WO2018070438A1 - Light-fast hard coat material - Google Patents

Light-fast hard coat material Download PDF

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Publication number
WO2018070438A1
WO2018070438A1 PCT/JP2017/036860 JP2017036860W WO2018070438A1 WO 2018070438 A1 WO2018070438 A1 WO 2018070438A1 JP 2017036860 W JP2017036860 W JP 2017036860W WO 2018070438 A1 WO2018070438 A1 WO 2018070438A1
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Prior art keywords
group
hard coat
poly
meth
curable composition
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PCT/JP2017/036860
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French (fr)
Japanese (ja)
Inventor
将幸 原口
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日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to KR1020197005911A priority Critical patent/KR102516524B1/en
Priority to JP2018545029A priority patent/JP6908896B2/en
Priority to CN201780053165.7A priority patent/CN109642000B/en
Publication of WO2018070438A1 publication Critical patent/WO2018070438A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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 light-resistant hard coat material (curable composition) useful as a material for forming a hard coat layer applied to the surface of various display elements such as a touch panel display and a liquid crystal display.
  • a large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM have been commercialized.
  • a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM.
  • smartphones and tablet PCs the number of capacitive touch panels having a multi-touch function is rapidly increasing.
  • Thin tempered glass is used on the surface of these touch panel displays, and a protective film is attached to the display surface in order to prevent the glass from scattering. Since the protective film uses a plastic film, it is more likely to be scratched than glass, and it is necessary to provide a hard coat layer having excellent scratch resistance on the surface.
  • a method is adopted in which a highly crosslinked structure is formed, that is, a crosslinked structure with low molecular mobility is formed to increase the surface hardness and provide resistance to external force. It is done.
  • polyfunctional acrylate materials currently used as hard coat layer forming materials are monomers that are liquid at room temperature, and are three-dimensionally cross-linked by radicals generated from a photopolymerization initiator.
  • the acrylate system is cured by ultraviolet rays (UV), and the time of UV irradiation is very short and energy saving, and is characterized by high productivity.
  • a means for forming a hard coat layer on the surface of the plastic film for example, a solution containing a polyfunctional acrylate, a photopolymerization initiator and an organic solvent is coated on the plastic film by gravure coating, and the organic solvent is dried and then cured by ultraviolet rays. Then, a means for forming a hard coat layer is employed. In order to express functions such as hardness and scratch resistance in the formed hard coat layer at a level having no practical problem, the hard coat layer is usually formed with a thickness of 1 to 15 ⁇ m.
  • the capacitive touch panel is operated by touching it with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time an operation is performed, causing problems that the visibility of the image on the display is remarkably impaired and the appearance of the display is impaired.
  • the fingerprint contains 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 display surface in order to prevent both of them from adhering. ing. From such a viewpoint, the touch panel display surface is desired to have antifouling properties against fingerprints and the like.
  • a method for imparting antifouling properties to the surface of the hard coat layer a method of adding a small amount of a fluorine-based surface modifier to the coating solution for forming the hard coat layer has been used.
  • the added fluorine-based compound is segregated on the surface of the hard coat layer due to its low surface energy, and imparts water repellency and oil repellency.
  • an oligomer having a number average molecular weight of about 1,000 to 5,000 called a perfluoropolyether having a poly (oxyperfluoroalkylene) chain is used from the viewpoint of water repellency and oil repellency. .
  • perfluoropolyether since perfluoropolyether has a high fluorine concentration, it is usually difficult to dissolve in an organic solvent used in a coating solution for forming a hard coat layer. Moreover, aggregation is caused in the formed hard coat layer.
  • a technique of adding an organic moiety to the perfluoropolyether is used.
  • a method of bonding active energy ray-curable sites represented by (meth) acrylate groups is used.
  • Patent Document 1 As an antifouling hard coat layer having scratch resistance, as a component for imparting antifouling properties to the hard coat layer surface, a plurality of poly (oxyperfluoroalkylene) chains having an isophorone skeleton at both ends thereof A technique using a compound having a (meth) acryloyl group via a urethane bond as a surface modifier is disclosed (Patent Document 1).
  • OCA optical transparent adhesive
  • the curable composition for forming the antifouling hard coat layer does not contain an ultraviolet absorber and a light stabilizer. There was a risk of peeling.
  • the ultraviolet absorber suppresses the generation of radicals from the polymerization initiator, and the light stabilizer captures and quenches the generated radicals. Therefore, when an ultraviolet absorber and a light stabilizer are added in advance to the curable composition for forming the antifouling hard coat layer, radical generation is suppressed and quenched even during the formation of the antifouling hard coat layer. In addition, the formation of the antifouling hard coat is inhibited, thereby causing deterioration of the scratch resistance. Moreover, there exists a kind which has absorption in 400 nm vicinity with a ultraviolet absorber, and when it adds excessively, the transparency of an antifouling
  • poly (oxyalkylene) is present at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group that plays a role as a surface modifier.
  • Group or a perfluoropolyether that binds an active energy ray polymerizable group via a poly (oxyalkylene) group and one urethane bond group, and a specific ultraviolet absorber and a specific light stabilizer The present invention has been completed by finding that a curable composition containing can have an excellent scratch resistance and can form an antifouling hard coat layer with excellent light resistance.
  • the present invention provides the first aspect as follows: (A) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (B) the active energy at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group or via the poly (oxyalkylene) group and one urethane bond group in this order; 0.1 to 10 parts by mass of perfluoropolyether to which a linear polymerizable group is bonded, (C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, A curable composition comprising (d) 1 to 3 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber and (e) 1 to 2 parts by mass of a hindered amine light stabilizer,
  • the hydroxyphenyltriazine ultraviolet absorber is A compound in which three phenyl groups directly bonded to the triazine ring are substituted with at least two hydroxy groups,
  • the hindered amine light stabilizer is a compound having a group represented by the formula [1].
  • the present invention relates to a curable composition.
  • R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a black dot represents a bond.
  • the curable composition according to the first aspect wherein the poly (oxyperfluoroalkylene) group is a group having — [OCF 2 ] — and — [OCF 2 CF 2 ] — as repeating units.
  • the poly (oxyperfluoroalkylene) group is a group having — [OCF 2 ] — and — [OCF 2 CF 2 ] — as repeating units.
  • the present invention relates to the curable composition according to the first aspect or the second aspect, wherein the poly (oxyalkylene) group is a poly (oxyalkylene) group having 5 to 12 repeating units.
  • the present invention relates to the curable composition according to any one of the first aspect to the third aspect, in which the poly (oxyalkylene) group is a poly (oxyethylene) group.
  • the present invention relates to the curable composition according to any one of the first to fourth aspects, wherein the active energy ray polymerizable group is a group having at least two active energy ray polymerizable moieties. .
  • the first to fifth aspects wherein the polyfunctional monomer of component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. It relates to the curable composition as described in any one of viewpoints.
  • the present invention relates to the curable composition according to any one of the first aspect to the sixth aspect, further including (f) a solvent.
  • a solvent As an 8th viewpoint, it is related with the cured film obtained from the curable composition as described in any one among a 1st viewpoint thru
  • the present invention relates to a hard coat film comprising a hard coat layer on at least one surface of a film base material, wherein the hard coat layer comprises the cured film described in the eighth aspect.
  • the hard coat film according to the ninth aspect wherein the hard coat layer has a thickness of 1 to 15 ⁇ m.
  • An eleventh aspect is a method for producing a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the curable composition according to any one of the first aspect to the seventh aspect is used. It is related with the manufacturing method of a hard coat film including the process of apply
  • An excellent hard coat film can be provided.
  • the hard coat film when a hard coat film is applied to a substrate surface such as a display surface, the hard coat film can be removed from the substrate (film) even after an adhesion process using an optical transparent adhesive. It is possible to provide a hard coat film that can suppress peeling of the hard coat layer and is excellent in light resistance.
  • the curable composition of the present invention includes: (A) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (B) the active energy at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group or via the poly (oxyalkylene) group and one urethane bond group in this order; 0.1 to 10 parts by mass of perfluoropolyether to which a linear polymerizable group is bonded, (C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
  • the present invention relates to a curable composition comprising (d) 1 to 3 parts by mass of a hydroxyphenyltriazine ultraviolet absorber and (e) 1 to 2 parts by mass of a hindered amine light stabilizer.
  • the components (a) to (e) will be described first.
  • the active energy ray-curable polyfunctional monomer refers to a monomer that is cured by a polymerization reaction that proceeds by irradiation with an active energy ray such as ultraviolet rays.
  • the preferable (a) active energy ray-curable polyfunctional monomer is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
  • the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
  • (meth) acrylic acid refers to acrylic acid and methacrylic acid.
  • polyfunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra.
  • pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.
  • the polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (—NHCOO—).
  • the polyfunctional urethane (meth) acrylate compound is obtained by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group, or a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol.
  • the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to such 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).
  • An acrylate, tripentaerythritol hepta (meth) acrylate, etc. are mentioned.
  • polyols examples include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these diols, succinic acid, malein Examples include polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as acids and adipic acid; polyether polyols; polycarbonate diols and the like.
  • the (a) active energy ray-curable polyfunctional monomer one kind is selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound, or two or more kinds are used. Can be used in combination. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound in combination. Moreover, it is preferable to use together 5 or more functional polyfunctional (meth) acrylate compound and 4 or less polyfunctional (meth) acrylate compound as said polyfunctional (meth) acrylate compound.
  • the polyfunctional urethane (meth) acrylate compound 20 with respect to 100 mass parts of polyfunctional (meth) acrylate compounds. It is preferable to use ⁇ 100 parts by mass, and it is more preferable to use 30 to 70 parts by mass. Furthermore, in the polyfunctional (meth) acrylate compound, when the polyfunctional (meth) acrylate compound having 5 or more functions and the polyfunctional (meth) acrylate compound having 4 or less functions are used in combination, the polyfunctional (meth) acrylate compound has 5 or more functions.
  • polyfunctional urethane (meth) acrylate compound 20 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound and polyfunctional (meth) acrylate compounds having a functionality of 4 or less with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound.
  • (Meth) acrylate compound to be used at 10 to 100 parts by mass Polyfunctional (meth) acrylate compound 20 to 100 parts by mass with respect to 100 parts by mass of polyfunctional (meth) acrylate compound and polyfunctional (meth) acrylate compound with a functionality of 4 or less with respect to 100 parts by mass of polyfunctional (meth) acrylate compound having 5 or more functions ) Use at 20-60 parts by mass of acrylate compound, Polyfunctional (meth) acrylate compound 100 parts by mass Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass and pentafunctional or higher polyfunctional (meth) acrylate compound 100 parts by mass ) Use at 10 to 100 parts by mass of acrylate compound, Polyfunctional (meth) acrylate compound 100 parts by mass Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass and pentafunctional or higher polyfunctional (meth) acrylate compound 100 parts by mass )
  • the acrylate compound is preferably used in an amount of 20 to
  • a perfluoropolyether (hereinafter also referred to as “(b) a perfluoropolyether having a polymerizable group at both ends”) to which an active energy ray polymerizable group is bonded 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.
  • the number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but 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 oxygen atoms are alternately connected, and the oxyperfluoroalkylene group is a carbon atom. This refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked.
  • — [OCF 2 ] (oxyperfluoromethylene group), — [OCF 2 CF 2 ] — (oxyperfluoroethylene group), — [OCF 2 CF 2 CF 2 ] — (oxyperfluoropropane) -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. In such a case, the bonds of plural types of oxyperfluoroalkylene groups are block bonds and random bonds. Any of these may be used.
  • — [OCF 2 ] (oxyperfluoromethylene group) and — [OCF 2 CF 2 ] are used. It is preferable to use a group having both of-(oxyperfluoroethylene group) as repeating units.
  • the bond of these repeating units may be either a block bond or a random bond.
  • the number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, as the total number of repeating units.
  • the weight average molecular weight (Mw) of the poly (oxyperfluoroalkylene) group measured in terms of polystyrene by gel permeation chromatography is 1,000 to 5,000, preferably 1,500 to 2,000. .
  • the number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyalkylene) group refers to a group having a structure in which an alkylene group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyalkylene group is a divalent alkylene having 1 to 4 carbon atoms. A group having a structure in which a group and an oxygen atom are linked. Examples of the alkylene group include an ethylene group, a 1-methylethylene group, a trimethylene group, and a tetramethylene group. The oxyalkylene groups may be used singly or in combination of two or more.
  • the bonds of the plural oxyalkylene groups may be either block bonds or random bonds. May be.
  • the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.
  • the number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is, for example, in the range of 1 to 15, and more preferably in the range of 5 to 12, for example, 7 to 12.
  • Examples of the active energy ray-polymerizable group that bonds the poly (oxyalkylene) group or the poly (oxyalkylene) group and one urethane bond group in this order include a (meth) acryloyl group and a urethane (meth) acryloyl group. Group, vinyl group and the like.
  • the active energy ray polymerizable group is not limited to one having one active energy ray polymerizable portion such as a (meth) acryloyl moiety, and may have two or more active energy ray polymerizable portions,
  • the following structures A1 to A5 and structures in which the acryloyl group in these structures is substituted with a methacryloyl group can be mentioned.
  • A represents one of the structures represented by the formulas [A1] to [A5]
  • PFPE represents the poly (oxyperfluoroalkylene) group
  • n is independently selected. Represents the number of repeating units of the oxyethylene group, preferably a number of 1 to 15, more preferably a number of 5 to 12, and still more preferably a number of 7 to 12.
  • the (b) perfluoropolyether having a polymerizable group at both ends of the present invention has a poly (oxyalkylene) group and one urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group.
  • a poly (oxyalkylene) group is bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, and a urethane bond is formed to each poly (oxyalkylene) group at both ends.
  • the active energy ray polymerizable group is preferably a perfluoropolyether which is a group having at least two active energy ray polymerizable moieties.
  • the perfluoropolyether having a polymerizable group at both ends is 0.1 to 10 parts by weight, preferably 100 parts by weight, preferably 100 parts by weight of the active energy ray-curable polyfunctional monomer. It is desirable to use at a ratio of 0.2 to 5 parts by mass.
  • the perfluoropolyether having a polymerizable group at both ends (b) is, for example, a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group.
  • the curable composition of the present invention includes (b) a poly (oxyalkylene) group or one poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group.
  • a poly (oxyalkylene) group or one poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group In addition to the perfluoropolyether to which the active energy ray polymerizable group is bonded through the urethane bonding group in this order, one end of the molecular chain containing the poly (oxyperfluoroalkylene) group is bonded through the poly (oxyalkylene) group.
