WO2020162329A1 - 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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- WO2020162329A1 WO2020162329A1 PCT/JP2020/003506 JP2020003506W WO2020162329A1 WO 2020162329 A1 WO2020162329 A1 WO 2020162329A1 JP 2020003506 W JP2020003506 W JP 2020003506W WO 2020162329 A1 WO2020162329 A1 WO 2020162329A1
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- Prior art keywords
- hard coat
- meth
- acrylate
- group
- film
- Prior art date
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- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 48
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- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection 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
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 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
- 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
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 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
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 210000002374 sebum Anatomy 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
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000004724 ultra fast liquid chromatography Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
-
- 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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
-
- 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
- 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
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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 such as touch panel displays and liquid crystal displays. Specifically, it relates to a curable composition capable of forming a hard coat layer having excellent scratch resistance and stain resistance durability even when cured in the atmosphere.
- Resin molded products are often used in mobile information terminals such as mobile phones and tablet computers, notebook computers, home appliances, and automobile interior and exterior parts.
- a hard coat layer having scratch resistance is usually provided on the outermost surface as a role of surface protection.
- a high-density crosslinked structure is formed, that is, a crosslinked structure having low molecular mobility is formed to increase the surface hardness and to resist external force.
- the method of giving is adopted.
- these hard coat layer forming materials at present, polyfunctional acrylate materials which are three-dimensionally crosslinked by radicals are most used.
- a portable information terminal device typified by a mobile phone is operated by a person holding it by hand and touching it with a finger. Therefore, every time it is touched with a hand, a fingerprint is attached to the screen or the case, and the appearance thereof is impaired.
- Fingerprints contain moisture derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the housing surface in order to prevent any of these from adhering. It is rare. From such a viewpoint, it is desired that the housing surface of the portable information terminal device has antifouling property against fingerprints and the like. However, even if the initial antifouling property has reached a considerable level, its function is often deteriorated during use because it is touched by humans every day. Therefore, durability of antifouling property in the use process has been a problem.
- a method of imparting antifouling property to the surface of the hard coat layer a method of adding a small amount of a fluorine-based surface modifier to the coating liquid for forming the hard coat layer has been used.
- the added fluorine compound is segregated on the surface of the hard coat layer due to its low surface energy, and water repellency and oil repellency are imparted.
- the fluorine-based compound an oligomer having a number average molecular weight of about 1,000 to 5,000 called perfluoropolyether having a poly(oxyperfluoroalkylene) chain is used from the viewpoint of water repellency and oil repellency. ..
- the perfluoropolyether has a high fluorine concentration, it is usually difficult to dissolve in the organic solvent used for the coating liquid for forming the hard coat layer. Further, the perfluoropolyether causes aggregation in the formed hard coat layer.
- a method of adding an organic moiety to the perfluoropolyether is used. Further, in order to impart scratch resistance, a method of bonding an active energy ray-curable site represented by a (meth)acrylate group is used.
- a poly(oxyalkylene) group is added to both ends of a poly(oxyperfluoroalkylene) chain. Also disclosed is a technique using a compound having a (meth)acryloyl group via one urethane bond as a surface modifier (Patent Document 1).
- dipentaerythritol poly(meth)acrylate containing dipentaerythritol hexa(meth)acrylate in a specific ratio and a specific perfluoropolyether. It was found that a curable composition containing the composition can form a hard coat layer having excellent scratch resistance and antifouling durability, and completed the present invention.
- the first aspect of the present invention is as follows.
- the (a) dipentaerythritol poly(meth)acrylate is a hexa(meth)acrylate based on the total amount of penta(meth)acrylate and hexa(meth)acrylate calculated according to the following formula from the measurement result
- the hexa-body ratio which is the ratio of 50 mol% or more and 100 mol% or less, relates to the curable composition.
- Hexa ratio [mol%] (AH 1 +AH 2 ) ⁇ (AP 1 +AP 2 +AH 1 +AH 2 ) ⁇ 100
- AP 1 Peak area of extracted ion chromatogram of proton adduct of dipentaerythritol penta(meth)acrylate
- AP 2 Peak area of extracted ion chromatogram of ammonium adduct of dipentaerythritol penta(meth)acrylate
- AH 1 Di Peak area of extracted ion chromatogram of proton adduct of pentaerythritol hexa(meth)acrylate
- AH 2 Peak area of extracted ion chromatogram of ammonium adduct of dipentaerythritol hexa(meth)acrylate
- the above (b ) The perfluor
- the curable composition according to the second aspect wherein the (b) perfluoropolyether has at least three active energy ray-polymerizable groups via urethane bonds at both ends of its molecular chain.
- the poly(oxyperfluoroalkylene) group has both a repeating unit —[OCF 2 ]— and a repeating unit —[OCF 2 CF 2 ]—, and these repeating units are block-bonded or random-bonded.
- the curable composition according to any one of the first to third aspects which is a group formed by a block bond and a random bond.
- the curable composition according to the fourth aspect wherein the (b) perfluoropolyether has a partial structure represented by the following formula [1].
- n is the total number of repeating units -[OCF 2 CF 2 ]- and repeating units -[OCF 2 ]-, and represents an integer of 5 to 30.
- the unit -[OCF 2 CF 2 ]- and the repeating unit -[OCF 2 ]- are bonded by a block bond, a random bond, or a block bond and a random bond.
- a sixth aspect relates to the curable composition according to any one of the first to fifth aspects, which further contains (d) a solvent.
- a seventh aspect relates to a cured film made of a cured product of the curable composition according to any one of the first to sixth aspects.
- An eighth aspect relates to a hard coat film having a hard coat layer on at least one surface of a film substrate, the hard coat layer comprising the cured film according to the seventh aspect.
- a ninth aspect is a hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer has the curability according to any one of the first to sixth aspects.
- the present invention relates to a hard coat film formed by a method including a step of applying a composition on a film substrate to form a coating film, and a step of irradiating the coating film with an active energy ray to cure the coating film.
- a tenth aspect relates to the hard coat film according to the eighth aspect or the ninth aspect, wherein the hard coat layer has a layer thickness of 1 ⁇ m to 10 ⁇ m.
- An eleventh aspect is a method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, the curable composition according to any one of the first to sixth aspects.
- the present invention relates to a method for producing a hard coat film, which comprises a step of applying a film on a film substrate to form a coating film, and a step of irradiating the coating film with an active energy ray in the atmosphere to cure the film.
