WO2022034733A1 - ハードコート用硬化性組成物 - Google Patents
ハードコート用硬化性組成物 Download PDFInfo
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- WO2022034733A1 WO2022034733A1 PCT/JP2021/021913 JP2021021913W WO2022034733A1 WO 2022034733 A1 WO2022034733 A1 WO 2022034733A1 JP 2021021913 W JP2021021913 W JP 2021021913W WO 2022034733 A1 WO2022034733 A1 WO 2022034733A1
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- perfluoropolyether
- formula
- film
- oxyperfluoroalkylene
- Prior art date
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- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 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
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 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
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-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
- 229920000570 polyether 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
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 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
- 239000010454 slate Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer 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
- 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
- 208000032521 type II spinal muscular atrophy Diseases 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F290/04—Polymers provided for in subclasses C08C or C08F
-
- 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
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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 can form a hard coat layer having excellent slipperiness, scratch resistance, abrasion resistance and water repellency. , With respect to a homogeneous curable composition free of suspended matter and sediment.
- touch panels have been introduced in various fields such as mobile information terminal devices such as mobile phones and tablet computers, notebook computers, home appliances, automobile interior and exterior products, and the surface of touch panels of display elements such as liquid crystal displays and organic EL displays. Is often operated by touching with a finger or a pen. When it is assumed that the touch panel is operated with a finger, the surface of the touch panel is required to have water-repellent and oil-repellent properties to facilitate removal of attached fingerprints, and further, the water- and oil-repellent properties are maintained even if the touch panel is repeatedly rubbed with a finger. Abrasion resistance is required.
- a surface coat layer for example, a hard coat layer is provided.
- the fluorine-containing compound Since the fluorine-containing compound exhibits high slipperiness and water repellency and oil repellency, it is used as a material for forming a hard coat layer.
- a method of adding a small amount of a fluorine-based surface modifier to a coating liquid forming a hard coat layer is used. It is used.
- Fluorine-based surface modifiers are known to segregate on the surface of the hardcourt layer due to the low surface energy of fluorine atoms.
- a method of increasing the surface hardness of the hard coat layer and imparting resistance to external force is adopted by forming a high-density crosslinked structure. ..
- a material for forming such a hard coat layer a polyfunctional acrylate-based material that is three-dimensionally crosslinked by radicals generated by irradiation with active energy rays is currently most used.
- a fluorine-based surface modifier added to the coating liquid forming the hard coat layer a material having an active energy ray-polymerizable group is generally used in order to impart scratch resistance and wear resistance to the hard coat layer. (Patent Document 1).
- Patent Document 2 in order to obtain durability characteristics 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, a fluorine atom is used. Immobilization of the contained molecular chains occurs, and the slipperiness of the hard coat layer is reduced. That is, there is a trade-off relationship between durability characteristics such as scratch resistance and wear resistance and slipperiness, and it is difficult to achieve both high characteristic levels. As a method for improving the trade-off relationship, there is a method of introducing a crosslinkable group at one end of a molecular chain, for example, a molecular chain containing a fluorine atom, but the characteristic level is not satisfactory.
- Perfluoropolyether (excluding (c) perfluoropolyether described later) 0.05 parts by mass to 5 parts by mass, (c) At the end of the molecular chain containing a poly (oxyperfluoroalkylene) group, the following formula [1], 0.05 to 5 parts by mass of a perfluoropolyether having a group represented by the formula [2] or a molecular weight of 1000 or more, (d) Polymerization in which a radical is generated by an active energy ray.
- a curable composition comprising 1 part by mass to 20 parts by mass of an initiator.
- R 1 represents a trifluoromethyl group, a fluoro group, a trifluoromethoxy group or a nitro group
- R 1 is a trifluoromethyl group or a trifluoromethoxy group.
- m represents an integer of 1 to 5
- R 1 represents a fluoro group
- m represents an integer of 2 to 5
- R 2 represents a methyl or methoxy group
- n represents a methyl group or a methoxy group.
- R 3 represents an alkyl group having 3 to 10 carbon atoms
- * represents a bond with the molecular chain containing the poly (oxyperfluoroalkylene) group of (c) perfluoropolyether.
- the perfluoropolyether (c) has, for example, a group represented by the formula [1], the formula [2] or the formula [3] at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group. Have.
- the (c) perfluoropolyether does not have, for example, the active energy ray-polymerizable group.
- the poly (oxyperfluoroalkylene) group of the (b) perfluoropolyether and the poly (oxyperfluoroalkylene) group of the (c) perfluoropolyether are, for example, repeating units- [CF 2 O]-and /. Or, if it has a repeating unit- [CF 2 CF 2 O] -and has both repeating units, it is a group consisting of these repeating units bound by block binding, random binding, or block binding and random binding. be.
- the molecular chain containing the poly (oxyperfluoroalkylene) group of the (b) perfluoropolyether and the molecular chain containing the poly (oxyperfluoroalkylene) group of the perfluoropolyether are, for example, the following formula [ 4] or has a structure represented by the formula [5].
- p is the total number of the repeating unit- [CF 2 CF 2 O]-and the repeating unit- [CF 2 O]-, and is 3 to 3 or more. Representing an integer of 30, the repeating unit- [CF 2 CF 2 O]-and the repeating unit- [CF 2 O] -are combined by block binding, random binding, or block binding and random binding. Therefore, q is the number of oxyethylene groups and represents an integer of 0 to 10.
- the ratio of the content of the (b) perfluoropolyether to the content of the (c) perfluoropolyether is, for example, 0.5 to 4.
- the curable composition of the first aspect of the present invention can further contain (e) a solvent.
- the second aspect of the present invention is a cured film obtained from the curable composition of the first aspect of the present invention.
- a third aspect of the present invention is a hardcoat film having a hardcoat layer on at least one surface of a film substrate, wherein the hardcoat layer is made of the cured film of the second aspect of the present invention. be.
- the hard coat layer comprises, for example, a step of applying the curable composition of the first aspect of the present invention on a film substrate to form a coating film, and a step of irradiating the coating film with active energy rays to cure the coating film. It is formed by the method including.
- the hard coat layer comprises, for example, a step of applying the curable composition of the first aspect of the present invention onto a film substrate to form a coating film, and a step of removing the solvent from the coating film by heating. It is formed by a method including a step of irradiating a coating film with active energy rays and curing the coating film.
- the film base material is composed of, for example, a plurality of layers, and has, for example, a lower layer of the hard coat layer on the surface of a resin film.
- the hardcourt layer has a film thickness of, for example, 1 ⁇ m to 20 ⁇ m.
