Classifications

• • 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
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—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
  • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
• • 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

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 touch panel displays and liquid crystal displays.
• a touch panel display using a liquid crystal display element or an OLED (organic EL) display element that can be operated by a person's finger is provided.
• the outermost surface of these touch panel displays has scratch resistance to prevent scratches from being generated on the surface of the touch panel by a finger or the like when a finger is operated by a person, and a fingerprint attached when a person touches it with a finger.
• a high-density crosslinked structure is formed, that is, a crosslinked structure having low molecular mobility is formed to increase the surface hardness and to resist external force.
• the method of giving is adopted.
• a material for forming these hard coat layers a polyfunctional acrylate-based material that is three-dimensionally crosslinked by radical polymerization with active energy rays is most used at present.
• a means for forming a hard coat layer on the surface of the transparent 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 or the like, and the organic solvent is dried, followed by UV irradiation.
• a means for forming a hard coat layer by curing is adopted.
• the thickness of the hard coat layer is usually 1 ⁇ m to 15 ⁇ m in order to exhibit functions such as hardness and scratch resistance at a level that causes no practical problems.
• some devices equipped with a touch panel display are used outdoors, and the touch panel surface and hard coat film are exposed to ultraviolet rays.
• Some transparent plastic films used as a base material for hard coat films are significantly yellowed and deteriorated by being exposed to ultraviolet rays for a short time.
• the hard coat layer is required to have light resistance in order to prevent yellowing and deterioration of the hard coat film due to ultraviolet rays.
• a commonly used method is to add an ultraviolet absorber to the curable composition that forms the hard coat layer.
• the ultraviolet absorber absorbs an active energy ray for causing a curing reaction by radical polymerization, it usually inhibits the formation of a three-dimensional crosslinked structure of a polyfunctional acrylate.
• the scratch resistance and the light resistance of the hard coat layer are in a trade-off relationship, and it has been an issue to make both properties compatible.
• a polyfunctional urethane (meth)acrylate oligomer and a triazine-based UV absorber together, a hard coat layer having both constant light resistance and scratch resistance on a plastic film having a problem of light resistance. has been reported (Patent Document 1).
• Patent Document 1 has relatively high light resistance to ultraviolet rays in the wavelength region of 300 nm or more, it has a problem of insufficient scratch resistance.
• the present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, in which poly(oxyalkylene) is present at both ends of its molecular chain.
• a curable composition containing a perfluoropolyether having an active energy ray-polymerizable group and a specific ultraviolet absorber on a plastic film having a problem in light resistance.
• the present invention has been completed by discovering that a hard coat layer having excellent light resistance not only to a wavelength of 300 nm or more but also to a wavelength of less than 300 nm and having excellent scratch resistance can be formed.
• the present invention as a first aspect, (A) 100 parts by mass of active energy ray-curable polyfunctional monomer, (B) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via urethane bonds (however, 0.05 parts by mass to 10 parts by mass, excluding perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.
• a curable composition comprising:
• the curable composition according to the first aspect wherein the (c) ultraviolet absorber has at least two hydroxy groups.
• the above-mentioned (b) perfluoropolyether has at least two active energy ray-polymerizable groups via urethane bonds at both ends of its molecular chain. It relates to a curable composition.
• the curable composition according to the third aspect wherein the (b) perfluoropolyether has at least three active energy ray-polymerizable groups via urethane bonds at both ends of its molecular chain.
• the poly(oxyperfluoroalkylene) group has both a repeating unit —[OCF 2 ]— and a repeating unit —[OCF 2 CF 2 ]—, and these repeating units are block-bonded or random-bonded.
• the curable composition according to any one of the first to fourth aspects which is a group formed by a block bond and a random bond.
• the curable composition according to the fifth aspect wherein the (c) perfluoropolyether has a partial structure represented by the following formula [1].