- a twelfth aspect relates to the manufacturing method according to the eleventh aspect, wherein the hard coat layer has a layer thickness of 1 ⁇ m to 10 ⁇ m.
- a curable composition useful for forming a composition can be provided. Further, according to the present invention, it is possible to provide a hard coat film having a hard coat layer formed of a cured product of the curable composition or a hard coat layer formed thereof, which is provided on the surface thereof, and has scratch resistance and appearance. It is possible to provide a hard coat film having excellent antifouling durability.
- the curable composition of the present invention specifically comprises (A) 100 parts by mass of dipentaerythritol poly(meth)acrylate, (B) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via urethane bonds (however, (Excluding perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.) 0.05 to 10 parts by mass, and (c) active energy ray
- the present invention relates to a curable composition containing 1 to 20 parts by mass of a polymerization initiator that generates radicals.
- each of the components (a) to (c) will be described first.
- dipentaerythritol Poly(meth)acrylate examples include dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, Mixtures of one or more compounds selected from the group consisting of dipentaerythritol di(meth)acrylate and dipentaerythritol mono(meth)acrylate, preferably dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth) ) A mixture of acrylate and dipentaerythritol tetra(meth)acrylate, more preferably a mixture of dipentaerythritol hexa(meth)acrylate, more preferably a mixture of dipentaerythritol he
- the dipentaerythritol poly(meth)acrylate of the present invention is the dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate contained in the dipentaerythritol poly(meth)acrylate.
- the ratio of (meth)acrylate (hereinafter, also simply referred to as “hexa-body ratio”) is 50 mol% or more and 100 mol% or less.
- the dipentaerythritol poly(meth)acrylate of the present invention contains dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate in a total amount of 50 mol based on the total amount of dipentaerythritol poly(meth)acrylate. % Or more, preferably 55 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more.
- the curable composition is cured in the atmosphere.
- the obtained cured film has sufficient scratch resistance.
- LC-MS liquid chromatography mass spectrometry
- Hexa ratio [mol%] (AH 1 +AH 2 ) ⁇ (AP 1 +AP 2 +AH 1 +AH 2 ) ⁇ 100
- the method for producing the dipentaerythritol poly(meth)acrylate is not particularly limited, and examples thereof include a method for producing an esterification reaction of dipentaerythritol and (meth)acrylic acid.
- a high molecular weight component such as an addition reaction between dipentaerythritol poly(meth)acrylates may be produced as a by-product other than dipentaerythritol poly(meth)acrylate.
- the curable composition of the present invention may contain the high molecular weight component, but it is preferable to use a composition obtained by purifying and removing the high molecular weight component.
- (B) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has active energy ray-polymerizable groups at both ends of its molecular chain via urethane bonds (provided that , Except for perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.)]
- the component (b) is a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, and a urethane bond is introduced at both ends of the molecular chain thereof without interposing the poly(oxyalkylene) group.
- a perfluoropolyether having an active energy ray-polymerizable group (hereinafter, also simply referred to as “(b) perfluoropolyether having a polymerizable group at both ends of a molecular chain”) is used.
- the component (b) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied. Further, the component (b) has excellent compatibility with the component (a), thereby suppressing the clouding of the hard coat layer and enabling the formation of a hard coat layer having a transparent appearance.
- the above poly(oxyalkylene) group means a group in which the number of repeating units of the oxyalkylene group is 2 or more and the alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
- the number of carbon atoms of the alkylene group in the above poly(oxyperfluoroalkylene) group is not particularly limited, but it is preferably 1 to 4 carbon atoms. That is, the poly(oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are alternately linked, and the oxyperfluoroalkylene group is a carbon atom. It refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked.
- examples thereof include groups such as -1,3-diyl group) and -[OCF 2 C(CF 3 )F]-(oxyperfluoropropane-1,2-diyl group).
- the above oxyperfluoroalkylene groups may be used alone or in combination of two or more, and in that case, the bonds of plural kinds of oxyperfluoroalkylene groups are a block bond and a random bond. Either of them may be used.
- poly(oxyperfluoroalkylene) groups -[OCF 2 ]-(oxyperfluoromethylene group) and -[OCF 2 CF 2 ] are used. It is preferable to use a group having both —(oxyperfluoroethylene group) as a repeating unit.
- repeating units: -[OCF 2 ]- and -[OCF 2 CF 2 ]- are in a molar ratio of [repeating unit: -[OCF 2 ]-]:
- [repeat Unit: —[OCF 2 CF 2 ]—] is preferably a group containing at a ratio of 2:1 to 1:2, and more preferably a group containing at a ratio of about 1:1.
- the bond of these repeating units may be either a block bond or a random bond.
- the total number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, and more preferably in the range of 7 to 21.
- the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the above poly(oxyperfluoroalkylene) group in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 3, It is 000.
- the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) is not limited to one having one active energy ray-polymerizable group such as a (meth)acryloyl group at both ends of the molecular chain. It may have one or more active energy ray-polymerizable groups at both ends of the molecular chain.
- the terminal structure containing the active energy ray-polymerizable groups the following formulas [A1] to [A A5] and the structures in which the acryloyl group in these structures is substituted with a methacryloyl group.
- Examples of such a perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) include compounds represented by the following formula [2].
- A represents one of the structures represented by the formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is substituted with a methacryloyl group
- PFPE represents Represents a poly(oxyperfluoroalkylene) group (provided that the side directly bonded to L 1 is an oxy terminal and the side bonded to an oxygen atom is a perfluoroalkylene terminal), and L 1 is 1 to 3 fluorine atoms.
- alkylene group of the fluorine atom 1 to carbon atoms substituted with three 2 or 3, -CH 2 CHF -, - CH 2 CF 2 -, - CHFCF 2 -, - CH 2 CH 2 CHF-, Examples thereof include —CH 2 CH 2 CF 2 — and —CH 2 CHFCF 2 —, and —CH 2 CF 2 — is preferable.
- Examples of the partial structure (A-NHC( ⁇ O)O) m L 2 — in the compound represented by the above formula [2] include structures represented by the following formulas [B1] to [B12].
- A represents one of the structures represented by the above formulas [A1] to [A5] and the structure in which the acryloyl group in these structures is substituted with a methacryloyl group.