- a fourth aspect of the present invention comprises a step of applying the curable composition of the first aspect of the present invention onto a film substrate to form a coating film, and a step of irradiating the coating film with active energy rays to cure the coating film. It is a method of manufacturing the laminated body of the film base material and a hard coat layer including.
- the film base material is composed of, for example, a plurality of layers, and has, for example, a lower layer of the hard coat layer on the surface of a resin film.
- a fifth aspect of the present invention is a perfluoropoly having a group represented by the above formula [1], formula [2] or formula [3] at the end of a molecular chain containing a poly (oxyperfluoroalkylene) group. It is an ether compound.
- the molecular chain containing the poly (oxyperfluoroalkylene) group has, for example, a structure represented by the above formula [4] or the above formula [5].
- the perfluoropolyether compound has, for example, a group represented by the formula [1], the formula [2] or the formula [3] at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group.
- the perfluoropolyether compound has, for example, a group represented by the formula [1], the formula [2] or the formula [3] at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group.
- the perfluoropolyether compound does not have, for example, an active energy ray-polymerizable group.
- a sixth aspect of the present invention is a molecule containing the perfluoropolyether compound of the fifth aspect of the present invention and a poly (oxyperfluoroalkylene) group having a structure represented by the above formula [4] or the formula [5].
- 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 be obtained.
- a curable composition useful for forming a cured film and a hard coat layer having high liquid repellency properties, and a hard coat layer having excellent these properties are provided.
- a coated film can be provided.
- the active energy ray-curable polyfunctional monomer (hereinafter, also simply referred to as “(a) polyfunctional monomer”) of the component (a) is cured by irradiating it with active energy rays such as ultraviolet rays to promote the polymerization reaction. It refers to a monomer having two or more active energy ray-polymerizable groups. Examples of the active energy ray-polymerizable group include (meth) acryloyl group and vinyl group.
- the (a) polyfunctional monomer preferable in the curable composition of the present invention a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound can be mentioned, and a polyfunctional urethane (meth) acrylate compound described later can be mentioned. Examples thereof include a monomer selected from the group consisting of a lactone-modified polyfunctional (meth) acrylate compound and a monomer selected from the group consisting of a lactone-modified polyfunctional (meth) acrylate compound.
- the (a) polyfunctional monomer one type from the group consisting of the above polyfunctional (meth) acrylate compounds can be used alone, or two or more types can be used in combination.
- the (meth) acrylate compound includes both an acrylate compound and a methacrylate compound, and for example, (meth) acrylic acid includes acrylic acid and methacrylic acid.
- the polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene modification include oxymethylene modification, oxyethylene modification, and oxypropylene modification.
- examples of the oxyalkylene-modified polyfunctional monomer include oxyalkylene-modified compounds in the polyfunctional (meth) acrylate compound or the polyfunctional urethane (meth) acrylate compound.
- the oxyalkylene-modified polyfunctional monomer can also be used alone or in combination of two or more.
- the (a) polyfunctional monomer a polyfunctional monomer having at least three active energy ray-polymerizable groups, for example, at least four can be used.
- a monomer selected from the group consisting of an oxyalkylene-modified polyfunctional (meth) acrylate compound having at least three active energy ray-polymerizable groups can be used as the (a) polyfunctional monomer.
- Examples of the polyfunctional (meth) acrylate compound include trimethylol propanetri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, and pentaerythritol di (meth) acrylate.
- pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are used.
- pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate
- dipentaerythritol penta (meth) acrylate dipentaerythritol hexa (meth) acrylate
- Examples of the oxyalkylene-modified polyfunctional (meth) acrylate compound include (meth) acrylate compounds of oxyalkylene-modified polyols.
- Examples of the polyol include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
- the polyfunctional urethane (meth) acrylate compound for example, a compound obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxy group, and a polyfunctional isocyanate, a (meth) acrylate having a hydroxy group, and a polyol. Examples thereof include compounds obtained by the reaction, but the polyfunctional urethane (meth) acrylate compounds that can be used in the present invention are not limited to these examples.
- Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
- Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. , And tripentaerythritol hepta (meth) acrylate.
- polyol for example, 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; polyether polyols; and polycarbonate diols, which are reaction products with aliphatic dicarboxylic acids such as adipic acid or dicarboxylic acid anhydrides.
- the polyfunctional monomer may be a lactone-modified polyfunctional (meth) acrylate compound, and ⁇ -caprolactone is preferable as the lactone to be modified.
- 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.
- ⁇ -caprolactone-modified dipentaerythritol hexa (meth) acrylate are examples of the lactone-modified polyfunctional (meth) acrylate compound.
- (B) Perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly (oxyperfluoroalkylene) group A perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly (oxyperfluoroalkylene) group of the component (b) is hereinafter simply referred to as “(b) perfluoropolyether”.
- (B) Perfluoropolyether excludes (c) perfluoropolyether described later.
- the preferred (b) perfluoropolyether in the curable composition of the present invention has an active energy ray-polymerizable group at the end of the molecular chain containing a poly (oxyperfluoroalkylene) group via a urethane bond.
- the end of the molecular chain containing the poly (oxyperfluoroalkylene) group may be any end of all or a part of the molecular chain.
- the molecular chain is linear, all ends and some ends of the molecular chain are both ends and one end of the linear molecular chain, respectively.
- Examples of the linking group between the poly (oxyperfluoroalkylene) group and the urethane bond include a hydrocarbon group having an ether bond, and the hydrocarbon group has at least one hydrogen atom substituted with a fluorine atom. It may have been.
- the perfluoropolyether together with the component (c) described later, serves as a surface modifier in the hardcoat layer formed from the curable composition of the present invention. Further, since (b) perfluoropolyether has excellent compatibility with (a) a polyfunctional monomer, white turbidity is suppressed and a hard coat layer having a transparent appearance can be formed.
- 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 group) as a repeating unit is preferable.
- the bond of these oxyperfluoroalkylene groups may be either a block bond or a random bond.
- the molecular chain containing the poly (oxyperfluoroalkylene) group preferably has a structure represented by the following formula [4] or formula [5].
- P in the above equations [4] and [5] is the total number of the repeating unit- [CF 2 CF 2 O]-and the number of repeating units- [CF 2 O]-, for example, 3. It represents an integer of 30 to 30, preferably 7 to 21, and the connection between the repeating unit- [CF 2 CF 2 O]-and the repeating unit- [CF 2 O]-is either a block bond or a random bond.
- Q in the above formula [5] is the number of oxyethylene groups and represents an integer of 0 to 10.
- Examples of the active energy ray-polymerizable group include (meth) acryloyl group and vinyl group.
- the perfluoropolyether is not limited to one having one active energy ray-polymerizable group at the end of the molecular chain containing a poly (oxyperfluoroalkylene) group, and is not limited to those having two or more active energy ray-polymerizable groups. It may have.
