Hard coat curable composition

Abstract

[Problem] To provide a homogeneous curable composition that is free of suspended matter and sediment, and is capable of forming a hard coat layer provided with high-standard characteristics, both in durability and in smoothness, as well as high liquid repellency when actual use thereof is assumed. [Solution] Provided is a curable composition that includes: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups per molecule; (b) 0.05 -2 parts by mass of perfluoropolyether having, via a poly(oxyalkylene) group, an active energy ray-polymerizable group only in one end of a molecular chain which includes a poly(oxyperfluoroalkylene) group, and having a weight average molecular weight of 1500-3500; and (c) 1-20 parts by mass of a polymerization initiator which generates radicals due to active energy rays.

Description

[Technical Field]

[0001] The present invention relates to a curable composition useful as a hard coat layer forming material applied to the surface of various display elements, and more particularly to a homogeneous curable composition that can form a hard coat layer with excellent slipperiness, scratch resistance, abrasion resistance, and water repellency, and is free of suspended and settled matter. [Background technology]

[0002] In recent years, touch panels have been introduced into a variety of devices, including mobile phones, tablet computers and other portable information terminals, notebook computers, home appliances, and automotive interior and exterior parts. Operation of these touch panels, such as liquid crystal displays and organic EL displays, is increasingly done by touching the surface with a finger or pen. When considering finger operation, the touch panel surface requires water and oil repellency to facilitate the removal of fingerprints, and also abrasion resistance to maintain this property even after repeated friction with a finger. Furthermore, when operating the touch panel surface with a finger or pen, smoothness is required for a comfortable feel. Additionally, scratch resistance is required to prevent damage. To impart these characteristics to the touch panel surface, a surface coating layer, such as a hard coat layer, is provided.

[0003] Fluorine-containing compounds exhibit high slipperiness and water / oil repellency, and are therefore used as materials for forming hard coat layers. For example, a method is used in which a small amount of fluorine-based surface modifier is added to the coating solution for forming the hard coat layer to create the composition. Fluorine-based surface modifiers are known to segregate onto the surface of the hard coat layer due to the low surface energy of fluorine atoms.

[0004] Generally, to impart scratch resistance and abrasion resistance to a hard coat layer, a method is employed that increases the surface hardness of the hard coat layer and provides resistance to external forces by forming a high-density crosslinked structure. Currently, polyfunctional acrylate-based materials that undergo three-dimensional crosslinking by radicals generated by active energy ray irradiation are the most commonly used materials for forming such hard coat layers. Fluorine-based surface modifiers added to the coating solution for forming the hard coat layer also generally use materials with active energy ray polymerizable groups to impart scratch resistance and abrasion resistance to the hard coat layer (Patent Document 1).

[0005] On the other hand, as described in Patent Document 2, when a fluorine-based surface modifier having crosslinking groups is used to obtain durable properties such as scratch resistance and abrasion resistance in the hard coat layer, the molecular chains containing fluorine atoms become immobilized, and the slipperiness of the hard coat layer decreases. In other words, there is a trade-off relationship between durable properties such as scratch resistance and abrasion resistance and slipperiness, and it is difficult to achieve high levels of both properties simultaneously.

[0006] To improve the aforementioned trade-off relationship, one method involves introducing a crosslinking group to only one end of a molecular chain containing fluorine atoms in order to increase the mobility of the fluorine atom-containing molecular chain. However, compared to the method of introducing crosslinking groups to both ends of the molecular chain containing fluorine atoms, while the slipperiness of the hard coat layer is superior, the durability is generally inferior, and the molecular chain containing fluorine atoms tends to aggregate, making the coating solution prone to clouding when preparing the coating solution for forming the hard coat layer. If the fluorine-based surface modifier aggregates in the coating solution for forming the hard coat layer, the molecular chain containing fluorine atoms will not sufficiently segregate on the surface of the hard coat layer when the hard coat layer is formed using the coating solution, and the original slipperiness, water repellency, and scratch resistance properties will not be exhibited.

[0007] To improve the solubility of fluorine-based surface modifiers, one could consider methods such as reducing the proportion of fluorine atoms in the modifier, for example, by shortening the molecular chain containing fluorine atoms. However, this would likely result in a decrease in the slipperiness and water repellency of the hard coat layer, making it difficult to achieve high levels of slipperiness and water repellency.

[0008] As a method for improving the solubility of fluorine-based surface modifiers, Patent Document 3 reports the use of a fluorine-containing polyether, which forms aggregates and causes turbidity in the hard coat agent composition, in combination with a fluorine-containing block copolymer that has excellent compatibility with the composition. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] International Publication No. 2016 / 163479 [Patent Document 2] Patent No. 6497449 [Patent Document 3] Japanese Patent Publication No. 2005-179613 [Overview of the project] [Problems that the invention aims to solve]

[0010] Since Patent Document 3 states that the fluorine-containing block copolymer is inferior to fluorine-containing polyether in water repellency and lubricity, it can be easily assumed that the fluorine concentration of the above-mentioned fluorine-containing block copolymer is lower than that of the above-mentioned fluorine-containing polyether, making it difficult to achieve both compatibility with the composition and good lubricity and water repellency. The present invention aims to provide a homogeneous, curable composition free of suspended and settled matter that can form a hard coat layer that achieves a high level of both durability and slipperiness, which are typically in a trade-off relationship. In addition to these, for practical use, the hard coat layer must also possess high liquid-repellent properties. [Means for solving the problem]

[0011] A first aspect of the present invention is a curable composition comprising: (a) 100 parts by mass of an active energy ray curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) 0.05 to 2 parts by mass of a perfluoropolyether having an active energy ray polymerizable group via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and having a weight-average molecular weight of 1500 to 3500; and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.