- the structure represented by the formula [B3] is preferable, and the combination of the formula [B3] and the formula [A3] is particularly preferable.
- n represents the total number of repeating units -[OCF 2 CF 2 ]- and the number of repeating units -[OCF 2 ]-, and is preferably an integer in the range of 5 to 30, An integer in the range of 7 to 21 is more preferable.
- the ratio of the number of repeating units —[OCF 2 CF 2 ]— to the number of repeating units —[OCF 2 ]— is preferably in the range of 2:1 to 1:2, and is approximately 1 It is more preferable that the ratio is in the range of 1:1.
- the bond of these repeating units may be either a block bond or a random bond.
- the perfluoropolyether having a polymerizable group at both ends of the molecular chain is 0.05 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned (a) dipentaerythritol poly(meth)acrylate. It is used in an amount of 0.1 part by mass, preferably 0.1 part by mass to 5 parts by mass. (B) By using perfluoropolyether having a polymerizable group at both ends of the molecular chain in a proportion of 0.05 parts by mass or more, the hard coat layer has sufficient antifouling properties (water repellency and oil repellency). Have.
- the perfluoropolyether having a polymerizable group at both ends of the molecular chain at a ratio of 10 parts by mass or less it is sufficiently compatible with (a) dipentaerythritol poly(meth)acrylate. , A hard coat layer with less white turbidity can be obtained.
- the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) is, for example, a compound represented by the following formula [3].
- PFPE, L 1 , L 2 and m have the same meanings as those in the formula [2].
- a polymerizable group for the hydroxy group present at both terminals of the compound represented by the formula [2].
- An isocyanate compound having, that is, a compound in which an isocyanato group is bonded to a bond in a structure represented by the above formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is replaced with a methacryloyl group for example, It can be obtained by reacting 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc.) to form a urethane bond.
- the curable composition of the present invention comprises (b) a poly(oxyperfluoroalkylene) group-containing perfluoropolyether, which has active energy ray polymerization at both ends of its molecular chain via urethane bonds.
- a perfluoropolyether having a polymerizable group provided that the poly(oxyperfluoroalkylene) group and the urethane bond do not have a poly(oxyalkylene) group.
- a perfluoropolyether having a hydroxy group at the end thereof (provided that the poly(oxyperfluoroalkylene) group is between the urethane bond and the poly(oxyperfluoroalkylene) group is between the hydroxy group.
- Perfluoropolyether having a hydroxy group (provided that a poly(oxyperfluoroalkylene) group is not present between the poly(oxyperfluoroalkylene) group and the hydroxy group.) [Has an active energy ray-polymerizable group Compound not included] may be included.
- the perfluoropolyether compound of the curable composition of the present invention has excellent compatibility with the component (a), thereby suppressing clouding of the hard coat layer to give a transparent appearance.
- the excellent effect of enabling formation of the hard coat layer to be exhibited is exhibited.
- a polymerization initiator that generates a radical by a preferable active energy ray is, for example, an active energy such as an electron beam, an ultraviolet ray, or an X-ray. It is a polymerization initiator that generates radicals by irradiation of rays, especially by irradiation of ultraviolet rays.
- polymerization initiator (c) examples include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenone. And biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. You may use these individually by 1 type or in mixture of 2 or more types.
- alkylphenones as the (c) polymerization initiator from the viewpoint of transparency, surface curability, and thin film curability.
- a cured film having further improved scratch resistance can be obtained.
- alkylphenones examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl) ⁇ -hydroxy such as 2-methylpropan-1-one and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one
- Alkylphenones 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one And ⁇ -aminoalkylphenones; 2,2-dimethoxy-1,2-diphenylethan-1-one; methyl phenylglyoxylate and the like.
- the (c) polymerization initiator is used in an amount of 1 part by mass to 20 parts by mass, preferably 2 parts by mass to 10 parts by mass, relative to 100 parts by mass of the above-mentioned (a) pentaerythritol poly(meth)acrylate. use.
- the curable composition of the present invention may further contain (d) a solvent, that is, in the form of a varnish (film forming material).
- a solvent that is, in the form of a varnish (film forming material).
- the above solvent is appropriately dissolved in the above components (a) to (c) in consideration of workability at the time of coating for forming a cured film (hard coat layer) described later and drying property before and after curing.
- aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetralin
- aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits and cyclohexane
- methyl chloride Methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene, and other halides
- Esters or ester ethers such as ethyl cellosolve acetate and propylene glycol monomethyl ether acetate; diethyl ether, tetrahydrofuran, 1,4-
- the amount of the solvent (d) is not particularly limited, it is used at a concentration such that the solid content concentration in the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass.
- the solid content concentration also referred to as non-volatile content concentration
- the solid content concentration means the solid content with respect to the total mass (total mass) of the components (a) to (d) (and optionally other additives) of the curable composition of the present invention. Indicates the content of the component (all components excluding the solvent component).
- additives generally added as necessary, for example, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant.
- a polymerization inhibitor for example, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant.
- the curable composition of the present invention can form a cured film by applying (coating) on a substrate to form a coating film, and irradiating the coating film with an active energy ray to polymerize (curing).
- the cured film is also an object of the present invention.
- the hard coat layer in the hard coat film described later can be made of the cured film.
- the base material in this case examples include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, Polyimide, epoxy resin, melamine resin, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass, slate, etc. Can be mentioned.
- the shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
- the coating method on the substrate is a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an inkjet method, a printing method (a relief printing method).
- An intaglio printing method, a lithographic printing method, a screen printing method, etc. can be appropriately selected, and among them, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating properties, a relief printing method can be used.
- the curable composition is filtered in advance using a filter having a pore size of about 0.2 ⁇ m and then applied to the coating.
- a solvent may be added to the curable composition, if necessary, to form a varnish.
- the various solvents described in the above [(d) solvent] can be mentioned.
- the coating film is preliminarily dried by a heating means such as a hot plate or an oven to remove the solvent, if necessary (solvent removing step).
- the conditions for heat drying at this time are preferably, for example, 40° C. to 120° C. and about 30 seconds to 10 minutes.
- the coating film is cured by irradiating 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.
- a light source used for ultraviolet ray irradiation sun rays, chemical lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs and the like can be used.
- Irradiation with active energy rays may be performed in the atmosphere or in an atmosphere of an inert gas such as nitrogen. Since the curable composition of the present invention has a sufficient effect even when cured in the atmosphere, irradiation in the atmosphere is sufficient from the viewpoint of labor and cost.