• n is the total number of repeating units -[OCF 2 CF 2 ]- and the number of repeating units -[OCF 2 ]-, and represents an integer of 5 to 30,
• the repeating unit —[OCF 2 CF 2 ]— and the repeating unit —[OCF 2 ]— are bonded by a block bond, a random bond, or a block bond and a random bond.
• the curable composition according to any one of the first to sixth aspects wherein a part or all of the (a) polyfunctional monomer is a polyfunctional (meth)acrylate compound. ..
• An eighth aspect relates to the curable composition according to any one of the first to seventh aspects, in which the (a) polyfunctional monomer is an oxyalkylene-modified polyfunctional monomer.
• the curability according to any one of the first aspect to the eighth aspect wherein the polyfunctional monomer (a) is a polyfunctional monomer having at least three active energy ray-polymerizable groups.
• Composition As a tenth aspect, the curable composition according to any one of the first to ninth aspects, further including (e) a solvent.
• An eleventh aspect relates to a cured film obtained from the curable composition according to any one of the first to tenth aspects.
• a twelfth aspect relates to a hard coat film having a hard coat layer on at least one surface of a film substrate, the hard coat layer comprising the cured film according to the eleventh aspect.
• a thirteenth aspect is a method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is described in any one of the first to tenth aspects. It relates to a method for producing a hard coat film, which comprises the steps of forming a coating film by applying the curable composition of (1) on a film substrate and irradiating the coating film with an active energy ray to cure the coating film.
• a curable composition which has excellent scratch resistance even in a thin film having a thickness of about 1 ⁇ m to 15 ⁇ m and which is useful in forming a hard coat layer and a hard coat layer having excellent 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 hardened film, which is provided on the surface, and the scratch resistance and the light resistance are improved. An excellent hard coat film can be provided.
• the present invention has excellent light resistance to ultraviolet rays in a wavelength region of not less than 300 nm and less than 300 nm, which is suitable for application to a substrate surface such as a display surface used outdoors, and has an excellent light resistance. It is possible to provide a hard coat film provided with a hard coat layer having excellent scratch resistance.
• the curable composition of the present invention specifically comprises (A) 100 parts by mass of active energy ray-curable polyfunctional monomer, (B) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via urethane bonds (however, 0.05 parts by mass to 10 parts by mass, excluding perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.
• the active energy ray-curable polyfunctional monomer of component (a) (hereinafter, also simply referred to as “(a) polyfunctional monomer”) is an activity that causes a polymerization reaction to proceed and cure upon irradiation with active energy rays such as ultraviolet rays. It refers to a monomer having two or more energy ray-polymerizable groups. Examples of the active energy ray-polymerizable group include (meth)acryloyl group and vinyl group.
• Examples of the preferable (a) active energy ray-curable polyfunctional monomer in the curable composition of the present invention include a monomer selected from the group consisting of polyfunctional (meth)acrylate compounds, and the polyfunctional urethane described below. Examples thereof include a monomer selected from the group consisting of (meth)acrylate compounds and a monomer selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds.
• the (a) active energy ray-curable polyfunctional monomer one kind selected from the group consisting of the polyfunctional (meth)acrylate compounds may be used alone, or two or more kinds may be used in combination.
• a (meth)acrylate compound means both an acrylate compound and a methacrylate compound.
• (meth)acrylic acid refers to acrylic acid and methacrylic acid.
• the polyfunctional monomer (a) may be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene modification include oxymethylene modification, oxyethylene modification, and oxypropylene modification.
• examples of the oxyalkylene-modified polyfunctional monomer include compounds obtained by modifying the above polyfunctional (meth)acrylate compound (or polyfunctional urethane (meth)acrylate compound) with oxyalkylene.
• the oxyalkylene-modified polyfunctional monomer may be used alone or in combination of two or more.
• the (a) polyfunctional monomer a polyfunctional monomer having at least 3 active energy ray-polymerizable groups, for example, at least 4 can be used.