[0012] Another aspect of the present invention is a curable composition comprising: (a) 100 parts by mass of an active energy ray curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) 0.05 to 2 parts by mass of a perfluoropolyether that is a reaction product of a starting material perfluoropolyether having a number average molecular weight of 1500 to 3000 and a hydroxyl group bonded to a poly(oxyalkylene) group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group that reacts with the hydroxyl group and an active energy ray polymerizable group; and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.

[0013] The (b) perfluoropolyether has the active energy ray polymerizable group via the poly(oxyalkylene) group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight-average molecular weight of 1500 to 3500.

[0014] The (b) perfluoropolyether has the active energy ray polymerizable group via a urethane bond bonded to the poly(oxyalkylene) group.

[0015] The aforementioned poly(oxyalkylene) group is a poly(oxyethylene) group.

[0016] The poly(oxyperfluoroalkylene) group has repeating unit -(CF2O)- and / or repeating unit -(CF2CF2O)-, and when having both repeating units, these repeating units are combined by block bonding, random bonding, or block bonding and random bonding.

[0017] The molecular chain containing the poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1].

Chemical formula

[0018] In the above formula [1], m and n each independently represent an integer of 1 or more.

[0019] The (b) perfluoropolyether is a compound represented by the following formula [2].

Chemical formula

[0020] The terminal group A is a group represented by the following formula [A1] or formula [A2].

Chemical formula

[0021] The curable composition of the present invention further contains (d) a solvent.

[0022] Another aspect of the present invention is a cured film obtained from the curable composition of the present invention.

[0023] Another aspect of the present invention is a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is made of the cured film.

[0024] The film substrate has a hard coat layer underneath the surface of the film substrate and the hard coat layer, and the film substrate is a resin film.

[0025] The hard coat layer has a thickness of 1 μm to 20 μm.

[0026] Another aspect of the present invention is a method for producing a hard coat film, comprising the steps 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 to cure it and form a hard coat layer.

[0027] Another aspect of the present invention is a method for producing a hard coat film, comprising the steps of: applying the curable composition of the present invention onto a film substrate to form a coating film; removing the solvent from the coating film by heating; and curing the coating film by irradiating it with active energy rays to form a hard coat layer.

[0028] A method for manufacturing a hard coat film, further comprising the step of forming a lower layer of the hard coat layer on the surface of the film substrate, wherein the film substrate is a resin film and the coating film is formed on the lower layer of the hard coat layer.

[0029] Another aspect of the present invention is a perfluoropolyether compound having an active energy ray polymerizable group via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and having a weight-average molecular weight of 1500 to 3500.

[0030] Another aspect of the present invention is a perfluoropolyether compound that is a reaction product of a starting material perfluoropolyether having a number average molecular weight of 1500 to 3000, having a hydroxyl group bonded to a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group that reacts with the hydroxyl group and an active energy ray polymerizable group.

[0031] The perfluoropolyether compound has the active energy ray polymerizable group via the poly(oxyalkylene) group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight-average molecular weight of 1500 to 3500.

[0032] The molecular chain containing the poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1]. [ka] (In the above formula [1], m is the number of repeating units -(CF2CF2O)-, and n is the number of repeating units -(CF2O)-, satisfying 5 ≤ (m + n) ≤ 30, where m and n each independently represent an integer of 0 or more, and where both repeating units are present, these repeating units are joined by block bonds, random bonds, or block bonds and random bonds, and q is the number of oxyethylene groups and represents an integer from 2 to 20.)

[0033] In the above formula [1], m and n each represent an integer of 1 or greater, independently of each other.

[0034] The perfluoropolyether compound is a compound represented by the following formula [2]. [ka] (In formula [2] above, m, n, and q are the same as defined in formula [1] above, and A represents a terminal group having the active energy ray polymerizable group, represented by the following formula [A1] or formula [A2].) [ka] (In the above formulas [A1] and [A2], R 1 and R 2 Each of the symbols independently represents a hydrogen atom or a methyl group, and * represents a bond with a urethane bond in the compound represented by formula [2] above. [Effects of the Invention]

[0035] According to the present invention, it is possible to provide a highly homogeneous curable composition useful for forming cured films and hard coat layers that achieve both excellent scratch resistance, abrasion resistance, and excellent slipperiness, even in thin films with a thickness of 1 μm to 20 μm. Furthermore, according to the present invention, it is possible to provide a hard coat film comprising a cured film obtained from the curable composition or a hard coat layer made of the cured film, thereby providing a hard coat film that excels in both durability properties such as scratch resistance and abrasion resistance and slipperiness, which are in a trade-off relationship. Moreover, according to the present invention, it is possible to provide a curable composition useful for forming cured films and hard coat layers that not only achieve both of the above properties but also impart high water-repellent properties, as well as a hard coat film comprising a hard coat layer that excels in these properties. [Modes for carrying out the invention]

[0036] <Curable composition> Each component of the curable composition of the present invention is described below.

[0037] [(a) Active energy ray curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule] (a) A polyfunctional monomer that has two or more (meth)acryloyl groups in one molecule and is curable by active energy rays (hereinafter also simply referred to as "(a) polyfunctional monomer") refers to a monomer that undergoes a polymerization reaction and hardens when irradiated with active energy rays such as ultraviolet light.

