Curable composition containing two perfluoropolyethers

Abstract

The present invention relates to a homogeneous curable composition which is free from suspended materials and sediment, and which is capable of forming a hard coat layer that achieves a good balance between endurance characteristics and sliding properties at high levels, while also having high liquid repellency that is sufficient for practical applications. The present invention provides a curable composition which contains: (a) an active energy ray-curable multifunctional monomer that has two or more (meth)acryloyl groups in each molecule; (b) a perfluoropolyether which has an active energy ray-polymerizable group at the ends of a molecular chain that contains a poly(oxyperfluoroalkylene) group, while having a weight average molecular weight of 1400 to 3500 (excluding a perfluoropolyether (c) described below); (c) a perfluoropolyether which has the active energy ray-polymerizable group at only one end of a molecular chain that contains a poly(oxyperfluoroalkylene) group, while having a weight average molecular weight of 1550 to 3500; and (d) a polymerization initiator which generates radicals by means of an active energy ray.

Description

Curable composition containing two perfluoropolyethers

[0001] The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display devices, and relates to a homogeneous curable composition capable of forming a hard coat layer having excellent slip properties, scratch resistance, abrasion resistance, and water repellency, and free of floating matter and sediment. The term "perfluoropolyether" used in the present invention refers to a compound having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group. Even if the molecular chain containing the poly(oxyperfluoroalkylene) group or the active energy ray-polymerizable group does not replace all of the hydrogen atoms of the hydrocarbon group, etc., with fluorine atoms, the "compound having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group" is still referred to as a "perfluoropolyether."

[0002] In recent years, touch panels have been introduced into a variety of devices, including mobile phones, tablet computers, and other portable information terminal devices, notebook computers, home appliances, and automotive interior and exterior components. Touch panel surfaces of display elements such as liquid crystal displays and organic electroluminescence (EL) displays are often operated by touching them with a finger or pen. When operating with a finger, the surface of the touch panel must be water- and oil-repellent to facilitate the removal of fingerprints, and must also be abrasion-resistant to maintain its water- and oil-repellent properties even when repeatedly rubbed with a finger. In addition, when operating the surface of a touch panel with a finger or pen, the surface must be slippery to provide a comfortable feel to the finger or pen. Furthermore, the surface of a touch panel must be scratch-resistant to prevent scratches. To impart these properties to the surface of a touch panel, a surface coating layer, such as a hard coating layer, is provided.

[0003] Fluorine-containing compounds exhibit high slip properties and water and 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 a fluorine-based surface modifier is added to a coating liquid for forming a hard coat layer to form a composition. It is known that fluorine-based surface modifiers segregate on 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 adopted in which a high-density crosslinked structure is formed to increase the surface hardness of the hard coat layer and provide resistance to external forces. Currently, multifunctional acrylate materials that undergo three-dimensional crosslinking by radicals generated by irradiation with active energy rays are most commonly used as materials for forming such hard coat layers. Furthermore, fluorine-based surface modifiers added to coating solutions for forming hard coat layers are generally materials having active energy ray-polymerizable groups to impart scratch resistance and abrasion resistance to the hard coat layer (Patent Document 1). From the viewpoint of scratch resistance and abrasion resistance, materials with a low acrylic equivalent, which are low molecular weight and have many active energy ray-polymerizable groups and can form a high-density crosslinked structure, are preferred.

[0005] On the other hand, as described in Patent Document 2, when a fluorine-based surface modifier having a crosslinkable group is used to obtain durable properties such as scratch resistance and abrasion resistance in a hard coat layer, the molecular chain containing fluorine atoms is fixed, and the slipperiness of the hard coat layer is reduced. In other words, there is a trade-off between durable properties such as scratch resistance and abrasion resistance and slipperiness, and it is difficult to achieve high levels of both properties at the same time.

[0006] To improve the trade-off relationship, there is a method of introducing a crosslinkable group only at one end of a molecular chain containing fluorine atoms in order to increase the mobility of the molecular chain containing fluorine atoms.However, compared with the method of introducing a crosslinkable group at both ends of a molecular chain containing fluorine atoms, although the slipperiness of the hard coat layer is excellent, the durability tends to be inferior.In addition, compared with the case of introducing a crosslinkable group at both ends of a molecular chain containing fluorine atoms, when a crosslinkable group is introduced only at one end of a molecular chain containing fluorine atoms, there is less steric hindrance to the molecular chain containing fluorine atoms, so the molecular chain containing fluorine atoms is more likely to aggregate, and when preparing a coating solution for forming a hard coat layer, the coating solution tends to become cloudy.

[0007] From the viewpoint of lubricity and water repellency, a fluorine-containing surface modifier having a high content of fluorine atoms is generally preferred, but there is a concern that the fluorine-containing surface modifier may aggregate in the coating liquid. If the fluorine-containing surface modifier aggregates in the coating liquid for forming a hard coat layer, when the hard coat layer is formed using the coating liquid, molecular chains containing fluorine atoms will not segregate sufficiently on the surface of the hard coat layer, and the original lubricity and water repellency properties will not be exhibited.

[0008] One possible approach to improve the solubility of the fluorine-based surface modifier is to reduce the fluorine atom content of the fluorine-based surface modifier. However, as mentioned above, this would 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.

[0009] As a method for improving the solubility of a fluorine-based surface modifier, Patent Document 3 reports the use of a fluorine-containing polyether, which forms aggregates when a hard coating composition is obtained and causes the composition to become cloudy, in combination with a fluorine-containing block copolymer that has excellent compatibility with the composition.

[0010] Patent Document 4 reports that by combining a linear polymer having a fluoropolyether main chain, an acrylic group at one or both ends of the molecular chain, and a fluorine content of 48% to 62% by mass with a linear polymer having a siloxane skeleton, a fluoropolyether main chain, a plurality of acrylic groups at both ends of the molecular chain, and a fluorine content of 25% to less than 45% by mass, the solubility of the linear polymer having a fluorine content of 48% to 62% by mass in the composition is improved, and a hard coat layer with excellent water repellency and slipperiness can be obtained. However, with regard to abrasion resistance, Patent Document 4 describes in paragraph

[0006] "abrasion resistance represented by slipperiness," and abrasion resistance is indirectly evaluated by slipperiness. Therefore, there are no specific examples regarding scratch resistance or abrasion resistance.

[0011] International Publication No. 2016 / 163479 Patent No. 6497449 JP 2005-179613 A International Publication No. 2020 / 170698

[0012] Since Patent Document 3 discloses that the fluorine-containing block copolymer described therein has inferior water repellency and lubricity compared to fluorine-containing polyethers, it is easy to imagine that the fluorine concentration of the fluorine-containing block copolymer is lower than that of the fluorine-containing polyethers, and it is difficult to achieve compatibility with the composition while also achieving slipperiness and water repellency. Patent Document 4 discloses that, regarding slipperiness, a linear polymer having a fluorine content of 48% to 62% by mass has the same slipperiness when the polymer has an acrylic group at one end of the molecular chain as when the polymer has acrylic groups at both ends of the molecular chain. Therefore, it is possible to assume that the slipperiness is not at a sufficient level. The present invention aims to provide a homogeneous curable composition free of suspended matter and sediment, which can form a hard coat layer that achieves a high level of durability and slipperiness, which are in a trade-off relationship. In addition, when considering practical use, the hard coat layer must also have high liquid repellency.

[0013] That is, the present invention provides a curable composition comprising: (a) an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) a perfluoropolyether (excluding the (c) perfluoropolyether described below) having an active energy ray-polymerizable group at an end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500; (c) a perfluoropolyether having the active energy ray-polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,550 to 3,500; and (d) a polymerization initiator that generates radicals when exposed to active energy rays.