- Examples of the terminal structure containing an active energy ray-polymerizable group include structures of the formulas [A1] to [A5] shown below, and structures in which the acryloyl group in these structures is replaced with a methacryloyl group.
- the structures of the formulas [A3], [A4] and [A5] having two or more active energy ray-polymerizable groups, and the structures in which the acryloyl group in these structures is replaced with a methacryloyl group. Is preferable.
- the content of (b) perfluoropolyether is 0.05 parts by mass to 5 parts by mass, preferably 0.1 part by mass with respect to 100 parts by mass of the (a) polyfunctional monomer. Parts to 5 parts by mass, more preferably 0.1 parts by mass to 1 part by mass.
- the content of (b) perfluoropolyether is 0.05 parts by mass or more, sufficient scratch resistance can be imparted to the hardcoat layer, and (b) the content of perfluoropolyether is high.
- the amount is 5 parts by mass or less, (a) a hard coat layer that is sufficiently compatible with the polyfunctional monomer and has less white turbidity can be obtained.
- Perfluoropolyether can be used alone or in combination of two or more. When two or more types are combined, one end (one end) of the molecular chain containing a poly (oxyperfluoroalkylene) group has an active energy ray-polymerizable group via a urethane bond, and the other of the molecular chain. Perfluoropolyether having a hydroxy group at one end (the other end) may be contained.
- the perfluoropolyether of the above is also simply referred to as “(c) perfluoropolyether” below.
- the perfluoropolyether has a group represented by the following formula [1], formula [2] or formula [3] at the end of the molecular chain containing the poly (oxyperfluoroalkylene) group, and has a group represented by the following formula [1], formula [2] or formula [3]. It differs from the above-mentioned (b) perfluoropolyether in that it has a molecular weight of 1000 or more.
- the definition of (c) the molecular chain containing the poly (oxyperfluoroalkylene) group of the perfluoropolyether and its terminal is the same as that of (b) perfluoropolyether.
- the molecular chain containing the poly (oxyperfluoroalkylene) group has a structure represented by the formula [4] or the formula [5].
- R 1 in the above formula [1] represents a trifluoromethyl group, a fluoro group, a trifluoromethoxy group or a nitro group
- R 1 represents a trifluoromethyl group, a trifluoromethoxy group or a nitro group
- m is Representing an integer of 1 to 5
- R 1 represents a fluorogroup
- m represents an integer of 2 to 5.
- R 2 represents a methyl group or a methoxy group, preferably a methyl group
- n represents 1, 2 or 3.
- R 3 in the above formula [3] represents an alkyl group having 3 to 10 carbon atoms, for example, an alkyl group having 3 to 6 carbon atoms.
- the perfluoropolyether (c) is, for example, a perfluoropolyether having a hydroxy group at the end of the structure represented by the above formula [4] or the formula [5] and the following formula [1a], formula [2a] or formula. It is obtained by reacting with the isocyanate compound represented by [3a].
- R1 and m in the above formula [1a], R2 and n in the above formula [2a], and R3 in the above formula [3a] are the above formulas [1], [2] and [2], respectively. 3] is synonymous with the definitions of R 1 , R 2 , R 3 , m and n.
- (C) Perfluoropolyether together with (b) perfluoropolyether, serves as a surface modifier in the hardcourt layer formed from the curable composition of the present invention. Further, since (c) perfluoropolyether has excellent compatibility with (b) perfluoropolyether, cloudiness is suppressed and a hard coat layer having a transparent appearance can be formed.
- the (c) perfluoropolyether When the molecular weight of the perfluoropolyether is 1000 or more, the (c) perfluoropolyether easily stays on the surface of the hard coat layer obtained from the curable composition of the present invention, and is excellent in slipperiness. A hard coat layer can be obtained. Further, when (c) the molecular weight of the pearl fluoropolyether is, for example, 4000 or less, (a) it is sufficiently compatible with the polyfunctional monomer, and a hard coat layer with less cloudiness can be obtained.
- the content of (c) perfluoropolyether is 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the (a) polyfunctional monomer, and (c).
- the ratio of the content of (b) perfluoropolyether to the content of perfluoropolyether is preferably 0.5 to 4.
- 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 slipperiness can be obtained.
- the content of (c) perfluoropolyether is 5 parts by mass or less, it is possible to obtain a hard coat layer that is sufficiently compatible with (b) perfluoropolyether and has less cloudiness.
- (C) Perfluoropolyether can be used alone or in combination of two or more. When two or more kinds are combined, a group represented by the above formula [1], the formula [2] or the formula [3] is attached to one end (one end) of the molecular chain containing a poly (oxyperfluoroalkylene) group. A perfluoropolyether having an active energy ray-polymerizable group or a hydroxy group may be contained at the other end (the other end) of the molecular chain thereof.
- the (c) perfluoropolyether is more preferably one that does not have the active energy ray-polymerizable group of the (b) perfluoropolyether.
- the preferred (d) polymerization initiator in the curable composition of the present invention is, for example, a polymerization initiator that generates radicals by active energy rays such as electron beams, ultraviolet rays, and X-rays, particularly by irradiation with ultraviolet rays.
- Examples of the polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides and benzophenones. , Biscmarins, bisimidazoles, titanocene, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salt and sulfonium salt. These polymerization initiators may be used alone or in combination of two or more.
- alkylphenones As the polymerization initiator, it is preferable to use (d) alkylphenones as the polymerization initiator. By using alkylphenones, a cured film with further improved scratch resistance can be obtained.
- alkylphenones examples include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl)-.
- ⁇ -Hydroxyalkyl such as 2-methylpropane-1-one, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropane-1-one Phenyls; 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, etc.
- ⁇ -Aminoalkylphenones 2,2-dimethoxy-1,2-diphenylethane-1-one; and methylphenylglycoxylate.
- the content of (d) the polymerization initiator is 1 part by mass to 20 parts by mass, preferably 2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the (a) polyfunctional monomer.
- the curable composition of the present invention may contain (e) a solvent as an optional component, that is, 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 at the time of coating the curable composition related to the formation of the cured film (hard coat layer) described later. It may be appropriately selected in consideration of the drying property before and after curing.
- aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetraline; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane; Halogens such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 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
- the content of the solvent (e) in the curable composition of the present invention is not particularly limited, but for example, the solid content concentration of the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50%. It is a concentration that becomes mass%.
- the solid content concentration also referred to as a non-volatile content concentration
- is a solid content also referred to as a non-volatile content concentration
- additives generally added to the curable composition of the present invention as needed such as a polymerization inhibitor, a photosensitizer, a leveling agent, and a surfactant, as long as the effects of the present invention are not impaired.