[0038] In the curable composition of the present invention, preferred (a) polyfunctional monomers include monomers selected from the group consisting of polyfunctional (meth)acrylate compounds, as well as monomers selected from the group consisting of polyfunctional urethane (meth)acrylate compounds, and monomers selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds, as described later. In the present invention, as (a) polyfunctional monomer, one or more of the above-mentioned group consisting of polyfunctional (meth)acrylate compounds can be used alone or in combination. In the present invention, (meth)acrylate compounds include both acrylate compounds and methacrylate compounds, and for example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

[0039] Furthermore, (a) the polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer, and examples of such oxyalkylene modification include oxymethylene modification, oxyethylene modification, and oxypropylene modification. Examples of the oxyalkylene-modified polyfunctional monomer include compounds obtained by oxyalkylene modification of the above-mentioned polyfunctional (meth)acrylate compound or polyfunctional urethane (meth)acrylate compound. The oxyalkylene-modified polyfunctional monomer can also be used individually or in combination of two or more types.

[0040] In addition, as a preferred (a) polyfunctional monomer in the present invention, we can list polyfunctional monomers having at least two (meth)acryloyl groups in one molecule, preferably at least three, and more preferably at least four (meth)acryloyl groups in one molecule.

[0041] Examples of the above polyfunctional (meth)acrylate compounds (compounds that do not have a urethane bond) include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and 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-decanediol 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 2,6Examples include decanedimethanol 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-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Among these, preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0042] Examples of the oxyalkylene-modified polyfunctional (meth)acrylate compounds mentioned above include (meth)acrylate compounds of polyols modified with oxyalkylene. Examples of the polyols include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0043] The above-mentioned polyfunctional urethane (meth)acrylate compound is a compound having multiple acryloyl groups or methacryloyl groups in one molecule and having one or more urethane bonds [-NHC(=O)O-], and may further have urea bonds [-NHC(=O)NH-]. Examples of the polyfunctional urethane (meth)acrylate compound include compounds obtained by the reaction of a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and compounds obtained by the reaction of a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group and a polyol, but the polyfunctional urethane (meth)acrylate compounds that can be used in the present invention are not limited to these examples.

[0044] Examples of the above-mentioned polyfunctional isocyanates include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate. Examples of the above-mentioned (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tripentaerythritol hepta(meth)acrylate. Examples of the above-mentioned polyols include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; polyester polyols, polyether polyols, and polycarbonate diols which are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic acid anhydrides such as succinic acid, maleic acid, and adipic acid.

[0045] (a) The polyfunctional monomer may be a lactone-modified polyfunctional (meth)acrylate compound, and ε-caprolactone is preferred as the lactone to be modified. Examples of the lactone-modified polyfunctional (meth)acrylate compound include ε-caprolactone-modified pentaerythritol tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tetra(meth)acrylate, ε-caprolactone-modified dipentaerythritol penta(meth)acrylate, and ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0046] [(b) Perfluoropolyethers having an active energy ray polymerizable group via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and having a weight-average molecular weight of 1500 to 3500] (b) A perfluoropolyether having an active energy ray polymerizable group via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group of component (b), and having a weight-average molecular weight of 1500 to 3500, is also hereinafter simply referred to as "(b) perfluoropolyether". (b) perfluoropolyether can be obtained, for example, by reacting a starting perfluoropolyether with a number-average molecular weight of 1500 to 3000, having a hydroxyl group bonded to a poly(oxyalkylene) group at only one end of a molecular chain containing the poly(oxyperfluoroalkylene) group, with a compound having a functional group that reacts with the hydroxyl group and the active energy ray polymerizable group. Examples of functional groups that react with the hydroxyl group include a hydroxyl group, a carboxyl group, and an isocyanate group. In the curable composition of the present invention, the preferred (b) perfluoropolyether has the active energy ray polymerizable group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, via a urethane bond bonded to the poly(oxyalkylene) group.

[0047] (b) Perfluoropolyether has a poly(oxyalkylene) group and therefore has excellent compatibility with (a) polyfunctional monomer, and (b) perfluoropolyether alone can play the role of a surface modifier in the hard coat layer formed from the curable composition of the present invention. A poly(oxyethylene) group is preferred as the poly(oxyalkylene) group.

[0048] (b) Perfluoropolyethers are not limited to those having one active energy ray polymerizable group via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, but may also have two or more active energy ray polymerizable groups. Examples of such active energy ray polymerizable groups include (meth)acryloyl groups and vinyl groups, and examples of terminal groups having such active energy ray polymerizable groups include the group represented by formula [A1] or formula [A2]. Of these terminal groups, the group represented by formula [A2] having two active energy ray polymerizable groups is preferred.

[0049] From the viewpoint of obtaining a cured film with good scratch resistance, the poly(oxyperfluoroalkylene) group described above is preferably a group having both -[CF2O]- (oxyperfluoromethylene group) and -[CF2CF2O]- (oxyperfluoroethylene group) as repeating units. In this case, the bonding of these oxyperfluoroalkylene groups may be either block bonding or random bonding.

[0050] (b) The perfluoropolyether preferably has a fluorine atom content of 35% by mass or more and 60% by mass or less, and more preferably 40% by mass or more and 55% by mass. If the fluorine atom content is 35% by mass or more, a hard coat layer with excellent water repellency and slipperiness can be obtained, and if it is 60% by mass or less, a hard coat layer that is well compatible with (a) the polyfunctional monomer and has little turbidity can be obtained.

[0051] (b) The weight-average molecular weight of the perfluoropolyether is 1500 to 3500, preferably 1600 to 3500, and more preferably 1700 to 3000. (b) When the weight-average molecular weight of the perfluoropolyether is within the above range, the (b) perfluoropolyether is more likely to remain on the surface of the hard coat layer obtained from the curable composition of the present invention, and the shear stress on the layer surface is sufficiently reduced, so that a hard coat layer with excellent slipperiness can be obtained. In addition, when the weight-average molecular weight of the (b) perfluoropolyether is within the above range, the hardness of the layer surface is appropriately adjusted, and a hard coat layer with excellent durability such as scratch resistance can be obtained. In other words, when the weight-average molecular weight of the (b) perfluoropolyether is within the above range, it is possible to achieve both slipperiness and durability.