[0014] (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 3 parts by mass of a perfluoropolyether (excluding the (c) perfluoropolyether described below) having an active energy ray-polymerizable group at an end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500; (c) 0.05 to 3 parts by mass of a perfluoropolyether having the active energy ray-polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,550 to 3,500; and (d) 0.5 to 20 parts by mass of a polymerization initiator that generates radicals when exposed to active energy rays.

[0015] (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 3 parts by mass of a perfluoropolyether having an active energy ray-polymerizable group at an end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500 (excluding the (c) perfluoropolyether described below); (c) 0.05 to 3 parts by mass of a perfluoropolyether that is a reaction product of a starting perfluoropolyether having a number average molecular weight of 1,200 to 3,000, having a hydroxy group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group reactive with the hydroxy group and the active energy ray-polymerizable group; and (d) 0.5 to 20 parts by mass of a polymerization initiator that generates radicals when exposed to active energy rays.

[0016] The (c) perfluoropolyether has the active energy ray-polymerizable group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1,550 to 3,500.

[0017] The (c) perfluoropolyether has an active energy ray-polymerizable group via a urethane bond.

[0018] The (c) perfluoropolyether has a fluorine atom content of 35% by mass to 65% by mass.

[0019] The poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has the repeating unit -(CF2O)- and / or the repeating unit -(CF2CF2O)-, and when it has both repeating units, it is a group in which these repeating units are bonded by block bonds, random bonds, or block bonds and random bonds.

[0020] The molecular chain containing a poly(oxyperfluoroalkylene) group of the perfluoropolyether (c) has a structure represented by the following formula [1]: (In the above formula [1], m represents the number of repeating units -(CFCFO)-, and n represents the number of repeating units -(CFO)-, and satisfy the relationship 5≦(m+n)≦30, m and n each independently represent an integer of 0 or more, and q represents the number of oxyethylene groups and represents an integer of 0 to 20.)

[0021] In the formula [1], m and n each independently represent an integer of 1 or more.

[0022] The (c) perfluoropolyether is a compound represented by the following formula [2]: (In the above formula [2], m, n, and q are defined as in the above formula [1], and A represents the terminal group having the active energy ray-polymerizable group.)

[0023] The terminal group A is a group represented by the following formula [A1] or [A2]. (In the above formula [A1] and formula [A2], R 1 and R 2 each independently represents a hydrogen atom or a methyl group, and * represents a bond to the urethane bond of the compound represented by formula [2].

[0024] The (b) perfluoropolyether has the active energy ray-polymerizable groups at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.

[0025] The molecular chain containing the poly(oxyperfluoroalkylene) group of the perfluoropolyether (b) has a structure represented by the following formula [3]: (In the above formula [3], r is the number of repeating units -(CFCFO)-, and s is the number of repeating units -(CFO)-, and satisfy the relationship 5≦(r+s)≦40, and r and s each independently represent an integer of 0 or greater, and when both repeating units are present, these repeating units are bonded by block bonds, random bonds, or block bonds and random bonds.)

[0026] In the formula [3], r and s each independently represent an integer of 1 or more.

[0027] The (b) perfluoropolyether is a compound represented by the following formula [4]: (In the above formula [4], r and s are defined as in the above formula [3], and A represents a terminal group having the above-mentioned active energy ray-polymerizable group.)

[0028] The terminal group A is a group represented by the following formula [A1] or [A2]. (In the above formula [A1] and formula [A2], R 1 and R 2 each independently represents a hydrogen atom or a methyl group, and * represents a bond to the urethane bond of the compound represented by formula [4].

[0029] The curable composition of the present invention further comprises (e) a solvent.

[0030] A cured film obtained from the curable composition.

[0031] A hard-coated film comprising a hard-coat layer on at least one surface of a film substrate, the hard-coat layer being made of the cured film.

[0032] The film substrate is a resin film, and has a lower layer of the hard coat layer between the surface of the film substrate and the hard coat layer.

[0033] The hard coat layer has a thickness of 1 μm to 20 μm.

[0034] A method for producing a hard coat film, comprising the steps of: applying the curable composition to a film substrate to form a coating film; and irradiating the coating film with active energy rays to cure it, thereby forming a hard coat layer.

[0035] A method for producing a hard coat film, comprising the steps of: applying the curable composition onto a film substrate to form a coating film; removing the solvent from the coating film by heating; and irradiating the coating film with active energy rays to cure it, thereby forming a hard coat layer.

[0036] The method for producing a hard coat film further comprises a 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 a coating film is formed on the lower layer of the hard coat layer.

[0037] A surface modifier comprising: a perfluoropolyether (A) (excluding the perfluoropolyether (B) described below) having an active energy ray-polymerizable group at an end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight-average molecular weight of 1,400 to 3,500; and a perfluoropolyether (B) having the active energy ray-polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight-average molecular weight of 1,550 to 3,500.

[0038] A surface modifier comprising a perfluoropolyether (A) (excluding the perfluoropolyether (B) described below) having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500, and a perfluoropolyether (B) which is a reaction product of a starting perfluoropolyether having a number average molecular weight of 1,200 to 3,000 and having a hydroxy group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group reactive with the hydroxy group and the active energy ray-polymerizable group.

[0039] The perfluoropolyether (B) has the active energy ray-polymerizable group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1,550 to 3,500.

[0040] The perfluoropolyether (B) has a fluorine atom content of 35 to 65% by mass.

[0041] The perfluoropolyether (A) has the active energy ray-polymerizable groups at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.

[0042] The molecular chain containing a poly(oxyperfluoroalkylene) group of the perfluoropolyether (A) has a structure represented by the following formula [3], and the molecular chain containing a poly(oxyperfluoroalkylene) group of the perfluoropolyether (B) has a structure represented by the following formula [1]: (In the above formulas [1] and [3], m is the number of -(CFCFO)- repeating units, and n is the number of -(CFO)- repeating units, and satisfies 5≦(m+n)≦30; m and n each independently represent an integer of 0 or greater; q is the number of oxyethylene groups and represents an integer of 0 to 20; r is the number of -(CFCFO)- repeating units, and s is the number of -(CFO)- repeating units, and satisfies 5≦(r+s)≦40; r and s each independently represent an integer of 0 or greater; and when both -(CFCFO)- and -(CFO)- repeating units are present, these repeating units are bonded via block bonds, random bonds, or block bonds and random bonds.)

[0043] In the formula [1], m and n each independently represent an integer of 1 or more, and in the formula [3], r and s each independently represent an integer of 1 or more.

[0044] The perfluoropolyether (A) is a compound represented by the following formula [4], and the perfluoropolyether (B) is a compound represented by the following formula [2]. (In the above formula [2] and formula [4], m, n, and q are defined as those in formula [1], r and s are defined as those in formula [3], A represents a terminal group having the active energy ray-polymerizable group, and the terminal group A is a group represented by the following formula [A1] or [A2].) (In the above formula [A1] and formula [A2], R 1 and R2 each independently represents a hydrogen atom or a methyl group, and * represents a bond to the urethane bond of the compound represented by formula [2] or formula [4].

[0045] According to the present invention, it is possible to provide a curable composition useful for forming a cured film and a hard coat layer that combines excellent scratch resistance, abrasion resistance, and excellent slippage, even in a thin film having a thickness of 1 μm to 20 μm. Furthermore, 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 comprising the cured film, and it is possible to provide a hard coat film that is excellent in both durability properties such as scratch resistance and abrasion resistance and slippage, which are in a trade-off relationship. Furthermore, according to the present invention, it is possible to provide a curable composition useful for forming a cured film and a hard coat layer that not only combines the above-mentioned properties but also has high water repellency, and a hard coat film having a hard coat layer that is excellent in these properties.

[0046] <Curable Composition> Each component of the curable composition of the present invention will be described below.