- the curable composition of the present invention can form a cured film by applying (coating) it on a substrate to form a coating film and irradiating the coating film with active energy rays to polymerize (cure) the coating film.
- the cured film is also the subject of the present invention. Further, as the hard coat layer in the hard coat film described later, one made of the above-mentioned cured film can be used.
- polyesters such as various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, polyimide, epoxy resin , Melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin), metal, wood, paper, glass, slate. Can be done.
- various resins polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN)
- TPU thermoplastic polyurethane
- TPU thermoplastic polyurethane
- polyolefin polyamide
- polyimide polyimide
- epoxy resin epoxy resin
- Melamine resin triacetyl
- the shape of these base materials may be a plate shape, a film shape, or a 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.
- a layer, a discoloration prevention layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer and the like may be formed as a lower layer of the hard coat layer, or a plurality of lower layers of the hard coat layer may be laminated.
- the layer formed on the surface of the base material is not particularly limited as long as the effect of the present invention is not impaired.
- the coating method on the substrate is 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 (toppan printing method). , Intaglio printing method, flat plate printing method, screen printing method, etc.), etc., can be used for the roll-to-roll method, and from the viewpoint of thin film coatability, the letterpress printing method can be used. In particular, it is desirable to use the gravure coat 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 for coating. At the time of application, a solvent may be further added to the curable composition, if necessary. As the solvent in this case, various solvents mentioned in the above-mentioned [(e) solvent] can be mentioned.
- the coating film is pre-dried by a heating means such as a hot plate or an oven as necessary to remove the solvent (solvent removal step). ..
- the conditions for heating and drying at this time are preferably, for example, 40 ° C. to 120 ° C. for about 30 seconds to 10 minutes.
- the coating film is cured by irradiating it with active energy rays such as ultraviolet rays.
- active energy rays include ultraviolet rays, electron beams and X-rays, and ultraviolet rays are particularly preferable.
- the light source used for ultraviolet irradiation for example, a sunbeam, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used. Further, after that, the polymerization may be completed by performing post-baking, specifically by heating using a heating means such as a hot plate or an oven.
- a heating means such as a hot plate or an oven.
- the thickness of the cured film formed is usually 0.1 ⁇ m to 50 ⁇ m, preferably 0.5 ⁇ m to 20 ⁇ m after drying and curing.
- the curable composition of the present invention can be used to produce a hardcourt film having a hardcourt layer on at least one surface (surface) of the film substrate.
- the hard-coated film is also an object of the present invention, and the hard-coated film is suitably used for protecting the surface of various display elements such as a touch panel and a liquid crystal display.
- the hard coat layer in the hard coat film of the present invention includes a step of applying the curable composition of the present invention on a film substrate to form a coating film, and a step of removing a solvent by heating if necessary, and the coating.
- the film can be formed by a method including a step of irradiating the film with active energy rays such as ultraviolet rays and curing the coating film.
- a method for producing a hard-coated film including a hard-coated layer on at least one surface of a film substrate including these steps is also an object of the present invention.
- Preferred resin films include, for example, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPUs), polycarbonates, polymethacrylates, polystyrenes and polyolefins. Examples thereof include films such as polyamide, polyimide, and triacetyl cellulose (TAC).
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- TPUs thermoplastic polyurethanes
- TMC triacetyl cellulose
- the film base material may be formed by laminating a plurality of layers.
- a primer layer for example, on the surface of the resin film, 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.
- a layer different from the resin film such as a discoloration prevention layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, and an electrode layer, may be laminated as a lower layer of the hard coat layer, and the lower layer of the hard coat layer may be laminated.
- a plurality of layers may be stacked.
- the layer laminated on the surface of the resin film is not particularly limited as long as the effect of the present invention is not impaired.
- the method for applying the curable composition of the present invention onto the film substrate (coating film forming step) and the method for irradiating the coating film with active energy rays (curing step) are described 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 for drying the coating film (solvent removing step) described in the above-mentioned ⁇ cured film> can be used.
- the layer thickness (thickness) of the hard coat layer thus obtained is, for example, 1 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 10 ⁇ m.
- a surface modifier containing a perfluoropolyether compound having an active energy ray-polymerizable group at the end of a molecular chain containing a poly (oxyperfluoroalkylene) group having a structure represented by the formula [5] is also present.
- the active energy ray-polymerizable group is an active energy ray-polymerizable group possessed by the (b) perfluoropolyether.
- the former perfluoropolyether compound preferably does not have the active energy ray-polymerizable group. Furthermore, the former perfluoropolyether compound itself is also the subject of the present invention.
- Coating device by bar coater PM-9050MC manufactured by SMT Co., Ltd.
- Bar OSG System Products Co., Ltd.
- Coating speed 4 m / min
- Oven device Sanki Instrumentation Co., Ltd.
- 2-layer clean oven (upper and lower type) PO-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 wear resistance test equipment Shinto Kagaku Co., Ltd.
- TRIBOGEAR TYPE 30S Scanning speed: 3200 mm / min Scanning distance: 50 mm (5)
- Contact angle device DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measurement temperature: 23 ° C (6)
- Dynamic friction coefficient ⁇ k measuring device Shinto Kagaku Co., Ltd.
- Total light transmittance, haze device Haze meter NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
- Polyfunctional acrylate PA1 Dipentaerythritol Penta acrylate / Hexa acrylate mixture [Aronix (registered trademark) M-403 manufactured by Toagosei Co., Ltd., penta body ratio 50% to 60% (catalog value)]
- Polyfunctional acrylate PA2 Oxyethylene-modified polyfunctional acrylate [New Frontier (registered trademark) MF-001 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.]
- Polyfunctional acrylate PA3 Polyfunctional urethane acrylate [Art Resin (registered trademark) UN-3320HS manufactured by Negami Kogyo Co., Ltd.]
- Polyfunctional acrylate PA4 Caprolactone-modified dipentaerythritol hexaacrylate [DPCA30 manufactured by Nippon Kayaku Co., Ltd.]
- PFPE1 A perfluoropolyether having two hydroxy groups at both ends of a molethritol
- PFPE2 Perfluoropolyether having two hydroxy groups at both ends of the molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group [Fluorolink (registered trademark) E10H manufactured by Solvay Specialty Polymers Co., Ltd.
- PFPE3 Perfluoropolyether having one hydroxy group at each end of the molecular chain containing a poly (oxyperfluoroalkylene) group without a poly (oxyalkylene) group [Fombin (registered trademark) D2 manufactured by Solvay Specialty Polymers Co., Ltd.