- post-baking may be performed, specifically, heating using a hot plate, an oven or the like to complete the polymerization.
- the thickness of the formed cured film is usually 0.01 ⁇ m to 50 ⁇ m, preferably 0.05 ⁇ m to 20 ⁇ m after drying and curing.
- a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced.
- the hard coat film is also an object of the present invention, and the hard coat film is preferably 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 comprises a step of applying the curable composition of the present invention onto a film substrate to form a coating film, and irradiating the coating film with active energy rays such as ultraviolet rays. It can be formed by a method including a step of curing the coating film.
- polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polycarbonate, polymethacrylate, polystyrene, polyolefin, Examples thereof include films of polyamide, polyimide, triacetyl cellulose and the like.
- the method described in the above ⁇ cured film> should be used.
- the curable composition of the present invention contains a solvent (in the form of varnish)
- a step of drying the coating film and removing the solvent may be included after the coating film forming step, if necessary.
- the coating film drying method (solvent removing step) described in the above ⁇ cured film> can be used.
- the thickness of the hard coat layer thus obtained is preferably 1 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m.
- a curable composition capable of forming a cured film having scratch resistance and stain resistance (water repellency and oil repellency) on its surface.
- the curable composition of the present invention is suitably used as a material for a scratch-resistant hard coat layer on the surface of various displays such as liquid crystal displays (LCD), plasma displays (PDP), organic EL displays (OLED), and touch panels.
- LCD liquid crystal displays
- PDP plasma displays
- OLED organic EL displays
- CV-110QC-G Lamp Heraeus High Pressure Mercury Lamp H-bulb Nitrogen purge box: Heraeus KK (4) LC-MS [LC] Device: Ultra high-performance liquid chromatograph Prominence (registered trademark) UFLC XR series column manufactured by Shimadzu Corporation Column: XBridge BEH C 18 (2.1 mm ⁇ 75 mm, 2.5 ⁇ m) manufactured by Nippon Waters Co., Ltd.
- PFPE1 Perfluoropolyether having two hydroxy groups at both ends of the molecular chain without interposing a poly(oxyalkylene) group
- PFPE2 Perfluoropolyether having a hydroxy group through poly(oxyalkylene) groups (repeating unit number 8 or 9) at both ends of the molecular chain
- BEI 1,1-bis(acryloyloxymethyl)ethyl isocyanate
- DOTDD Dioctyltin dineodecanoate
- Neostan registered trademark
- U-830 manufactured by Nitto Kasei Co., Ltd.
- SM3 Perfluoropolyether having a (meth)acryloy
- SM4 Perfluoropolyether having a (meth)acryloyl group at one end of the molecular chain
- DAC-HP Fingerprint adhesion inhibitor Optool (registered trademark) DAC-HP, manufactured by Daikin Industries, Ltd., non-volatile content 20 mass% solution
- DPHA80 Dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [Shin-Nakamura Chemical Co., Ltd.
- DPHA66 Dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [Aronix (registered trademark) M-406 manufactured by Toagosei Co., Ltd., penta-body 25-35% (catalog value), hexa-body ratio 66 mol% (LC-MS) )]
- DPHA51 Mixture of dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate [Aronix (registered trademark) M-404 manufactured by Toagosei Co., Ltd., 30-40% penta form (catalog value), 51 mol% hexa form (LC-MS) )]
- DPHA47 Dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [KA
- hexa-form ratio in the used dipentaerythritol penta/hexaacrylate was calculated by the following formula from the measurement result of LC-MS, and the average value of four measurements was used.
- Hexa ratio [mol%] (AH 1 +AH 2 ) ⁇ (AP 1 +AP 2 +AH 1 +AH 2 ) ⁇ 100
- Peak area AH 1 : XIC peak area of proton adduct of dipentaerythritol hexaacrylate (m/z 579.207)
- Examples 1 to 3, Comparative Examples 1 to 5 The following components were mixed according to the description in Table 1 to prepare a curable composition having the solid content concentration shown in Table 1.
- the solid content refers to components other than the solvent.
- “parts” means “parts by mass”.
- Polyfunctional monomer 100 parts by mass of polyfunctional monomer described in Table 1
- Surface modifier Amount of surface modifier described in Table 1 (converted to solid content).
- Polymerization initiator O2959 2.5 parts by mass
- Solvent PGME in the amount described in Table 1
- This curable composition was applied onto an A4 size double-sided easy-adhesion-treated PET film [Lumirror (registered trademark) U403 manufactured by Toray Industries, Inc., thickness 100 ⁇ m] with a bar coater to obtain a coating film.
- the coating film was dried in an oven at 120° C. for 3 minutes to remove the solvent.
- a hard coat film having a hard coat layer (cured film) having a layer (film) thickness of about 5 ⁇ m is obtained by irradiating the obtained film with UV light having an exposure dose of 1,300 mJ/cm 2 in the atmosphere. Was produced.
- the layer (film) thickness of about 5 ⁇ m A hard coat film having the hard coat layer (cured film) was prepared.
- dipentaerythritol polyacrylate a curable composition of Examples 1 to 3 in which a dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture having a hexa body ratio of 50 mol% or more was blended.
- the hard coat film produced by using has excellent scratch resistance even when the curable composition is cured in the atmosphere.
- dipentaerythritol polyacrylate it was prepared using the curable compositions of Comparative Example 1 and Comparative Example 2 in which a dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture having a hexa body ratio of less than 50 mol% was blended.
- the hard coat film did not have excellent scratch resistance when the curable composition was cured in the atmosphere.
- dipentaerythritol polyacrylate a mixture of dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate having a hexa body ratio of 50 mol% or more, a poly(oxyalkylene) group and one urethane bond were prepared.
- the hard coat films produced using the curable compositions of Comparative Examples 3 to 5 did not have excellent scratch resistance when the curable compositions were cured in the atmosphere.
- the hard coat films produced by using the curable compositions of Examples 1 to 3 have excellent antifouling durability.
- the hexa-body ratio (dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate relative to the total amount of dipentaerythritol hexa(meth)acrylate
- the ratio of (meth)acrylate) is 50 mol% or more and dipentaerythritol poly(meth)acrylate and a specific perfluoropolyether are combined into a curable composition for the first time when cured in the atmosphere. Even if there is, a hard coat film having excellent scratch resistance can be obtained.