[0052] In the curable composition of the present invention, the content of (b) perfluoropolyether is 0.05 parts by mass to 2 parts by mass per 100 parts by mass of the (a) polyfunctional monomer. When the content of (b) perfluoropolyether is 0.05 parts by mass or more, (b) perfluoropolyether is sufficiently present on the surface of the hard coat layer obtained from the curable composition of the present invention, so that a hard coat layer with excellent slipperiness can be obtained. Furthermore, when the content of (b) perfluoropolyether is 2 parts by mass or less, a hard coat layer that is well compatible with (a) polyfunctional monomer and has little turbidity can be obtained.

[0053] (b) Perfluoropolyethers may be used individually or in combination of two or more types.

[0054] [(c) Polymerization initiator] In the curable composition of the present invention, preferred (c) polymerization initiators are polymerization initiators that generate radicals by active energy rays such as electron beams, ultraviolet rays, and X-rays, particularly by ultraviolet irradiation.

[0055] (c) Examples of polymerization initiators include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinone diazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These polymerization initiators may be used individually or in combination of two or more. In the present invention, from the viewpoint of transparency, surface curability, and thin film curability, it is preferable to use alkylphenones as the (c) polymerization initiator. By using alkylphenones, a cured film with improved scratch resistance can be obtained.

[0056] Examples of the alkylphenones mentioned above include α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; α-aminoalkylphenones such as 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one; 2,2-dimethoxy-1,2-diphenylethane-1-one; and methyl phenylglyoxylate.

[0057] In the curable composition of the present invention, the content of (c) polymerization initiator is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, per 100 parts by mass of the polyfunctional monomer (a).

[0058] [(d) solvent] The curable composition of the present invention may contain (d) a solvent as an optional component, i.e., it may be in the form of a varnish. The solvent (d) should be appropriately selected considering the solubility and dispersibility of components (a) to (c), as well as the workability of the curable composition during application for the formation of the cured film (hard coat layer) described later, and the drying properties before and after curing.

[0059] As the solvent (d) above, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halides such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and o-dichlorobenzene; esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of solvents include ethers such as propylene glycol mono-n-propyl ether (PGME), propylene glycol mono-isopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); and sulfoxides such as dimethyl sulfoxide (DMSO), as well as solvents obtained by mixing two or more of these solvents.

[0060] In the curable composition of the present invention, the content of (d) solvent is not particularly limited, but for example, it is a concentration such that the solid content concentration of 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) represents the content of solids (all components excluding the solvent component) relative to the total mass (total mass) of the components (a) to (d) and other additives of the curable composition of the present invention.

[0061] [Other additives] Furthermore, the curable composition of the present invention may optionally contain one or more commonly added additives, such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, adhesion promoters, plasticizers, ultraviolet absorbers, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc., either alone or in combination of two or more, as long as the effects of the present invention are not impaired.

[0062] <Cured film> The curable composition of the present invention can be applied (coated) onto a substrate to form a coating film, and a cured film can be formed by irradiating the coating film with active energy rays to polymerize (cure) it. This cured film is also a subject of the present invention. Furthermore, the hard coat layer in the hard coat film described later can be made of the above cured film.

[0063] Examples of the above-mentioned substrates include various resins (polyesters such as polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetylcellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin), metal, wood, paper, glass, and slate. The shape of these substrates may be in the form of a plate, film, or three-dimensional molded body. Furthermore, on the surface of the above-mentioned substrates, for example, a primer layer, ultraviolet absorption layer, infrared absorption layer, near-infrared absorption layer, electromagnetic wave absorption layer, color correction layer, refractive index adjustment layer, weather-resistant layer, anti-reflective layer, antistatic layer, discoloration prevention layer, gas barrier layer, water vapor barrier layer, light scattering layer, electrode layer, etc. may be formed as a layer beneath the hard coat layer, and multiple layers beneath the hard coat layer may be laminated. The layer formed on the surface of the above-mentioned substrate is not particularly limited as long as it does not impair the effects of the present invention.

[0064] The coating method on the above-mentioned substrate can be appropriately selected from cast coating, spin coating, blade coating, dip coating, roll coating, spray coating, bar coating, die coating, inkjet, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.), with the roll-to-roll method being particularly suitable. From the viewpoint of thin-film coating, it is desirable to use relief printing, especially gravure coating. It is preferable to filter the curable composition of the present invention beforehand using a filter with a pore size of about 0.2 μm before coating. When coating, a solvent may be added to the curable composition as needed. In this case, various solvents listed in [(e) Solvent] above can be used.

[0065] After applying the curable composition of the present invention to a substrate to form a coating film, the coating film is pre-dried using a heating means such as a hot plate or oven as needed to remove the solvent (solvent removal step). The heating and drying conditions at this time are preferably, for example, 40°C to 120°C for about 30 seconds to 10 minutes. After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams and X-rays, with ultraviolet rays being particularly preferred. Examples of light sources used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps and UV-LEDs. Furthermore, polymerization may be completed by post-baking, specifically by heating using a heating means such as a hot plate or oven.

[0066] The thickness of the formed cured film is typically 0.1 μm to 20 μm, preferably 0.5 μm to 10 μm, after drying and curing.

[0067] <Hard coat film> Using the curable composition of the present invention, a hard coat film can be manufactured having a hard coat layer on at least one surface of a film substrate. This hard coat film is also a subject of the present invention and is suitably used, for example, to protect the surface of various display elements such as touch panels and liquid crystal displays.