- PFPE4 Perfluoropolyether (1H, 1H-perfluoro-3,6,9-trioxatridecane-1-ol) having one hydroxy group at one end without a poly (oxyalkylene) group [ExfluorResearch C10GOL molecular weight 548.1 (catalog value)]
- N1 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Showa Denko Corporation Karenz (registered trademark) BEI]
- N2 Propyl isocyanate [Tokyo Chemical Industry Co., Ltd.]
- N3 Butyl isocyanate [Tokyo Chemical Industry Co., Ltd.]
- N4 Hexyl isocyanate [Tokyo Chemical Industry Co., Ltd.]
- N5 2,4-Difluorophenyl isocyanate
- N6 4- (trifluoromethyl) phenyl isocyan
- Example 1 Production of component SMB1 of surface modifier
- PFPE2 2.22 g (1.5 mmol), N2 0.25 g (3.0 mmol), DOTDD 0.025 g (total mass of PFPE2 and N2) 0.01 times the amount) and 2.5 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB1.
- the obtained SMB1 corresponds to the component (c) of the curable composition of the present invention.
- Example 2 Production of component SMB2 of surface modifier
- PFPE2 2.19 g (1.5 mmol), N3 0.29 g (3.0 mmol), DOTDD 0.025 g (total mass of PFPE2 and N3) 0.01 times the amount) and 2.5 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB2.
- the obtained SMB2 corresponds to the component (c) of the curable composition of the present invention.
- Example 3 Production of component SMB3 of surface modifier
- the total mass of PFPE2 2.12 g (1.4 mmol), N4 0.36 g (2.8 mmol), and DOTDD 0.025 g (PFPE2 and N4) 0.01 times the amount) and 2.5 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB3.
- the obtained SMB3 corresponds to the component (c) of the curable composition of the present invention.
- Example 4 Production of component SMB4 of surface modifier
- PFPE2 0.42 g (2.8 mmol) of N5, and 0.025 g of DOTDD (total mass of PFPE2 and N5) are added. 0.01 times the amount) and 2.5 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB4.
- the obtained SMB4 corresponds to the component (c) of the curable composition of the present invention.
- Example 5 Production of component SMB5 of surface modifier
- PFPE2 1.98 g (1.3 mmol), N6 0.49 g (2.6 mmol), DOTDD 0.025 g (total mass of PFPE2 and N6) 0.01 times the amount) and 2.5 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB5.
- the obtained SMB5 corresponds to the component (c) of the curable composition of the present invention.
- Example 6 Production of component SMB6 of surface modifier
- PFPE2 1.98 g (1.3 mmol), N7 0.49 g (2.6 mmol), DOTDD 0.025 g (total mass of PFPE2 and N7) 0.01 times the amount) and 2.5 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB6.
- the obtained SMB6 corresponds to the component (c) of the curable composition of the present invention.
- Example 7 Production of component SMB7 of surface modifier
- the total mass of PFPE2 2.34 g (1.6 mmol), N8 0.63 g (3.2 mmol), and DOTDD 0.030 g (PFPE2 and N8) 0.01 times the amount) and 3.0 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB7.
- the obtained SMB7 corresponds to the component (c) of the curable composition of the present invention.
- Example 8 Production of component SMB8 of surface modifier
- the total mass of PFPE2 4.09 g (2.2 mmol), N9 1.10 g (4.4 mmol), and DOTDD 0.052 g (PFPE2 and N9) 0.01 times the amount) and 5.3 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB8.
- the obtained SMB8 corresponds to the component (c) of the curable composition of the present invention.
- Example 9 Production of component SMB9 of surface modifier
- the total mass of PFPE2 2.44 g (1.6 mmol), N10 0.53 g (3.2 mmol), and DOTDD 0.030 g (PFPE2 and N10) 0.01 times the amount) and 3.0 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB9.
- the obtained SMB9 corresponds to the component (c) of the curable composition of the present invention.
- Example 11 Production of component SMB11 of surface modifier
- the total mass of PFPE3 4.17 g (2.1 mmol), N6 1.01 g (4.2 mmol), and DOTDD 0.052 g (PFPE3 and N6) 0.01 times the amount) and 5.2 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB11.
- the obtained SMB11 corresponds to the component (c) of the curable composition of the present invention.
- Example 12 Production of component SMB12 of surface modifier
- the total mass of PFPE3 4.34 g (2.2 mmol), N9 0.86 g (4.4 mmol), and DOTDD 0.052 g (PFPE3 and N9) 0.01 times the amount) and 5.3 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB12.
- the obtained SMB12 corresponds to the component (c) of the curable composition of the present invention.
- Example 13 Production of component SMB13 of surface modifier PFPE2 4.11 g (2.7 mmol), N6 0.51 g (2.7 mmol), N1 0.66 g (2.7 mmol), DOTDD 0 in a screw tube. .053 g (0.01 times the total mass of PFPE2, N6 and N1) and 4.67 g of MEK were charged. The obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB13. The obtained SMB13 corresponds to the component (c) of the curable composition of the present invention.
- Example 14 Production of component SMB14 of surface modifier
- the total mass of PFPE4 4.85 g (3.4 mmol), N6 0.63 g (3.4 mmol), and DOTDD 0.025 g (PFPE4 and N6) 0.01 times the amount) and 2.5 g of MEK were charged.
- the obtained mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of the desired perfluoropolyether compound SMB14.
- the perfluoropolyether compounds of Comparative Examples 1 to 6 obtained by reacting perfluoropolyether PFPE2 with any one of the following isocyanate compound groups N11 to N16.
- the results of SMB15 to SMB20 were that the cohesive force was high and the solubility was low.
- Examples 15 to 38, Comparative Examples 7 to 15 Each component shown in Table 2 was mixed to prepare a curable composition having a solid content concentration shown in Table 2.
- the solid content refers to a component other than the solvent.
- [part] represents [parts by mass] and [%] represents [% by mass].
- the polyfunctional acrylate and the surface modifier in Table 2 each represent a solid content.
- a bar coater was applied to these curable compositions on an A4 size PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., 100 ⁇ m thick] on which both sides were easily adhered to form a primer layer.
- A4 size PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., 100 ⁇ m thick] on which both sides were easily adhered to form a primer layer.
- the coating was dried in an oven at 60 ° C. for 8 minutes to remove the solvent.
- the obtained film was exposed to UV light having an exposure amount of 300 mJ / cm 2 under a nitrogen atmosphere to prepare a hard coat film having a hard coat layer (cured film).
- composition homogeneity The appearance of each prepared curable composition was visually confirmed and evaluated according to the following criteria.
- Sctch resistance The surface of the hard coat layer of the obtained hard coat film is reciprocated 5000 times with a stroke of 50 mm by applying a load of 1 kg with steel wool [BONSTAR (registered trademark) # 0000 (ultra-fine)] attached to a reciprocating wear tester.
