウエット膜厚15μm(乾燥後膜厚3μm)
塗布速度:4m/分
(2)膜厚測定
装置:フィルメトリクス(株)製 F20 膜厚測定システム
(3)オーブン
装置:三基計装(株)製 2層式クリーンオーブン(上下式)PO-250-45-D
(4)UV硬化
装置:ヘレウス(株)製 CV-110QC-G
ランプ:ヘレウス(株)製 無電極ランプH-bulb
(5)耐擦傷性試験及び耐摩耗性試験
装置:新東科学(株)製 往復摩耗試験機 TRIBOGEAR TYPE:30S
走査速度:3200mm/分
走査距離:50mm
(6)接触角測定
装置:協和界面科学(株)製 DropMaster DM-501
測定温度:23℃
(7)動摩擦係数測定
装置:新東科学(株)製 荷重変動型摩擦磨耗試験システム TRIBOGEAR(登
録商標)TYPE:HHS2000
プローブ:0.6mmR サファイアピン
荷重:200g
走査速度:2mm/秒
走査距離:10mm
(8)全光線透過率、ヘーズ測定
装置:日本電色工業(株)製 ヘーズメーターNDH5000
(9)重量平均分子量測定
ゲル浸透クロマトグラフィー(GPC)
装置:東ソー(株)製 HLC-8420GPC
カラム:東ソー(株)製 TSKgelG2000HXL、TSKgelG3000HXL
測定温度:40℃
溶離液:テトラヒドロフラン
検出:RI
(10)燃焼イオンクロマトグラフィー
自動試料燃焼装置システム:日東精工アナリテック(株)(旧(株)三菱ケミカルアナリテック)製 AQF-2100 H
イオンクロマトグラフ:サーモフィッシャーサイエンティフィック(株)製 Dionex Integrion
試料:2mg
吸収液:2.7mM炭酸ナトリウム+0.3mM炭酸水素ナトリウム水溶液
溶離液:2.7mM炭酸ナトリウム+0.3mM炭酸水素ナトリウム水溶液
カラム:サーモフィッシャーサイエンティフィック(株)製 AG-12A/AS-12A
流量:1.5mL/分
検出器:電気伝導度(サプレッサー使用)
標準試料:ふっ化物イオン標準液(F-1000)富士フイルム和光純薬(株)(旧和光純薬工業(株))製
試料中の溶媒にフッ素原子を含む溶媒を含まない場合は、溶媒を含んだ状態のままフッ素濃度を測定し、固形分濃度から溶質のフッ素濃度を換算し、算出した。試料中の溶媒にフッ素原子を含む溶媒が含まれる場合は、ハロゲン水分計を用い、120℃20分の条件で試料溶媒を揮発させ、質量変化が一定になり溶媒が全て揮発したと判断できた試料を用いてフッ素濃度を測定した。
多官能アクリレートPA1:ジペンタエリスリトールペンタアクリレート/ヘキサアクリレート混合物[東亞合成(株)製 アロニックス(登録商標)M-403]
多官能アクリレートPA2:オキシエチレン変性多官能アクリレート[第一工業製薬(株)製 ニューフロンティア(登録商標)MF-001]
多官能アクリレートPA3:多官能ウレタンアクリレート[根上工業(株)製 アートレジン(登録商標)UN-3320HS]
多官能アクリレートPA4:ペンタエリスリトールトリアクリレート/ペンタエリスリトールテトラアクリレート[日本化薬(株)製 PET30]
PFPE1:両末端それぞれにポリ(オキシアルキレン)基を介さずヒドロキシ基を2つ有する下記構造のパーフルオロポリエーテル[ソルベイスペシャルティポリマーズ社製 Fomblin(登録商標)T4 19F-NMR及び1H-NMRによる分析結果から算出された数平均分子量2200]
PFPE2:片末端のみにポリ(オキシアルキレン)基を介さずヒドロキシ基を1つ有する下記構造のパーフルオロポリエーテル[ソルベイスペシャルティポリマーズ社製 7324X 19F-NMR及び1H-NMRによる分析結果から算出された数平均分子量1750~1950]
PFPE3:片末端のみにポリ(オキシエチレン)基を介し、ヒドロキシ基を1つ有する下記構造のパーフルオロポリエーテル[ソルベイスペシャルティポリマーズ社製 Fomblin(登録商標)4102X 19F-NMR及び1H-NMRによる分析結果から算出された数平均分子量1900]
PFPE4:片末端のみにポリ(オキシアルキレン)基を介さずヒドロキシ基を1つ有する下記構造のパーフルオロポリエーテル [Apollo Scientific社製 FO2 分子量978.15]
N1:1,1-ビス(アクリロイルオキシメチル)エチルイソシアネート[昭和電工(株)製 カレンズ(登録商標)BEI]