[0068] The hard coat layer in the hard coat film of the present invention can be formed by a method comprising the steps of applying the curable composition of the present invention onto a film substrate to form a coating film, removing the solvent by heating as necessary, and curing the coating film by irradiating it with active energy rays such as ultraviolet light. A method for manufacturing a hard coat film comprising these steps, in which a hard coat layer is provided on at least one surface of a film substrate, is also subject to the present invention.

[0069] As the above-mentioned film substrate, various transparent resin films suitable for optical applications are used from among the substrates listed in the <cured film> section above. Preferred resin films include, for example, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrene, polyolefins, polyamides, polyimides, and triacetylcellulose (TAC).

[0070] The above-mentioned film substrate may be formed by laminating multiple layers. For example, layers different from the resin film, such as a primer layer, ultraviolet absorption layer, infrared absorption layer, near-infrared absorption layer, electromagnetic wave absorption layer, color correction layer, refractive index adjustment layer, weather-resistant layer, anti-reflective layer, antistatic layer, discoloration prevention layer, gas barrier layer, water vapor barrier layer, light scattering layer, and electrode layer, may be laminated on the surface of the resin film as layers beneath the hard coat layer, and multiple layers beneath the hard coat layer may be laminated. The layers laminated on the surface of the above-mentioned resin film are not particularly limited as long as they do not impair the effects of the present invention.

[0071] Furthermore, the method for applying the curable composition of the present invention onto the above-mentioned film substrate (coating film formation step) and the method for irradiating the coating film with active energy rays (curing step) can be the method described above under <Cured Film>. In addition, if the curable composition of the present invention contains a solvent (in the form of a varnish), a step of drying the coating film and removing the solvent may be included after the coating film formation step, if necessary. In that case, the method for drying the coating film (solvent removal step) described above under <Cured Film> can be used.

[0072] The thickness (film thickness) of the resulting hard coat layer is, for example, 1 μm to 20 μm, preferably 1 μm to 10 μm.

[0073] <Perfluoropolyether compounds> The present invention also applies to perfluoropolyether compounds, which are reaction products of a starting material perfluoropolyether with a number average molecular weight of 1500 to 3000, having a hydroxyl group bonded to a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group that reacts with the hydroxyl group and an active energy ray polymerizable group. [Examples]

[0074] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus and conditions used for sample preparation and analysis of physical properties in the examples are as follows.

[0075] (1) Coating by bar coater Equipment: PM-9050MC manufactured by SMT Co., Ltd. Bars: OSG System Products Co., Ltd. A-Bar OSP-30 Maximum wet film thickness 30 μm (dry film thickness 6 μm) or OSP-15 Maximum wet film thickness 15 μm (dry film thickness 3 μm) Application speed: 4m / min (2) Film thickness measurement Equipment: F20 film thickness measurement system manufactured by Filmetrics Co., Ltd. (3) Oven Equipment: PO-250-45-D, a two-layer clean oven (upper and lower type) manufactured by Sanki Keisou Co., Ltd. (4)UV curing Equipment: Heraeus Corporation CV-110QC-G Lamp: Heraeus H-bulb electrodeless lamp (manufactured by Heraeus Co., Ltd.) (5) Scratch resistance test and abrasion resistance test Equipment: Shinto Scientific Co., Ltd. Reciprocating wear testing machine TRIBOGEAR TYPE:30S Scanning speed: 3200 mm / min Scanning distance: 50mm (6) Contact angle measurement Equipment: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measurement temperature: 23℃ (7) Measurement of the coefficient of dynamic friction Equipment: TRIBOGEAR, a load-variable friction wear testing system manufactured by Shinto Kagaku Co., Ltd. (Registered Trademark) TYPE: HHS2000 Probe: 0.6mmR sapphire pin Load: 200g Scanning speed: 2 mm / second Scanning distance: 10mm (8) Total light transmittance, haze measurement Equipment: Haze meter NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd. (9) Weight average molecular weight measurement Gel permeation chromatography (GPC) Equipment: HLC-8420GPC manufactured by Tosoh Corporation Columns: TSKgelG2000HXL and TSKgelG3000HXL, manufactured by Tosoh Corporation. Measurement temperature: 40℃ Eluent: Tetrahydrofuran Detection: RI (10) Combustion Ion Chromatography Automatic sample combustion system: AQF-2100 H manufactured by Nitto Seikou Analytech Co., Ltd. (formerly Mitsubishi Chemical Analytech Co., Ltd.) Ion chromatograph: Dionex Integrion, manufactured by Thermo Fisher Scientific Co., Ltd. Sample: 2 mg Absorbent solution: 2.7 mM sodium carbonate + 0.3 mM sodium bicarbonate aqueous solution Eluent: 2.7 mM sodium carbonate + 0.3 mM sodium bicarbonate aqueous solution Column: Thermo Fisher Scientific Co., Ltd. AG-12A / AS-12A Flow rate: 1.5mL / min Detector: Electrical conductivity (with suppressor) Standard sample: Fluoride ion standard solution (F-1000), manufactured by Fujifilm Wako Pure Chemical Corporation (formerly Wako Pure Chemical Industries, Ltd.). If the solvent in the sample did not contain fluorine atoms, the fluorine concentration was measured while the sample still contained the solvent, and the fluorine concentration of the solute was calculated by converting it from the solid content concentration.