  • Compound unbound active energy ray-polymerizable group] perfluoropolyether having a sheet group may be included.
  • a polymerization initiator that generates radicals by a preferable active energy ray is, for example, active energy such as electron beam, ultraviolet ray, and X-ray. It is a polymerization initiator that generates radicals by irradiation with ultraviolet rays, in particular.
  • polymerization initiator (c) examples include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones.
  • alkylphenones as the polymerization initiator (c) from the viewpoints of transparency, surface curability, and thin film curability.
  • alkylphenones By using alkylphenones, a cured film with improved scratch resistance can be obtained.
  • the polymerization initiator is used in a ratio of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Is desirable.
  • the curable composition of the present invention is characterized by using a hydroxyphenyltriazine-based ultraviolet absorber as the component (d).
  • a hydroxyphenyltriazine-based ultraviolet absorber in the above hydroxyphenyl triazine-based ultraviolet absorber, the compound in which three phenyl groups directly bonded to the triazine ring are substituted with at least two hydroxy groups, or directly bonded to the triazine ring.
  • the hard material produced from this photocurable composition by using together the specific (d) hydroxyphenyl triazine type ultraviolet absorber and the specific (e) hindered amine light stabilizer mentioned later.
  • a coated film is applied to the surface of a substrate such as a display surface, even when an adhesive step using an optical transparent adhesive is performed, peeling of the hard coat layer from the hard coat film can be suppressed, and the film and the hard coat layer The hard coat film excellent in light resistance can be obtained.
  • hydroxyphenyl triazine-based ultraviolet absorber examples include a hydroxyphenyl triazine compound represented by the following formula (U1).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, a hydroxy group, a phenyl group, or an ether bond, an ester bond and A group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms, which may contain one or more bonds selected from the group consisting of amide bonds,
  • the phenyl group, alkyl group and alkoxy group may be substituted with a hydroxy group, provided that when any of R 1 to R 8 is not a phenyl group, at least one of R 1 to R 8 represents a hydroxy group. .
  • the alkyl group having 1 to 18 carbon atoms may have a branched structure or a cyclic structure.
  • the alkoxy group having 1 to 18 carbon atoms has a structure in which the alkyl group having 1 to 18 carbon atom
  • Examples of the ultraviolet absorber include 2,4-bis (4-butoxy-2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine [Tinuvin 460 manufactured by BASF Corporation]. ] 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine [ADEKA STAB (registered trademark) LA-F70 manufactured by ADEKA Corporation], 2, 4,6-tris (2-hydroxy-4- (1- (octyloxycarbonyl) ethoxy) phenyl) -1,3,5-triazine [BASF Tinuvin 477], 2,4-di ([1,1 '-Biphenyl] -4-yl) -6- (2-hydroxy-4- (1- (isooctyloxycarbonyl) ethoxy) phenyl) -1,3,5-tria [BASF Tinuvin 479], 2,4-bis (2-hydroxy-4-o
  • the hydroxyphenyltriazine-based UV absorber is in a proportion of 1 to 3 parts by weight, preferably 2 to 3 parts by weight, based on 100 parts by weight of the above-mentioned (a) active energy ray-curable polyfunctional monomer. It is desirable to use in.
  • a hindered amine light stabilizer is used as the component (e), and in particular, a hindered amine light stabilizer selected from a compound formed by bonding a group represented by the formula [1] is used. It is characterized by adopting.
  • R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a black dot represents a bond.
  • alkyl group having 1 to 10 carbon atoms represented by Ra examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl, isoamyl, neopentyl, tert-amyl, sec-isoamyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl Groups and the like.
  • hindered amine light stabilizers for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [Tinvin 770 manufactured by BASF Corporation, and Adeka Stub manufactured by ADEKA Corporation.
  • ADK STAB registered trademark
  • LA-68 butane-1,2,3,4-tetracarboxylic acid bis (1,2,2,5,5-pentamethyl-4-piperidyl) ester and ⁇ , ⁇ , ⁇ ′ , ⁇ '-tetramethyl-2, , 8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol polycondensate
  • ADKA STAB registered trademark
  • LA-63P manufactured by ADEKA Corporation
  • Ciasorb Industries UV-3346 manufactured by Cytec Industries, Inc.] poly [(6-morpholino-1,3,5-triazine-2,4-diyl)
  • the (e) hindered amine light stabilizer is desirably used in a ratio of 1 to 2 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.
  • the curable composition of the present invention may further contain (f) a solvent, that is, may be in the form of a varnish (film forming material).
  • the solvent is appropriately selected in consideration of the workability at the time of coating and the drying property before and after curing for dissolving the components (a) to (e) and forming a cured film (hard coat layer) described later.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, Halogenated hydrocarbons such as methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve Acetate, propylene glycol monomethyl ether acetate, etc.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetralin
  • Stealth or ester ethers diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl Ethers such as ether and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol and isobutyl Alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol Alcohols such as ethylene glycol; amide
  • the amount of the solvent (f) used is not particularly limited.
  • the solvent is used at a concentration such that the solid content in the curable composition of the present invention is 1 to 70% by mass, preferably 5 to 50% by mass.
  • the solid content concentration also referred to as the non-volatile content concentration
  • the solid content concentration means the solid content relative to the total mass (total mass) of the components (a) to (f) (and other additives as required) of the curable composition of the present invention. The content of (all solvent components are removed) is expressed.
  • the curable composition of the present invention as long as the effects of the present invention are not impaired, are generally added as necessary, for example, polymerization accelerators, polymerization inhibitors, photosensitizers, leveling. Agents, surfactants, adhesion-imparting agents, plasticizers, UV absorbers other than those mentioned above, light stabilizers other than those mentioned above, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc. You may mix.
  • the curable composition of this invention can form a cured film by apply
  • the cured film is also an object of the present invention.
  • the hard coat layer in the hard coat film mentioned later can consist of this cured film.
  • the base material in this case examples include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, Acetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass, slate, and the like.
  • 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 base material 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 ink jet method, a printing method (a relief plate, an intaglio plate).
  • Lithographic printing, screen printing, etc. can be selected as appropriate, and in particular, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating, a relief printing method, particularly a gravure coating method is used. It is desirable. It is preferable that the curable composition is filtered in advance using a filter having a pore diameter of about 0.2 ⁇ m or the like and then used for coating.
  • the coating film is pre-dried with a hot plate or an oven as necessary to remove the solvent (solvent removal step).
  • solvent removal step The heat drying conditions at this time are preferably 40 to 120 ° C. and about 30 seconds to 10 minutes, for example.
  • the coating film is cured by irradiating active energy rays such as ultraviolet rays.
  • Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable.
  • a light source used for ultraviolet irradiation sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
  • polymerization may be completed by performing post-baking, specifically by heating using a hot plate, an oven or the like.
  • the thickness of the formed cured film is usually 0.01 to 50 ⁇ m, preferably 0.05 to 20 ⁇ m after drying and curing.
  • a hard coat film provided with a hard coat layer on at least one surface (surface) of a film substrate can be produced using the curable composition of the present invention.
  • the hard coat film is also an object of the present invention, and the hard coat film is suitably used for protecting the surface of various display elements such as 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 on 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.
  • various transparent resin films that can be used for optical applications among the substrates mentioned in the above-mentioned ⁇ cured film> are used.
  • a resin selected from polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose, etc.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • polycarbonate polymethacrylate
  • polystyrene polyolefin
  • polyamide polyamide
  • polyimide polyimide
  • the process of drying this coating film and removing a solvent as needed can be included after a coating-film formation process.
  • the drying method (solvent removal process) of the coating film quoted to the above-mentioned ⁇ cured film> can be used.
  • the thickness of the hard coat layer thus obtained is preferably 1 to 20 ⁇ m, more preferably 1 to 10 ⁇ m.
  • Bar coat application device PM-9050MC manufactured by SMT Co., Ltd.
  • Bar OSG System Products A-Bar OSP-30, maximum wet film thickness 30 ⁇ m (corresponding to wire bar # 12)
  • Application speed 4 m / min
  • Oven Equipment Dust dryer DRC433FA manufactured by Advantech Toyo Co., Ltd.
  • UV curing device CV-110QC-G manufactured by Heraeus Co., Ltd.
  • Lamp Heraeus high pressure mercury lamp H-bulb
  • GPC Gel permeation chromatography
  • Equipment HLC-8220GPC manufactured by Tosoh Corporation Column: Shodex (registered trademark) GPC KF-804L, GPC KF-805L manufactured by Showa Denko K.K.
  • Light resistance test apparatus Accelerated weather resistance tester QUV (registered trademark) / se manufactured by Q-Lab Light source: UVA-340 type lamp Test conditions: 0.76 W / cm 2 , 60 ° C., under dew condensation Test time: 72 hours (8) Yellowness Device: Spectrocolorimeter CM-700d manufactured by Konica Minolta Co., Ltd. Measurement mode: specular reflection removal (SCE) mode (9) Scratch test Device: Reciprocating wear tester manufactured by Shinto Kagaku Co., Ltd. TRIBOGEAR TYPE: 30S Load: 250 g / cm 2 Scanning speed: 3m / min
  • PFPE Perfluoropolyether having a hydroxy group via a poly (oxyalkylene) group (repeating unit number 8 to 9) at both ends
  • BEI 1,1-bis (acryloyloxymethyl) ethyl isocyanate
  • DBTDL Dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]
  • DPHA Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture
  • PETA Pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture [Shin-Nakamura Chemical Co., Ltd.
  • NK ester A-TMM-3LM-N] UA 6-functional aliphatic urethane acrylate oligomer
  • I2959 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one
  • I2959 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one
  • UVA1 2,4,6-tris (2-hydroxy-4- (1- (octyloxycarbonyl) ethoxy) phenyl) -1,3,5-triazine
  • UVA2 2,4-bis (4-butoxy-2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine
  • UVA3 2,4-di ([1,1′-bipheny
  • HALS1 Bis (1,2,2,6,6, -pentamethylpiperidin-4-yl) sebacate [Tinvin 292 manufactured by BASF Japan Ltd.]
  • HALS2 bis (2,2,6,6, -tetramethyl-N-octyloxypiperidin-4-yl) sebacate [Tinvin 123 manufactured by BASF Japan Ltd.]
  • MEK Methyl ethyl ketone
  • PGME Propylene glycol monomethyl ether
  • the weight average molecular weight Mw measured by GPC of the obtained SM1 in terms of polystyrene was 3,400, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.1.
  • the fluorine content calculated from the F1 quantitative analysis of SM1 was 36% by mass.
  • This curable composition was bar-coated on an A4-sized double-sided easy-adhesion treated PET film [Lumirror (registered trademark) U403, manufactured by Toray Industries, Inc., thickness 100 ⁇ m] to obtain a coating film.
  • This coating film was dried in an oven at 120 ° C. for 3 minutes to remove the solvent.
  • the obtained film was exposed to UV light having an exposure amount of 300 mJ / cm 2 in a nitrogen atmosphere to expose a hard coat film having a hard coat layer (cured film) having a thickness of about 6 ⁇ m.
  • the light resistance, yellowness, and scratch resistance of the hard coat film obtained from each curable composition were evaluated. The procedure for each evaluation is shown below. The results are also shown in Table 2.
  • the layer surface color (L * a * b * color system) was measured and evaluated according to the following criteria. A: b * ⁇ 1.0 C: b * ⁇ 1.0
  • perfluoropolyether SM1 in which an acryloyl group is bonded to both ends via a poly (oxyalkylene) group and one urethane bonding group is used.
  • UVA1 to UVA3 specific ultraviolet absorbers
  • HALS1 specific hindered amine light stabilizers
  • the curable composition of the present invention which is a combination of a specific hydroxyphenyl triazine-based ultraviolet absorber and a hindered amine light stabilizer and added together with a specific perfluoropolyether as a surface modifier Only the product can realize satisfactory scratch resistance and light resistance in the hard coat layer produced from the composition, and a hard coat film satisfying these performances can be obtained.

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Abstract

[Problem] To provide a material for forming a hard coat layer that exhibits high scratch resistance and lightfastness. [Solution] Provided is a curable composition that contains: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) 0.1-10 parts by mass of a perfluoropolyether in which an active energy ray-polymerizable group is bonded to both terminals of a poly(oxyperfluoroalkylene) group-containing molecular chain via a poly(oxyalkylene) group, or via a poly(oxyalkylene) group and one urethane bond in that order; (c) 1-20 parts by mass of a polymerization initiator that generates radicals upon irradiation with active energy rays; (d) 1-3 parts by mass of a hydroxyphenyltriazine-based ultraviolet radiation absorber; and (e) 1-2 parts by mass of a hindered amine-based photostabilizer. Also provided are a hard coating film provided with a hard coating layer formed from the composition, and a method for producing the hard coating film.

Description

耐光性ハードコート材Light-resistant hard coat material
　本発明は、タッチパネルディスプレイ、液晶ディスプレイ等の各種表示素子等の表面に適用されるハードコート層の形成材料として有用な耐光性ハードコート材（硬化性組成物）に関する。 The present invention relates to a light-resistant hard coat material (curable composition) useful as a material for forming a hard coat layer applied to the surface of various display elements such as a touch panel display and a liquid crystal display.
　パーソナルコンピューター、携帯電話、携帯ゲーム機器、ＡＴＭ等のフラットパネルディスプレイにタッチパネルが搭載された製品が非常に数多く商品化されている。特に、スマートフォンやタブレットＰＣの登場により、マルチタッチ機能を有する静電容量式タッチパネルが一気にその搭載数を伸ばしている。 A large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM have been commercialized. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels having a multi-touch function is rapidly increasing.
　これらタッチパネルディスプレイ表面には薄い強化ガラスが用いられており、このガラスが飛散するのを防止するためにディスプレイ表面に保護フィルムが貼り付けられる。保護フィルムは、プラスチックフィルムを用いるためガラスより傷が付き易く、その表面に耐擦傷性に優れるハードコート層を設けることが必要となる。プラスチックフィルム表面に耐擦傷性を付与するには、例えば高度の架橋構造を形成する、すなわち分子運動性の低い架橋構造を形成することで表面硬度を高め、外力への抵抗性を与える手法が採られる。
　これらのハードコート層形成材料として現在最も用いられている多官能アクリレート系材料は、その多くが常温で液状のモノマーであり、光重合開始剤から発生したラジカルにより３次元架橋する。アクリレート系は紫外線（ＵＶ）で硬化し、ＵＶを照射する時間は非常に短時間で省エネルギーであることから、生産性が高いことが特徴である。プラスチックフィルム表面にハードコート層を形成する手段としては、例えば多官能アクリレート、光重合開始剤及び有機溶媒を含む溶液をプラスチックフィルムにグラビアコートなどでコーティングを行い、有機溶媒を乾燥後、紫外線により硬化し、ハードコート層を形成する手段が採用される。形成したハードコート層において、硬度、耐擦傷性などの機能を実用上問題のないレベルで発現させるために、通常、ハードコート層の厚さは１～１５μｍで形成されている。 Thin tempered glass is used on the surface of these touch panel displays, and a protective film is attached to the display surface in order to prevent the glass from scattering. Since the protective film uses a plastic film, it is more likely to be scratched than glass, and it is necessary to provide a hard coat layer having excellent scratch resistance on the surface. In order to impart scratch resistance to the surface of a plastic film, for example, a method is adopted in which a highly crosslinked structure is formed, that is, a crosslinked structure with low molecular mobility is formed to increase the surface hardness and provide resistance to external force. It is done.