N2:2-アクリロイルオキシエチルイソシアネート[昭和電工(株)製 カレンズ(登録商標)AOI]
SMA6:ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有するパーフルオロポリエーテル[ダイキン工業(株)製 オプツール(登録商標)DAC-HP、不揮発分20質量%溶液、GPCによるポリスチレン換算で測定される重量平均分子量:Mwは1521、分散度:Mw/Mnは1.1(Mnは数平均分子量)、燃焼イオンクロマトグラフィーにより算出されたパーフルオロポリエーテル化合物中のフッ素原子の含有割合35質量%]
SMA7:ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の両末端に活性エネルギー線重合性基を合計4つ有するパーフルオロポリエーテル[ソルベイスペシャルティポリマーズ社製 Fluorolink(登録商標)AD-1700、不揮発分70質量%溶液、GPCによるポリスチレン換算で測定される重量平均分子量:Mwは3973、分散度:Mw/Mnは2.1、燃焼イオンクロマトグラフィーにより算出されたパーフルオロポリエーテル化合物中のフッ素原子の含有割合29質量%]
DOTDD:ジネオデカン酸ジオクチル錫[日東化成(株)製 ネオスタン(登録商標)U-830]
MEK:メチルエチルケトン
PGME:プロピレングリコールモノメチルエーテル
PGMEA:プロピレングリコールモノメチルエーテルアセテート
MeOH:メタノール
O2959:2-ヒドロキシ-1-(4-(2-ヒドロキシエトキシ)フェニル)-2-メチルプロパン-1-オン[IGM Resins社製 OMNIRAD(登録商標)2959]
AN1:PEDOT-PSS水分散液[Sigma-Aldrich社製 PEDOT-PSS 3.0質量%乃至4.0質量%水分散液 高導電性グレード 製品番号655201]
スクリュー管に、PFPE1 1.19g(0.5mmol)、N1 0.52g(2.0mmol)、DOTDD 0.017g(PFPE1及びN1の合計質量の0.01倍量)、及びPGMEA 1.67gを仕込んだ。この混合物を、スターラーチップを用いて室温(およそ23℃)で72時間撹拌して、目的のパーフルオロポリエーテル化合物SMA1の50質量%PGMEA溶液を得た。得られたSMA1のGPCによるポリスチレン換算で測定される重量平均分子量:Mwは2494、分散度:Mw/Mnは1.0であった。また、燃焼イオンクロマトグラフィーにより算出されたSMA1中のフッ素原子の含有割合は42質量%であった。
スクリュー管に、PFPE2 2.20g(1.2mmol)、N1 0.28g(1.2mmol)、DOTDD 0.025g(PFPE2及びN1の合計質量の0.01倍量)、及びMEK 0.6gを仕込んだ。この混合物を、スターラーチップを用いて室温(およそ23℃)で72時間撹拌して、目的のパーフルオロポリエーテル化合物SMA2の80質量%MEK溶液を得た。得られたSMA2のGPCによるポリスチレン換算で測定される重量平均分子量:Mwは1710、分散度:Mw/Mnは1.0であった。また、燃焼イオンクロマトグラフィーにより算出されたSMA2中のフッ素原子の含有割合は63質量%であった。
スクリュー管に、PFPE3 3.08g(1.6mmol)、N1 0.39g(1.6mmol)、DOTDD 0.035g(PFPE3及びN1の合計質量の0.01倍量)、及びPGMEA 3.5gを仕込んだ。この混合物を、スターラーチップを用いて室温(およそ23℃)で72時間撹拌して、目的のパーフルオロポリエーテル化合物SMA3の50質量%PGMEA溶液を得た。得られたSMA3のGPCによるポリスチレン換算で測定される重量平均分子量:Mwは1908、分散度:Mw/Mnは1.0であった。また、燃焼イオンクロマトグラフィーにより算出されたSMA3中のフッ素原子の含有割合は47質量%であった。
スクリュー管に、PFPE4 2.78g(2.9mmol)、N1 0.68g(2.9mmol)、DOTDD 0.035g(PFPE4及びN1の合計質量の0.01倍量)、及びPGMEA 3.5gを仕込んだ。この混合物を、スターラーチップを用いて室温(およそ23℃)で72時間撹拌して、目的のパーフルオロポリエーテル化合物SMA4の50質量%PGMEA溶液を得た。得られたSMA4のGPCによるポリスチレン換算で測定される重量平均分子量:Mwは1299、分散度:Mw/Mnは1.0であった。また、燃焼イオンクロマトグラフィーにより算出されたSMA4中のフッ素原子の含有割合は51質量%であり、SMA4の構造から理論的に算出されるフッ素原子の含有割合51質量%と同程度の値を示した。