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Abstract
Description
このような観点から、携帯情報端末機器の筐体表面には、指紋などに対する防汚性を有していることが望まれている。しかし、初期の防汚性はかなりのレベルに達しているとしても、人が毎日手で触れるため、使用中にその機能が低下する場合が多い。そのため、使用過程での防汚性の耐久性が課題であった。
このようなパーフルオロポリエーテルに、有機溶媒に対する溶解性及びハードコート層における分散性を付与するために、パーフルオロポリエーテルに有機部位を付加する手法が用いられている。更に、耐擦傷性を付与するために、(メタ)アクリレート基に代表される活性エネルギー線硬化性部位を結合させる手法が用いられている。
これまで、耐擦傷性を有した防汚性ハードコート層として、ハードコート層表面に防汚性を付与する成分として、ポリ(オキシパーフルオロアルキレン)鎖の両末端に、ポリ(オキシアルキレン)基及び1つのウレタン結合を介して(メタ)アクリロイル基を有する化合物を、表面改質剤として用いた技術が開示されている(特許文献1)。
一方、大気下で光硬化させたハードコート層は、窒素雰囲気下で該組成物を硬化させたハードコート層に比べて、十分な耐擦傷性が得られず、また防汚性の耐久性が劣る場合があるという課題もあった。
(a)ジペンタエリスリトールポリ(メタ)アクリレート100質量部、
(b)ポリ(オキシパーフルオロアルキレン)基を含むパーフルオロポリエーテルであって、その分子鎖の両末端に、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パーフルオロポリエーテル(但し、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にポリ(オキシアルキレン)基を有するパーフルオロポリエーテルを除く。)0.05質量部~10質量部、及び
(c)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~20質量部
を含み、
前記(a)ジペンタエリスリトールポリ(メタ)アクリレートは、液体クロマトグラフィー質量分析法の測定結果から下記式に従い算出された、ペンタ(メタ)アクリレートとヘキサ(メタ)アクリレートの総量に対するヘキサ(メタ)アクリレートの割合であるヘキサ体比率が50mol%以上100mol%以下である、硬化性組成物に関する。
ヘキサ体比率[mol%]=(AH1+AH2)÷(AP1+AP2+AH1+AH2)×100
AP1:ジペンタエリスリトールペンタ(メタ)アクリレートのプロトン付加体の抽出イオンクロマトグラムのピーク面積
AP2:ジペンタエリスリトールペンタ(メタ)アクリレートのアンモニウム付加体の抽出イオンクロマトグラムのピーク面積
AH1:ジペンタエリスリトールヘキサ(メタ)アクリレートのプロトン付加体の抽出イオンクロマトグラムのピーク面積
AH2:ジペンタエリスリトールヘキサ(メタ)アクリレートのアンモニウム付加体の抽出イオンクロマトグラムのピーク面積
第2観点として、前記(b)パーフルオロポリエーテルは、その分子鎖の両末端それぞれにおいてウレタン結合を介して活性エネルギー線重合性基を少なくとも2つ有する、第1観点に記載の硬化性組成物に関する。
第3観点として、前記(b)パーフルオロポリエーテルは、その分子鎖の両末端それぞれにおいてウレタン結合を介して活性エネルギー線重合性基を少なくとも3つ有する、第2観点に記載の硬化性組成物に関する。
第4観点として、前記ポリ(オキシパーフルオロアルキレン)基が、繰り返し単位-[OCF2]-及び繰り返し単位-[OCF2CF2]-の双方を有し、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、第1観点乃至第3観点のうち何れか一つに記載の硬化性組成物に関する。
第5観点として、前記(b)パーフルオロポリエーテルが下記式[1]で表される部分構造を有する、第4観点に記載の硬化性組成物に関する。
第6観点として、さらに(d)溶媒を含む、第1観点乃至第5観点のうち何れか一つに記載の硬化性組成物に関する。
第7観点として、第1観点乃至第6観点のうち何れか一つに記載の硬化性組成物の硬化物からなる硬化膜に関する。
第8観点として、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第7観点に記載の硬化膜からなる、ハードコートフィルムに関する。
第9観点として、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、第1観点乃至第6観点のうち何れか一つ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に関する。
第10観点として、前記ハードコート層が1μm~10μmの層厚を有する、第8観点又は第9観点に記載のハードコートフィルムに関する。
第11観点として、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の製造方法であって、第1観点乃至第6観点のうち何れか一つ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、該塗膜に大気下で活性エネルギー線を照射し硬化する工程とを含む、ハードコートフィルムの製造方法に関する。
第12観点として、前記ハードコート層が1μm~10μmの層厚を有する、第11観点に記載の製造方法に関する。
また、本発明によれば、前記硬化性組成物の硬化物からなる硬化膜又はそれより形成されるハードコート層が表面に付与されたハードコートフィルムを提供することができ、耐擦傷性及び外観に優れ且つ防汚耐久性を有するハードコートフィルムを提供することができる。
本発明の硬化性組成物は、詳細には、
(a)ジペンタエリスリトールポリ(メタ)アクリレート100質量部、
(b)ポリ(オキシパーフルオロアルキレン)基を含むパーフルオロポリエーテルであって、その分子鎖の両末端に、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パーフルオロポリエーテル(但し、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にポリ(オキシアルキレン)基を有するパーフルオロポリエーテルを除く。)0.05質量部~10質量部、及び
(c)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~20質量部
を含む、硬化性組成物に関する。
以下、まず上記(a)~(c)の各成分について説明する。
(a)ジペンタエリスリトールポリ(メタ)アクリレートとしては、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールジ(メタ)アクリレート及びジペンタエリスリトールモノ(メタ)アクリレートからなる群から選択される1種以上の化合物の混合物、好ましくは、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート及びジペンタエリスリトールテトラ(メタ)アクリレートの混合物、より好ましくはジペンタエリスリトールヘキサ(メタ)アクリレート及びジペンタエリスリトールペンタ(メタ)アクリレートの混合物又はジペンタエリスリトールヘキサ(メタ)アクリレートが挙げられる。
なお、本発明において(メタ)アクリレート化合物とは、アクリレート化合物とメタクリレート化合物の両方をいう。また(メタ)アクリル酸は、アクリル酸とメタクリル酸の両方をいう。