[0076] Also, the abbreviations represent the following meanings. Polyfunctional acrylate PA1: Dipentaerythritol pentaacrylate / hexacrylate mixture [Aronix (registered trademark) M-403 manufactured by Toagosei Co., Ltd.] Polyfunctional acrylate PA2: Oxyethylene-modified polyfunctional acrylate [New Frontier (registered trademark) MF-001 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] Polyfunctional acrylate PA3: Polyfunctional urethane acrylate [Art Resin (registered trademark) UN-3320HS manufactured by Negami Kogyo Co., Ltd.] Polyfunctional acrylate PA4: Pentaerythritol triacrylate / pentaerythritol tetraacrylate [PET30 manufactured by Nippon Kayaku Co., Ltd.] PFPE1: Perfluoropolyether having one hydroxy group via a poly(oxyethylene) group only at one end, with the following structure [Fomblin (registered trademark) 4102X manufactured by Solvay Specialty Polymers] 19 F-NMR and 1 Number average molecular weight calculated from the analysis results by H-NMR: 1900

Chemical formula

Chemical formula

[0077] [Manufacturing Example 1] Production of perfluoropolyether compound SMA1 A screw-cap tube was filled with 3.08 g (1.6 mmol) of PFPE1, 0.39 g (1.6 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE1 and N1), and 3.5 g of PGMEA. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA1. The weight-average molecular weight (Mw) of the obtained SMA1, measured in polystyrene equivalent by GPC, was 1908, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA1, calculated by combustion ion chromatography, was 47% by mass.

[0078] [Manufacturing Example 2] Production of the perfluoropolyether compound SMA2 A screw-cap tube was filled with 3.23 g (1.7 mmol) of PFPE1, 0.24 g (1.7 mmol) of N2, 0.035 g of DOTDD (0.01 times the total mass of PFPE1 and N2), and 3.5 g of PGMEA. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA2. The weight-average molecular weight (Mw) of the obtained SMA2, measured in polystyrene equivalent by GPC, was 1894, and the dispersion ratio (Mw / Mn) was 1.1.

[0079] [Manufacturing Example 3] Production of the perfluoropolyether compound SMA3 A screw-cap tube was filled with 3.20 g (1.7 mmol) of PFPE1, 0.26 g (1.7 mmol) of N3, 0.035 g of DOTDD (0.01 times the total mass of PFPE1 and N3), and 3.5 g of PGMEA. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA3. The weight-average molecular weight (Mw) of the obtained SMA3, measured in polystyrene equivalent by GPC, was 1868, and the dispersion ratio (Mw / Mn) was 1.1.

[0080] [Manufacturing Example 4] Production of the perfluoropolyether compound SMA4 A screw-cap tube was filled with 2.20 g (1.2 mmol) of PFPE2, 0.28 g (1.2 mmol) of N1, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N1), and 0.6 g of MEK. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain an 80% by mass MEK solution of the target perfluoropolyether compound SMA4. The weight-average molecular weight (Mw) of the obtained SMA4, measured in polystyrene equivalent by GPC, was 1710, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA4, calculated by combustion ion chromatography, was 63% by mass.

[0081] [Manufacturing Example 5] Production of perfluoropolyether compound SMA5 A screw-cap tube was filled with 2.78 g (2.9 mmol) of PFPE3, 0.68 g (2.9 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE3 and N1), and 3.5 g of PGMEA. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA5. The weight-average molecular weight (Mw) of the obtained SMA5, measured in polystyrene equivalent by GPC, was 1299, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA5, calculated by combustion ion chromatography, was 51% by mass, which is comparable to the 51% fluorine atom content theoretically calculated from the structure of SMA5.

[0082] [Manufacturing Example 6] Production of perfluoropolyether compound SMA6 A screw-cap tube was filled with 2.41 g (4.4 mmol) of PFPE4, 1.05 g (4.4 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE4 and N1), and 3.5 g of PGMEA. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA6. The weight-average molecular weight (Mw) of the obtained SMA6, measured in polystyrene equivalent by GPC, was 1029, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA5, calculated by combustion ion chromatography, was 46% by mass, which is comparable to the theoretically calculated fluorine atom content of 47% by mass from the structure of SMA5.

[0083] [Examples 1 to 8, Comparative Examples 1 to 4] Each component listed in Table 1 was mixed to prepare a curable composition with the solid content concentration listed in Table 1. Here, solid content refers to components other than the solvent. In Table 2, [parts] represents [parts by mass] and [%] represents [mass%]. In Table 1, the polyfunctional acrylate and surface modifier each represent solid content.

[0084] [Table 1]

[0085] These curable compositions were applied by bar coating onto an A4-sized PET film [Toray Industries, Inc., Lumirror® U403 (also known as U40), 100 μm thick] with a primer layer formed on both sides by easy-adhesion treatment, to obtain a coating film. This coating film was dried in a 60°C oven for 8 minutes to remove the solvent. The obtained film was exposed to a nitrogen atmosphere at an exposure of 300 mJ / cm². 2 By irradiating and exposing the film with UV light, a hard coat film having a hard coat layer (cured film) with a thickness of 3 μm or 6 μm was fabricated.