Most of these polyfunctional acrylate materials currently used as hard coat layer forming materials are monomers that are liquid at room temperature, and are three-dimensionally cross-linked by radicals generated from a photopolymerization initiator. The acrylate system is cured by ultraviolet rays (UV), and the time of UV irradiation is very short and energy saving, and is characterized by high productivity. As a means for forming a hard coat layer on the surface of the plastic film, for example, a solution containing a polyfunctional acrylate, a photopolymerization initiator and an organic solvent is coated on the plastic film by gravure coating, and the organic solvent is dried and then cured by ultraviolet rays. Then, a means for forming a hard coat layer is employed. In order to express functions such as hardness and scratch resistance in the formed hard coat layer at a level having no practical problem, the hard coat layer is usually formed with a thickness of 1 to 15 μm.
　ところで、静電容量式タッチパネルでは人間の指で触れることにより操作を行う。このため、操作を行う度にタッチパネルの表面に指紋が付着し、ディスプレイの画像の視認性が著しく損なわれたり、ディスプレイの外観が損なわれたりするという問題が発生している。指紋には汗由来の水分及び皮脂由来の油分が含まれており、それらの何れも付着しにくくするために、ディスプレイ表面のハードコート層には撥水性及び撥油性を付与することが強く望まれている。
　このような観点から、タッチパネルディスプレイ表面には、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、静電容量式タッチパネルでは、人が毎日指で触れるため、初期の防汚性はかなりのレベルに達しているとしても、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。 By the way, the capacitive touch panel is operated by touching it with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time an operation is performed, causing problems that the visibility of the image on the display is remarkably impaired and the appearance of the display is impaired. The fingerprint contains 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 display surface in order to prevent both of them from adhering. ing.
From such a viewpoint, the touch panel display surface is desired to have antifouling properties against fingerprints and the like. However, in a capacitive touch panel, since a person touches it with a finger every day, even if the initial antifouling property has reached a considerable level, its function often deteriorates during use. Therefore, the durability of the antifouling property in the process of use has been a problem.
　従来、ハードコート層表面に防汚性を付与する手法として、ハードコート層を形成する塗布液にフッ素系表面改質剤を少量添加する手法が用いられている。添加されたフッ素系化合物は、その低表面エネルギーによりハードコート層の表面に偏析され、撥水性及び撥油性が付与される。フッ素系化合物としては、撥水性、撥油性の観点から、ポリ（オキシパーフルオロアルキレン）鎖を有したパーフルオロポリエーテルと呼ばれる１，０００～５，０００程度の数平均分子量を有するオリゴマーが用いられる。しかし、パーフルオロポリエーテルは高いフッ素濃度を有しているため、通常、ハードコート層を形成する塗布液に使用される有機溶媒には溶解し難い。また、形成されたハードコート層においては凝集を起こす。
　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、防汚性をハードコート層表面に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、イソホロン骨格を有する複数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）。 Conventionally, as a method for imparting antifouling properties to the surface of the hard coat layer, a method of adding a small amount of a fluorine-based surface modifier to the coating solution for forming the hard coat layer has been used. The added fluorine-based compound is segregated on the surface of the hard coat layer due to its low surface energy, and imparts water repellency and oil repellency. As the fluorine compound, an oligomer having a number average molecular weight of about 1,000 to 5,000 called a perfluoropolyether having a poly (oxyperfluoroalkylene) chain is used from the viewpoint of water repellency and oil repellency. . However, since perfluoropolyether has a high fluorine concentration, it is usually difficult to dissolve in an organic solvent used in a coating solution for forming a hard coat layer. Moreover, aggregation is caused in the formed hard coat layer.
In order to provide such perfluoropolyether with solubility in an organic solvent and dispersibility in the hard coat layer, a technique of adding an organic moiety to the perfluoropolyether is used. Furthermore, in order to impart scratch resistance, a method of bonding active energy ray-curable sites represented by (meth) acrylate groups is used.
Conventionally, as an antifouling hard coat layer having scratch resistance, as a component for imparting antifouling properties to the hard coat layer surface, a plurality of poly (oxyperfluoroalkylene) chains having an isophorone skeleton at both ends thereof A technique using a compound having a (meth) acryloyl group via a urethane bond as a surface modifier is disclosed (Patent Document 1).
　一方、防汚性ハードコートフィルムをディスプレイ表面等の基材表面で使用するために、防汚性ハードコート層が形成された面とは反対の面を、光学透明接着剤（ＯＣＡ）を用いて、基材表面に貼り付ける必要がある。ＯＣＡは加熱及び活性エネルギー線を照射することで硬化し、接着機能を発揮する。活性エネルギー線照射により硬化するＯＣＡの場合、防汚性ハードコート側から、活性エネルギー線を照射することにより硬化を行うが、その際に、照射された活性エネルギー線により、防汚性ハードコート層中に残存する未反応の重合開始剤からラジカルが生成する。そして、生成したラジカルが開始種となって、未反応の活性エネルギー線多官能モノマーの重合が過度に進行し、防汚性ハードコート層が脆化され、防汚性ハードコート層及びフィルム間の密着性の低下が引き起こされ、防汚性ハードコート層が剥離するという問題が生じる。密着性の低下を防ぐため、一般的に用いられる手法として、防汚性ハードコート層を形成する硬化性組成物中に、予め、紫外線吸収剤及び光安定剤を添加しておく手法がある（特許文献２）。 On the other hand, in order to use the antifouling hard coat film on the surface of a substrate such as a display surface, the surface opposite to the surface on which the antifouling hard coat layer is formed using an optical transparent adhesive (OCA) It is necessary to affix on the substrate surface. OCA is cured by heating and irradiating active energy rays, and exhibits an adhesive function. In the case of OCA that is cured by irradiation with active energy rays, curing is performed by irradiating active energy rays from the antifouling hard coat side. At that time, the antifouling hard coat layer is irradiated by the irradiated active energy rays. Radicals are generated from the unreacted polymerization initiator remaining therein. And the generated radical becomes the starting species, the polymerization of the unreacted active energy ray polyfunctional monomer proceeds excessively, the antifouling hard coat layer is embrittled, and between the antifouling hard coat layer and the film Decrease in adhesiveness is caused, causing a problem that the antifouling hard coat layer is peeled off. In order to prevent a decrease in adhesion, a commonly used technique is to add an ultraviolet absorber and a light stabilizer in advance to the curable composition for forming the antifouling hard coat layer ( Patent Document 2).
特開２０１３－７６０２９号公報JP 2013-76029 A 特開２０１６－１２５０４９号公報JP 2016-125049 A
　特許文献１に具体的に記載された方法では、防汚性ハードコート層を形成する硬化性組成物中は紫外線吸収剤及び光安定剤を含まないため、防汚性ハードコート層のフィルムからの剥離が生じる恐れがあった。
　また、特許文献２に具体的に記載された方法では、紫外線吸収剤は重合開始剤からのラジカル発生を抑制し、また、光安定性剤は発生したラジカルを補足しクエンチする。したがって、予め、防汚性ハードコート層を形成する硬化性組成物に紫外線吸収剤及び光安定剤は添加した場合、防汚性ハードコート層の形成時においても、ラジカル発生の抑制及びクエンチが生じ、防汚性ハードコートの形成が阻害されることで、耐擦傷性の悪化を引き起こす。また、紫外線吸収剤は、４００ｎｍ近傍に吸収を有する種類もあり、過剰に添加した場合は、防汚性ハードコート層の透明性が損なわれる場合もある。 In the method specifically described in Patent Document 1, the curable composition for forming the antifouling hard coat layer does not contain an ultraviolet absorber and a light stabilizer. There was a risk of peeling.
In the method specifically described in Patent Document 2, the ultraviolet absorber suppresses the generation of radicals from the polymerization initiator, and the light stabilizer captures and quenches the generated radicals. Therefore, when an ultraviolet absorber and a light stabilizer are added in advance to the curable composition for forming the antifouling hard coat layer, radical generation is suppressed and quenched even during the formation of the antifouling hard coat layer. In addition, the formation of the antifouling hard coat is inhibited, thereby causing deterioration of the scratch resistance. Moreover, there exists a kind which has absorption in 400 nm vicinity with a ultraviolet absorber, and when it adds excessively, the transparency of an antifouling | hard-wearing hard-coat layer may be impaired.
　本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、表面改質剤としての役割を果たすポリ（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、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基を介して活性エネルギー線重合性基を結合するパーフルオロポリエーテルを添加するとともに、特定の紫外線吸収剤と特定の光安定剤とを含む硬化性組成物が、優れた耐擦傷性を有し、且つ耐光性に優れた防汚性ハードコート層を形成可能であることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that poly (oxyalkylene) is present at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group that plays a role as a surface modifier. ) Group or a perfluoropolyether that binds an active energy ray polymerizable group via a poly (oxyalkylene) group and one urethane bond group, and a specific ultraviolet absorber and a specific light stabilizer The present invention has been completed by finding that a curable composition containing can have an excellent scratch resistance and can form an antifouling hard coat layer with excellent light resistance.
　すなわち本発明は、第１観点として、
（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）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して、活性エネルギー線重合性基を結合するパーフルオロポリエーテル０．１～１０質量部、
（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１～２０質量部、
（ｄ）ヒドロキシフェニルトリアジン系紫外線吸収剤１～３質量部、及び
（ｅ）ヒンダードアミン系光安定剤１～２質量部
を含む硬化性組成物であって、
前記ヒドロキシフェニルトリアジン系紫外線吸収剤は、
トリアジン環に直接結合する３つのフェニル基が少なくとも２つ以上のヒドロキシ基で置換された化合物であるか、又は、
トリアジン環に直接結合する３つのフェニル基のうち少なくとも１つのフェニル基の水素原子がフェニル基で置換され、且つ、トリアジン環に直接結合する３つのフェニル基が合計で少なくとも１つ以上のヒドロキシ基で置換された化合物であり、
前記ヒンダードアミン系光安定剤は、式［１］で表される基を有する化合物である、
硬化性組成物に関する。
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒａは水素原子、又は炭素原子数１乃至１０のアルキル基を表し、黒点は結合手を表す。）
　第２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、－［ＯＣＦ２］－及び－［ＯＣＦ２ＣＦ２］－を繰り返し単位として有する基である、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、前記ポリ（オキシアルキレン）基が、５～１２の繰返し単位数を有するポリ（オキシアルキレン）基である、第１観点又は第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（オキシアルキレン）基がポリ（オキシエチレン）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、前記活性エネルギー線重合性基が活性エネルギー線重合性部分を少なくとも２つ以上有する基である、第１観点乃至第４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６観点として、前記成分（ａ）の多官能モノマーが、多官能（メタ）アクリレート化合物及び多官能ウレタン（メタ）アクリレート化合物からなる群から選ばれる少なくとも１つである、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、さらに（ｆ）溶媒を含む、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に関する。
　第８観点として、第１観点乃至第７観点のうち何れか一つに記載の硬化性組成物より得られる硬化膜に関する。
　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８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１０観点として、前記ハードコート層が１～１５μｍの膜厚を有する、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７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、該塗膜に活性エネルギー線を照射し硬化する工程を含む、ハードコートフィルムの製造方法に関する。 That is, the present invention provides the first aspect as follows:
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) the active energy at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group or via the poly (oxyalkylene) group and one urethane bond group in this order; 0.1 to 10 parts by mass of perfluoropolyether to which a linear polymerizable group is bonded,
(C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
A curable composition comprising (d) 1 to 3 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber and (e) 1 to 2 parts by mass of a hindered amine light stabilizer,
The hydroxyphenyltriazine ultraviolet absorber is
A compound in which three phenyl groups directly bonded to the triazine ring are substituted with at least two hydroxy groups, or
At least one of the three phenyl groups directly bonded to the triazine ring is substituted with a phenyl group, and the three phenyl groups directly bonded to the triazine ring are a total of at least one hydroxy group. A substituted compound,
The hindered amine light stabilizer is a compound having a group represented by the formula [1].
The present invention relates to a curable composition.
Figure JPOXMLDOC01-appb-C000002
 (In the formula, R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a black dot represents a bond.)
As a second aspect, the curable composition according to the first aspect, wherein the poly (oxyperfluoroalkylene) group is a group having — [OCF 2 ] — and — [OCF 2 CF 2 ] — as repeating units. About.
As a third aspect, the present invention relates to the curable composition according to the first aspect or the second aspect, wherein the poly (oxyalkylene) group is a poly (oxyalkylene) group having 5 to 12 repeating units.
As a fourth aspect, the present invention relates to the curable composition according to any one of the first aspect to the third aspect, in which the poly (oxyalkylene) group is a poly (oxyethylene) group.
As a fifth aspect, the present invention relates to the curable composition according to any one of the first to fourth aspects, wherein the active energy ray polymerizable group is a group having at least two active energy ray polymerizable moieties. .
As a sixth aspect, the first to fifth aspects, wherein the polyfunctional monomer of component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. It relates to the curable composition as described in any one of viewpoints.
As a seventh aspect, the present invention relates to the curable composition according to any one of the first aspect to the sixth aspect, further including (f) a solvent.
As an 8th viewpoint, it is related with the cured film obtained from the curable composition as described in any one among a 1st viewpoint thru | or a 7th viewpoint.
As a ninth aspect, the present invention relates to a hard coat film comprising a hard coat layer on at least one surface of a film base material, wherein the hard coat layer comprises the cured film described in the eighth aspect.
As a tenth aspect, the hard coat film according to the ninth aspect, wherein the hard coat layer has a thickness of 1 to 15 μm.