ジペンタエリスリトールヘキサ(メタ)アクリレートの割合を50mol%以上とすることで、硬化性組成物を大気下で硬化させて形成される硬化膜が十分な耐擦傷性を有するものとなる。
ヘキサ体比率[mol%]=(AH1+AH2)÷(AP1+AP2+AH1+AH2)×100
AP1:ジペンタエリスリトールペンタアクリレートのプロトン付加体(m/z=525.197)の抽出イオンクロマトグラム(以下、「XIC」と称する)のピーク面積
AP2:ジペンタエリスリトールペンタアクリレートのアンモニウム付加体(m/z=542.223)のXICのピーク面積
AH1:ジペンタエリスリトールヘキサアクリレートのプロトン付加体(m/z=579.207)のXICのピーク面積
AH2:ジペンタエリスリトールヘキサアクリレートのアンモニウム付加体(m/z=596.234)のXICのピーク面積
本発明では、(b)成分として、ポリ(オキシパーフルオロアルキレン)基を含むパーフルオロポリエーテルであって、その分子鎖の両末端に、ポリ(オキシアルキレン)基を介さず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パーフルオロポリエーテル(以下、単に「(b)分子鎖の両末端に重合性基を有するパーフルオロポリエーテル」とも称する)を使用する。(b)成分は、本発明の硬化性組成物を適用するハードコート層における表面改質剤としての役割を果たす。
また、(b)成分は、(a)成分との相溶性に優れ、それにより、ハードコート層が白濁するのを抑制して、透明な外観を呈するハードコート層の形成を可能とする。
尚、上記のポリ(オキシアルキレン)基とは、オキシアルキレン基の繰り返し単位数が2以上であり且つオキシアルキレン基におけるアルキレン基は無置換のアルキレン基である基を意図する。
上記オキシパーフルオロアルキレン基は、一種を単独で使用してもよく、或いは二種以上を組み合わせて使用してもよく、その場合、複数種のオキシパーフルオロアルキレン基の結合はブロック結合及びランダム結合の何れであってもよい。
中でも上記ポリ(オキシパーフルオロアルキレン)基として、繰り返し単位:-[OCF2]-と-[OCF2CF2]-とが、モル比率で[繰り返し単位:-[OCF2]-]:[繰り返し単位:-[OCF2CF2]-]=2:1~1:2となる割合で含む基であることが好ましく、およそ1:1となる割合で含む基であることがより好ましい。これら繰り返し単位の結合は、ブロック結合及びランダム結合の何れであってもよい。
上記オキシパーフルオロアルキレン基の繰り返し単位数は、その繰り返し単位数の総計として5~30の範囲であることが好ましく、7~21の範囲であることがより好ましい。
また、上記ポリ(オキシパーフルオロアルキレン)基のゲル浸透クロマトグラフィー(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、1,000~5,000、好ましくは1,500~3,000である。
上記式[B1]~式[B12]で表される構造の中で、式[B1]及び式[B2]がm=1の場合に相当し、式[B3]~式[B6]がm=2の場合に相当し、式[B7]~式[B9]がm=3の場合に相当し、式[B10]~式[B12]がm=5の場合に相当する。
これらの中でも、式[B3]で表される構造が好ましく、特に式[B3]と式[A3]の組合せが好ましい。
上記式[1]中のnは、繰り返し単位-[OCF2CF2]-の数と、繰り返し単位-[OCF2]-の数との総数を表し、5~30の範囲の整数が好ましく、7~21の範囲の整数がより好ましい。また、前記繰り返し単位-[OCF2CF2]-の数と、前記繰り返し単位-[OCF2]-の数との比率は、2:1~1:2の範囲であることが好ましく、およそ1:1の範囲とすることがより好ましい。これら繰り返し単位の結合は、ブロック結合及びランダム結合の何れであってもよい。
(b)分子鎖の両末端に重合性基を有するパーフルオロポリエーテルを0.05質量部以上の割合で使用することで、ハードコート層が十分な防汚性(撥水性及び撥油性)を有する。また、(b)分子鎖の両末端に重合性基を有するパーフルオロポリエーテルを10質量部以下の割合で使用することで、(a)ジペンタエリスリトールポリ(メタ)アクリレートと十分に相溶し、より白濁の少ないハードコート層が得られる。
本発明の硬化性組成物において好ましい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(以下、単に「(c)重合開始剤」とも称する)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。
上記(c)重合開始剤としては、例えばベンゾイン類、アルキルフェノン類、チオキサントン類、アゾ類、アジド類、ジアゾ類、o-キノンジアジド類、アシルホスフィンオキシド類、オキシムエステル類、有機過酸化物、ベンゾフェノン類、ビスクマリン類、ビスイミダゾール類、チタノセン類、チオール類、ハロゲン化炭化水素類、トリクロロメチルトリアジン類、及びヨードニウム塩、スルホニウム塩などのオニウム塩類等が挙げられる。これらは一種単独で或いは二種以上を混合して用いてもよい。
中でも本発明では、透明性、表面硬化性、薄膜硬化性の観点から(c)重合開始剤として、アルキルフェノン類を使用することが好ましい。アルキルフェノン類を使用することにより、耐擦傷性がより向上した硬化膜を得ることができる。
本発明の硬化性組成物は、更に(d)溶媒を含んでいてもよく、すなわちワニス(膜形成材料)の形態としてもよい。
上記溶媒としては、前記(a)成分~(c)成分を溶解し、また後述する硬化膜(ハードコート層)形成にかかる塗工時の作業性や硬化前後の乾燥性等を考慮して適宜選択すればよく、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン、テトラリン等の芳香族炭化水素類;n-ヘキサン、n-ヘプタン、ミネラルスピリット、シクロヘキサン等の脂肪族又は脂環式炭化水素類;塩化メチル、臭化メチル、ヨウ化メチル、ジクロロメタン、クロロホルム、四塩化炭素、トリクロロエチレン、パークロロエチレン、o-ジクロロベンゼン等のハロゲン化物類;酢酸エチル、酢酸プロピル、酢酸ブチル、メトキシブチルアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル類又はエステルエーテル類;ジエチルエーテル、テトラヒドロフラン、1,4-ジオキサン、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ-n-プロピルエーテル、プロピレングリコールモノイソプロピルエーテル、プロピレングリコールモノ-n-ブチルエーテル等のエーテル類;アセトン、メチルエチルケトン、メチルイソブチルケトン、ジ-n-ブチルケトン、シクロヘキサノン等のケトン類;メタノール、エタノール、n-プロパノール、イソプロピルアルコール、n-ブタノール、イソブチルアルコール、tert-ブチルアルコール、2-エチルヘキシルアルコール、ベンジルアルコール、エチレングリコール等のアルコール類;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン等のアミド類;ジメチルスルホキシド等のスルホキシド類、並びにこれらの溶媒のうち2種以上を混合した溶媒が挙げられる。
(d)溶媒の使用量は特に限定されないが、例えば本発明の硬化性組成物における固形分濃度が1質量%~70質量%、好ましくは5質量%~50質量%となる濃度で使用する。ここで固形分濃度(不揮発分濃度とも称する)とは、本発明の硬化性組成物の前記(a)成分~(d)成分(及び所望によりその他添加剤)の総質量(合計質量)に対する固形分(全成分から溶媒成分を除いたもの)の含有量を表す。