[0047] [(a) Active Energy Ray-Curable Polyfunctional Monomer Having Two or More (Meth)acryloyl Groups in One Molecule] The active energy ray-curable polyfunctional monomer of the component (a) having two or more (meth)acryloyl groups in one molecule (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 rays.

[0048] Preferred examples of the (a) polyfunctional monomer in the curable composition of the present invention include a monomer selected from the group consisting of polyfunctional (meth)acrylate compounds, a monomer selected from the group consisting of polyfunctional urethane (meth)acrylate compounds described below, and a monomer selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds. In the present invention, the (a) polyfunctional monomer can be one selected from the group consisting of the above polyfunctional (meth)acrylate compounds, or a combination of two or more selected from the group consisting of the above polyfunctional (meth)acrylate compounds. In the present invention, the (meth)acrylate compound includes both an acrylate compound and a methacrylate compound, and for example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

[0049] The (a) polyfunctional monomer may also be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene-modified monomer include oxymethylene-modified, oxyethylene-modified, and oxypropylene-modified. Examples of the oxyalkylene-modified polyfunctional monomer include oxyalkylene-modified compounds of the above-mentioned polyfunctional (meth)acrylate compounds or polyfunctional urethane (meth)acrylate compounds. The oxyalkylene-modified polyfunctional monomers can also be used alone or in combination of two or more.

[0050] In addition, preferred examples of the polyfunctional monomer (a) in the present invention include a polyfunctional monomer having at least three (meth)acryloyl groups in one molecule, for example, at least four (meth)acryloyl groups in one molecule, such as a monomer selected from the group consisting of oxyalkylene-modified polyfunctional (meth)acrylate compounds having at least three (meth)acryloyl groups in one molecule.

[0051] Examples of the polyfunctional (meth)acrylate compound (provided that it does 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. 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 2,6] 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 can be mentioned. 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.

[0052] Examples of the oxyalkylene-modified polyfunctional (meth)acrylate compound 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.

[0053] The polyfunctional urethane (meth)acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and having one or more urethane bonds [—NHC(═O)O—], and may further have a urea bond [—NHC(═O)NH—]. Examples of the polyfunctional urethane (meth)acrylate compound include a compound obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxy group, and a compound obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxy group, and a polyol, but the polyfunctional urethane (meth)acrylate compound that can be used in the present invention is not limited to these examples.

[0054] Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate. Examples of the (meth)acrylate having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tripentaerythritol hepta(meth)acrylate. Examples of the polyol include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; polyester polyols that are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, and adipic acid; polyether polyols; and polycarbonate diols.

[0055] The (a) polyfunctional monomer may be a lactone-modified polyfunctional (meth)acrylate compound, and the modifying lactone is preferably ε-caprolactone. 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.

[0056] [(b) Perfluoropolyether Having an Active Energy Ray-Polymerizable Group at the Terminal of a Molecular Chain Containing a Poly(oxyperfluoroalkylene) Group and Having a Weight-Average Molecular Weight of 1,400 to 3,500] The (b) component perfluoropolyether having an active energy ray-polymerizable group at the terminal of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight-average molecular weight of 1,400 to 3,500 will hereinafter be referred to simply as "(b) perfluoropolyether." (b) perfluoropolyether excludes the (c) perfluoropolyether described below. The (b) perfluoropolyether preferred in the curable composition of the present invention has an active energy ray-polymerizable group at the terminal of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond. The terminals of the molecular chain containing the poly(oxyperfluoroalkylene) group may be either all terminals or some terminals of the molecular chain. When the molecular chain is linear, all terminals and some terminals of the molecular chain refer to both terminals and one terminal of the linear molecular chain, respectively. The linking group between the poly(oxyperfluoroalkylene) group and the urethane bond may be, for example, a hydrocarbon group having an ether bond, and at least one hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. In addition, the preferred (b) perfluoropolyether does not have a silicon atom in its chemical structure.

[0057] The perfluoropolyether (b), together with the component (c) described below, serves as a surface modifier in the hard coat layer formed from the curable composition of the present invention. Furthermore, the perfluoropolyether (b) has excellent compatibility with the polyfunctional monomer (a), which prevents cloudiness and enables the formation of a hard coat layer with a transparent appearance.

[0058] From the viewpoint of obtaining a cured film with good scratch resistance, the poly(oxyperfluoroalkylene) group is preferably a group having both -[CF2O]- (oxyperfluoromethylene group) and -[CF2CF2O]- (oxyperfluoroethylene group) as repeating units. In this case, the bonds of these oxyperfluoroalkylene groups may be either block bonds or random bonds.

[0059] (b) perfluoropolyether is not limited to the one that has one active energy ray polymerizable group at the end of the molecular chain that comprises poly(oxyperfluoroalkylene) group, but can also have two or more active energy ray polymerizable groups.As this active energy ray polymerizable group, for example, (meth)acryloyl group and vinyl group can be enumerated, and as the terminal group that has this active energy ray polymerizable group, for example, can be enumerated as the group represented by the formula [A1] or formula [A2].Among these terminal groups, the group that has two active energy ray polymerizable groups and is represented by the formula [A2] is preferred.

[0060] From the viewpoint of obtaining a cured film with good scratch resistance, (b) perfluoropolyether is more preferably one having active energy ray polymerizable groups at both ends of molecular chain containing poly(oxyperfluoroalkylene) group, and more preferably one having a large number of said active energy ray polymerizable groups in one molecule.The number of said polymerizable groups is preferably 2 or more, more preferably 3 or more, at each end of molecular chain containing poly(oxyperfluoroalkylene) group.

[0061] (b) When the weight average molecular weight of the perfluoropolyether is 1,400 to 3,500, a hard coat layer having excellent scratch resistance, abrasion resistance, and slipperiness can be obtained.

[0062] In the curable composition of the present invention, the content of (b) perfluoropolyether is, for example, 0.05 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.05 to 3 parts by mass, preferably 0.1 to 3 parts by mass, more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the (a) polyfunctional monomer. When the content of (b) perfluoropolyether is 0.05 parts by mass or more, sufficient scratch resistance can be imparted to the hard coat layer, and when the content of (b) perfluoropolyether is 3 parts by mass or less, it is sufficiently compatible with the (a) polyfunctional monomer, and a hard coat layer with little cloudiness can be obtained.

[0063] (b) Perfluoropolyethers can be used singly or in combination of two or more. When two or more types are combined, a perfluoropolyether having an active energy ray polymerizable group at one end (one end) of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond and having a hydroxy group at the other end (the other end) of the molecular chain may be included.

[0064] [(c) Perfluoropolyether having the active energy ray polymerizable group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500] The perfluoropolyether (c) having the active energy ray polymerizable group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500 will be referred to simply as "(c) perfluoropolyether" below. (c) perfluoropolyether can be obtained, for example, by reacting a raw material perfluoropolyether having a number average molecular weight of 1200 to 3000 and having a hydroxy group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group with a compound having a functional group reactive with the hydroxy group and the active energy ray polymerizable group. Examples of the functional group reactive with the hydroxy group include a hydroxy group, a carboxy group, and an isocyanate group. "Furthermore, it is preferable that the raw material perfluoropolyether has a group containing a fluorine atom at the end opposite to the end having a hydroxy group, and more preferably a trifluoromethoxy group. The (c) perfluoropolyether having the fluorine atom-containing group at the end opposite to the end having the active energy ray-polymerizable group can sufficiently migrate to the surface of the hard coat layer, and can exhibit excellent water repellency and slip properties."

[0065] (c) perfluoropolyether is not limited to those that have one active energy ray polymerizable group at only one end of molecular chain that comprises poly(oxyperfluoroalkylene) group, but may have two or more active energy ray polymerizable groups.As this active energy ray polymerizable group, for example, (meth)acryloyl group and vinyl group can be enumerated, and as the terminal group that has this active energy ray polymerizable group, for example, can be enumerated as the group represented by the formula [A1] or formula [A2].Among these terminal groups, the group that has two active energy ray polymerizable groups and is represented by the formula [A2] is preferred.