スクリュー管に、PFPE5 2.41g(4.4mmol)、N1 1.05g(4.4mmol)、DOTDD 0.035g(PFPE5及びN1の合計質量の0.01倍量)、及びPGMEA 3.5gを仕込んだ。この混合物を、スターラーチップを用いて室温(およそ23℃)で72時間撹拌して、目的のパーフルオロポリエーテル化合物SMA5の50質量%PGMEA溶液を得た。得られたSMA5のGPCによるポリスチレン換算で測定される重量平均分子量:Mwは1029、分散度:Mw/Mnは1.0であった。また、燃焼イオンクロマトグラフィーにより算出されたSMA5中のフッ素原子の含有割合は46質量%であり、SMA5の構造から理論的に算出されるフッ素原子の含有割合47質量%と同程度の値を示した。
スクリュー管に、PFPE6 3.66g(2.4mmol)、N2 0.67g(4.8mmol)、DOTDD 0.054g(PFPE6及びN2の合計質量の0.01倍量)、及びPGMEA 4.4gを仕込んだ。この混合物を、スターラーチップを用いて室温(およそ23℃)で72時間撹拌して、目的のパーフルオロポリエーテル化合物SMA8の50質量%PGMEA溶液を得た。得られたSMA8のGPCによるポリスチレン換算で測定される重量平均分子量:Mwは1609、分散度:Mw/Mnは1.0であった。また、燃焼イオンクロマトグラフィーにより算出されたSMA8中のフッ素原子の含有割合は54質量%であった。
表1に記載の各成分を混合し、表1に記載の固形分濃度の硬化性組成物を調製した。ここで固形分とは溶媒以外の成分を指す。また、表1中、[部]とは[質量部]を、[%]は[質量%]を表す。なお、表1中の多官能アクリレート及び表面改質剤はそれぞれ固形分を表す。
表2に記載の各成分を混合し、表2に記載の固形分濃度の硬化性組成物を調製した。ここで固形分とは溶媒以外の成分を指す。また、表2中、[部]とは[質量部]を、[%]は[質量%]を表す。なお、表2中の多官能アクリレート及び表面改質剤はそれぞれ固形分を表す。
[組成物均質性]
調製した各硬化性組成物の外観を目視で確認し、以下の基準に従い評価した。
A:透明溶液(浮遊物、沈降物及び相分離何れも無し)
C:浮遊物、沈降物及び相分離のうち何れか有り
[耐擦傷性]
得られたハードコートフィルムのハードコート層表面を、往復摩耗試験機に取り付けたスチールウール[ボンスター(BONSTAR)(登録商標)#0000(超極細)]で1kgの荷重を掛けてストローク50mmで5000往復擦った。その後、前記ストローク50mmの両端5mm幅の範囲を除いた領域内における傷の程度を目視で確認、加えて傷がハードコート層表面であることをマイクロスコープ (キーエンス株式会社)で確認し、以下の基準A、B及びCに従い評価した。なお、ハードコート層として実際の使用を想定した場合、少なくともBであることが求められ、Aであることが望ましい。
A:傷無し(傷0本)
B:傷発生(長さ1mm乃至9mmの傷1本乃至4本)
C:傷発生(長さ1mm乃至9mmの傷5本以上、又は長さ1cm以上の傷1本以上)
[撥水性]
水1μLをハードコート層表面に付着させ、その5秒後の接触角θを5回測定し、その平均値から以下の基準に従い評価した。なお、ハードコート層として実際の使用を想定した場合、Aであることが望ましい。尚、水を付着直後に接触角を測定すると、値として高くかつ安定しないため、本測定では水を付着させてから5秒後に接触角を測定した。
A:θ>105°
B:100°≦θ≦105°
C:θ<100°
[耐摩耗性]
ハードコート層表面を、往復摩耗試験機に取り付けた円筒形消しゴム[Minoan社製 RUBBER STICK、φ6.0mm]で1kgの荷重を掛けて2,500往復擦った。その擦った部分に水1μLを付着させ、その5秒後の接触角θを5点測定し、その平均値を接触角値とし、以下の基準に従い評価した。なお、ハードコート層として実際の使用を想定した場合、少なくともBであることが求められ、Aであることが望ましい。
A:θ≧90°
B:85°≦θ<90°
C:85°<θ
[滑り性]