An eleventh aspect is a method for producing a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the curable composition according to any one of the first aspect to the seventh aspect is used. It is related with the manufacturing method of a hard coat film including the process of apply | coating on a film base material, and forming a coating film, and the process of irradiating an active energy ray to this coating film and hardening.
　本発明によれば、厚さ１～１５μｍ程度の薄膜においても優れた耐擦傷性を有し、且つ耐光性に優れる硬化膜及びハードコート層の形成に有用な硬化性組成物を提供することができる。
　また、本発明によれば、前記硬化性組成物より得られ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、耐擦傷性及び耐光性に優れるハードコートフィルムを提供することができる。
　特に本発明によれば、ハードコートフィルムをディスプレイ表面等の基材表面に適用する際、光学透明接着剤を用いた接着工程を経た後においても、該ハードコートフィルムの基材（フィルム）からのハードコート層の剥離を抑制でき、耐光性に優れるハードコートフィルムを提供することができる。 According to the present invention, it is possible to provide a curable composition useful for the formation of a cured film and a hard coat layer having excellent scratch resistance even in a thin film having a thickness of about 1 to 15 μm and excellent in light resistance. it can.
Further, according to the present invention, it is possible to provide a hard coat film having a cured film obtained from the curable composition or a hard coat layer formed from the cured film, which is provided on the surface. An excellent hard coat film can be provided.
In particular, according to the present invention, when a hard coat film is applied to a substrate surface such as a display surface, the hard coat film can be removed from the substrate (film) even after an adhesion process using an optical transparent adhesive. It is possible to provide a hard coat film that can suppress peeling of the hard coat layer and is excellent in light resistance.
＜硬化性組成物＞
　本発明の硬化性組成物は、詳細には、
（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）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して、活性エネルギー線重合性基を結合するパーフルオロポリエーテル０．１～１０質量部、
（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１～２０質量部、
（ｄ）ヒドロキシフェニルトリアジン系紫外線吸収剤１～３質量部、及び
（ｅ）ヒンダードアミン系光安定剤１～２質量部
を含む硬化性組成物に関する。
　以下、まず上記（ａ）～（ｅ）の各成分について説明する。 <Curable composition>
In detail, the curable composition of the present invention includes:
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) the active energy at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group or via the poly (oxyalkylene) group and one urethane bond group in this order; 0.1 to 10 parts by mass of perfluoropolyether to which a linear polymerizable group is bonded,
(C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
The present invention relates to a curable composition comprising (d) 1 to 3 parts by mass of a hydroxyphenyltriazine ultraviolet absorber and (e) 1 to 2 parts by mass of a hindered amine light stabilizer.
Hereinafter, the components (a) to (e) will be described first.
［（ａ）活性エネルギー線硬化性多官能モノマー］
　活性エネルギー線硬化性多官能モノマーとは、紫外線等の活性エネルギー線を照射することで重合反応が進行し、硬化するモノマーを指す。
　本発明の硬化性組成物において好ましい（ａ）活性エネルギー線硬化性多官能モノマーとしては、多官能（メタ）アクリレート化合物及び多官能ウレタン（メタ）アクリレート化合物からなる群から選択されるモノマーである。
　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。例えば（メタ）アクリル酸は、アクリル酸とメタクリル酸をいう。 [(A) Active energy ray-curable polyfunctional monomer]
The active energy ray-curable polyfunctional monomer refers to a monomer that is cured by a polymerization reaction that proceeds by irradiation with an active energy ray such as ultraviolet rays.
In the curable composition of the present invention, the preferable (a) active energy ray-curable polyfunctional monomer is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
　上記多官能（メタ）アクリレート化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、エトキシ化ジペンタエリスリトールヘキサ（メタ）アクリレート、エトキシ化グリセリントリ（メタ）アクリレート、エトキシ化ビスフェノールＡジ（メタ）アクリレート、１，３－プロパンジオールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、２－メチル－１，８－オクタンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ビス（２－ヒドロキシエチル）イソシアヌレートジ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デカンジメタノールジ（メタ）アクリレート、ジオキサングリコールジ（メタ）アクリレート、２－ヒドロキシ－１－アクリロイルオキシ－３－メタクリロイルオキシプロパン、２－ヒドロキシ－１，３－ジ（メタ）アクリロイルオキシプロパン、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン、ビス［４－（メタ）アクリロイルチオフェニル］スルフィド、ビス［２－（メタ）アクリロイルチオエチル］スルフィド、１，３－アダマンタンジオールジ（メタ）アクリレート、１，３－アダマンタンジメタノールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等を挙げることができる。
　中でも好ましいものとして、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等を挙げることができる。 Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate , Ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated bisphenol Nord A di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclo [5.2.1.0 2, 6] de Candimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9 -Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantane Diol di (meth) acrylate, , 3-adamantane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.
Among them, preferred are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.
　上記多官能ウレタン（メタ）アクリレート化合物は、１分子内にアクリロイル基又はメタクリロイル基を複数有し、ウレタン結合（－ＮＨＣＯＯ－）を一つ以上有する化合物である。
　例えば上記多官能ウレタン（メタ）アクリレート化合物としては、多官能イソシアネートとヒドロキシ基を有する（メタ）アクリレートとの反応により得られるもの、多官能イソシアネートとヒドロキシ基を有する（メタ）アクリレートとポリオールとの反応により得られるものなどが挙げられるが、本発明で使用可能な多官能ウレタン（メタ）アクリレート化合物はかかる例示のみに限定されるものではない。 The polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (—NHCOO—).
For example, the polyfunctional urethane (meth) acrylate compound is obtained by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group, or a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol. However, the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to such examples.
　なお上記多官能イソシアネートとしては、例えば、トリレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート等が挙げられる。
　また上記ヒドロキシ基を有する（メタ）アクリレートとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、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ペンタ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート等が挙げられる。
　そして上記ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール等のジオール類；これらジオール類とコハク酸、マレイン酸、アジピン酸等の脂肪族ジカルボン酸類又はジカルボン酸無水物類との反応生成物であるポリエステルポリオール；ポリエーテルポリオール；ポリカーボネートジオール等が挙げられる。 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). An acrylate, tripentaerythritol hepta (meth) acrylate, etc. are mentioned.
Examples of the polyol include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these diols, succinic acid, malein Examples include polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as acids and adipic acid; polyether polyols; polycarbonate diols and the like.
　本発明では、上記（ａ）活性エネルギー線硬化性多官能モノマーとして、上記多官能（メタ）アクリレート化合物及び上記多官能ウレタン（メタ）アクリレート化合物からなる群から一種を単独で、或いは二種以上を組合せて使用することができる。得られる硬化物の耐擦傷性の観点から、多官能（メタ）アクリレート化合物及び多官能ウレタン（メタ）アクリレート化合物を併用することが好ましい。また、上記多官能（メタ）アクリレート化合物として、５官能以上の多官能（メタ）アクリレート化合物及び４官能以下の多官能（メタ）アクリレート化合物を併用することが好ましい。
　また、上記多官能（メタ）アクリレート化合物と上記多官能ウレタン（メタ）アクリレート化合物とを組み合わせて使用する場合、多官能（メタ）アクリレート化合物１００質量部に対し、多官能ウレタン（メタ）アクリレート化合物２０～１００質量部を使用することが好ましく、３０～７０質量部を使用することがより好ましい。
　さらに、上記多官能（メタ）アクリレート化合物において、上記５官能以上の多官能（メタ）アクリレート化合物と上記４官能以下の多官能（メタ）アクリレート化合物とを組み合わせて使用する場合、５官能以上の多官能（メタ）アクリレート化合物１００質量部に対し、４官能以下の多官能（メタ）アクリレート化合物１０～１００質量部を使用することが好ましく、２０～６０質量部を使用することがより好ましい。
　また、多官能（メタ）アクリレート化合物１００質量部に対し多官能ウレタン（メタ）アクリレート化合物２０～１００質量部かつ５官能以上の多官能（メタ）アクリレート化合物１００質量部に対し４官能以下の多官能（メタ）アクリレート化合物１０～１００質量部にて使用すること、
多官能（メタ）アクリレート化合物１００質量部に対し多官能ウレタン（メタ）アクリレート化合物２０～１００質量部かつ５官能以上の多官能（メタ）アクリレート化合物１００質量部に対し４官能以下の多官能（メタ）アクリレート化合物２０～６０質量部にて使用すること、
多官能（メタ）アクリレート化合物１００質量部に対し多官能ウレタン（メタ）アクリレート化合物３０～７０質量部かつ５官能以上の多官能（メタ）アクリレート化合物１００質量部に対し４官能以下の多官能（メタ）アクリレート化合物１０～１００質量部にて使用すること、
多官能（メタ）アクリレート化合物１００質量部に対し多官能ウレタン（メタ）アクリレート化合物３０～７０質量部かつ５官能以上の多官能（メタ）アクリレート化合物１００質量部に対し４官能以下の多官能（メタ）アクリレート化合物２０～６０質量部にて使用することが好ましい。 In the present invention, as the (a) active energy ray-curable polyfunctional monomer, one kind is selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound, or two or more kinds are used. Can be used in combination. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound in combination. Moreover, it is preferable to use together 5 or more functional polyfunctional (meth) acrylate compound and 4 or less polyfunctional (meth) acrylate compound as said polyfunctional (meth) acrylate compound.
Moreover, when using the said polyfunctional (meth) acrylate compound and the said polyfunctional urethane (meth) acrylate compound in combination, the polyfunctional urethane (meth) acrylate compound 20 with respect to 100 mass parts of polyfunctional (meth) acrylate compounds. It is preferable to use ˜100 parts by mass, and it is more preferable to use 30 to 70 parts by mass.
Furthermore, in the polyfunctional (meth) acrylate compound, when the polyfunctional (meth) acrylate compound having 5 or more functions and the polyfunctional (meth) acrylate compound having 4 or less functions are used in combination, the polyfunctional (meth) acrylate compound has 5 or more functions. It is preferable to use 10 to 100 parts by mass of a tetrafunctional or lower polyfunctional (meth) acrylate compound with respect to 100 parts by mass of the functional (meth) acrylate compound, and it is more preferable to use 20 to 60 parts by mass.
In addition, polyfunctional urethane (meth) acrylate compound 20 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound and polyfunctional (meth) acrylate compounds having a functionality of 4 or less with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound. (Meth) acrylate compound to be used at 10 to 100 parts by mass,
Polyfunctional (meth) acrylate compound 20 to 100 parts by mass with respect to 100 parts by mass of polyfunctional (meth) acrylate compound and polyfunctional (meth) acrylate compound with a functionality of 4 or less with respect to 100 parts by mass of polyfunctional (meth) acrylate compound having 5 or more functions ) Use at 20-60 parts by mass of acrylate compound,
Polyfunctional (meth) acrylate compound 100 parts by mass Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass and pentafunctional or higher polyfunctional (meth) acrylate compound 100 parts by mass ) Use at 10 to 100 parts by mass of acrylate compound,
Polyfunctional (meth) acrylate compound 100 parts by mass Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass and pentafunctional or higher polyfunctional (meth) acrylate compound 100 parts by mass ) The acrylate compound is preferably used in an amount of 20 to 60 parts by mass.
［（ｂ）ポリ（オキシパーフルオロアルキレン）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して、活性エネルギー線重合性基を結合するパーフルオロポリエーテル］
　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）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して、活性エネルギー線重合性基を結合するパーフルオロポリエーテル（以降、単に「（ｂ）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。 [(B) Active via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond group in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group Perfluoropolyether binding energy beam polymerizable groups]
In the present invention, as the component (b), a poly (oxyalkylene) group and one urethane bonding group are bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group. Through this order, a perfluoropolyether (hereinafter also referred to as “(b) a perfluoropolyether having a polymerizable group at both ends”) to which an active energy ray polymerizable group is bonded 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.
　上記ポリ（オキシパーフルオロアルキレン）基におけるアルキレン基の炭素原子数は特に限定されないが、好ましくは炭素原子数１～４であることが好ましい。すなわち、上記ポリ（オキシパーフルオロアルキレン）基は、炭素原子数１～４の２価のフッ化炭素基と酸素原子が交互に連結した構造を有する基を指し、オキシパーフルオロアルキレン基は炭素原子数１～４の２価のフッ化炭素基と酸素原子が連結した構造を有する基を指す。具体的には、－［ＯＣＦ２］－（オキシパーフルオロメチレン基）、－［ＯＣＦ２ＣＦ２］－（オキシパーフルオロエチレン基）、－［ＯＣＦ２ＣＦ２ＣＦ２］－（オキシパーフルオロプロパン－１，３－ジイル基）、－［ＯＣＦ２Ｃ（ＣＦ３）Ｆ］－（オキシパーフルオロプロパン－１，２－ジイル基）等の基が挙げられる。
　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。 The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but 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 oxygen atoms are alternately connected, and the oxyperfluoroalkylene group is a carbon atom. This refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked. Specifically, — [OCF 2 ] — (oxyperfluoromethylene group), — [OCF 2 CF 2 ] — (oxyperfluoroethylene group), — [OCF 2 CF 2 CF 2 ] — (oxyperfluoropropane) -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. In such a case, the bonds of plural types of oxyperfluoroalkylene groups are block bonds and random bonds. Any of these may be used.
　これらの中でも、耐擦傷性が良好となる硬化膜が得られる観点から、ポリ（オキシパーフルオロアルキレン）基として、－［ＯＣＦ２］－（オキシパーフルオロメチレン基）と－［ＯＣＦ２ＣＦ２］－（オキシパーフルオロエチレン基）の双方を繰り返し単位として有する基を用いることが好ましい。
　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１，５００～２，０００である。 Among these, from the viewpoint of obtaining a cured film having good scratch resistance, as the poly (oxyperfluoroalkylene) group, — [OCF 2 ] — (oxyperfluoromethylene group) and — [OCF 2 CF 2 ] are used. It is preferable to use a group having both of-(oxyperfluoroethylene group) as repeating units.
Among them, as the poly (oxyperfluoroalkylene) group, the repeating unit: — [OCF 2 ] — and — [OCF 2 CF 2 ] — are represented by a molar ratio of [Repeating unit: — [OCF 2 ] —]: [Repeating Unit: — [OCF 2 CF 2 ] —] = 2: 1 to 1: 2 is preferable, and a group including about 1: 1 is more preferable. The bond of these repeating units may be either a block bond or a random bond.
The number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, as the total number of repeating units.
The weight average molecular weight (Mw) of the poly (oxyperfluoroalkylene) group measured in terms of polystyrene by gel permeation chromatography is 1,000 to 5,000, preferably 1,500 to 2,000. .