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、酸化防止剤、貯蔵安定剤、帯電防止剤、無機充填剤、顔料、染料等を適宜配合してよい。
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、硬化膜を形成できる。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を該硬化膜からなるものとすることができる。
この場合の前記基材としては、例えば、各種樹脂(ポリカーボネート、ポリメタクリレート、ポリスチレン、ポリエチレンテレフタレート(PET)やポリエチレンナフタレート(PEN)等のポリエステル、ポリウレタン、熱可塑性ポリウレタン(TPU)、ポリオレフィン、ポリアミド、ポリイミド、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース、アクリロニトリル-ブタジエン-スチレン共重合体(ABS)、アクリロニトリル-スチレン共重合体(AS)、ノルボルネン系樹脂等)、金属、木材、紙、ガラス、スレート等を挙げることができる。これら基材の形状は板状、フィルム状又は3次元成形体でもよい。
基材上に硬化性組成物を塗布し塗膜を形成した後、必要に応じてホットプレート、オーブン等の加熱手段で塗膜を予備乾燥して溶媒を除去する(溶媒除去工程)。この際の加熱乾燥の条件としては、例えば、40℃~120℃で、30秒~10分程度とすることが好ましい。
活性エネルギー線の照射は、大気下であっても、窒素等の不活性ガス雰囲気下であっても構わない。本発明の硬化性組成物は、大気下で硬化させた場合であっても十分な効果が得られるため、手間やコストの観点から、大気下で照射すれば十分である。
さらにその後、ポストベークを行うことにより、具体的にはホットプレート、オーブンなどを用いて加熱することにより重合を完結させてもよい。
なお、形成される硬化膜の厚さは、乾燥、硬化後において、通常0.01μm~50μm、好ましくは0.05μm~20μmである。
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や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。
また前記フィルム基材上への硬化性組成物の塗布方法(塗膜形成工程)及び塗膜への活性エネルギー線照射方法(硬化工程)は、前述の<硬化膜>に挙げた方法を用いることができる。また本発明の硬化性組成物に溶媒が含まれる(ワニス形態の)場合、塗膜形成工程の後、必要に応じて該塗膜を乾燥し溶媒除去する工程を含むことができる。その場合、前述の<硬化膜>に挙げた塗膜の乾燥方法(溶媒除去工程)を用いることができる。
こうして得られたハードコート層の層厚は、好ましくは1μm~20μm、より好ましくは1μm~10μmである。
なお、実施例において、試料の調製及び物性の分析に用いた装置及び条件は、以下の通りである。
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-22、最大ウエット膜厚22μm(ワイヤーバー#9相当)
塗布速度:4m/分
(2)オーブン
装置:アドバンテック東洋(株)製 無塵乾燥器 DRC433FA
(3)UV硬化
装置:ヘレウス(株)製 CV-110QC-G
ランプ:ヘレウス(株)製 高圧水銀ランプH-bulb
窒素パージボックス:ヘレウス(株)製
(4)LC-MS
[LC]
装置:(株)島津製作所製 超高速液体クロマトグラフ Prominence(登録商標)UFLC XRシリーズ
カラム:日本ウォーターズ(株)製 XBridge BEH C18(2.1mm×75mm、2.5μm)
カラム温度:40℃
検出器:UV(210nm)
移動相A:0.1質量%ギ酸超純水溶液
移動相B:0.1質量%ギ酸アセトニトリル溶液
流速:0.3mL/分
グラジエント: 0分[移動相A:移動相B=98:2(体積比)]
12分[移動相A:移動相B=2:98(体積比)]
15分[移動相A:移動相B=2:98(体積比)]
試料濃度:0.5mg/mL(アセトニトリル溶液)
注入量:1μL
[MS]
装置:(株)エービー・サイエックス製 TripleTOF 5600+
イオン化:ESI
モード:Positive
スキャンレンジ:m/z=50~1,000
(5)ゲル浸透クロマトグラフィー(GPC)
装置:東ソー(株)製 HLC-8220GPC
カラム:昭和電工(株)製 Shodex(登録商標)GPC K-804L、GPC K-805L
カラム温度:40℃
溶離液:テトラヒドロフラン
検出器:RI
(6)耐擦傷性試験
装置:新東科学(株)製 往復摩耗試験機 TRIBOGEAR TYPE:30S
走査速度:5,000mm/分
走査距離:50mm
(7)接触角測定
装置:協和界面科学(株)製 DropMaster DM-501
測定温度:23℃
PFPE1: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]
PFPE2:分子鎖の両末端にポリ(オキシアルキレン)基(繰返し単位数8又は9)を介してヒドロキシ基を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 5147X]
BEI: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]
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]
SM3:分子鎖の片末端に(メタ)アクリロイル基を有するパーフルオロポリエーテル[信越化学工業(株)製 フッ素系防汚添加剤 KY-1203、不揮発分20質量%MEK/MIBK溶液]
SM4:分子鎖の片末端に(メタ)アクリロイル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 指紋付着防止剤 オプツール(登録商標)DAC-HP、不揮発分20質量%溶液]
DPHA80:ジペンタエリスリトールペンタアクリレート/ジペンタエリスリトールヘキサアクリレート混合物[新中村化学工業(株)製 NKエステルA-DPH、ヘキサ体比率80mol%(LC-MS)]
DPHA66:ジペンタエリスリトールペンタアクリレート/ジペンタエリスリトール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-406、ペンタ体25-35%(カタログ値)、ヘキサ体比率66mol%(LC-MS)]
DPHA51:ジペンタエリスリトールペンタアクリレート/ジペンタエリスリトール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-404、ペンタ体30-40%(カタログ値)、ヘキサ体比率51mol%(LC-MS)]
DPHA47:ジペンタエリスリトールペンタアクリレート/ジペンタエリスリトールヘキサアクリレート混合物[日本化薬(株)製 KAYARAD DPHA、ヘキサ体比率47mol%(LC-MS)]
DPHA33:ジペンタエリスリトールペンタアクリレート/ジペンタエリスリトール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50-60%(カタログ値)、ヘキサ体比率33mol%(LC-MS)]
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