• a monomer selected from the group consisting of oxyalkylene-modified polyfunctional (meth)acrylate compounds having at least three active energy ray-polymerizable groups can be used.
• Examples of the polyfunctional (meth)acrylate compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, penta Erythritol tri(meth)acrylate, 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,
• preferable polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like. ..
• Examples of the oxyalkylene-modified polyfunctional (meth)acrylate compound include (oxy)alkylene-modified (meth)acrylate compounds of polyols.
• Examples of the polyol include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol 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 bond (—NHCOO—).
• Examples of the polyfunctional urethane (meth)acrylate compound include those obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxy group, a polyfunctional isocyanate, a (meth)acrylate having a hydroxy group, and a polyol. Examples thereof include those obtained by the reaction, but the polyfunctional urethane (meth)acrylate compound usable in the present invention is not limited to these examples.
• Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like.
• Examples of the (meth)acrylate having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate. Examples thereof include acrylate and tripentaerythritol hepta(meth)acrylate.
• polystyrene resin examples include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol; these diols and succinic acid, maleic acid.
• diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol; these diols and succinic acid, maleic acid.
• polyester polyols, polyether polyols, polycarbonate diols and the like which are reaction products of aliphatic dicarboxylic acids such as acids and adipic acid or dicarboxylic acid anhydrides.
• the active energy ray polyfunctional monomer may be a lactone modified polyfunctional (meth)acrylate compound, and ⁇ -caprolactone is preferable as the lactone to be modified.
• the lactone-modified polyfunctional (meth)acrylate compound include ⁇ -caprolactone-modified pentaerythritol tri(meth)acrylate, ⁇ -caprolactone-modified pentaerythritol tetra(meth)acrylate, ⁇ -caprolactone-modified dipentaerythritol penta(meth). Examples thereof include acrylates and ⁇ -caprolactone-modified dipentaerythritol hexa(meth)acrylate.
• (B) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has active energy ray-polymerizable groups at both ends of its molecular chain via urethane bonds (provided that , Except for perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.)]
• the component (b) is a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, and a urethane bond is introduced at both ends of the molecular chain thereof without interposing the poly(oxyalkylene) group.
• a perfluoropolyether having an active energy ray-polymerizable group (hereinafter, also simply referred to as “(b) perfluoropolyether having a polymerizable group at both ends of a molecular chain”) is used.
• the component (b) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied. Further, the component (b) has excellent compatibility with the component (a), thereby suppressing the clouding of the hard coat layer and enabling the formation of a hard coat layer having a transparent appearance.
• the above poly(oxyalkylene) group means a group in which the number of repeating units of the oxyalkylene group is 2 or more and the alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
• the number of carbon atoms of the alkylene group in the above poly(oxyperfluoroalkylene) group is not particularly limited, but it is preferably 1 to 4 carbon atoms. That is, the poly(oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are alternately linked, and the oxyperfluoroalkylene group is a carbon atom. It refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked.
• examples thereof include groups such as -1,3-diyl group) and -[OCF 2 C(CF 3 )F]-(oxyperfluoropropane-1,2-diyl group).
• the above oxyperfluoroalkylene groups may be used alone or in combination of two or more, and in that case, the bonds of plural kinds of oxyperfluoroalkylene groups are a block bond and a random bond. Either of them may be used.
• poly(oxyperfluoroalkylene) groups -[OCF 2 ]-(oxyperfluoromethylene group) and -[OCF 2 CF 2 ] are used. It is preferable to use a group having both —(oxyperfluoroethylene group) as a repeating unit.
• repeating units: -[OCF 2 ]- and -[OCF 2 CF 2 ]- are in a molar ratio of [repeating unit: -[OCF 2 ]-]:
• [repeat Unit: —[OCF 2 CF 2 ]—] is preferably a group containing at a ratio of 2:1 to 1:2, and more preferably a group containing at a ratio of about 1:1.
• the bond of these repeating units may be either a block bond or a random bond.