- A, B and C Assuming actual use as a hard coat layer, it is required to be at least B, and preferably A.
- the surface of the hard coat layer was rubbed 2,500 times with a cylindrical eraser [RUBBER STICK, ⁇ 6.0 mm manufactured by Minoan] attached to a reciprocating wear tester under a load of 1 kg. 1 ⁇ L of water was attached to the rubbed portion, the contact angle ⁇ 5 seconds later was measured at 5 points, and the average value was taken as the contact angle value and evaluated according to the following criteria.
- the dynamic friction coefficient ⁇ k at five points on the surface of the hard coat layer was measured, and the average value was evaluated according to the following criteria. The smaller the value of the dynamic friction coefficient value, the smaller the friction with the probe used, which is a measure of slipperiness. The smaller the dynamic friction coefficient value, the better the slipperiness when touched. Therefore, the smaller the dynamic friction coefficient value, the better.
- the curable composition of Examples 15 to 36 is any one of polyfunctional acrylates PA1 to PA4, perfluoropolyether compounds SMA1 to SMA3, and perfluoropolyethers PFPE1 to PFPE3. It contains perfluoropolyether compounds SMB1 to SMB12 obtained by reacting any one of the isocyanate compound groups N2 to N10 with one of the above-mentioned isocyanate compounds. Then, as shown in Table 3, the curable compositions of Examples 15 to 36 showed excellent homogeneity, and the hard coat film provided with the hard coat layer obtained from the curable composition was excellent. It showed slipperiness, scratch resistance, water repellency and abrasion resistance.
- the curable compositions of Examples 37 and 38 react the isocyanate compounds N6 and N1 with the polyfunctional acrylate PA1, the perfluoropolyether compound SMA1, and the perfluoropolyether PFPE2. It contains the perfluoropolyether compound SMB13 obtained. And, as shown in Table 3, the curable compositions of Examples 37 and 38 showed excellent homogeneity, and the hard coat film provided with the hard coat layer obtained from the curable composition was excellent. It showed slipperiness, scratch resistance, water repellency and abrasion resistance.
- the curable compositions of Comparative Examples 7 to 9 contain the polyfunctional acrylate PA1 and the perfluoropolyether compounds SMA1 to SMA3, and are like the SMB1 to SMB13 (c). It does not contain any ingredients.
- the curable compositions of Comparative Examples 7 to 9 show the same level of homogeneity as the curable compositions of Examples 15 to 38, and Comparative Examples.
- the hard coat film comprising the hard coat layer obtained from the curable compositions of 7 to 9 is compared with the hard coat film including the hard coat layer obtained from the curable compositions of Examples 15 to 38. The result was that the scratch resistance and water repellency were at the same level, but the slipperiness was inferior.
- the curable compositions of Comparative Example 10 and Comparative Example 11 are obtained by reacting the polyfunctional acrylate PA1 and the perfluoropolyether PFPE2 with the isocyanate compound N7 or N8. It contains the fluoropolyether compound SMB6 or SMB7 and does not contain the component (b) such as SMA1 to SMA3. Then, as shown in Table 3, the curable compositions of Comparative Example 10 and Comparative Example 11 became cloudy due to the formation of suspended matter, and were compared with the curable compositions of Examples 15 to 38.
- the hard coat film having the hard coat layer obtained from Comparative Example 10 and Comparative Example 11 includes the hard coat layer obtained from the curable compositions of Examples 15 to 38. The results were inferior in slipperiness, scratch resistance, water repellency and abrasion resistance as compared with the hard coat film.
- the curable compositions of Comparative Examples 12 to 14 contain a polyfunctional acrylate PA1, a perfluoropolyether compound SMA1, and perfluoropolyethers PFPE1 to PFPE3.
- the curable compositions of Comparative Examples 12 to 14 have low solubility of the perfluoropolyethers PFPE1 to PFPE3, so that the curable composition is caused by the formation of suspended matter.
- White turbidity and phase separation of the substance occurred, resulting in inferior homogeneity as compared with the curable compositions of Examples 15 to 38.
- the curable composition of Comparative Example 15 contained the isocyanate compound N6 with respect to the polyfunctional acrylate PA1, the perfluoropolyether compound SMA1, and the perfluoropolyether PFPE4 having a molecular weight of 548.1. It contains the perfluoropolyether compound SMB14 obtained by the reaction.
- the curable composition of Comparative Example 15 showed the same level of homogeneity as the curable composition of Examples 15 to 38, and the curable composition of Comparative Example 15 was shown.
- the hardcoat film comprising the hardcoat layer obtained from the material has the same level of scratch resistance as the hardcoat film comprising the hardcoat layer obtained from the curable compositions of Examples 15 to 38.
- the perfluoropolyether compound SMB14 has a molecular weight of less than 1000 and has a lower molecular weight than the other perfluoropolyether compounds SMB1 to SMB13. It is considered that the slipperiness was inferior due to the difficulty in staying.