[0086] The homogeneity of each curable composition, as well as the scratch resistance, water repellency, abrasion resistance, slipperiness, and haze of the resulting hard coat films, were evaluated. The evaluation procedure is described below. The results are also shown in Table 2. [Composition homogeneity] The appearance of each prepared curable composition was visually inspected and evaluated according to the following criteria. A: Clear solution (no suspended solids, settled solids, or phase separation) C: Presence of any of the following: suspended solids, settled solids, or phase separation. [Scratch resistance] The hard coat layer surface of the obtained hard coat film was rubbed 2500 times with a 1kg load using steel wool [BONSTAR (registered trademark) #0000 (ultra-fine)] attached to a reciprocating abrasion tester, with a stroke of 50mm. Afterwards, the degree of scratches in the area excluding the 5mm width at both ends of the 50mm stroke was visually inspected, and in addition, it was confirmed using a microscope (KEYENCE Corporation) that the scratches were on the hard coat layer surface, and evaluated according to the following criteria A, B, and C. In the case of actual use as a hard coat layer, at least B is required, and A is desirable. A: No scratches (0 scratches) B: Injury (1 to 4 scratches, 1 mm to 9 mm in length) C: Injury (five or more injuries between 1 mm and 9 mm in length, or one or more injuries of 1 cm or longer) [Water repellency] 1 μL of water was applied to the surface of the hard coat layer, and the contact angle θ was measured five times after 10 seconds. The average value was then evaluated according to the following criteria. For actual use as a hard coat layer, a rating of at least B is required, and A is desirable. A: θ≧105° B: 90°≦θ<105° C:θ<90° [Abrasion resistance] The surface of the hard coat layer was rubbed 2,500 times with a cylindrical eraser [Minoan RUBBER STICK, φ6.0 mm] attached to a reciprocating abrasion tester, under a load of 1 kg. 1 μL of water was applied to the rubbed area, and the contact angle θ was measured at 5 points after 5 seconds. The average value was used as the contact angle value and evaluated according to the following criteria. Ideally, a value of A is desirable when considering actual use of the hard coat layer. A: θ≧90° B: 80°≦θ<90° C:80°<θ [Slippery] The coefficient of dynamic friction μ' was measured at five locations on the surface of the hard coat layer, and its average value was evaluated according to the following criteria. A smaller coefficient of dynamic friction indicates less friction with the probe used, serving as an indicator of slipperiness. A smaller coefficient of dynamic friction is preferable because it results in better slipperiness when touched. A:μ'≦0.035 B: 0.035 < μ' ≦ 0.050 C:μ'>0.050 [Hayes] For reference, the haze was measured at three locations on the surface of the hard coat layer, and the average value was calculated. The haze of the PET film used as the substrate in this study [Lumirror® U403 (also known as U40), manufactured by Toray Industries, Inc., with a thickness of 100 μm] was 1.6.

[0087] [Table 2]

[0088] As shown in Table 1, the curable compositions of Examples 1 to 8 contain polyfunctional acrylates PA1 to PA4 and perfluoropolyether PFPE1, which has a number-average molecular weight of 1900 and has one hydroxyl group bonded to a poly(oxyethylene) group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and are obtained by reacting one of the isocyanate compounds N1 to N3 having the active energy ray polymerizable group with SMA1 with a weight-average molecular weight of 1908, SMA2 with a weight-average molecular weight of 1894, or SMA3 with a weight-average molecular weight of 1868. As shown in Table 2, the curable compositions of Examples 1 to 8 exhibited excellent homogeneity, and the hard coat films having a hard coat layer obtained from these curable compositions showed excellent slipperiness, scratch resistance, water repellency, and abrasion resistance.

[0089] On the other hand, as shown in Table 1, the curable composition of Comparative Example 1 contains a polyfunctional acrylate PA1 and a perfluoropolyether compound PFPE2 with a number average molecular weight of 1750 to 1950, having one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group without a poly(oxyalkylene) group, to which the isocyanate compound N1 having the active energy ray polymerizable group is reacted with the isocyanate compound N1 having the active energy ray polymerizable group, to which the curable composition of Comparative Example 2 contains a polyfunctional acrylate PA1 and a perfluoropolyether compound PFPE3 with a molecular weight of 978.15. As shown in Table 2, the curable compositions of Comparative Examples 1 and 2 had poor homogeneity. In addition, the hard coat films equipped with the hard coat layer obtained from these curable compositions had high cohesive forces of SMA4 and SMA5, preventing sufficient segregation of SMA4 and SMA5 on the surface of the hard coat layer. As a result, they exhibited inferior slipperiness and abrasion resistance compared to the hard coat films equipped with the hard coat layer obtained from the curable compositions of Examples 1 to 8.

[0090] Furthermore, as shown in Table 1, the curable composition of Comparative Example 3 contains polyfunctional acrylate PA1 and SMA6 with a weight-average molecular weight of 1029, obtained by reacting a perfluoropolyether compound PFPE4 with a molecular weight of 548.1, which has one hydroxyl group without a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having the active energy ray polymerizable group. As shown in Table 2, although the curable composition of Comparative Example 3 has good homogeneity, the hard coat film having a hard coat layer obtained from this curable composition had inferior slipperiness, scratch resistance, and abrasion resistance compared to the hard coat films having hard coat layers obtained from the curable compositions of Examples 1 to 8, because the molecular chain containing the poly(oxyperfluoroalkylene) group of SMA6 was short.

[0091] Furthermore, as shown in Table 1, the curable composition of Comparative Example 4 contains a polyfunctional acrylate PA1 and a perfluoropolyether compound SMA7 with a weight-average molecular weight of 3973, which has active energy ray polymerizable groups at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group. As shown in Table 2, although the curable composition of Comparative Example 4 has good homogeneity, the hard coat film having a hard coat layer obtained from this curable composition has reduced molecular mobility of the poly(oxyperfluoroalkylene) chain because SMA7 has active energy ray polymerizable groups at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group. As a result, it exhibits inferior slipperiness and abrasion resistance compared to the hard coat films having hard coat layers obtained from the curable compositions of Examples 1 to 8.

Claims

1. (a) 100 parts by mass of an active energy ray curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule, (b) 0.05 to 2 parts by mass of a perfluoropolyether having an active energy ray polymerizable group via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and having a weight-average molecular weight of 1500 to 3500, and (c) comprising 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, The molecular chain containing the poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1], A curable composition wherein the (b) perfluoropolyether is a compound represented by the following formula [2]. 【Chemistry 1】 (In formula [1] above, m is the number of repeating units -(CF₂CF₂O)-, and n is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (m + n) ≤ 30, where m and n each independently represent integers of 0 or more, and where both repeating units are present, these repeating units are combined by block bonds, random bonds, or block bonds and random bonds, and q is the number of oxyethylene groups and represents an integer from 2 to 20.) 【Chemistry 2】 (In formula [2] above, m, n, and q have the same meanings as in formula [1] above, and A represents a terminal group represented by the following formula [A1] or formula [A2] having the active energy ray polymerizable group.) 【Transformation 3】 (In formulas [A1] and [A2] above, R1 and R2 each independently represent a hydrogen atom or a methyl group, and * represents a bond with a urethane bond in the compound represented by formula [2].)