• the total number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, and more preferably in the range of 7 to 21.
• the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the above poly(oxyperfluoroalkylene) group in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 3, It is 000.
• the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) is not limited to one having one active energy ray-polymerizable group such as a (meth)acryloyl group at both ends of the molecular chain. It may have one or more active energy ray-polymerizable groups at both ends of the molecular chain.
• the terminal structure containing the active energy ray-polymerizable groups the following formulas [A1] to [A A5] and the structures in which the acryloyl group in these structures is substituted with a methacryloyl group.
• Examples of such a perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) include compounds represented by the following formula [2].
• A represents one of the structures represented by the formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is substituted with a methacryloyl group
• PFPE represents Represents a poly(oxyperfluoroalkylene) group (provided that the side directly bonded to L 1 is an oxy terminal and the side bonded to an oxygen atom is a perfluoroalkylene terminal), and L 1 is 1 to 3 fluorine atoms.
• alkylene group of the fluorine atom 1 to carbon atoms substituted with three 2 or 3, -CH 2 CHF -, - CH 2 CF 2 -, - CHFCF 2 -, - CH 2 CH 2 CHF-, Examples thereof include —CH 2 CH 2 CF 2 — and —CH 2 CHFCF 2 —, and —CH 2 CF 2 — is preferable.
• Examples of the partial structure (A-NHC( ⁇ O)O) m L 2 — in the compound represented by the above formula [2] include structures represented by the following formulas [B1] to [B12].
• A represents one of the structures represented by the above formulas [A1] to [A5] and the structure in which the acryloyl group in these structures is substituted with a methacryloyl group.
• the structure represented by the formula [B3] is preferable, and the combination of the formula [B3] and the formula [A3] is particularly preferable.
• n represents the total number of repeating units -[OCF 2 CF 2 ]- and the number of repeating units -[OCF 2 ]-, and is preferably an integer in the range of 5 to 30, An integer in the range of 7 to 21 is more preferable.
• the ratio of the number of repeating units —[OCF 2 CF 2 ]— to the number of repeating units —[OCF 2 ]— is preferably in the range of 2:1 to 1:2, and is approximately 1 It is more preferable that the ratio is in the range of 1:1.
• the bond of these repeating units may be either a block bond or a random bond.
• the perfluoropolyether having a polymerizable group at both ends of the molecular chain is 0.05 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. It is used in an amount of 0.1 part by mass, preferably 0.1 part by mass to 5 parts by mass. (B) By using the perfluoropolyether having a polymerizable group at both ends of the molecular chain in a proportion of 0.05 parts by mass or more, sufficient scratch resistance can be imparted to the hard coat layer.
• the perfluoropolyether having a polymerizable group at both ends of the molecular chain in a proportion of 10 parts by mass or less, it is sufficiently compatible with (a) the active energy ray-curable polyfunctional monomer.
• a hard coat layer with less white turbidity can be obtained.
• the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) is, for example, a compound represented by the following formula [3].
• PFPE, L 1 , L 2 and m have the same meanings as those in the formula [2].
• a polymerizable group for the hydroxy group present at both terminals of the compound represented by the formula [2].
• An isocyanate compound having, that is, a compound in which an isocyanato group is bonded to a bond in a structure represented by the above formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is replaced with a methacryloyl group for example, It can be obtained by reacting 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc.) to form a urethane bond.
• the curable composition of the present invention comprises (b) a poly(oxyperfluoroalkylene) group which is a perfluoropolyether, and has active energy ray-polymerizable properties at both ends of its molecular chain via urethane bonds.
• poly(oxyperfluoroalkylene) A perfluoropolyether containing a group, which has an active energy ray-polymerizable group at one end (one end) of its molecular chain through a urethane bond, and the other end of the molecular chain (the other end).