ヘキサ体比率[mol%]=(AH1+AH2)÷(AP1+AP2+AH1+AH2)×100
AP1:ジペンタエリスリトールペンタアクリレートのプロトン付加体(m/z=525.197)のXICのピーク面積
AP2:ジペンタエリスリトールペンタアクリレートのアンモニウム付加体(m/z=542.223)のXICのピーク面積
AH1:ジペンタエリスリトールヘキサアクリレートのプロトン付加体(m/z=579.207)のXICのピーク面積
AH2:ジペンタエリスリトールヘキサアクリレートのアンモニウム付加体(m/z=596.234)のXICのピーク面積
スクリュー管に、PFPE1 1.19g(0.5mmol)、BEI0.52g(2.0mmol)、DOTDD0.017g(PFPE1及びBEIの合計質量の0.01倍量)、及びMEK1.67g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24時間撹拌して、目的化合物であるSM1の50質量%MEK溶液を得た。
得られたSM1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3,000、分散度:Mw(重量平均分子量)/Mn(数平均分子量)は1.2であった。
スクリュー管に、PFPE2 1.05g(0.5mmol)、BEI0.26g(1.0mmol)、DOTDD0.013g(PFPE2及びBEIの合計質量の0.01倍量)、及びMEK1.30g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24時間撹拌して、目的化合物であるSM2の50質量%MEK溶液を得た。
得られたSM2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3,100、分散度:Mw/Mnは1.1であった。
表1の記載に従って以下の各成分を混合し、表1に記載の固形分濃度の硬化性組成物を調製した。なお、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]を表す。
(1)多官能モノマー:表1に記載の多官能モノマー 100質量部
(2)表面改質剤:表1に記載の表面改質剤を表1に記載の量(固形分換算)
(3)重合開始剤:O2959 2.5質量部
(4)溶媒:PGMEを表1に記載の量
また、硬化条件を、前記大気下、露光量1,300mJ/cm2から、窒素雰囲気下、露光量300mJ/cm2に変更した以外は同様に操作して、およそ5μmの層(膜)厚を有するハードコート層(硬化膜)を有するハードコートフィルムを作製した。
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[ボンスター販売(株)製 ボンスター(登録商標)#0000(超極細)]で1kg/cm2の荷重を掛けて1,000往復擦り、白色光源下で、傷の程度を目視で確認し以下の基準A及びCに従い評価した。
A:傷無し
C:傷が発生
上記擦傷試験の前後のハードコート層表面の水接触角から、その維持率[%](=試験後接触角÷試験前接触角×100)を算出し防汚耐久性として評価した。なお、接触角は、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点で測定し、その平均値を接触角値とした。
一方、ジペンタエリスリトールポリアクリレートとして、ヘキサ体比率が50mol%よりも低いジペンタエリスリトールペンタアクリレート/ジペンタエリスリトールヘキサアクリレート混合物を配合した比較例1及び比較例2の硬化性組成物を用いて作製したハードコートフィルムは、硬化性組成物を大気下で硬化した場合には優れた耐擦傷性を有しないものであった。
Claims (12)
- (a)ジペンタエリスリトールポリ(メタ)アクリレート100質量部、
(b)ポリ(オキシパーフルオロアルキレン)基を含むパーフルオロポリエーテルであって、その分子鎖の両末端に、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パーフルオロポリエーテル(但し、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にポリ(オキシアルキレン)基を有するパーフルオロポリエーテルを除く。)0.05質量部~10質量部、及び
(c)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~20質量部
を含み、
前記(a)ジペンタエリスリトールポリ(メタ)アクリレートは、液体クロマトグラフィー質量分析法の測定結果から下記式に従い算出された、ペンタ(メタ)アクリレートとヘキサ(メタ)アクリレートの総量に対するヘキサ(メタ)アクリレートの割合であるヘキサ体比率が50mol%以上100mol%以下である、硬化性組成物。
ヘキサ体比率[mol%]=(AH1+AH2)÷(AP1+AP2+AH1+AH2)×100
AP1:ジペンタエリスリトールペンタ(メタ)アクリレートのプロトン付加体の抽出イオンクロマトグラムのピーク面積
AP2:ジペンタエリスリトールペンタ(メタ)アクリレートのアンモニウム付加体の抽出イオンクロマトグラムのピーク面積
AH1:ジペンタエリスリトールヘキサ(メタ)アクリレートのプロトン付加体の抽出イオンクロマトグラムのピーク面積
AH2:ジペンタエリスリトールヘキサ(メタ)アクリレートのアンモニウム付加体の抽出イオンクロマトグラムのピーク面積 - 前記(b)パーフルオロポリエーテルは、その分子鎖の両末端それぞれにおいてウレタン結合を介して活性エネルギー線重合性基を少なくとも2つ有する、請求項1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は、その分子鎖の両末端それぞれにおいてウレタン結合を介して活性エネルギー線重合性基を少なくとも3つ有する、請求項2に記載の硬化性組成物。
- 前記ポリ(オキシパーフルオロアルキレン)基が、繰り返し単位-[OCF2]-及び繰り返し単位-[OCF2CF2]-の双方を有し、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3のうち何れか一項に記載の硬化性組成物。
- さらに(d)溶媒を含む、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。
- 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の硬化物からなる硬化膜。
- 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7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6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。
- 前記ハードコート層が1μm~10μmの層厚を有する、請求項8又は請求項9に記載の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の製造方法であって、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、該塗膜に大気下で活性エネルギー線を照射し硬化する工程とを含む、ハードコートフィルムの製造方法。
- 前記ハードコート層が1μm~10μmの層厚を有する、請求項11に記載の製造方法。
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