2. (a) 100 parts by mass of an active energy ray curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule, (b) 0.05 to 2 parts by mass of a perfluoropolyether which is a reaction product of a raw material perfluoropolyether having a number average molecular weight of 1500 to 3000, having a hydroxyl group bonded to a poly(oxyalkylene) group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group that reacts with the hydroxyl group and an active energy ray polymerizable group, and (c) comprising 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, The molecular chain containing the poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1], A curable composition wherein the (b) perfluoropolyether is a compound represented by the following formula [2]. 【Chemistry 4】 (In formula [1] above, m is the number of repeating units -(CF₂CF₂O)-, and n is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (m + n) ≤ 30, where m and n each independently represent integers of 0 or more, and where both repeating units are present, these repeating units are combined by block bonds, random bonds, or block bonds and random bonds, and q is the number of oxyethylene groups and represents an integer from 2 to 20.) 【Transformation 5】 (In formula [2] above, m, n, and q have the same meanings as in formula [1] above, and A represents a terminal group represented by the following formula [A1] or formula [A2] having the active energy ray polymerizable group.) 【Transformation 6】 (In formulas [A1] and [A2] above, R1 and R2 each independently represent a hydrogen atom or a methyl group, and * represents a bond with a urethane bond in the compound represented by formula [2].)

3. The curable composition according to claim 2, wherein the perfluoropolyether (b) has a weight-average molecular weight of 1500 to 3500.

4. The curable composition according to any one of claims 1 to 3, wherein in formula [1], m and n each independently represent an integer of 1 or more.

5. (d) The curable composition according to any one of claims 1 to 4, further comprising a solvent.

6. A cured film obtained from the curable composition according to any one of claims 1 to 5.

7. A hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is made of the cured film described in claim 6.

8. The hard coat film according to claim 7, wherein the hard coat layer has a lower layer between the surface of the film substrate and the hard coat layer, and the film substrate is a resin film.

9. The hard coat film according to claim 7 or claim 8, wherein the hard coat layer has a thickness of 1 μm to 20 μm.

10. A method for producing a hard coat film, comprising the steps of: applying a curable composition according to any one of claims 1 to 5 onto a film substrate to form a coating film; and irradiating the coating film with active energy rays to cure it and form a hard coat layer.

11. A method for producing a hard coat film, comprising the steps of: applying the curable composition described in claim 5 onto a film substrate to form a coating film; removing the solvent from the coating film by heating; and curing the coating film by irradiating it with active energy rays to form a hard coat layer.

12. A method for manufacturing a hard coat film according to claim 10 or claim 11, further comprising the step of forming a lower layer of the hard coat layer on the surface of the film substrate, wherein the film substrate is a resin film and the coating film is formed on the lower layer of the hard coat layer.

13. A perfluoropolyether compound having an active energy ray polymerizable group via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and having a weight-average molecular weight of 1500 to 3500, The molecular chain containing the poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1], A perfluoropolyether compound wherein the perfluoropolyether compound is a compound represented by the following formula [2]. 【Transformation 7】 (In the above formula [1], m is the repeating unit - (CF ２ CF ２ O) Number of - and n is the repeating unit - (CF ２ O) A number satisfying 5 ≤ (m + n) ≤ 30, where m and n each independently represent non-negative integers, and if both repeating units exist, these repeating units are formed by block combinations, random combinations, or block combinations and random combinations, where q is the number of oxyethylene groups and represents an integer between 2 and 20. 【Transformation 8】 (In formula [2] above, m, n, and q have the same meanings as in formula [1] above, and A represents a terminal group represented by the following formula [A1] or formula [A2] having the active energy ray polymerizable group.) 【Chemistry 9】 (In the above formulas [A1] and [A2], R １ and R ２ Each of the symbols independently represents a hydrogen atom or a methyl group, and * represents the bond between the compound represented by formula [2] and the urethane bond.

14. A perfluoropolyether compound is a reaction product of a starting material perfluoropolyether having a number average molecular weight of 1500 to 3000, having a hydroxyl group bonded to a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group that reacts with the hydroxyl group and an active energy ray polymerizable group, wherein the molecular chain containing the poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1], A perfluoropolyether compound wherein the perfluoropolyether compound is a compound represented by the following formula [2]. 【Chemistry 10】 (In formula [1] above, m is the number of repeating units -(CF₂CF₂O)-, and n is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (m + n) ≤ 30, where m and n each independently represent integers of 0 or more, and where both repeating units are present, these repeating units are combined by block bonds, random bonds, or block bonds and random bonds, and q is the number of oxyethylene groups and represents an integer from 2 to 20.) 【Chemistry 11】 (In formula [2] above, m, n, and q have the same meanings as in formula [1] above, and A represents a terminal group represented by the following formula [A1] or formula [A2] having the active energy ray polymerizable group.) 【Chemistry 12】 (In formulas [A1] and [A2] above, R1 and R2 each independently represent a hydrogen atom or a methyl group, and * represents a bond with a urethane bond in the compound represented by formula [2].)

15. The perfluoropolyether compound according to claim 14, wherein the weight-average molecular weight is 1500 to 3500.

16. The perfluoropolyether compound according to any one of claims 13 to 15, wherein in formula [1], m and n each independently represent an integer of 1 or more.

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