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Abstract
Description
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)活性エネルギー線硬化性多官能モノマー]
(a)成分の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、硬化する活性エネルギー線重合性基を2つ以上有するモノマーを指す。前記活性エネルギー線重合性基として、例えば、(メタ)アクリロイル基及びビニル基が挙げられる。
(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する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。
(c)成分のポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に、式[1]、式[2]又は式[3]で表される基を有する分子量1000以上、例えば1000乃至4000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、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に下記式[1]、式[2]又は式[3]で表される基を有し、且つ分子量1000以上であることが、前記(b)パーフルオロポリエーテルと相違する。一方、(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)基を含む分子鎖、及びその末端の定義については、前記(b)パーフルオロポリエーテルと共通する。したがって、前記ポリ(オキシパーフルオロアルキレン)基を含む分子鎖として、前記式[4]又は式[5]で表される構造を有することが好ましい。
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もよい。
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、前記式[1]、式[2]又は式[3]で表される基を有するパーフルオロポリエーテル化合物、及び前記式[4]又は式[5]で表される構造を有するポリ(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するパーフルオロポリエーテル化合物を含む表面改質剤も、本発明の対象である。前記活性エネルギー線重合性基は、前記(b)パーフルオロポリエーテルが有する活性エネルギー線重合性基である。前者のパーフルオロポリエーテル化合物は、前記活性エネルギー線重合性基を有さないものが好ましい。さらに、前者のパーフルオロポリエーテル化合物自体も本発明の対象である。
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-30、最大ウエット膜厚30μm
塗布速度:4m/分
(2)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
(3)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
(4)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
(5)接触角
装置:協和界面科学(株)製 DropMaster DM-501
測定温度:23℃
(6)動摩擦係数μk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
(7)全光線透過率、ヘーズ
装置:日本電色工業(株)製 ヘーズメーター NDH5000
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、ペンタ体割合50%乃至60%(カタログ値)]
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:カプロラクトン変性ジペンタエリスリトールヘキサアクリレート[日本化薬(株)製 DPCA30]
PFPE1: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 NMRによる分析結果から算出された数平均分子量2200]
PFPE2: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それぞれにポリ(オキシアルキレン)基を介してヒドロキシ基を2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)E10H NMRによる分析結果から算出された数平均分子量1818]
PFPE3: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1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 Fomblin(登録商標)D2 NMRによる分析結果から算出された数平均分子量1500]
PFPE4:片末端にポリ(オキシアルキレン)基を介さずヒドロキシ基を1つ有するパーフルオロポリエーテル(1H,1H-パーフルオロ-3,6,9-トリオキサトリデカン-1-オール)[Exfluor Research社製 C10GOL 分子量548.1(カタログ値)]
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:プロピルイソシアネート[東京化成工業(株)]
N3:ブチルイソシアネート[東京化成工業(株)]
N4:ヘキシルイソシアネート[東京化成工業(株)]
N5:2,4-ジフルオロフェニルイソシアネート[東京化成工業(株)]
N6:4-(トリフルオロメチル)フェニルイソシアネート[東京化成工業(株)]
N7:3-(トリフルオロメチル)フェニルイソシアネート[東京化成工業(株)]
N8:3-(トリフルオロメトキシ)フェニルイソシアネート[東京化成工業(株)]
N9:パラ-トルエンスルフォニルイソシアネート[東京化成工業(株)]
N10:4-ニトロフェニルイソシアネート[東京化成工業(株)]
N11:4-フルオロフェニルイソシアネート[東京化成工業(株)]
N12:フェニルイソシアネート[東京化成工業(株)]
N13:パラ-トリルイソシアネート[東京化成工業(株)]
N14:パラ-メトキシフェニルイソシアネート[東京化成工業(株)]
N15:3,5-ジメチルフェニルイソシアネート[東京化成工業(株)]
N16:2,6-ジメチルフェニルイソシアネート[東京化成工業(株)]
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]
SMA2: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]
SMA3: 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(株)製 オプツールDAC-HP、不揮発分20質量%溶液]
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]
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
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MEK 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%MEK溶液を得た。得られたSMA1は、本発明の硬化性組成物の(b)成分に該当する。
スクリュー管に、PFPE2 2.22g(1.5mmol)、N2 0.25g(3.0mmol)、DOTDD 0.025g(PFPE2及びN2の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB1の50質量%MEK溶液を得た。得られたSMB1は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 2.19g(1.5mmol)、N3 0.29g(3.0mmol)、DOTDD 0.025g(PFPE2及びN3の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB2の50質量%MEK溶液を得た。得られたSMB2は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 2.12g(1.4mmol)、N4 0.36g(2.8mmol)、DOTDD 0.025g(PFPE2及びN4の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB3の50質量%MEK溶液を得た。得られたSMB3は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 2.05g(1.4mmol)、N5 0.42g(2.8mmol)、DOTDD 0.025g(PFPE2及びN5の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB4の50質量%MEK溶液を得た。得られたSMB4は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 1.98g(1.3mmol)、N6 0.49g(2.6mmol)、DOTDD 0.025g(PFPE2及びN6の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB5の50質量%MEK溶液を得た。得られたSMB5は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 1.98g(1.3mmol)、N7 0.49g(2.6mmol)、DOTDD 0.025g(PFPE2及びN7の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB6の50質量%MEK溶液を得た。得られたSMB6は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 2.34g(1.6mmol)、N8 0.63g(3.2mmol)、DOTDD 0.030g(PFPE2及びN8の合計質量の0.01倍量)、及びMEK 3.0gを仕込んだ。得られた混合物を、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SMB7の50質量%MEK溶液を得た。得られたSMB7は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 4.09g(2.2mmol)、N9 1.10g(4.4mmol)、DOTDD 0.052g(PFPE2及びN9の合計質量の0.01倍量)、及びMEK 5.3gを仕込んだ。得られた混合物を、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SMB8の50質量%MEK溶液を得た。得られたSMB8は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 2.44g(1.6mmol)、N10 0.53g(3.2mmol)、DOTDD 0.030g(PFPE2及びN10の合計質量の0.01倍量)、及びMEK 3.0gを仕込んだ。得られた混合物を、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SMB9の50質量%MEK溶液を得た。得られたSMB9は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE1 1.87g(0.8mmol)、N6 0.41g(3.2mmol)、DOTDD 0.025g(PFPE1及びN6の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB10の50質量%MEK溶液を得た。得られたSMB10は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE3 4.17g(2.1mmol)、N6 1.01g(4.2mmol)、DOTDD 0.052g(PFPE3及びN6の合計質量の0.01倍量)、及びMEK 5.2gを仕込んだ。得られた混合物を、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SMB11の50質量%MEK溶液を得た。得られたSMB11は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE3 4.34g(2.2mmol)、N9 0.86g(4.4mmol)、DOTDD 0.052g(PFPE3及びN9の合計質量の0.01倍量)、及びMEK 5.3gを仕込んだ。得られた混合物を、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SMB12の50質量%MEK溶液を得た。得られたSMB12は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE2 4.11g(2.7mmol)、N6 0.51g(2.7mmol)、N1 0.66g(2.7mmol)、DOTDD 0.053g(PFPE2、N6及びN1の合計質量の0.01倍量)、及びMEK 4.67gを仕込んだ。得られた混合物を、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SMB13の50質量%MEK溶液を得た。得られたSMB13は、本発明の硬化性組成物の(c)成分に該当する。