　上記ポリ（オキシアルキレン）基におけるアルキレン基の炭素原子数は特に限定されないが、好ましくは炭素原子数１～４であることが好ましい。すなわち、上記ポリ（オキシアルキレン）基は、炭素原子数１～４のアルキレン基と酸素原子が交互に連結した構造を有する基を指し、オキシアルキレン基は炭素原子数１～４の２価のアルキレン基と酸素原子が連結した構造を有する基を指す。上記アルキレン基としては、エチレン基、１－メチルエチレン基、トリメチレン基、テトラメチレン基等が挙げられる。
　上記オキシアルキレン基は、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（オキシアルキレン）基は、ポリ（オキシエチレン）基であることが好ましい。
　上記ポリ（オキシアルキレン）基におけるオキシアルキレン基の繰り返し単位数は、例えば１～１５の範囲であり、例えば５～１２の範囲、例えば７～１２の範囲であることがより好ましい。 The number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyalkylene) group refers to a group having a structure in which an alkylene group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyalkylene group is a divalent alkylene having 1 to 4 carbon atoms. A group having a structure in which a group and an oxygen atom are linked. Examples of the alkylene group include an ethylene group, a 1-methylethylene group, a trimethylene group, and a tetramethylene group.
The oxyalkylene groups may be used singly or in combination of two or more. In that case, the bonds of the plural oxyalkylene groups may be either block bonds or random bonds. May be.
Among these, the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.
The number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is, for example, in the range of 1 to 15, and more preferably in the range of 5 to 12, for example, 7 to 12.
　上記ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して結合する活性エネルギー線重合性基としては、（メタ）アクリロイル基、ウレタン（メタ）アクリロイル基、ビニル基等が挙げられる。 Examples of the active energy ray-polymerizable group that bonds the poly (oxyalkylene) group or the poly (oxyalkylene) group and one urethane bond group in this order include a (meth) acryloyl group and a urethane (meth) acryloyl group. Group, vinyl group and the like.
　上記活性エネルギー線重合性基は、（メタ）アクリロイル部分等の活性エネルギー線重合性部分を１つ有するものに限られず、２つ以上の活性エネルギー線重合性部分を有するものであってもよく、例えば、以下に示すＡ１～Ａ５の構造、及びこれらの構造中のアクリロイル基をメタクリロイル基に置換した構造が挙げられる。 The active energy ray polymerizable group is not limited to one having one active energy ray polymerizable portion such as a (meth) acryloyl moiety, and may have two or more active energy ray polymerizable portions, For example, the following structures A1 to A5 and structures in which the acryloyl group in these structures is substituted with a methacryloyl group can be mentioned.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　このような（ｂ）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して、工業的製造が容易であるという点から、以下に示す化合物及びこれらの化合物中のアクリロイル基をメタクリロイル基に置換した化合物を好ましい例として挙げることができる。なお、構造式中、Ａは前記式［Ａ１］～式［Ａ５］で表される構造のうちの１つを表し、ＰＦＰＥは前記ポリ（オキシパーフルオロアルキレン）基を表し、ｎはそれぞれ独立してオキシエチレン基の繰り返し単位数を表し、好ましくは１～１５の数を表し、より好ましくは５～１２の数を表し、さらに好ましくは７～１２の数を表す。
Figure JPOXMLDOC01-appb-C000004
 As the perfluoropolyether having a polymerizable group at both ends (b), the following compounds and compounds obtained by substituting acryloyl groups in these compounds with methacryloyl groups from the viewpoint of easy industrial production Can be mentioned as a preferred example. In the structural formula, A represents one of the structures represented by the formulas [A1] to [A5], PFPE represents the poly (oxyperfluoroalkylene) group, and n is independently selected. Represents the number of repeating units of the oxyethylene group, preferably a number of 1 to 15, more preferably a number of 5 to 12, and still more preferably a number of 7 to 12.
Figure JPOXMLDOC01-appb-C000004
　中でも、本発明の（ｂ）両末端に重合性基を有するパーフルオロポリエーテルは、ポリ（オキシパーフルオロアルキレン）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して、すなわち、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ポリ（オキシアルキレン）基がそれぞれ結合し、該両端の各ポリ（オキシアルキレン）基にそれぞれウレタン結合基が１つ結合し、そして該両端の各ウレタン結合に活性エネルギー線重合性基がそれぞれ結合したパーフルオロポリエーテルであることが好ましい。さらに、前記パーフルオロポリエーテルにおいて、活性エネルギー線重合性基が少なくとも２つ以上の活性エネルギー線重合性部分を有する基であるパーフルオロポリエーテルであることが好ましい。 Among them, the (b) perfluoropolyether having a polymerizable group at both ends of the present invention has a poly (oxyalkylene) group and one urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group. Through these groups in this order, that is, a poly (oxyalkylene) group is bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, and a urethane bond is formed to each poly (oxyalkylene) group at both ends. It is preferably a perfluoropolyether in which one group is bonded and an active energy ray polymerizable group is bonded to each urethane bond at both ends. Further, in the perfluoropolyether, the active energy ray polymerizable group is preferably a perfluoropolyether which is a group having at least two active energy ray polymerizable moieties.
　本発明において（ｂ）両末端に重合性基を有するパーフルオロポリエーテルは、前述の（ａ）活性エネルギー線硬化性多官能モノマー１００質量部に対して、０．１～１０質量部、好ましくは０．２～５質量部の割合で使用することが望ましい。 In the present invention, (b) the perfluoropolyether having a polymerizable group at both ends is 0.1 to 10 parts by weight, preferably 100 parts by weight, preferably 100 parts by weight of the active energy ray-curable polyfunctional monomer. It is desirable to use at a ratio of 0.2 to 5 parts by mass.
　上記（ｂ）両末端に重合性基を有するパーフルオロポリエーテルは、例えば、ポリ（オキシパーフルオロアルキレン）基の両末端にポリ（オキシアルキレン）基を介してヒドロキシ基を有する化合物において、その両端のヒドロキシ基に対して２－（メタ）アクリロイルオキシエチルイソシアネートや１，１－ビス（（メタ）アクリロイルオキシメチル）エチルイソシアネート等の重合性基を有するイソシアネート化合物をウレタン化反応させる方法、（メタ）アクリル酸クロリド又はクロロメチルスチレンを脱塩酸反応させる方法、（メタ）アクリル酸を脱水反応させる方法、無水イタコン酸をエステル化反応させる方法などにより得られる。
　中でも、ポリ（オキシパーフルオロアルキレン）基の両末端にポリ（オキシアルキレン）基を介してヒドロキシ基を有する化合物において、その両端のヒドロキシ基に対して、２－（メタ）アクリロイルオキシエチルイソシアネートや１，１－ビス（（メタ）アクリロイルオキシメチル）エチルイソシアネート等の重合性基を有するイソシアネート化合物をウレタン化反応させる方法、或いは、該ヒドロキシ基に対して（メタ）アクリル酸クロリド又はクロロメチルスチレンを脱塩酸反応させる方法が、反応が容易である点で特に好ましい。 The perfluoropolyether having a polymerizable group at both ends (b) is, for example, a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group. A urethanization reaction of an isocyanate compound having a polymerizable group such as 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate with respect to the hydroxy group of (meth) It can be obtained by a method of dehydrochlorinating acrylic acid chloride or chloromethylstyrene, a method of dehydrating (meth) acrylic acid, a method of esterifying itaconic anhydride, and the like.
In particular, in a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, 2- (meth) acryloyloxyethyl isocyanate or 1 , 1-bis ((meth) acryloyloxymethyl) ethyl isocyanate or other isocyanate compounds having a polymerizable group, or (meth) acrylic acid chloride or chloromethylstyrene is removed from the hydroxy group. The method of reacting with hydrochloric acid is particularly preferable because the reaction is easy.
　なお本発明の硬化性組成物には、（ｂ）ポリ（オキシパーフルオロアルキレン）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して、活性エネルギー線重合性基を結合するパーフルオロポリエーテルに加えて、ポリ（オキシパーフルオロアルキレン）基を含む分子鎖の一端にポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して、活性エネルギー線重合性基を結合し、且つその他端にポリ（オキシアルキレン）基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や、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端にポリ（オキシアルキレン）基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［活性エネルギー線重合性基を結合していない化合物］が含まれていてもよい。 In addition, the curable composition of the present invention includes (b) a poly (oxyalkylene) group or one poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group. In addition to the perfluoropolyether to which the active energy ray polymerizable group is bonded through the urethane bonding group in this order, one end of the molecular chain containing the poly (oxyperfluoroalkylene) group is bonded through the poly (oxyalkylene) group. Or a perfluoropolyether having a poly (oxyalkylene) group and one urethane bond group in this order to bind an active energy ray-polymerizable group and having a hydroxy group at the other end via a poly (oxyalkylene) group Or a poly (oxyalkylene) group on both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group. Compound unbound active energy ray-polymerizable group] perfluoropolyether having a sheet group may be included.
［（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］
　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、あるいはヨードニウム塩、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。 [(C) Polymerization initiator that generates radicals by active energy rays]
In the curable composition of the present invention, a polymerization initiator that generates radicals by a preferable active energy ray (hereinafter, also simply referred to as “(c) polymerization initiator”) is, for example, active energy such as electron beam, ultraviolet ray, and X-ray. It is a polymerization initiator that generates radicals by irradiation with ultraviolet rays, in particular.
Examples of the polymerization initiator (c) include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones. Biscumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, or 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.
Among them, in the present invention, it is preferable to use alkylphenones as the polymerization initiator (c) from the viewpoints of transparency, surface curability, and thin film curability. By using alkylphenones, a cured film with improved scratch resistance can be obtained.
　上記アルキルフェノン類としては、例えば、１－ヒドロキシシクロヘキシル＝フェニル＝ケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、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、２－ヒドロキシ－１－（４－（４－（２－ヒドロキシ－２－メチルプロピオニル）ベンジル）フェニル）－２－メチルプロパン－１－オン等のα－ヒドロキシアルキルフェノン類；２－メチル－１－（４－（メチルチオ）フェニル）－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタン－１－オン等のα－アミノアルキルフェノン類；２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン；フェニルグリオキシル酸メチルなどが挙げられる。 Examples of the alkylphenones include 1-hydroxycyclohexyl = phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) Α) such as phenyl) -2-methylpropan-1-one, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one -Hydroxyalkylphenones; 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 Α-aminoalkylphenones such as -one; 2,2-dimethoxy-1,2-diphenylethane-1-one; And methyl reoxylate.
　本発明において（ｃ）重合開始剤は、前述の（ａ）活性エネルギー線硬化性多官能モノマー１００質量部に対して、１～２０質量部、好ましくは２～１０質量部の割合で使用することが望ましい。 In the present invention, (c) the polymerization initiator is used in a ratio of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Is desirable.
［（ｄ）ヒドロキシフェニルトリアジン系紫外線吸収剤］
　本発明の硬化性組成物には（ｄ）成分としてヒドロキシフェニルトリアジン系紫外線吸収剤を使用することを特徴とする。
　特に本発明では、上記ヒドロキシフェニルトリアジン系紫外線吸収剤において、トリアジン環に直接結合する３つのフェニル基が少なくとも２つ以上のヒドロキシ基で置換された化合物であるか、又は、トリアジン環に直接結合する３つのフェニル基のうち少なくとも１つのフェニル基の水素原子がフェニル基で置換され、且つ、トリアジン環に直接結合する３つのフェニル基が合計で少なくとも１つ以上のヒドロキシ基で置換された化合物を採用する。
　このように、本発明において、特定の（ｄ）ヒドロキシフェニルトリアジン系紫外線吸収剤と後述する特定の（ｅ）ヒンダードアミン系光安定剤とを併用することにより、該光硬化性組成物より作製したハードコートフィルムをディスプレイ表面等の基材表面に適用する際、光学透明接着剤を用いた接着工程を経た場合においても、該ハードコートフィルムからのハードコート層の剥離を抑制でき、フィルムとハードコート層との密着性を好適に維持することができ、耐光性に優れたハードコートフィルムとすることができる。 [(D) Hydroxyphenyltriazine UV absorber]
The curable composition of the present invention is characterized by using a hydroxyphenyltriazine-based ultraviolet absorber as the component (d).
In particular, in the present invention, in the above hydroxyphenyl triazine-based ultraviolet absorber, the compound in which three phenyl groups directly bonded to the triazine ring are substituted with at least two hydroxy groups, or directly bonded to the triazine ring. Employs a compound in which at least one of the three phenyl groups is substituted with a phenyl group, and a total of three phenyl groups directly bonded to the triazine ring are substituted with at least one hydroxy group To do.
Thus, in this invention, the hard material produced from this photocurable composition by using together the specific (d) hydroxyphenyl triazine type ultraviolet absorber and the specific (e) hindered amine light stabilizer mentioned later. When a coated film is applied to the surface of a substrate such as a display surface, even when an adhesive step using an optical transparent adhesive is performed, peeling of the hard coat layer from the hard coat film can be suppressed, and the film and the hard coat layer The hard coat film excellent in light resistance can be obtained.
　前記ヒドロキシフェニルトリアジン系紫外線吸収剤として、好ましくは、下記式（Ｕ１）で表されるヒドロキシフェニルトリアジン化合物を挙げることができる。
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８はそれぞれ独立して、水素原子、ヒドロキシ基、フェニル基、又は、エーテル結合、エステル結合及びアミド結合からなる群から選択される１つ以上の結合を含んでいてもよい炭素原子数１乃至１８のアルキル基及び炭素原子数１乃至１８のアルコキシ基からなる群から選択される基であって、前記フェニル基、アルキル基及びアルコキシ基はヒドロキシ基で置換されていてもよく、但し、Ｒ１乃至Ｒ８がいずれもフェニル基でない場合、Ｒ１乃至Ｒ８のうち少なくとも１つがヒドロキシ基を表す。） Preferred examples of the hydroxyphenyl triazine-based ultraviolet absorber include a hydroxyphenyl triazine compound represented by the following formula (U1).
Figure JPOXMLDOC01-appb-C000005
 (Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, a hydroxy group, a phenyl group, or an ether bond, an ester bond and A group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms, which may contain one or more bonds selected from the group consisting of amide bonds, The phenyl group, alkyl group and alkoxy group may be substituted with a hydroxy group, provided that when any of R 1 to R 8 is not a phenyl group, at least one of R 1 to R 8 represents a hydroxy group. .)