ハードコート層表面の5箇所の動摩擦係数を測定し、その平均値から評価した。なお、動摩擦係数値は、その値が小さいほど使用プローブとの摩擦が小さいことを示し、滑り性の一目安となる。動摩擦係数値が小さいほど触った際の滑り性が良好となるため、動摩擦係数値が小さいほど好ましい。
[ヘーズ]
参考値として、ハードコート層表面の3箇所のヘーズを測定し、その平均値を算出した。尚、基材として、今回使用したPETフィルム[東レ(株)製 ルミラー(登録商標)U403(別称U40)、厚み100μm]のヘーズは1.6である。
Claims (32)
- (a)(メタ)アクリロイル基を1分子中に2個以上有する活性エネルギー線硬化性多官能モノマー、
(b)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(但し、後述する(c)パーフルオロポリエーテルを除く)、
(c)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500のパーフルオロポリエーテル、及び
(d)活性エネルギー線によりラジカルを発生する重合開始剤を含む、硬化性組成物。 - (a)(メタ)アクリロイル基を1分子中に2個以上有する活性エネルギー線硬化性多官能モノマー100質量部、
(b)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(但し、後述する(c)パーフルオロポリエーテルを除く)0.05質量部乃至3質量部、
(c)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500のパーフルオロポリエーテル0.05質量部乃至3質量部、及び
(d)活性エネルギー線によりラジカルを発生する重合開始剤0.5質量部乃至20質量部を含む、硬化性組成物。 - (a)(メタ)アクリロイル基を1分子中に2個以上有する活性エネルギー線硬化性多官能モノマー100質量部、
(b)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(但し、後述する(c)パーフルオロポリエーテルを除く)0.05質量部乃至3質量部、
(c)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみにヒドロキシ基を有する数平均分子量が1200乃至3000の原料パーフルオロポリエーテルと、該ヒドロキシ基と反応する官能基及び前記活性エネルギー線重合性基を有する化合物との反応生成物であるパーフルオロポリエーテル0.05質量部乃至3質量部、及び
(d)活性エネルギー線によりラジカルを発生する重合開始剤0.5質量部乃至20質量部を含む、硬化性組成物。 - 前記(c)パーフルオロポリエーテルが、前記ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500である、請求項3に記載の硬化性組成物。
- 前記(c)パーフルオロポリエーテルが、ウレタン結合を介して活性エネルギー線重合性基を有する、請求項1乃至請求項4のうち何れか一項に記載の硬化性組成物。
- 前記(c)パーフルオロポリエーテルが、フッ素原子の含有割合が35質量%乃至65質量%である、請求項1乃至請求項5のうち何れか一項に記載の硬化性組成物。
- 前記(c)パーフルオロポリエーテルのポリ(オキシパーフルオロアルキレン)基が、繰り返し単位-(CF2O)-及び/又は繰り返し単位-(CF2CF2O)-を有し、双方の繰り返し単位を有する場合には、これら繰り返し単位をブロック結合、ランダム結合、又は、ブロック結合及びランダム結合にて結合してなる基である、請求項1乃至請求項6のうち何れか一項に記載の硬化性組成物。
- 前記式[1]中、m及びnはそれぞれ独立して1以上の整数を表す、請求項8に記載の硬化性組成物。
- 前記(b)パーフルオロポリエーテルが、前記ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の両末端に前記活性エネルギー線重合性基を有する、請求項1乃至請求項11のうち何れか一項に記載の硬化性組成物。
- 前記式[3]中、r及びsはそれぞれ独立して1以上の整数を表す、請求項13に記載の硬化性組成物。
- (e)溶媒をさらに含む、請求項1乃至請求項16のうち何れか一項に記載の硬化性組成物。
- 請求項1乃至請求項17のうち何れか一項に記載の硬化性組成物より得られる硬化膜。