[0066] The (c) perfluoropolyether, together with the (b) perfluoropolyether, serves as a surface modifier in the hard coat layer formed from the curable composition of the present invention.In addition, the (c) perfluoropolyether has excellent compatibility with the (b) perfluoropolyether, so that the cloudiness is suppressed and a hard coat layer exhibiting a transparent appearance can be formed.In addition, the (c) perfluoropolyether preferably has a poly(oxyalkylene) group from the viewpoint of compatibility with the (a) polyfunctional monomer.As the poly(oxyalkylene) group, a poly(oxyethylene) group is preferred.

[0067] The preferred (c) perfluoropolyether in the curable composition of the present invention has an active energy ray-polymerizable group via a urethane bond at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group. From the viewpoint of obtaining a cured film with good scratch resistance, the poly(oxyperfluoroalkylene) group is preferably a group having both -[CFO]- (oxyperfluoromethylene group) and -[CFCFO]- (oxyperfluoroethylene group) as repeating units. In this case, the bonds of these oxyperfluoroalkylene groups may be either block bonds or random bonds.

[0068] The fluorine atom content of (c) perfluoropolyether is, for example, 35% by mass to 65% by mass, preferably 40% by mass to 65% by mass, and more preferably 45% by mass to 65% by mass. If the fluorine atom content is 35% by mass or more, a hard coat layer having excellent water repellency and slipperiness can be obtained, but if it exceeds 65% by mass, there is a risk that the fluorine atom content will be insufficient to be compatible with (a) the polyfunctional monomer, and sufficient properties cannot be obtained.

[0069] The weight-average molecular weight of (c) perfluoropolyether is 1550 to 3500, preferably 1600 to 3500, more preferably 1700 to 3500. When the weight-average molecular weight of (c) perfluoropolyether is within the above range, the (c) 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 small, so that a hard coat layer with excellent slipperiness can be obtained. In addition, when the weight-average molecular weight of (c) perfluoropolyether is within the above range, the hardness of the layer surface can be 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 (c) perfluoropolyether is within the above range, it is possible to achieve both slipperiness and durability.

[0070] In the curable composition of the present invention, the content of the (c) perfluoropolyether is, for example, 0.05 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.05 to 3 parts by mass relative to 100 parts by mass of the (a) polyfunctional monomer. When the content of the (c) perfluoropolyether is 0.05 parts by mass or more, the (c) perfluoropolyether is sufficiently present on the surface of the hard coat layer obtained from the curable composition of the present invention, thereby obtaining a hard coat layer with excellent slipperiness. Furthermore, when the content of the (c) perfluoropolyether is 3 parts by mass or less, the (c) perfluoropolyether is sufficiently miscible with the (b) perfluoropolyether, thereby obtaining a hard coat layer with little opacity. Furthermore, the content of the (c) perfluoropolyether relative to 100 parts by mass of the (b) perfluoropolyether is, for example, 10 to 800 parts by mass, more preferably 10 to 500 parts by mass, and even more preferably 10 to 400 parts by mass.

[0071] (c) The perfluoropolyethers may be used singly or in combination of two or more.

[0072] [(d) Polymerization Initiator] The (d) polymerization initiator preferred in the curable composition of the present invention is, for example, a polymerization initiator that generates radicals when exposed to active energy rays such as electron beams, ultraviolet rays, and X-rays, particularly ultraviolet rays.

[0073] Examples of the (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azo compounds, azides, diazo compounds, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazoles, titanocene compounds, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These polymerization initiators may be used alone or in combination of two or more. In the present invention, from the viewpoints of transparency, surface curability, and thin film curability, it is preferable to use alkylphenones as the (d) polymerization initiator. The use of alkylphenones makes it possible to obtain a cured film with improved scratch resistance.

[0074] Examples of the alkylphenones include α-hydroxyalkylphenones such as 1-hydroxycyclohexyl phenyl 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-diphenylethan-1-one; and methyl phenylglyoxylate.

[0075] In the curable composition of the present invention, the content of the (d) polymerization initiator is, for example, 0.5 to 20 parts by mass, preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the (a) polyfunctional monomer.

[0076] [(e) Solvent] The curable composition of the present invention may contain (e) solvent as an optional component, i.e., may be in the form of a varnish. The (e) solvent may be appropriately selected in consideration of the solubility / dispersibility of the components (a) to (d), the workability during application of the curable composition for forming a cured film (hard coat layer) described below, the drying properties before and after curing, etc.

[0077] Examples of the (e) solvent include 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. ethers such as propylene glycol mono-n-propyl ether (PGME), propylene glycol monoisopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclopentanone, 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 mixtures of two or more of these solvents.

[0078] The content of the solvent (e) in the curable composition of the present invention is not particularly limited, but is, for example, a concentration such that the solid content concentration of the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass. Here, the solid content concentration (also referred to as non-volatile content concentration) represents the content of the solid content (all components excluding the solvent component) relative to the total mass (total mass) of the components (a) to (e) and other additives in the curable composition of the present invention.

[0079] [Other Additives] Furthermore, the curable composition of the present invention may contain, as needed, one or more of the additives that are generally added, such as a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion imparting agent, a plasticizer, an ultraviolet absorber, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, and a dye, which may be blended alone or in combination, as long as the effects of the present invention are not impaired.

[0080] <Cured film> The curable composition of the present invention can be applied (coated) onto a substrate to form a coating film, and the coating film can be polymerized (cured) by irradiating it with active energy rays to form a cured film, and the cured film is also within the scope of the present invention. In addition, the cured film can be used as a hard coat layer in a hard coat film described below.

[0081] Examples of the substrate 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, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin), metal, wood, paper, glass, and slate. These substrates may be in the form of a plate, film, or three-dimensional molded article. Furthermore, on the surface of the substrate, for example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near-infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather-resistant layer, an antireflection layer, an antistatic layer, a discoloration preventing layer, a gas barrier layer, a water vapor barrier layer, a light-scattering layer, an electrode layer, or the like may be formed as an underlayer of the hard coat layer, or a plurality of underlayers of the hard coat layer may be laminated. The layer formed on the surface of the substrate is not particularly limited as long as it does not impair the effects of the present invention.

[0082] The method for applying the composition to the substrate can be appropriately selected from cast coating, spin coating, blade coating, dip coating, roll coating, spray coating, bar coating, die coating, inkjet printing, and printing methods (such as relief printing, intaglio printing, lithographic printing, and screen printing). Among these, roll-to-roll methods are preferred. From the viewpoint of thin-film coating properties, relief printing, particularly gravure coating, is preferred. The curable composition of the present invention is preferably filtered beforehand using a filter having a pore size of approximately 0.2 μm before application. If necessary, a solvent may be added to the curable composition during application. Examples of the solvent include the various solvents listed in the above section [(e) Solvent].

[0083] After the curable composition of the present invention is applied to a substrate to form a coating film, the coating film is pre-dried as needed using a heating means such as a hot plate or oven to remove the solvent (solvent removal step). The heat drying conditions are preferably, for example, 40°C to 120°C and 30 seconds to 10 minutes. After drying, the coating film is cured by irradiating it with active energy rays such as ultraviolet light. Examples of active energy rays include ultraviolet light, electron beams, and X-rays, with ultraviolet light being particularly preferred. Examples of light sources that can be used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. The polymerization may then be completed by post-baking, specifically by heating using a heating means such as a hot plate or oven.

[0084] The thickness of the cured film formed after drying and curing is usually 0.1 to 20 μm, preferably 0.5 to 10 μm.