スクリュー管に、PFPE4 4.85g(3.4mmol)、N6 0.63g(3.4mmol)、DOTDD 0.025g(PFPE4及びN6の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB14の50質量%MEK溶液を得た。
スクリュー管に、PFPE2 2.09g(1.4mmol)、N11 0.38g(2.8mmol)、DOTDD 0.025g(PFPE2及びN11の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB15の50質量%MEK溶液を得た。
スクリュー管に、PFPE2 2.14g(1.4mmol)、N12 0.34g(2.8mmol)、DOTDD 0.025g(PFPE2及びN12の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB16の50質量%MEK溶液を得た。
スクリュー管に、PFPE2 2.10g(1.4mmol)、N13 0.37g(2.8mmol)、DOTDD 0.025g(PFPE2及びN13の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB17の50質量%MEK溶液を得た。
スクリュー管に、PFPE2 2.48g(1.7mmol)、N14 0.49g(3.4mmol)、DOTDD 0.030g(PFPE2及びN14の合計質量の0.01倍量)、及びMEK 3.0gを仕込んだ。得られた混合物を、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SMB18の50質量%MEK溶液を得た。
スクリュー管に、PFPE2 2.07g(1.4mmol)、N15 0.41g(2.8mmol)、DOTDD 0.025g(PFPE2及びN15の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB19の50質量%MEK溶液を得た。
スクリュー管に、PFPE2 2.07g(1.4mmol)、N16 0.41g(2.8mmol)、DOTDD 0.025g(PFPE2及びN16の合計質量の0.01倍量)、及びMEK 2.5gを仕込んだ。得られた混合物を、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SMB20の50質量%MEK溶液を得た。
各パーフルオロポリエーテル化合物の50質量%MEK溶液の均質性を評価した。評価の手順を以下に示す。結果を表1に併せて示す。
[溶液の均質性]
得られた各パーフルオロポリエーテル化合物の50質量%MEK溶液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(浮遊物及び沈降物何れも無し)
C:浮遊物及び沈降物何れも有り
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10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、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≧105°
B:90°≦θ<105°
C:θ<90°
[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:80°≦θ<90°
C:80°<θ
[滑り性]
ハードコート層表面の5箇所の動摩擦係数μkを測定し、その平均値から以下の基準に従い評価した。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。
A:μk≦0.05
B:0.05<μk≦0.07
C:μk>0.07
[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 (24)
- (a)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する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5質量部、
(c)ポリ(オキシパーフルオロアルキレン)基を含む分子鎖の末端に、下記式[1]、式[2]又は式[3]で表される基を有する分子量1000以上のパーフルオロポリエーテル0.05質量部乃至5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1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)基を含む分子鎖の両末端それぞれに前記式[1]、式[2]又は式[3]で表される基を有する、請求項1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、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に前記式[1]、式[2]又は式[3]で表される基を有する、請求項1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前記活性エネルギー線重合性基を有さないものである、請求項1乃至請求項3のうち何れか一項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のポリ(オキシパーフルオロアルキレン)基及び前記(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4のうち何れか一項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のポリ(オキシパーフルオロアルキレン)基を含む分子鎖、及び前記(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)基を含む分子鎖が、下記式[4]又は式[5]で表される構造を有する、請求項5に記載の硬化性組成物。
(上記式[4]及び式[5]中、pは、繰り返し単位-[CF2CF2O]-の数と、繰り返し単位-[CF2O]-の数との総数であって3乃至30の整数を表し、前記繰り返し単位-[CF2CF2O]-と、前記繰り返し単位-[CF2O]-は、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り、qはオキシエチレン基の数であって0乃至10の整数を表す。) - 前記(c)パーフルオロポリエーテルの含有量に対する前記(b)パーフルオロポリエーテルの含有量の比は0.5乃至4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。
- (e)溶媒をさらに含む、請求項1乃至請求項7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8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9に記載の硬化膜からなる、ハードコートフィルム。
- 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1乃至請求項8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する工程とを含む方法により形成されてなる、ハードコートフィルム。
- 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8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する工程とを含む方法により形成されてなる、ハードコートフィルム。
- 前記フィルム基材が複数の層から成る、請求項10乃至請求項12のうち何れか一項に記載のハードコートフィルム。
- 前記フィルム基材が樹脂製フィルムの表面に前記ハードコート層の下層を有する、請求項10乃至請求項13のうち何れか一項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10乃至請求項14のうち何れか一項に記載のハードコートフィルム。
- 請求項1乃至請求項8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する工程とを含む、該フィルム基材とハードコート層との積層体の製造方法。
- 前記フィルム基材が複数の層から成る、請求項16に記載の積層体の製造方法。
- 前記フィルム基材が樹脂製フィルムの表面に前記ハードコート層の下層を有する、請求項16又は請求項17に記載の積層体の製造方法。
- 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、下記式[1]、式[2]又は式[3]で表される基を有する、パーフルオロポリエーテル化合物。
- 前記パーフルオロポリエーテル化合物が、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それぞれに前記式[1]、式[2]又は式[3]で表される基を有する、請求項19又は請求項20に記載のパーフルオロポリエーテル化合物。
- 前記パーフルオロポリエーテル化合物が、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に前記式[1]、式[2]又は式[3]で表される基を有する、請求項19又は請求項20に記載のパーフルオロポリエーテル化合物。
- 前記パーフルオロポリエーテル化合物が活性エネルギー線重合性基を有さないものである、請求項19乃至請求項22のうち何れか一項に記載のパーフルオロポリエーテル化合物。
- 請求項19乃至請求項23のうち何れか一項に記載のパーフルオロポリエーテル化合物、及び下記式[4]又は式[5]で表される構造を有するポリ(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するパーフルオロポリエーテル化合物を含む、表面改質剤。
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WO2015060458A1 (ja) * | 2013-10-25 | 2015-04-30 | 日産化学工業株式会社 | ヒドロキシ基を有するパーフルオロポリエーテルを含む重合性組成物 |
WO2016163479A1 (ja) * | 2015-04-07 | 2016-10-13 | 日産化学工業株式会社 | 耐擦傷性コーティング用硬化性組成物 |
WO2018056370A1 (ja) * | 2016-09-21 | 2018-03-29 | 日産化学工業株式会社 | 耐擦傷性ハードコート材 |
WO2020213485A1 (ja) * | 2019-04-18 | 2020-10-22 | Dic株式会社 | 構造体、構造体の製造方法、熱交換機用部材及び熱交換器 |
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US3671497A (en) * | 1970-12-18 | 1972-06-20 | Nasa | Polyurethane resins from hydroxy terminated perfluoro ethers |
WO2003002628A1 (en) * | 2001-06-27 | 2003-01-09 | Daikin Industries, Ltd. | Surface-treating agent composition and process for producing the same |
JP2004331704A (ja) * | 2003-04-30 | 2004-11-25 | Shin Etsu Chem Co Ltd | プライマー組成物 |
JP2012241060A (ja) * | 2011-05-17 | 2012-12-10 | Yokohama Rubber Co Ltd:The | 硬化性樹脂組成物 |
WO2015060458A1 (ja) * | 2013-10-25 | 2015-04-30 | 日産化学工業株式会社 | ヒドロキシ基を有するパーフルオロポリエーテルを含む重合性組成物 |
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WO2018056370A1 (ja) * | 2016-09-21 | 2018-03-29 | 日産化学工業株式会社 | 耐擦傷性ハードコート材 |
WO2020213485A1 (ja) * | 2019-04-18 | 2020-10-22 | Dic株式会社 | 構造体、構造体の製造方法、熱交換機用部材及び熱交換器 |
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