• a perfluoropolyether having a hydroxy group at the end (provided that the poly(oxyperfluoroalkylene) group is between the urethane bond and the poly(oxyperfluoroalkylene) group is between the hydroxy group. No. oxyalkylene) group) or a poly(oxyperfluoroalkylene) group-containing perfluoropolyether represented by the above formula [3], in which hydroxy groups are present at both ends of the molecular chain.
• Group-containing perfluoropolyether (provided that there is no poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the hydroxy group.) [has an active energy ray-polymerizable group No compound] may be included.
• the curable composition of the present invention is characterized by using an ultraviolet absorber having a benzophenone skeleton as the component (c).
• an ultraviolet absorber having a benzophenone skeleton As the component (c).
• a compound having at least two hydroxy groups that is, a compound in which at least two hydrogen atoms in two benzene rings constituting the benzophenone skeleton are substituted with a hydroxy group is used. It is preferable to adopt.
• a hard coat layer having excellent light resistance not only to wavelengths of 300 nm or more but also to wavelengths of less than 300 nm can be formed.
• the hard coat film including the hard coat layer can be a hard coat film having excellent light resistance, which is suitable for application to the surface of a base material such as a display surface used outdoors.
• Examples of the ultraviolet absorber having a benzophenone skeleton include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ',4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone (oxybenzone-3), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5
• Examples thereof include sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone and 4-hydroxy-3-carboxybenzophenone.
• the ultraviolet absorber (c) having a benzophenone skeleton is 0.1 to 30 parts by mass, preferably 1 part by mass with respect to 100 parts by mass of the active energy ray-curable polyfunctional monomer (a). It is desirable to use it in a proportion of about 15 parts by mass.
• a polymerization initiator that generates a radical by a preferable active energy ray is, for example, an active energy such as an electron beam, an ultraviolet ray or an X-ray. It is a polymerization initiator that generates radicals by irradiation of rays, especially by irradiation of ultraviolet rays.
• Examples of the (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, and benzophenone. And biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. You may use these individually by 1 type or in mixture of 2 or more types.
• acylphosphine oxides and alkylphenones as the (d) polymerization initiator from the viewpoints of transparency, surface curability, and thin film curability.
• acylphosphine oxides and the alkylphenones By using the acylphosphine oxides and the alkylphenones, a cured film having further improved scratch resistance can be obtained.
• acylphosphine oxides examples include phenylbis(2,4,6-trimethoxybenzoyl)phosphine oxide and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
• alkylphenones examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl) ⁇ -hydroxy such as 2-methylpropan-1-one and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one
• Alkylphenones 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one And ⁇ -aminoalkylphenones; 2,2-dimethoxy-1,2-diphenylethan-1-one; methyl phenylglyoxylate and the like.
• the proportion of the polymerization initiator (d) is 1 part by mass to 20 parts by mass, preferably 2 parts by mass to 10 parts by mass, relative to 100 parts by mass of the active energy ray-curable polyfunctional monomer (a). It is desirable to use.
• the curable composition of the present invention may further contain (e) a solvent, that is, in the form of a varnish (film forming material).
• a solvent that is, in the form of a varnish (film forming material).
• the above solvent is appropriately dissolved in the above components (a) to (d) in consideration of workability at the time of coating for forming a cured film (hard coat layer) described later and drying property before and after curing. Just select it.
• aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits and cyclohexane; methyl chloride, methyl bromide, Halides such as methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Esters or ester ethers such as glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4-dio
• Solvents may be mentioned.
• the amount of the solvent (e) used is not particularly limited, it is used at a concentration such that the solid content concentration in the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass.
• the solid content concentration also referred to as non-volatile content concentration
• the solid content concentration means the solid content with respect to the total mass (total mass) of the components (a) to (d) (and optionally other additives) of the curable composition of the present invention. Indicates the content of the component (all components excluding the solvent component).
• additives generally added as necessary, for example, a polymerization accelerator, a polymerization inhibitor, a photosensitizer, leveling Agents, surfactants, adhesion promoters, plasticizers, ultraviolet absorbers other than the above, light stabilizers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc. Good.