[0085] <Hard Coat Film> Using the curable composition of the present invention, a hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced. The hard coat film is also within the scope of the present invention, and the hard coat film is suitably used for protecting the surfaces of various display elements such as touch panels and liquid crystal displays.

[0086] The hard coat layer in the hard coat film of the present invention can be formed by a method including the steps of applying the curable composition of the present invention to a film substrate to form a coating film, removing the solvent by heating as necessary, and irradiating the coating film with active energy rays such as ultraviolet rays to cure the coating film. A method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, including these steps, is also within the scope of the present invention.

[0087] As the film substrate, various transparent resin films usable for optical applications among the substrates listed in the above <Cured film> can be used. Preferred resin films include films of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose (TAC), and the like.

[0088] The film substrate may be formed by laminating a plurality of layers. For example, a layer different from the resin film, such as a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near-infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather-resistant layer, an antireflection layer, an antistatic layer, a discoloration preventing layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, or an electrode layer, may be laminated on the surface of the resin film as an underlayer of the hard coat layer, or a plurality of underlayers of the hard coat layer may be laminated. The layer laminated on the surface of the resin film is not particularly limited as long as it does not impair the effects of the present invention.

[0089] The method for applying the curable composition of the present invention to the film substrate (coating film forming step) and the method for irradiating the coating film with active energy rays (curing step) can be the methods listed above in <Cured film>. When the curable composition of the present invention contains a solvent (in the form of a varnish), the coating film may be dried to remove the solvent after the coating film forming step, if necessary. In this case, the method for drying the coating film (solvent removal step) listed above in <Cured film> can be used.

[0090] The thickness (film thickness) of the hard coat layer thus obtained is, for example, 1 μm to 20 μm, and preferably 1 μm to 10 μm.

[0091] <Surface Modifier> The present invention also covers a perfluoropolyether (A) (excluding the perfluoropolyether (B) described below) having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight-average molecular weight of 1,400 to 3,500, and a surface modifier containing a perfluoropolyether (B) having the active energy ray-polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight-average molecular weight of 1,550 to 3,500. Furthermore, the present invention also includes perfluoropolyether (A) (however, excluding the perfluoropolyether (B) described below), which has active energy ray polymerizable group at the end of molecular chain containing poly (oxyperfluoroalkylene) group, and has weight average molecular weight of 1400 to 3500, and the raw material perfluoropolyether has hydroxyl group at only one end of molecular chain containing poly (oxyperfluoroalkylene) group, and number average molecular weight of 1200 to 3000, and the surface modifier containing perfluoropolyether (B), which is the reaction product of the compound having functional group that reacts with this hydroxyl group and the active energy ray polymerizable group.It should be noted that "perfluoropolyether (A)" is the same as the above-mentioned (b) perfluoropolyether, and "perfluoropolyether (B)" is the same as the above-mentioned (c) perfluoropolyether.

[0092] 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. In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows:

[0093] (1) Coating by bar coater Apparatus: PM-9050MC manufactured by SMT Corporation Bar: A-Bar OSP-15 manufactured by OSG System Products Co., Ltd. Maximum wet film thickness 15 μm (film thickness after drying 3 μm) Coating speed: 4 m / min (2) Film thickness measurement Apparatus: F20 Film thickness measurement system manufactured by Filmetrics Inc. (3) Oven Apparatus: Two-layer clean oven (top and bottom type) PO-250-45-D manufactured by Sanki Keiso Co., Ltd. (4) UV curing Apparatus: CV-110QC-G manufactured by Heraeus Co., Ltd. Lamp: Electrodeless lamp H-bulb manufactured by Heraeus Co., Ltd. (5) Scratch resistance test and abrasion resistance test Apparatus: Reciprocating abrasion tester TRIBOGEAR TYPE: 30S manufactured by Shinto Scientific Co., Ltd. Scanning speed: 3200 mm / min. Scanning distance: 50 mm (6) Contact angle measurement Apparatus: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measurement temperature: 23°C (7) Dynamic friction coefficient measurement Apparatus: Load-varying friction and wear test system TRIBOGEAR (registered trademark) TYPE: HHS2000 manufactured by Shinto Scientific Co., Ltd. Probe: 0.6 mmR sapphire pin Load: 200 g Scanning speed: 2 mm / sec. Scanning distance: 10 mm (8) Total light transmittance, haze measurement Apparatus: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. (9) Weight-average molecular weight measurement Gel permeation chromatography (GPC) Apparatus: HLC-8420GPC manufactured by Tosoh Corporation Column: manufactured by Tosoh Corporation TSKgel G2000HXL, TSKgel G3000HXL Measurement temperature: 40°C Eluent: tetrahydrofuran Detection: RI (10) Combustion ion chromatography Automatic sample combustion system: AQF-2100 H manufactured by Nitto Seiko Analytech Co., Ltd. (formerly Mitsubishi Chemical Analytech Co., Ltd.) Ion chromatograph: Dionex Integration manufactured by Thermo Fisher Scientific Co., Ltd. Sample: 2 mg Absorption 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: AG-12A / AS-12A manufactured by Thermo Fisher Scientific Co., Ltd. Flow rate: 1.5 mL / min Detector: Electrical conductivity (suppressor used)Standard sample: Fluoride ion standard solution (F-1000) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (formerly Wako Pure Chemical Industries, Ltd.) When the solvent in the sample did not contain a solvent containing fluorine atoms, the fluorine concentration was measured while the solvent was still present, and the fluorine concentration of the solute was calculated by converting it from the solids concentration. When the solvent in the sample contained a solvent containing fluorine atoms, a halogen moisture meter was used to volatilize the sample solvent at 120°C for 20 minutes, and the fluorine concentration was measured using a sample when the mass change became constant and it was determined that the solvent had all volatilized.