- フィルム基材の少なくとも一方の面にハードコート層を備えるハードコートフィルムであって、該ハードコート層が請求項18に記載の硬化膜からなる、ハードコートフィルム。
- 前記フィルム基材の表面と前記ハードコート層との間にハードコート層の下層を有し該フィルム基材が樹脂製フィルムである、請求項19に記載のハードコートフィルム。
- 前記ハードコート層が1μm乃至20μmの膜厚を有する、請求項19又は請求項20に記載のハードコートフィルム。
- 請求項1乃至請求項17のうち何れか一項に記載の硬化性組成物をフィルム基材上に塗布し塗膜を形成する工程と、該塗膜に活性エネルギー線を照射し硬化させてハードコート層を形成する工程を含む、ハードコートフィルムの製造方法。
- 請求項17に記載の硬化性組成物をフィルム基材上に塗布し塗膜を形成する工程と、加熱により該塗膜から前記溶媒を除去する工程と、該塗膜に活性エネルギー線を照射し硬化させてハードコート層を形成する工程を含む、ハードコートフィルムの製造方法。
- 前記フィルム基材の表面にハードコート層の下層を形成する工程をさらに含み、該フィルム基材が樹脂製フィルムであって、該ハードコート層の下層上に前記塗膜を形成する、請求項22又は請求項23に記載のハードコートフィルムの製造方法。
- ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(A)(但し、後述するパーフルオロポリエーテル(B)を除く)、及び
ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500のパーフルオロポリエーテル(B)を含む、表面改質剤。 - ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に活性エネルギー線重合性基を有し、且つ重量平均分子量が1400乃至3500のパーフルオロポリエーテル(A)(但し、後述するパーフルオロポリエーテル(B)を除く)、及び
ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみにヒドロキシ基を有する数平均分子量が1200乃至3000の原料パーフルオロポリエーテルと、該ヒドロキシ基と反応する官能基及び前記活性エネルギー線重合性基を有する化合物との反応生成物であるパーフルオロポリエーテル(B)を含む、表面改質剤。 - 前記パーフルオロポリエーテル(B)が、前記ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の片末端のみに前記活性エネルギー線重合性基を有し、且つ重量平均分子量が1550乃至3500である、請求項26に記載の表面改質剤。
- 前記パーフルオロポリエーテル(B)が、フッ素原子の含有割合が35質量%乃至65質量%である、請求項25乃至請求項27のうち何れか一項に記載の表面改質剤。
- 前記パーフルオロポリエーテル(A)が、前記ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の両末端に前記活性エネルギー線重合性基を有する、請求項25乃至請求項28のうち何れか一項に記載の表面改質剤。
- 前記パーフルオロポリエーテル(A)のポリ(オキシパーフルオロアルキレン)基を含む分子鎖が下記式[3]で表される構造を有し、前記パーフルオロポリエーテル(B)のポリ(オキシパーフルオロアルキレン)基を含む分子鎖が下記式[1]で表される構造を有する、請求項25乃至請求項29のうち何れか一項に記載の表面改質剤。
- 前記式[1]中m及びnはそれぞれ独立して1以上の整数を表し、前記式[3]中r及びsはそれぞれ独立して1以上の整数を表す、請求項30に記載の表面改質剤。
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WO1996023828A1 (en) * | 1995-01-30 | 1996-08-08 | Dsm N.V. | Radiation curable composition comprising fluorinated urethane oligomer |
JP2005126453A (ja) * | 2003-10-21 | 2005-05-19 | Tdk Corp | ハードコート剤組成物及びこれを用いた光情報媒体 |
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