• inorganic fine particles such as titanium oxide or organic fine particles such as polymethylmethacrylate particles may be blended.
• the curable composition of the present invention can form a cured film by applying (coating) on a substrate to form a coating film, and irradiating the coating film with an active energy ray to polymerize (curing).
• the cured film is also an object of the present invention.
• the hard coat layer in the hard coat film described later can be made of the cured film.
• the base material in this case examples include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, Polyimide, epoxy resin, melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based 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 substrate is a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an inkjet method, a printing method (a relief printing method).
• An intaglio printing method, a lithographic printing method, a screen printing method, etc. can be appropriately selected, and among them, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating properties, a relief printing method can be used.
• the curable composition is filtered in advance using a filter having a pore size of about 0.2 ⁇ m and then applied to the coating.
• a solvent may be further added to the curable composition, if necessary.
• the various solvents mentioned in the above [(e) solvent] can be mentioned.
• the coating film is preliminarily dried by a heating means such as a hot plate or an oven to remove the solvent, if necessary (solvent removing step).
• the conditions for heat drying at this time are preferably, for example, 40° C. to 120° C. and about 30 seconds to 10 minutes.
• the coating film is cured by irradiating with active energy rays such as ultraviolet rays.
• active energy rays include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable.
• a light source used for ultraviolet ray irradiation sun rays, chemical lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs and the like can be used.
• the polymerization may be completed by performing post-baking, specifically, heating with a heating means such as a hot plate or an oven.
• the thickness of the formed cured film is usually 0.01 ⁇ m to 50 ⁇ m, preferably 0.05 ⁇ m to 20 ⁇ m after drying and curing.
• a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced.
• the hard coat film is also an object of the present invention, and the hard coat film is preferably used for protecting the surface of various display elements such as touch panels and liquid crystal displays.
• the hard coat layer in the hard coat film of the present invention comprises a step of applying the curable composition of the present invention onto a film substrate to form a coating film, and irradiating the coating film with active energy rays such as ultraviolet rays. It can be formed by a method including a step of curing the coating film.
• a method for producing a hard coat film having a hard coat layer on at least one surface of a film base, including these steps, is also an object of the present invention.
• polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polycarbonate, polymethacrylate, polystyrene, polyolefin, Examples thereof include films of polyamide, polyimide, triacetyl cellulose (TAC) and the like.
• the method described in the above ⁇ cured film> should be used.
• the curable composition of the present invention contains a solvent (in the form of varnish)
• a step of drying the coating film and removing the solvent may be included after the coating film forming step, if necessary.
• the coating film drying method (solvent removing step) described in the above ⁇ cured film> can be used.
• the layer thickness (film thickness) of the hard coat layer thus obtained is preferably 1 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m.
• HLC-8220GPC Column: Shodex (registered trademark) GPC K-804L, GPC K-805L manufactured by Showa Denko KK Column temperature: 40°C Eluent: Tetrahydrofuran Detector: RI (5) Scratch resistance test device: Reciprocating abrasion tester TRIBOGEAR TYPE: 30S manufactured by Shinto Kagaku Co., Ltd. Scanning speed: 4,500 mm/min Scanning distance: 50 mm (6) Light resistance test device: Q-Lab Co. accelerated weather resistance tester QUV (registered trademark)/se Light source: UVB-313 type lamp Test conditions: 0.89 W/cm 2 , 50° C. Test time: 6 hours (7) Color difference meter device: Konica Minolta Co., Ltd. spectrophotometer CM-700d Measurement mode: Transmission mode
• A1 Oxyethylene-modified polyfunctional acrylate [Aronix (registered trademark) MT-3553 manufactured by Toagosei Co., Ltd.]
• A2 Oxyethylene-modified pentaerythritol tetraacrylate [KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd.]
• A3 Mixture of dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate [KAYARAD (registered trademark) DN-0075 manufactured by Nippon Kayaku Co., Ltd.]