[0094] The abbreviations have the following meanings: Multifunctional acrylate PA1: dipentaerythritol pentaacrylate / hexaacrylate mixture [Aronix (registered trademark) M-403, manufactured by Toagosei Co., Ltd.] Multifunctional acrylate PA2: oxyethylene-modified multifunctional acrylate [New Frontier (registered trademark) MF-001, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] Multifunctional acrylate PA3: multifunctional urethane acrylate [Art Resin (registered trademark) UN-3320HS, manufactured by Negami Chemical Industrial Co., Ltd.] Multifunctional acrylate PA4: pentaerythritol triacrylate / pentaerythritol tetraacrylate [PET30, manufactured by Nippon Kayaku Co., Ltd.] PFPE1: perfluoropolyether having two hydroxy groups at each end without a poly(oxyalkylene) group, and having the following structure [Fomblin (registered trademark) T4, manufactured by Solvay Specialty Polymers] 19 F-NMR and 1 Number average molecular weight calculated from H-NMR analysis results: 2200 (In the above formula, r represents the number of repeating units -(CF2CF2O)- and s represents the number of repeating units -(CF2O)-, and the relationship 5≦(r+s)≦40 is satisfied, and r and s each independently represent an integer of 0 or more.) PFPE2: Perfluoropolyether having one hydroxy group at only one end without a poly(oxyalkylene) group, and having the following structure [7324X manufactured by Solvay Specialty Polymers] 19 F-NMR and 1 Number average molecular weight calculated from the results of H-NMR analysis: 1750 to 1950] (In the above formula, m is the number of repeating units -(CF2CF2O)-, and n is the number of repeating units -(CF2O)-, and the number satisfies 5≦(m+n)≦30, and m and n each independently represent an integer of 0 or more.) PFPE3: A perfluoropolyether having one hydroxy group at only one end via a poly(oxyethylene) group, and having the following structure [Fomblin (registered trademark) 4102X manufactured by Solvay Specialty Polymers] 19 F-NMR and 1 Number average molecular weight calculated from H-NMR analysis results: 1900 (In the above formula, m is the number of repeating units -(CF2CF2O)-, and n is the number of repeating units -(CF2O)-, and satisfy the relationship 5≦(m+n)≦30, m and n each independently represent an integer of 0 or more, and q is the number of oxyethylene groups and represents an integer of 2 to 20.) PFPE4: A perfluoropolyether having one hydroxy group at only one end without a poly(oxyalkylene) group, and having the following structure [FO2, manufactured by Apollo Scientific, molecular weight 978.15] PFPE5: Perfluoropolyether (1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol) having one hydroxy group at only one end without a poly(oxyalkylene) group, and having the following structure [C10GOL, molecular weight 548.1, manufactured by Exfluor Research] PFPE6: A perfluoropolyether having one hydroxy group at each end without a poly(oxyalkylene) group, and having the following structure [Fomblin (registered trademark) D2 manufactured by Solvay Specialty Polymers] 19 F-NMR and 1 Number average molecular weight calculated from H-NMR analysis results: 1550 (In the above formula, m is the number of repeating units -(CF2CF2O)-, and n is the number of repeating units -(CF2O)-, and 5≦(m+n)≦30 is satisfied, and m and n each independently represent an integer of 0 or more.) N1: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI, manufactured by Showa Denko K.K.] N2: 2-acryloyloxyethyl isocyanate [Karenz (registered trademark) AOI, manufactured by Showa Denko K.K.] SMA6: Perfluoropolyether [manufactured by Daikin Industries, Ltd.] having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group. OPTOOL (registered trademark) DAC-HP, 20% by mass non-volatile solution, weight average molecular weight measured by GPC in terms of polystyrene: Mw is 1521, dispersity: Mw / Mn is 1.1 (Mn is number average molecular weight), content of fluorine atoms in the perfluoropolyether compound calculated by combustion ion chromatography: 35% by mass] SMA7: perfluoropolyether having a total of four active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group [Fluorolink (registered trademark) AD-1700, manufactured by Solvay Specialty Polymers, 70% by mass non-volatile solution, weight average molecular weight measured by GPC in terms of polystyrene: Mw is 3973, dispersity: Mw / Mn is 2.1, content of fluorine atoms in the perfluoropolyether compound calculated by combustion ion chromatography: 29% by mass] DOTDD: dioctyltin dineodecanoate [manufactured by Nitto Kasei Co., Ltd. Neostan (registered trademark) U-830] MEK: methyl ethyl ketone PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate MeOH: methanol O2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [OMNIRAD (registered trademark) 2959, manufactured by IGM Resins] AN1: PEDOT-PSS aqueous dispersion [PEDOT-PSS 3.0% to 4.0% by mass aqueous dispersion, high conductivity grade, manufactured by Sigma-Aldrich, product number 655201]

[0095] [Production Example 1] Production of surface modifier component SMA1 1.19 g (0.5 mmol) of PFPE1, 0.52 g (2.0 mmol) of N1, 0.017 g of DOTDD (0.01 times the total mass of PFPE1 and N1), and 1.67 g of PGMEA were charged into a screw tube. This mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer tip to obtain a 50 mass% 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 2494, and the dispersity (Mw / Mn) was 1.0. The fluorine atom content in SMA1 calculated by combustion ion chromatography was 42 mass%.

[0096] [Production Example 2] Production of surface modifier component SMA2 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 were charged into a screw tube. This mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer tip to obtain an 80 mass% MEK solution of the target perfluoropolyether compound SMA2. The weight average molecular weight (Mw) of the obtained SMA2 measured in terms of polystyrene by GPC was 1710, and the dispersity (Mw / Mn) was 1.0. The fluorine atom content in SMA2 calculated by combustion ion chromatography was 63 mass%.

[0097] [Production Example 3] Production of surface modifier component SMA3 3.08 g (1.6 mmol) of PFPE3, 0.39 g (1.6 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE3 and N1), and 3.5 g of PGMEA were charged into a screw tube. This mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer tip to obtain a 50 mass% 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 1908, and the dispersity (Mw / Mn) was 1.0. The fluorine atom content in SMA3 calculated by combustion ion chromatography was 47 mass%.

[0098] [Production Example 4] Production of surface modifier component SMA4 2.78 g (2.9 mmol) of PFPE4, 0.68 g (2.9 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE4 and N1), and 3.5 g of PGMEA were charged into a screw tube. This mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer tip to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA4. The weight average molecular weight (Mw) of the obtained SMA4 measured in polystyrene equivalent by GPC was 1299, and the dispersity (Mw / Mn) was 1.0. The fluorine atom content in SMA4 calculated by combustion ion chromatography was 51 mass%, which was similar to the fluorine atom content (51 mass%) theoretically calculated from the structure of SMA4.

[0099] [Production Example 5] Production of surface modifier component SMA5 2.41 g (4.4 mmol) of PFPE5, 1.05 g (4.4 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE5 and N1), and 3.5 g of PGMEA were charged into a screw tube. This mixture was stirred at room temperature (approximately 23 ° C) for 72 hours using a stirrer tip to obtain a 50 mass% 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 1029, and the dispersity (Mw / Mn) was 1.0. In addition, the fluorine atom content in SMA5 calculated by combustion ion chromatography was 46 mass%, which was similar to the fluorine atom content of 47 mass% theoretically calculated from the structure of SMA5.

[0100] [Production Example 6] Production of surface modifier component SMA8 3.66 g (2.4 mmol) of PFPE6, 0.67 g (4.8 mmol) of N2, 0.054 g of DOTDD (0.01 times the total mass of PFPE6 and N2), and 4.4 g of PGMEA were charged into a screw tube. This mixture was stirred at room temperature (approximately 23 ° C) for 72 hours using a stirrer tip to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA8. The weight average molecular weight (Mw) of the obtained SMA8 measured in polystyrene equivalent by GPC was 1609, and the dispersity (Mw / Mn) was 1.0. The fluorine atom content in SMA8 calculated by combustion ion chromatography was 54 mass%.

[0101] [Examples 1 to 9, Comparative Examples 1 to 13] The components shown in Table 1 were mixed to prepare curable compositions having the solid content concentrations shown in Table 1. Here, the solid content refers to components other than the solvent. In Table 1, [parts] represents [parts by mass] and [%] represents [% by mass]. In Table 1, the polyfunctional acrylate and surface modifier each represent the solid content.

[0102]

[0103] These curable compositions were applied with a bar coater onto an A4-sized PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., thickness 100 μm] on both sides of which a primer layer had been formed by easy-adhesion treatment, to obtain a coating film. This coating film was dried in an oven at 60°C for 8 minutes to remove the solvent. The obtained film was then exposed to light at an exposure dose of 300 mJ / cm under a nitrogen atmosphere. 2 The film was exposed to UV light of 1000 kJ / cm 2 , thereby producing a hard coat film having a hard coat layer (cured film).

[0104] [Examples 10 to 11, Comparative Examples 14 to 15] The components shown in Table 2 were mixed to prepare curable compositions having the solid content concentrations shown in Table 2. Here, the solid content refers to components other than the solvent. In Table 2, [parts] represents [parts by mass] and [%] represents [% by mass]. In Table 2, the polyfunctional acrylate and surface modifier each represent the solid content.

[0105]

[0106] These curable compositions were applied with a bar coater onto an A4-sized PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., thickness 100 μm] on both sides of which a primer layer had been formed by easy-adhesion treatment, to obtain a coating film. This coating film was dried in an oven at 65°C for 3 minutes to remove the solvent. The obtained film was then exposed to light at an exposure dose of 300 mJ / cm under a nitrogen atmosphere. 2 The film was exposed to UV light of 1000 kJ / cm 2 , thereby producing a hard coat film having a hard coat layer (cured film).