　上記炭素原子数１乃至１８のアルキル基としては、分岐構造、環状構造を有していてもよく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基（ラウリル基）、トリデシル基、テトラデシル基（ミリスチル基）、ペンタデシル基、ヘキサデシル基（パルミチル基）、ヘプタデシル基、オクタデシル基（ステアリル基）等が挙げられる。
　また上記炭素原子数１乃至１８のアルコキシ基は、上記炭素原子数１乃至１８のアルキル基が酸素原子に結合した構造を有し、これらは、分岐構造、環状構造を有していてもよい。 The alkyl group having 1 to 18 carbon atoms may have a branched structure or a cyclic structure. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group Hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl Group, octadecyl group (stearyl group) and the like.
The alkoxy group having 1 to 18 carbon atoms has a structure in which the alkyl group having 1 to 18 carbon atoms is bonded to an oxygen atom, and these may have a branched structure or a cyclic structure.
　上記紫外線吸収剤としては、例えば、２，４－ビス（４－ブトキシ－２－ヒドロキシフェニル）－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン［ＢＡＳＦ社製　Ｔｉｎｕｖｉｎ　４６０］、２，４，６－トリス（２－ヒドロキシ－４－ヘキシルオキシ－３－メチルフェニル）－１，３，５－トリアジン［（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－Ｆ７０］、２，４，６－トリス（２－ヒドロキシ－４－（１－（オクチルオキシカルボニル）エトキシ）フェニル）－１，３，５－トリアジン［ＢＡＳＦ社製　Ｔｉｎｕｖｉｎ　４７７］、２，４－ジ（［１，１’－ビフェニル］－４－イル）－６－（２－ヒドロキシ－４－（１－（イソオクチルオキシカルボニル）エトキシ）フェニル）－１，３，５－トリアジン［ＢＡＳＦ社製　Ｔｉｎｕｖｉｎ　４７９］、２，４－ビス（２－ヒドロキシ－４－オクチルオキシフェニル）－６－（２，４－ジメチルフェニル）－１，３，５－トリアジン、２，４，６－トリス（２－ヒドロキシ－４－オクチルオキシフェニル）－１，３，５－トリアジン等が挙げられる。 Examples of the ultraviolet absorber include 2,4-bis (4-butoxy-2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine [Tinuvin 460 manufactured by BASF Corporation]. ] 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine [ADEKA STAB (registered trademark) LA-F70 manufactured by ADEKA Corporation], 2, 4,6-tris (2-hydroxy-4- (1- (octyloxycarbonyl) ethoxy) phenyl) -1,3,5-triazine [BASF Tinuvin 477], 2,4-di ([1,1 '-Biphenyl] -4-yl) -6- (2-hydroxy-4- (1- (isooctyloxycarbonyl) ethoxy) phenyl) -1,3,5-tria [BASF Tinuvin 479], 2,4-bis (2-hydroxy-4-octyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6 -Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine and the like.
　本発明において（ｄ）ヒドロキシフェニルトリアジン系紫外線吸収剤は、前述の（ａ）活性エネルギー線硬化性多官能モノマー１００質量部に対して、１～３質量部、好ましくは２～３質量部の割合で使用することが望ましい。 In the present invention, (d) the hydroxyphenyltriazine-based UV absorber is in a proportion of 1 to 3 parts by weight, preferably 2 to 3 parts by weight, based on 100 parts by weight of the above-mentioned (a) active energy ray-curable polyfunctional monomer. It is desirable to use in.
［（ｅ）ヒンダードアミン系光安定剤］
　本発明の硬化性組成物には（ｅ）成分としてヒンダードアミン系光安定剤を使用し、特に、式［１］で表される基が結合してなる化合物から選択されるヒンダードアミン系光安定剤を採用することを特徴とする。
Figure JPOXMLDOC01-appb-C000006
 　上記式［１］中、Ｒａは水素原子、又は炭素原子数１乃至１０のアルキル基を表し、黒点は結合手を表す。 [(E) Hindered amine light stabilizer]
In the curable composition of the present invention, a hindered amine light stabilizer is used as the component (e), and in particular, a hindered amine light stabilizer selected from a compound formed by bonding a group represented by the formula [1] is used. It is characterized by adopting.
Figure JPOXMLDOC01-appb-C000006
 In the above formula [1], R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a black dot represents a bond.
　Ｒａが表す炭素原子数１乃至１０のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソアミル基、ネオペンチル基、ｔｅｒｔ－アミル基、ｓｅｃ－イソアミル基、シクロペンチル基、ｎ－ヘキシル基、シクロヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等が挙げられる。 Examples of the alkyl group having 1 to 10 carbon atoms represented by Ra include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl, isoamyl, neopentyl, tert-amyl, sec-isoamyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl Groups and the like.
　このようなヒンダードアミン系光安定剤としては市販品も使用し得、例えば、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート［ＢＡＳＦ社製　Ｔｉｎｕｖｉｎ　７７０、（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－７７Ｙ、同ＬＡ－７７Ｇ］、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート［ＢＡＳＦ社製　Ｔｉｎｕｖｉｎ　２９２、（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－７２］、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）＝２－（（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルフェニル）メチル）－２－ブチルマロネート［ＢＡＳＦ社製　Ｔｉｎｕｖｉｎ　１４４］、テトラキス（２，２，６，６－テトラメチル－４－ピペリジル）１，２，３，４－ブタンテトラカルボキシレート［（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－５７］、テトラキス（１，２，２，６，６－ペンタメチル－４－ピペリジル）１，２，３，４－ブタンテトラカルボキシレート［（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－５２］、ビス（２，２，６，６－テトラメチル－４－ピペリジル）ビス（トリデシル）１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）ビス（トリデシル）１，２，３，４－ブタンテトラカルボキシレート、Ｃ１２－２０及びＣ１６－１８不飽和脂肪酸２，２，６，６－テトラメチル－４－ピペリジルエステル［サイテック・インダストリーズ社製　サイアソーブ（登録商標）ＵＶ－３８５３］、ポリ［オキシ（２，２，６，６－テトラメチル－４－ピペリジン－１，４－ジイル）エチレンオキシスクシニロイル］と１，５，８，１２－テトラキス（４，６－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－１，３，５－トリアジン－２－イル）－１，５，８，１２－テトラアザドデカンの混合物［ＢＡＳＦ社製　Ｔｉｎｕｖｉｎ　１１１ＦＤＬ］、ポリ［（６－ｔｅｒｔ－オクチルアミノ－１，３，５－トリアジン－２，４－ジイル）（（２，２，６，６－テトラメチル－４－ピペリジル）イミノ）ヘキサメチレン（（２，２，６，６－テトラメチル－４－ピペリジル）イミノ）］［ＢＡＳＦ社製　ＣＨＩＭＡＳＳＯＲＢ（登録商標）９４４］、２，４，６－トリクロロ－１，３，５－トリアジンと、Ｎ，Ｎ’－ビス（２，２，６，６－テトラメチル－４－ピペリジル）－１，６－ヘキサメチレンジアミン、Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミン、ジブチルアミンとの重縮合物［ＢＡＳＦ社製　ＣＨＩＭＡＳＳＯＲＢ（登録商標）２０２０］、ブタン－１，２，３，４－テトラカルボン酸ビス（２，２，５，５－テトラメチル－４－ピペリジル）エステルとβ，β，β’，β’－テトラメチル－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン－３，９－ジエタノールとの重縮合物［（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－６８］、ブタン－１，２，３，４－テトラカルボン酸ビス（１，２，２，５，５－ペンタメチル－４－ピペリジル）エステルとβ，β，β’，β’－テトラメチル－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン－３，９－ジエタノールとの重縮合物［（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－６３Ｐ］、ポリ［（６－モルホリノ－１，３，５－トリアジン－２，４－ジイル）（（２，２，６，６－テトラメチル－４－ピペリジル）イミノ）ヘキサメチレン（（２，２，６，６－テトラメチル－４－ピペリジル）イミノ）］［サイテック・インダストリーズ社製　サイアソーブ（登録商標）ＵＶ－３３４６］、ポリ［（６－モルホリノ－１，３，５－トリアジン－２，４－ジイル）（（１，２，２，６，６－ペンタメチル－４－ピペリジル）イミノ）ヘキサメチレン（（１，２，２，６，６－ペンタメチル－４－ピペリジル）イミノ）］［サイテック・インダストリーズ社製　サイアソーブ（登録商標）ＵＶ－３５２９］、２，２，６，６－テトラメチル－４－ピペリジルメタクリレート［（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－８７］、１，２，２，６，６－ペンタメチル－４－ピペリジルメタクリレート［（株）ＡＤＥＫＡ製　アデカスタブ（登録商標）ＬＡ－８２］等が挙げられる。 Commercially available products may be used as such hindered amine light stabilizers, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [Tinvin 770 manufactured by BASF Corporation, and Adeka Stub manufactured by ADEKA Corporation. (Registered trademark) LA-77Y, LA-77G], bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (Tinvin 292 manufactured by BASF Corporation, Adeka Stub (registered trademark) manufactured by ADEKA Corporation) LA-72], bis (1,2,2,6,6-pentamethyl-4-piperidyl) = 2-((4-hydroxy-3,5-di-tert-butylphenyl) methyl) -2-butylmalo Nate [Tinvin 144 manufactured by BASF Corporation], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 Butanetetracarboxylate [ADEKA STAB (registered trademark) LA-57 manufactured by ADEKA Corporation], tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate [ADEKA STAB (registered trademark) LA-52, manufactured by ADEKA Corporation], bis (2,2,6,6-tetramethyl-4-piperidyl) bis (tridecyl) 1,2,3,4-butanetetracarboxylate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) 1,2,3,4-butanetetracarboxylate, C 12-20 and C 16-18 unsaturated fatty acids 2,2 , 6,6-Tetramethyl-4-piperidyl ester [Siasorb (registered trademark) UV-3853 manufactured by Cytec Industries, Ltd.], poly [O (2,2,6,6-tetramethyl-4-piperidine-1,4-diyl) ethyleneoxysuccinyloxy] and 1,5,8,12-tetrakis (4,6-bis (N-butyl- Mixture of N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl) -1,5,8,12-tetraazadodecane [BASF Tinuvin 111FDL], poly [(6-tert-octylamino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexa Methylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)] [CHIMASSORB (registered trademark) 944 made by BASF], 2,4,6-trichloro-1,3,5-triazine, N N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl ) A polycondensation product of amine and dibutylamine [CHIMASSORB (registered trademark) 2020 manufactured by BASF Corporation], bis (2,2,5,5-tetramethyl-4-butane-1,2,3,4-tetracarboxylate) Piperidyl) ester and polycondensate of β, β, β ′, β′-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol [Adeka Co., Ltd. Manufactured by ADK STAB (registered trademark) LA-68], butane-1,2,3,4-tetracarboxylic acid bis (1,2,2,5,5-pentamethyl-4-piperidyl) ester and β, β, β ′ , Β'-tetramethyl-2, , 8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol polycondensate [ADEKA STAB (registered trademark) LA-63P manufactured by ADEKA Corporation], poly [(6-morpholino-1, 3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) Imino)] [Ciasorb Industries UV-3346 manufactured by Cytec Industries, Inc.], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) ((1,2,2,6, 6-pentamethyl-4-piperidyl) imino) hexamethylene ((1,2,2,6,6-pentamethyl-4-piperidyl) imino)] [Saiso manufactured by Cytec Industries, Inc. (Registered trademark) UV-3529], 2,2,6,6-tetramethyl-4-piperidyl methacrylate [ADEKA STAB (registered trademark) LA-87 manufactured by ADEKA Corporation], 1,2,2,6,6 -Pentamethyl-4-piperidyl methacrylate [ADEKA STAB (registered trademark) LA-82 manufactured by ADEKA Corporation] and the like.
　本発明において（ｅ）ヒンダードアミン系光安定剤は、前述の（ａ）活性エネルギー線硬化性多官能モノマー１００質量部に対して、１～２質量部の割合で使用することが望ましい。 In the present invention, the (e) hindered amine light stabilizer is desirably used in a ratio of 1 to 2 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.
［（ｆ）溶媒］
　本発明の硬化性組成物は、更に（ｆ）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）～（ｅ）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炭化水素類；酢酸エチル、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；Ｎ－メチル－２－ピロリドン等の複素環式化合物類、並びにこれらの２種以上の混合溶媒が挙げられる。
　これら（ｆ）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１～７０質量％、好ましくは５～５０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）～（ｆ）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。 [(F) Solvent]
The curable composition of the present invention may further contain (f) a solvent, that is, may be in the form of a varnish (film forming material).
The solvent is appropriately selected in consideration of the workability at the time of coating and the drying property before and after curing for dissolving the components (a) to (e) and forming a cured film (hard coat layer) described later. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, Halogenated hydrocarbons such as methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve Acetate, propylene glycol monomethyl ether acetate, etc. Stealth or ester ethers; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl Ethers such as ether and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol and isobutyl Alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol Alcohols such as ethylene glycol; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; heterocyclic compounds such as N-methyl-2-pyrrolidone; 2 or more types of mixed solvents are mentioned.
The amount of the solvent (f) used is not particularly limited. For example, the solvent is used at a concentration such that the solid content in the curable composition of the present invention is 1 to 70% by mass, preferably 5 to 50% by mass. Here, the solid content concentration (also referred to as the non-volatile content concentration) means the solid content relative to the total mass (total mass) of the components (a) to (f) (and other additives as required) of the curable composition of the present invention. The content of (all solvent components are removed) is expressed.
［その他添加物］
　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、重合促進剤、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、上記以外の紫外線吸収剤、上記以外の光安定剤、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。 [Other additives]
The curable composition of the present invention, as long as the effects of the present invention are not impaired, are generally added as necessary, for example, polymerization accelerators, polymerization inhibitors, photosensitizers, leveling. Agents, surfactants, adhesion-imparting agents, plasticizers, UV absorbers other than those mentioned above, light stabilizers other than those mentioned above, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc. You may mix.
＜硬化膜＞
　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。 <Curing film>
The curable composition of this invention can form a cured film by apply | coating (coating) on a base material, forming a coating film, and irradiating an active energy ray to this coating film and superposing | polymerizing (hardening). The cured film is also an object of the present invention. Moreover, the hard coat layer in the hard coat film mentioned later can consist of this cured film.