• A4 10 functional urethane acrylate [ART RESIN (registered trademark) UN-904 manufactured by Negami Kogyo Co., Ltd.]
• A5 Caprolactone-modified dipentaerythritol hexaacrylate [KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku
• Examples 1 to 12, Comparative Examples 1 to 10 The following components were mixed according to the description in Table 1 to prepare a curable composition.
• “parts” means “parts by mass”.
• This curable composition was applied onto the film base material (A4 size) shown in Table 1 by a bar coater to obtain a coating film.
• the coating film was dried in an oven at 65° C. for 3 minutes to remove the solvent.
• a film was made.
• the scratch resistance and light resistance of the obtained hard coat film were evaluated.
• the procedure for evaluation of scratch resistance and light resistance is shown below.
• the results are also shown in Table 2.
• [Scratch resistance] The surface of the hard coat layer of the hard coat film was applied with steel wool [Bonster (registered trademark) #0000 (superfine) manufactured by Bonster Sales Co., Ltd.] attached to the reciprocating abrasion tester under a load of 350 g/cm 2 to obtain 10 Two-way rubbing, the degree of scratches (number and length) were visually confirmed and evaluated according to the following criteria A, B and C. When actually used as the hard coat layer, at least B is required, and A is desirable.
• the yellowness index (YI2) was measured by the same method using the color difference meter.
• the difference (YI2-YI1) in the yellowness index between before the light resistance test and after the light resistance test was defined as ⁇ YI and evaluated according to the following criteria A and C.
• Hard coat films (Examples 1 to 12) provided with a hard coat layer prepared by using a curable composition in which perfluoropolyether SM having four acryloyl groups through a bond are respectively incorporated are scratch resistant. It was shown that the light resistance is not impaired, and excellent light resistance in the UVB (ultraviolet B wave) region can be exhibited in any film substrate of TPU and PC.
• Comparative Example 1 and Comparative Example 4 curing of Comparative Example 1 and Comparative Example 4 using A1 as a polyfunctional monomer, UVA-3 having a triazine skeleton as an ultraviolet absorber, SM as a surface modifier, and TPU and PC as a film substrate, respectively. It was shown that the hard coat film including the hard coat layer prepared from the functional composition has excellent light resistance but inferior scratch resistance.
• a UVA-5 having a cyanoacrylate skeleton is used as an ultraviolet absorber
• the hard coat film was shown to have poor light resistance.
• the hard coat film including the hard coat layer prepared from the composition was excellent in scratch resistance, but was inferior in light resistance because the ultraviolet absorber was not added.
• Comparative Example 9 and Comparative Example 10 in which A1 was used as a polyfunctional monomer UVA-1 having a benzophenone skeleton was used as an ultraviolet absorber, a surface modifier was not added, and TPU and PC were used as film base materials, respectively.
• the hard coat film including the hard coat layer prepared from the curable composition was excellent in light resistance, but was inferior in scratch resistance because the surface modifier was not added.
• the hardenability satisfying the scratch resistance and the light resistance can be obtained only when the curable composition is a combination of the polyfunctional monomer, the ultraviolet absorber having the benzophenone skeleton and the perfluoropolyether.
• a coated film can be obtained.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Materials Engineering (AREA)
• Paints Or Removers (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Laminated Bodies (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=71948085

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (8)

Family Cites Families (13)

• 2020
  • 2020-01-30 CN CN202080013139.3A patent/CN113423513B/zh active Active
  • 2020-01-30 JP JP2020571140A patent/JP7332988B2/ja active Active
  • 2020-01-30 KR KR1020217026124A patent/KR102584186B1/ko active Active
  • 2020-01-30 WO PCT/JP2020/003456 patent/WO2020162322A1/ja not_active Ceased
  • 2020-02-03 TW TW109103175A patent/TWI843800B/zh active

Patent Citations (8)

Also Published As

Similar Documents

Legal Events