[0107] The homogeneity of each curable composition, as well as the scratch resistance, water repellency, abrasion resistance, slipperiness, and haze of the obtained hard coat film were evaluated. The evaluation procedures are shown below. The results are also shown in Tables 3 and 4. [Composition homogeneity] The appearance of each prepared curable composition was visually confirmed and evaluated according to the following criteria. A: Transparent solution (no floating matter, sediment, or phase separation) C: Presence of floating matter, sediment, or phase separation [Scratch resistance] The hard coat layer surface of the obtained hard coat film was rubbed 5,000 times with steel wool [BONSTAR (registered trademark) #0000 (ultrafine)] attached to a reciprocating abrasion tester under a load of 1 kg with a stroke of 50 mm. Thereafter, the degree of scratches in the area excluding the 5 mm wide ranges at both ends of the 50 mm stroke was visually confirmed, and in addition, it was confirmed using a microscope (Keyence Corporation) that the scratches were on the surface of the hard coat layer, and the evaluation was performed according to the following criteria A, B, and C. Note that, when actual use as a hard coat layer is assumed, at least B is required, and A is preferable. A: No scratches (0 scratches) B: Scratches occurred (1 to 4 scratches with a length of 1 mm to 9 mm) C: Scratches occurred (5 or more scratches with a length of 1 mm to 9 mm, or 1 or more scratches with a length of 1 cm or more) [Water repellency] 1 μL of water was applied to the surface of the hard coat layer, and the contact angle θ after 5 seconds was measured 5 times, and the average value was used to evaluate according to the following criteria. Note that, when actual use as a hard coat layer is assumed, A is preferable. Note that when the contact angle is measured immediately after application of water, the value is high and unstable, so in this measurement, the contact angle was measured 5 seconds after application of water. A: θ>105° B: 100°≦θ≦105° C: θ<100° [Abrasion resistance] The surface of the hard coat layer is rubbed with a cylindrical eraser [Minoan's RUBBER STICK, φ6.0mm] attached to a reciprocating abrasion tester, with a load of 1 kg, 2,500 times. 1 μL of water is applied to the rubbed part, and the contact angle θ is measured at 5 points after 5 seconds, and the average value is taken as the contact angle value, and evaluated according to the following criteria. Note that, when assuming actual use as a hard coat layer, it is required to be at least B, and it is desirable to be A.A: θ≧90° B: 85°≦θ<90° C: 85°<θ [Slipperiness] The dynamic friction coefficient was measured at five locations on the surface of the hard coat layer, and the average value was used for evaluation. The smaller the dynamic friction coefficient value, the smaller the friction with the probe used, and serves as a guide to slipperiness. The smaller the dynamic friction coefficient value, the better the slipperiness when touched, so the smaller the dynamic friction coefficient value, the more preferable. [Haze] As a reference value, 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 [Lumirror (registered trademark) U403 (also known as U40), 100 μm thick, manufactured by Toray Industries, Inc.] was 1.6.

[0108]

[0109]

[0110] As shown in Table 1, the curable compositions of Examples 1 to 8 comprised polyfunctional acrylates PA1 to PA4, and a perfluoropolyether SMA1 having an active energy ray-polymerizable group at each end of a molecular chain containing a poly(oxyperfluoroalkylene) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further comprising SMA2 having a weight-average molecular weight of 1710 or SMA3 having a weight-average molecular weight of 1908, obtained by reacting a perfluoropolyether compound PFPE2 or PFPE3 having a number-average molecular weight of 1750 to 1950 and having one hydroxy group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group with an isocyanate compound N1 having the active energy ray-polymerizable group. As shown in Table 3, the curable compositions of Examples 1 to 8 exhibited excellent homogeneity, and the hard coat films having hard coat layers obtained from the curable compositions exhibited excellent slip properties, scratch resistance, water repellency, and abrasion resistance.

[0111] As shown in Table 1, the curable composition of Example 9 comprises a polyfunctional acrylate PA1, a perfluoropolyether SMA6 having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group, a weight average molecular weight of 1521, and a fluorine atom content of 35% by mass, and further comprises a perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 and having one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and an isocyanate compound N1 having the active energy ray polymerizable group, and a weight average molecular weight of 1710, obtained by reacting the SMA2. As shown in Table 3, the curable composition of Example 9 exhibits excellent homogeneity, and the hard coat film having a hard coat layer obtained from the curable composition exhibits excellent slip properties, water repellency, and abrasion resistance. The hard coat film having a hard coat layer obtained from the curable composition of Example 9 was slightly inferior in scratch resistance to the hard coat films having hard coat layers obtained from the curable compositions of Examples 1 to 8, but exhibited excellent property levels in the other items shown in Table 2.

[0112] On the other hand, as shown in Table 1, the curable composition of Comparative Example 1 comprises a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having an active energy ray polymerizable group at each end of the molecular chain containing a poly(oxyperfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further comprises a perfluoropolyether compound PFPE4 having a molecular weight of 978.15 and one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and an isocyanate compound N1 having the active energy ray polymerizable group, which is obtained by reacting the perfluoropolyether compound PFPE4 with the active energy ray polymerizable group, and has a weight average molecular weight of 1299 and a fluorine atom content of 51% by mass. As shown in Table 3, the curable composition of Comparative Example 1 exhibits excellent homogeneity, but the hard coat film having a hard coat layer obtained from the curable composition exhibits poorer slip properties and abrasion resistance than the hard coat films obtained from the curable compositions of Examples 1 to 9. These results show that even if a perfluoropolyether having an active energy ray polymerizable group at only one end of a molecular chain containing an (oxyperfluoroalkylene) group with a high fluorine atom content is used, the slipperiness and abrasion resistance are poor, and that the weight-average molecular weight of the perfluoropolyether is important for slipperiness and abrasion resistance.

[0113] In addition, as shown in Table 1, the curable composition of Comparative Example 2 comprises a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having an active energy ray polymerizable group at each end of the molecular chain containing a poly(oxyperfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass; and further comprises a perfluoropolyether compound PFPE5 having a molecular weight of 548.10 and having one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and a weight average molecular weight of 1029 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the SMA5 having a fluorine atom content of 47% by mass. And, as shown in Table 3, the curable composition of Comparative Example 2 exhibits excellent homogeneity, but the hard coat film having a hard coat layer obtained from the curable composition exhibits poor results in terms of slipperiness, scratch resistance, and abrasion resistance. These results also show that the use of a perfluoropolyether having an active energy ray polymerizable group at only one end of a molecular chain containing an (oxyperfluoroalkylene) group with a high fluorine atom content does not necessarily result in excellent slip properties, scratch resistance, and abrasion resistance, and that the weight-average molecular weight of the perfluoropolyether is important for slip properties, scratch resistance, and abrasion resistance.

[0114] As shown in Table 1, the curable compositions of Comparative Examples 3 and 4 contain polyfunctional acrylate PA1, and SMA4 and SMA5, which have a weight-average molecular weight of 1,299 and a weight-average molecular weight of 1,029, obtained by reacting a perfluoropolyether compound PFPE4 having a molecular weight of 978.15 and a perfluoropolyether compound PFPE5 having a molecular weight of 548.10, each of which has one hydroxy group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having an active energy ray-polymerizable group. They also contain SMA2 and SMA2, which have a weight-average molecular weight of 1,710, obtained by reacting a perfluoropolyether compound PFPE2 having a number-average molecular weight of 1,750 to 1,950, each of which has one hydroxy group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having an active energy ray-polymerizable group. As shown in Table 3, the curable compositions of Comparative Examples 3 and 4 were inferior in homogeneity, and the hard coat films having hard coat layers obtained from these curable compositions exhibited poor slip properties, scratch resistance, and abrasion resistance. This is thought to be because the weight-average molecular weights of SMA4 and SMA5 were small, preventing the aggregation structure of SMA2 from being broken down and failing to improve solubility in the coating solution. As a result, SMA2 aggregated in the coating solution, preventing sufficient segregation of SMA2 on the surface of the hard coat layer, resulting in poor slip properties, scratch resistance, and abrasion resistance.