Examples of the base material in this case include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, Acetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass, slate, and the like. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
　前記基材上への塗布方法は、キャストコート法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、スプレーコート法、バーコート法、ダイコート法、インクジェット法、印刷法（凸版、凹版、平版、スクリーン印刷等）等を適宜選択し得、中でもロール・ツー・ロール（ｒｏｌｌ－ｔｏ－ｒｏｌｌ）法に利用でき、また薄膜塗布性の観点から、凸版印刷法、特にグラビアコート法を用いることが望ましい。なお事前に孔径が０．２μｍ程度のフィルタなどを用いて硬化性組成物を濾過した後、塗布に供することが好ましい。なお塗布する際、必要に応じて該硬化性組成物に溶剤を添加してワニスの形態としてもよい。この場合の溶剤としては前述の［（ｆ）溶媒］で挙げた種々の溶媒を挙げることができる。
　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又はオーブン等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。
　乾燥後、紫外線等の活性エネルギー線を照射して、塗膜を硬化させる。活性エネルギー線としては、紫外線、電子線、Ｘ線等が挙げられ、特に紫外線が好ましい。紫外線照射に用いる光源としては、太陽光線、ケミカルランプ、低圧水銀灯、高圧水銀灯、メタルハライドランプ、キセノンランプ、ＵＶ－ＬＥＤ等が使用できる。
　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０．０１～５０μｍ、好ましくは０．０５～２０μｍである。 The coating method on the base material 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 ink jet method, a printing method (a relief plate, an intaglio plate). , Lithographic printing, screen printing, etc.) can be selected as appropriate, and in particular, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating, a relief printing method, particularly a gravure coating method is used. It is desirable. It is preferable that the curable composition is filtered in advance using a filter having a pore diameter of about 0.2 μm or the like and then used for coating. In addition, when apply | coating, it is good also as a form of a varnish by adding a solvent to this curable composition as needed. Examples of the solvent in this case include various solvents mentioned in the above-mentioned [(f) Solvent].
After the curable composition is applied on the substrate to form a coating film, the coating film is pre-dried with a hot plate or an oven as necessary to remove the solvent (solvent removal step). The heat drying conditions at this time are preferably 40 to 120 ° C. and about 30 seconds to 10 minutes, for example.
After drying, the coating film is cured by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
Furthermore, after that, polymerization may be completed by performing post-baking, specifically by heating using a hot plate, an oven or the like.
The thickness of the formed cured film is usually 0.01 to 50 μm, preferably 0.05 to 20 μm after drying and curing.
＜ハードコートフィルム＞
　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等の表面を保護するために好適に用いられる。 <Hard coat film>
A hard coat film provided with a hard coat layer on at least one surface (surface) of a film substrate can be produced using the curable composition of the present invention. The hard coat film is also an object of the present invention, and the hard coat film is suitably used for protecting the surface of various display elements such as a touch panel and a liquid crystal display.
　本発明のハードコートフィルムにおけるハードコート層は、前述の本発明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、該塗膜に紫外線等の活性エネルギー線を照射し該塗膜を硬化させる工程を含む方法により形成することができる。 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 on 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.
　前記フィルム基材としては、前述の＜硬化膜＞で挙げた基材のうち、光学用途に使用可能な各種の透明な樹脂製フィルムが用いられる。好ましくは例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）などのポリエステル、ポリカーボネート、ポリメタクリレート、ポリスチレン、ポリオレフィン、ポリアミド、ポリイミド、トリアセチルセルロース等から選択される樹脂製フィルムが挙げられる。
　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）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膜厚は、好ましくは１～２０μｍ、より好ましくは１～１０μｍである。 As the film substrate, various transparent resin films that can be used for optical applications among the substrates mentioned in the above-mentioned <cured film> are used. Preferably, for example, a resin selected from polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose, etc. A film is mentioned.
Moreover, the application method (coating film formation process) of the curable composition on the film substrate and the active energy ray irradiation method (curing process) to the coating film use the method described in the above <cured film>. Can do. Moreover, when a solvent is contained in the curable composition of this invention (varnish form), the process of drying this coating film and removing a solvent as needed can be included after a coating-film formation process. In that case, the drying method (solvent removal process) of the coating film quoted to the above-mentioned <cured film> can be used.
The thickness of the hard coat layer thus obtained is preferably 1 to 20 μm, more preferably 1 to 10 μm.
　以下、実施例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。
　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。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.
（１）バーコート塗布
　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（ワイヤーバー＃１２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
（４）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　ＫＦ－８０４Ｌ、ＧＰＣ　ＫＦ－８０５Ｌ
　カラム温度：４０℃
　溶離液：テトラヒドロフラン
　検出器：ＲＩ
（５）イオンクロマトグラフィー（Ｆ定量分析）
　装置：日本ダイオネクス（株）製　ＩＣＳ－１５００
　溶媒：（２．７ｍｍｏｌ　Ｎａ２ＣＯ３　＋　０．３ｍｍｏｌ　ＮａＨＣＯ３）／Ｌ水溶液
　検出器：電気伝導度
（６）膜厚
　装置：フィルメトリクス（株）製　卓上式膜厚測定システムＦ２０
（７）耐光性試験
　装置：Ｑ－Ｌａｂ社製　促進耐候性試験機　ＱＵＶ（登録商標）／ｓｅ
　光源：ＵＶＡ－３４０型ランプ
　試験条件：０．７６Ｗ／ｃｍ２、６０℃、結露下
　試験時間：７２時間
（８）黄色度
　装置：コニカミノルタ（株）製　分光測色計　ＣＭ－７００ｄ
　測定モード：正反射光除去（ＳＣＥ）モード
（９）擦傷試験
　装置：新東科学（株）製　往復摩耗試験機　ＴＲＩＢＯＧＥＡＲ　ＴＹＰＥ：３０Ｓ
　荷重：２５０ｇ／ｃｍ２
　走査速度：３ｍ／分 (1) Bar coat application device: PM-9050MC manufactured by SMT Co., Ltd.
Bar: OSG System Products A-Bar OSP-30, maximum wet film thickness 30μm (corresponding to wire bar # 12)
Application speed: 4 m / min (2) Oven Equipment: Dust dryer DRC433FA manufactured by Advantech Toyo Co., Ltd.
(3) UV curing device: CV-110QC-G manufactured by Heraeus Co., Ltd.
Lamp: Heraeus high pressure mercury lamp H-bulb
(4) Gel permeation chromatography (GPC)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) GPC KF-804L, GPC KF-805L manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI
(5) Ion chromatography (F quantitative analysis)
Equipment: ICS-1500 manufactured by Nippon Dionex Co., Ltd.
Solvent: (2.7 mmol Na 2 CO 3 + 0.3 mmol NaHCO 3 ) / L aqueous solution Detector: Electrical conductivity (6) film thickness Device: Tabletop thickness measurement system F20 manufactured by Filmetrics Co., Ltd.
(7) Light resistance test apparatus: Accelerated weather resistance tester QUV (registered trademark) / se manufactured by Q-Lab
Light source: UVA-340 type lamp Test conditions: 0.76 W / cm 2 , 60 ° C., under dew condensation Test time: 72 hours (8) Yellowness Device: Spectrocolorimeter CM-700d manufactured by Konica Minolta Co., Ltd.
Measurement mode: specular reflection removal (SCE) mode (9) Scratch test Device: Reciprocating wear tester manufactured by Shinto Kagaku Co., Ltd. TRIBOGEAR TYPE: 30S
Load: 250 g / cm 2
Scanning speed: 3m / min
　また、略記号は以下の意味を表す。
ＰＦＰＥ：両末端にポリ（オキシアルキレン）基（繰返し単位数８～９）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］
ＤＢＴＤＬ：ジラウリン酸ジブチル錫［東京化成工業（株）製］
ＤＰＨＡ：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　ＫＡＹＡＬＡＤ　ＤＮ－００７５］
ＰＥＴＡ：ペンタエリスリトールトリアクリレート／ペンタエリスリトールテトラアクリレート混合物［新中村化学工業（株）製　ＮＫエステル　Ａ－ＴＭＭ－３ＬＭ－Ｎ］
ＵＡ：６官能脂肪族ウレタンアクリレートオリゴマー［ダイセル・オルネクス（株）製　ＥＢＥＣＲＹＬ（登録商標）５１２９］
Ｉ２９５９：２－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［ＢＡＳＦジャパン（株）製　ＩＲＧＡＣＵＲＥ（登録商標）２９５９］
ＵＶＡ１：２，４，６－トリス（２－ヒドロキシ－４－（１－（オクチルオキシカルボニル）エトキシ）フェニル）－１，３，５－トリアジン［ＢＡＳＦジャパン（株）製　Ｔｉｎｕｖｉｎ　４７７］
ＵＶＡ２：２，４－ビス（４－ブトキシ－２－ヒドロキシフェニル）－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン［ＢＡＳＦジャパン（株）製　Ｔｉｎｕｖｉｎ　４６０］
ＵＶＡ３：２，４－ジ（［１，１’－ビフェニル］－４－イル）－６－（２－ヒドロキシ－４－（１－（イソオクチルオキシカルボニル）エトキシ）フェニル）－１，３，５－トリアジン［ＢＡＳＦジャパン（株）製　Ｔｉｎｕｖｉｎ　４７９］
ＵＶＡ４：２，４－ビス（２，４－ジメチルフェニル）－６－（４－（３－（２－エチルヘキシルオキシ）－２－ヒドロキシプロポキシ）－２－ヒドロキシフェニル）－１，３，５－トリアジン［ＢＡＳＦジャパン（株）製　Ｔｉｎｕｖｉｎ　４０５］
ＵＶＡ５：２－（２－ヒドロキシ－３－（２－フェニルプロパン－２－イル）－５－（１，１，３，３－テトラメチルブチル）フェニル）－２Ｈ－ベンゾトリアゾール［ＢＡＳＦジャパン（株）製　Ｔｉｎｕｖｉｎ　９２８］
ＨＡＬＳ１：セバシン酸ビス（１，２，２，６，６，－ペンタメチルピペリジン－４－イル）［ＢＡＳＦジャパン（株）製　Ｔｉｎｕｖｉｎ　２９２］
ＨＡＬＳ２：セバシン酸ビス（２，２，６，６，－テトラメチル－Ｎ－オクチルオキシピペリジン－４－イル）［ＢＡＳＦジャパン（株）製　Ｔｉｎｕｖｉｎ　１２３］
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 Abbreviations represent the following meanings.
PFPE: Perfluoropolyether having a hydroxy group via a poly (oxyalkylene) group (repeating unit number 8 to 9) at both ends [Fluorolink 5147X manufactured by Solvay Specialty Polymers]
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko KK]
DBTDL: Dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]
DPHA: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [KAYALAD DN-0075 manufactured by Nippon Kayaku Co., Ltd.]
PETA: Pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture [Shin-Nakamura Chemical Co., Ltd. NK ester A-TMM-3LM-N]
UA: 6-functional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129, manufactured by Daicel Ornex Co., Ltd.]
I2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [IRGACURE (registered trademark) 2959, manufactured by BASF Japan Ltd.]
UVA1: 2,4,6-tris (2-hydroxy-4- (1- (octyloxycarbonyl) ethoxy) phenyl) -1,3,5-triazine [Tinuvin 477 manufactured by BASF Japan Ltd.]
UVA2: 2,4-bis (4-butoxy-2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine [Tinuvin 460 manufactured by BASF Japan Ltd.]
UVA3: 2,4-di ([1,1′-biphenyl] -4-yl) -6- (2-hydroxy-4- (1- (isooctyloxycarbonyl) ethoxy) phenyl) -1,3,5 -Triazine [Tinvin 479, manufactured by BASF Japan Ltd.]
UVA4: 2,4-bis (2,4-dimethylphenyl) -6- (4- (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -2-hydroxyphenyl) -1,3,5-triazine [Tinuvin 405 manufactured by BASF Japan Ltd.]
UVA5: 2- (2-hydroxy-3- (2-phenylpropan-2-yl) -5- (1,1,3,3-tetramethylbutyl) phenyl) -2H-benzotriazole [BASF Japan K.K. Made Tinuvin 928]
HALS1: Bis (1,2,2,6,6, -pentamethylpiperidin-4-yl) sebacate [Tinvin 292 manufactured by BASF Japan Ltd.]
HALS2: bis (2,2,6,6, -tetramethyl-N-octyloxypiperidin-4-yl) sebacate [Tinvin 123 manufactured by BASF Japan Ltd.]
MEK: Methyl ethyl ketone PGME: Propylene glycol monomethyl ether
［製造例１］両末端にポリ（オキシアルキレン）基及び１つのウレタン結合基を介してアクリロイル基を結合するパーフルオロポリエーテルＳＭ１の製造
　スクリュー管に、ＰＦＰＥ　１．０５ｇ（０．５ｍｍｏｌ）、ＢＥＩ　０．２６ｇ（１．０ｍｍｏｌ）、ＤＢＴＤＬ　１０ｍｇ（０．０１６ｍｍｏｌ）、及びＭＥＫ　１．３１ｇ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時間撹拌した。この反応混合物をＭＥＫ　３．９２ｇで希釈して、目的化合物であるＳＭ１の２０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３，４００、分散度：Ｍｗ（重量平均分子量）／Ｍｎ（数平均分子量）は１．１であった。また、ＳＭ１のＦ定量分析から算出したフッ素含有量は３６質量％であった。 [Production Example 1] Production of perfluoropolyether SM1 in which an acryloyl group is bonded to both ends via a poly (oxyalkylene) group and one urethane bond group. PFPE 1.05 g (0.5 mmol), BEI 0.26 g (1.0 mmol), DBTDL 10 mg (0.016 mmol), and MEK 1.31 g were charged. The mixture was stirred for 24 hours at room temperature (approximately 23 ° C.) using a stirrer tip. This reaction mixture was diluted with 3.92 g of MEK to obtain a 20 mass% MEK solution of SM1, which is the target compound.
The weight average molecular weight Mw measured by GPC of the obtained SM1 in terms of polystyrene was 3,400, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.1. The fluorine content calculated from the F1 quantitative analysis of SM1 was 36% by mass.
［実施例１～４、比較例１～７］
　表１の記載に従って以下の各成分を混合し、固形分濃度４０質量％の硬化性組成物を調製した。なお、表中、［部］とは［質量部］を表す。
（１）多官能モノマー：ＤＰＨＡ　１．０ｇ（５０質量部）、ＵＡ　０．６ｇ（３０質量部）、及びＰＥＴＡ　０．４ｇ（２０質量部）
（２）表面改質剤：製造例１に従って製造したＳＭ１溶液　０．１ｇ（ＳＭ１として１質量部）
（３）重合開始剤：Ｉ２９５９　０．１ｇ（５質量部）
（４）紫外線吸収剤：表１に記載の成分を、有効成分として表１に記載の量
（５）光安定剤：表１に記載の成分を、表１に記載の量
（６）溶媒：ＰＧＭＥ　表１に記載の量 [Examples 1 to 4, Comparative Examples 1 to 7]
According to the description in Table 1, the following components were mixed to prepare a curable composition having a solid content of 40% by mass. In the table, [part] represents [part by mass].
(1) Polyfunctional monomer: DPHA 1.0 g (50 parts by mass), UA 0.6 g (30 parts by mass), and PETA 0.4 g (20 parts by mass)
(2) Surface modifier: SM1 solution produced according to Production Example 1 0.1 g (1 part by mass as SM1)
(3) Polymerization initiator: I2959 0.1 g (5 parts by mass)
(4) Ultraviolet absorber: the amount described in Table 1 as the active ingredient and the amount described in Table 1 (5) Light stabilizer: the component described in Table 1 and the amount described in Table 1 (6) Solvent: PGME Amounts listed in Table 1
　この硬化性組成物を、Ａ４サイズの両面易接着処理ＰＥＴフィルム［東レ（株）製　ルミラー（商標登録）Ｕ４０３、厚み１００μｍ］上にバーコート塗布し、塗膜を得た。この塗膜を１２０℃のオーブンで３分間乾燥させ溶媒を除去した。得られた膜を、窒素雰囲気下、露光量３００ｍＪ／ｃｍ２のＵＶ光を照射し露光することで、およそ６μｍの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。 This curable composition was bar-coated on an A4-sized double-sided easy-adhesion treated PET film [Lumirror (registered trademark) U403, manufactured by Toray Industries, Inc., thickness 100 μm] to obtain a coating film. This coating film was dried in an oven at 120 ° C. for 3 minutes to remove the solvent. The obtained film was exposed to UV light having an exposure amount of 300 mJ / cm 2 in a nitrogen atmosphere to expose a hard coat film having a hard coat layer (cured film) having a thickness of about 6 μm.
　各硬化性組成物から得られたハードコートフィルムの、耐光性、黄色度、耐擦傷性を評価した。各評価の手順を以下に示す。結果を表２に併せて示す。 The light resistance, yellowness, and scratch resistance of the hard coat film obtained from each curable composition were evaluated. The procedure for each evaluation is shown below. The results are also shown in Table 2.
［耐光性］
　ハードコートフィルムの促進耐候性試験機を用いた試験前後の、ハードコート層のＰＥＴフィルムへの密着性を測定し、耐光性を評価した。密着性は、ハードコート層にガイド［コーテック（株）製　クロスカットガイドＣＣＩ－２］を使用して２５マス（５×５、２ｍｍ間隔）の直角格子パターンの切込みを入れ、幅２４ｍｍの透明テープ［ニチバン（株）製　セロテープ（登録商標）ＣＴ－２４］を用いたクロスカット法（ＪＩＳ　Ｋ　５６００－５－６に準拠）を用い、以下の基準に従い評価した。
　Ａ：２５マス全てが剥離しない
　Ｃ：剥離したマスがある [Light resistance]
The adhesion of the hard coat layer to the PET film before and after the test using the accelerated weather resistance tester of the hard coat film was measured to evaluate the light resistance. For adhesion, a hard coat layer is cut with a square grid pattern of 25 squares (5 × 5, 2 mm spacing) using a guide [Cortech Co., Ltd. Cross Cut Guide CCI-2], and a transparent tape with a width of 24 mm. The cross-cut method (based on JIS K 5600-5-6) using [Nichiban Co., Ltd. Cellotape (registered trademark) CT-24] was used and evaluated according to the following criteria.
A: All 25 squares do not peel C: There is a peeled square
［黄色度］
　ハードコートフィルムの裏面（ハードコート層が形成されていない面）に白色のあて板［Ｌ＊＝８６．６、ａ＊＝－１．０、ｂ＊＝－０．４］を置き、ハードコート層表面の色（Ｌ＊ａ＊ｂ＊表色系）を測定し、以下の基準に従い評価した。
　Ａ：ｂ＊＜１．０
　Ｃ：ｂ＊≧１．０ [Yellowness]
A white coating plate [L * = 86.6, a * = − 1.0, b * = − 0.4] is placed on the back surface of the hard coat film (the surface on which the hard coat layer is not formed), and the hard coat film is placed. The layer surface color (L * a * b * color system) was measured and evaluated according to the following criteria.
A: b * <1.0
C: b * ≧ 1.0
［耐擦傷性］
　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２５０ｇ／ｃｍ２の荷重を掛けて３，０００往復擦り、その擦った部分に油性マーカー［ゼブラ（株）製　マッキー極細（青）、細側を使用］で線を描いた。続けて描いた線を不織布ワイパー［旭化成（株）製　ＢＥＭＣＯＴ（登録商標）Ｍ－１］で拭き取り、傷の程度を目視で確認し以下の基準に従い評価した。
　Ａ：傷がつかず油性マーカーで描いた線がきれいに拭き取れる
　Ｃ：油性マーカーのインクが傷に入り込み拭き取れない [Abrasion resistance]
The hard coat layer surface was rubbed back and forth for 3,000 with a load of 250 g / cm 2 with steel wool [Bonster Sales Co., Ltd. Bonstar (registered trademark) # 0000 (super extra fine)] attached to a reciprocating wear tester, A line was drawn on the rubbed portion with an oil-based marker [Mckey extra fine (blue), using fine side made by Zebra Co., Ltd.]. Subsequently, the drawn line was wiped off with a non-woven wiper [BEMCOT (registered trademark) M-1 manufactured by Asahi Kasei Co., Ltd.], and the degree of scratches was visually confirmed and evaluated according to the following criteria.
A: The line drawn with the oil-based marker can be wiped clean without scratching. C: The ink of the oil-based marker enters the wound and cannot be wiped off.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表１及び表２に示すように、ハードコート層における表面改質剤として両末端にポリ（オキシアルキレン）基及び１つのウレタン結合基を介して、アクリロイル基を結合するパーフルオロポリエーテルＳＭ１を用い、さらに、特定の紫外線吸収剤（ＵＶＡ１～ＵＶＡ３）及び特定のヒンダードアミン系光安定剤ＨＡＬＳ１をぞれぞれ特定量使用した実施例１乃至実施例４の硬化性組成物を用いて作製した各ハードコートフィルムは、促進耐候性試験機を用いて７２時間光照射前後においても、ハードコート層のＰＥＴフィルムへの密着性に優れ、すなわち耐光性に優れるとする結果が得られ、また、黄色度が低く耐擦傷性に優れる結果となった。 As shown in Tables 1 and 2, as a surface modifier in the hard coat layer, perfluoropolyether SM1 in which an acryloyl group is bonded to both ends via a poly (oxyalkylene) group and one urethane bonding group is used. Furthermore, each of the hardware produced using the curable compositions of Examples 1 to 4 using specific amounts of specific ultraviolet absorbers (UVA1 to UVA3) and specific hindered amine light stabilizers HALS1. The coated film is excellent in adhesion to the PET film of the hard coat layer even before and after light irradiation for 72 hours using an accelerated weathering tester, that is, excellent in light resistance. The result was low and excellent in scratch resistance.
　一方、本発明で規定した以外の紫外線吸収剤（ＵＶＡ４、ＵＶＡ５）を使用した場合、密着性（耐光性）が良好であり、黄色度は低いものの、耐擦傷性に劣る結果となり（比較例１及び比較例２）、また、本発明で規定した以外の光安定剤（ＨＡＬＳ２）を使用した場合、黄色度の結果や耐擦傷性は良好なものの、光照射後の密着性が低く、耐光性に劣る結果となった（比較例３）。
　また、規定量を超えて紫外線吸収剤を使用した場合には黄色度が大きくなった（比較例４）。
　さらに規定量を下回る量で光安定剤を使用した場合（比較例５）、紫外線吸収剤と光安定剤の一方のみを使用した場合（比較例６及び比較例７）では、黄色度の結果や耐擦傷性は良好なものの、光照射後の密着性が低く、耐光性に劣る結果となった。 On the other hand, when ultraviolet absorbers (UVA4, UVA5) other than those specified in the present invention are used, the adhesion (light resistance) is good and the yellowness is low, but the scratch resistance is poor (Comparative Example 1). And Comparative Example 2), and when a light stabilizer (HALS2) other than that specified in the present invention is used, the result of yellowness and scratch resistance are good, but the adhesion after light irradiation is low, and the light resistance (Comparative Example 3).
Moreover, yellowness became large when the ultraviolet absorber was used exceeding a prescribed amount (Comparative Example 4).
Further, when the light stabilizer is used in an amount below the specified amount (Comparative Example 5), when only one of the ultraviolet absorber and the light stabilizer is used (Comparative Example 6 and Comparative Example 7), Although the scratch resistance was good, the adhesion after light irradiation was low, resulting in poor light resistance.
　以上、実施例の結果に示すように、特定のヒドロキシフェニルトリアジン系紫外線吸収剤とヒンダードアミン系光安定剤を組み合わせ、表面改質剤としての特定のパーフルオロポリエーテルとともに添加した本発明の硬化性組成物のみが、該組成物より作製したハードコート層において満足する耐擦傷性及び耐光性を実現でき、これらの性能を満足するハードコートフィルムを得ることができる。 As described above, as shown in the results of the examples, the curable composition of the present invention, which is a combination of a specific hydroxyphenyl triazine-based ultraviolet absorber and a hindered amine light stabilizer and added together with a specific perfluoropolyether as a surface modifier Only the product can realize satisfactory scratch resistance and light resistance in the hard coat layer produced from the composition, and a hard coat film satisfying these performances can be obtained.

Claims (11)

  1. （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）基を含む分子鎖の両末端に、ポリ（オキシアルキレン）基を介して又はポリ（オキシアルキレン）基及び１つのウレタン結合基をこの順に介して、活性エネルギー線重合性基を結合するパーフルオロポリエーテル０．１～１０質量部、
    （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１～２０質量部、
    （ｄ）ヒドロキシフェニルトリアジン系紫外線吸収剤１～３質量部、及び
    （ｅ）ヒンダードアミン系光安定剤１～２質量部
    を含む硬化性組成物であって、
    前記ヒドロキシフェニルトリアジン系紫外線吸収剤は、
    トリアジン環に直接結合する３つのフェニル基が少なくとも２つ以上のヒドロキシ基で置換された化合物であるか、又は、
    トリアジン環に直接結合する３つのフェニル基のうち少なくとも１つのフェニル基の水素原子がフェニル基で置換され、且つ、トリアジン環に直接結合する３つのフェニル基が合計で少なくとも１つ以上のヒドロキシ基で置換された化合物であり、
    前記ヒンダードアミン系光安定剤は、式［１］で表される基を有する化合物である、
    硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒａは水素原子、又は炭素原子数１乃至１０のアルキル基を表し、黒点は結合手を表す。）     (A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
    (B) the active energy at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group or via the poly (oxyalkylene) group and one urethane bond group in this order; 0.1 to 10 parts by mass of perfluoropolyether to which a linear polymerizable group is bonded,
    (C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
    A curable composition comprising (d) 1 to 3 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber and (e) 1 to 2 parts by mass of a hindered amine light stabilizer,
    The hydroxyphenyltriazine ultraviolet absorber is
    A compound in which three phenyl groups directly bonded to the triazine ring are substituted with at least two hydroxy groups, or
    At least one of the three phenyl groups directly bonded to the triazine ring is substituted with a phenyl group, and the three phenyl groups directly bonded to the triazine ring are a total of at least one hydroxy group. A substituted compound,
    The hindered amine light stabilizer is a compound having a group represented by the formula [1].
    Curable composition.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a black dot represents a bond.)
  2. 前記ポリ（オキシパーフルオロアルキレン）基が、－［ＯＣＦ２］－及び－［ＯＣＦ２ＣＦ２］－を繰り返し単位として有する基である、請求項１に記載の硬化性組成物。 The curable composition according to claim 1, wherein the poly (oxyperfluoroalkylene) group is a group having-[OCF 2 ]-and-[OCF 2 CF 2 ]-as repeating units.
  3. 前記ポリ（オキシアルキレン）基が、５～１２の繰返し単位数を有するポリ（オキシアルキレン）基である、請求項１又は請求項２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the poly (oxyalkylene) group is a poly (oxyalkylene) group having 5 to 12 repeating units.
  4. 前記ポリ（オキシアルキレン）基がポリ（オキシエチレン）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。 The curable composition according to any one of claims 1 to 3, wherein the poly (oxyalkylene) group is a poly (oxyethylene) group.
  5. 前記活性エネルギー線重合性基が活性エネルギー線重合性部分を少なくとも２つ以上有する基である、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。 The curable composition according to any one of claims 1 to 4, wherein the active energy ray polymerizable group is a group having at least two active energy ray polymerizable portions.
  6. 前記成分（ａ）の多官能モノマーが、多官能（メタ）アクリレート化合物及び多官能ウレタン（メタ）アクリレート化合物からなる群から選ばれる少なくとも１つである、請求項１乃至請求項５のうち何れか一項に記載の硬化性組成物。 The polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. The curable composition according to one item.
  7. さらに（ｆ）溶媒を含む、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。 The curable composition according to any one of claims 1 to 6, further comprising (f) a solvent.
  8. 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より得られる硬化膜。 The cured film obtained from the curable composition as described in any one of Claims 1 thru | or 7.
  9. 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に記載の硬化膜からなる、ハードコートフィルム。 A hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to claim 8.
  10. 前記ハードコート層が１～１５μｍの膜厚を有する、請求項９に記載のハードコートフィルム。 The hard coat film according to claim 9, wherein the hard coat layer has a thickness of 1 to 15 μm.
  11. 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７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、該塗膜に活性エネルギー線を照射し硬化する工程を含む、ハードコートフィルムの製造方法。 It is a manufacturing method of the hard coat film which equips at least one surface of a film base material with a hard coat layer, Comprising: The curable composition as described in any one of Claims 1 thru | or 7 on a film base material. A method for producing a hard coat film, comprising: a step of applying and forming a coating film;
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US11958994B2 (en) * 2019-03-29 2024-04-16 Dai Nippon Printing Co., Ltd. Sheet, ornamental material, and resin composition
JP6998483B1 (en) 2020-11-20 2022-01-18 株式会社Ｄｎｐファインケミカル Ink composition
WO2022107732A1 (en) * 2020-11-20 2022-05-27 株式会社Ｄｎｐファインケミカル Ink composition
JP2022082412A (en) * 2020-11-20 2022-06-01 株式会社Ｄｎｐファインケミカル Ink composition

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JP6908896B2 (en) 2021-07-28
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TW201827531A (en) 2018-08-01
CN109642000B (en) 2021-11-19
CN109642000A (en) 2019-04-16
TWI753955B (en) 2022-02-01

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