[0115] As shown in Table 1, the curable composition of Comparative Example 5 comprises a polyfunctional acrylate PA1 and a perfluoropolyether SMA7 having active energy ray-polymerizable groups at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, a weight-average molecular weight of 3973, and a fluorine atom content of 29% by mass; and further comprises a perfluoropolyether compound PFPE2 having a number-average molecular weight of 1750 to 1950 and having one hydroxy group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and SMA2 having a weight-average molecular weight of 1710 obtained by reacting an isocyanate compound N1 having the active energy ray-polymerizable group with the perfluoropolyether compound PFPE2. As shown in Table 3, the curable composition of Comparative Example 5 exhibited excellent homogeneity and excellent slip properties, but the hard coat film having a hard coat layer obtained from the curable composition exhibited poor scratch resistance and abrasion resistance. These results demonstrate that good slip properties do not necessarily lead to good scratch resistance and abrasion resistance. The hard coat film having a hard coat layer obtained from the curable composition of Comparative Example 5 was inferior in scratch resistance and abrasion resistance to the hard coat films having hard coat layers obtained from the curable compositions of Examples 1 to 9. This is thought to be because the weight average molecular weight of SMA7 was larger than those of SMA1 and SMA6, resulting in a lower immobilization ability in the film. In addition, the fluorine atom content of SMA7 was smaller than those of SMA1 and SMA6, resulting in poor compatibility between SMA2 and SMA7, resulting in a state of phase separation between SMA2 and SMA7 on the surface of the hard coat layer.

[0116] As shown in Table 1, the curable composition of Comparative Example 6 contained a polyfunctional acrylate PA1 and a perfluoropolyether compound PFPE2 having a number-average molecular weight of 1,750 to 1,950 and a hydroxy group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and SMA2 having a weight-average molecular weight of 1,710 obtained by reacting the isocyanate compound N1 having the active energy ray-polymerizable group with the perfluoropolyether compound PFPE2. As shown in Table 3, the curable composition of Comparative Example 6 was inferior in homogeneity to the curable composition of Example 1 in which SMA1 was added to the curable composition of Comparative Example 6. Furthermore, the hard coat film having a hard coat layer obtained from the curable composition of Comparative Example 6 exhibited inferior results in terms of slipperiness, scratch resistance, water repellency, and abrasion resistance compared to the hard coat film having a hard coat layer obtained from the curable composition of Example 1. This is thought to be because the coating solution did not contain a perfluoropolyether having an active energy ray-polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group, which acts as a solubility aid for SMA2, and having a weight-average molecular weight of 1,400 to 3,500, causing SMA2 to aggregate in the coating solution.

[0117] As shown in Table 1, the curable composition of Comparative Example 7 contained SMA3, which had a weight-average molecular weight of 1908 and was obtained by reacting a perfluoropolyether compound PFPE3 having a number-average molecular weight of 1900 and a hydroxy group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group with an isocyanate compound N1 having an active energy ray-polymerizable group. As shown in Table 3, the curable composition of Comparative Example 7 had excellent homogeneity, but the hard coat film having a hard coat layer obtained from the curable composition exhibited inferior results in abrasion resistance and water repellency compared to the hard coat films having hard coat layers obtained from the curable compositions of Examples 2 to 4 in which SMA1 was added to the curable composition of Comparative Example 7. This is thought to be because the use of SMA3 alone resulted in a strong cohesive force of SMA3, which made it more likely to aggregate inside the film, preventing sufficient segregation of SMA3 on the surface of the hard coat layer, and also because SMA3 has an active energy ray-polymerizable group at only one end, resulting in low immobilization ability in the film.

[0118] As shown in Table 1, the curable composition of Comparative Example 8 contains SMA4, which has a weight average molecular weight of 1299 and is obtained by reacting a perfluoropolyether compound PFPE4 having a molecular weight of 978.15 and a hydroxy group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group with an isocyanate compound N1 having the active energy ray-polymerizable group. As shown in Table 3, the curable composition of Comparative Example 8 is inferior in homogeneity to the curable composition of Comparative Example 1, in which SMA1 is added to the curable composition of Comparative Example 8. The hard coat film having a hard coat layer obtained from the curable composition of Comparative Example 8 exhibited poor results in terms of slipperiness, scratch resistance, and abrasion resistance. This is thought to be due to the fact that SMA4 aggregates inside the film, preventing sufficient segregation of SMA4 on the surface of the hard coat layer, and the molecular chain containing the poly(oxyperfluoroalkylene) group of SMA4 is short.

[0119] In addition, as shown in Table 1, the curable composition of Comparative Example 9 contains SMA5, which has a weight average molecular weight of 1029 and is obtained by reacting a perfluoropolyether compound PFPE5 having a molecular weight of 548.1 and one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group with an isocyanate compound N1 having an active energy ray polymerizable group. As shown in Table 3, although the curable composition of Comparative Example 9 has excellent homogeneity, the hard coat film having a hard coat layer obtained from the curable composition exhibits poor results in terms of slipperiness, water repellency, scratch resistance, and abrasion resistance due to the short molecular chain containing a poly(oxyperfluoroalkylene) group.

[0120] Furthermore, as shown in Table 1, the curable composition of Comparative Example 10 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having an active energy ray-polymerizable group at each end of a molecular chain containing a poly(oxyperfluoroalkylene) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass. As shown in Table 3, the curable composition of Comparative Example 10 has excellent homogeneity, and a hard coat film having a hard coat layer obtained from the curable composition is excellent in water repellency, scratch resistance, and abrasion resistance. However, compared with a hard coat film having a hard coat layer obtained from the curable composition of Example 1 in which SMA2 was added to the curable composition of Comparative Example 10, the hard coat film did not contain SMA2 and therefore exhibited inferior slipperiness. This is thought to be because SMA1 has eight acrylic groups per molecule, which provides high immobilization ability in the film, resulting in excellent scratch resistance and abrasion resistance. However, the high immobilization ability reduces the molecular mobility of SMA1, resulting in poor slipperiness.

[0121] Judging from the evaluation results of the hard coat films having hard coat layers obtained from the curable compositions of Comparative Examples 5 and 10 shown in Table 3, it was suggested that there is a trade-off between slip properties and scratch resistance.

[0122] Furthermore, as shown in Table 1, the curable composition of Comparative Example 12 contains polyfunctional acrylate PA1 and perfluoropolyether SMA7, which has active energy ray-polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, and which has a weight-average molecular weight of 3973 and a fluorine atom content of 29 mass%. As shown in Table 3, the curable composition of Comparative Example 12 is excellent in homogeneity, but the hard coat film having a hard coat layer obtained from this curable composition exhibits inferior slip properties compared to the hard coat film having a hard coat layer obtained from the curable composition of Comparative Example 5, in which SMA2 was added to the curable composition of Comparative Example 12, because it did not contain SMA2. These results suggest that the hard coat film obtained from the curable composition containing as a surface modifier a perfluoropolyether having an active energy ray polymerizable group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group has superior slip properties compared to the hard coat film obtained from the curable composition containing as a surface modifier only a perfluoropolyether having an active energy ray polymerizable group at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group.

[0123] Furthermore, as shown in Table 1, the curable composition of Comparative Example 13 contains a polyfunctional acrylate PA1, and a perfluoropolyether SMA1 having an active energy ray-polymerizable group at each end of the molecular chain containing a poly(oxyperfluoroalkylene) group, a weight-average molecular weight of 2,494, and a fluorine atom content of 42 mass%, and further contains SMA8 having a weight-average molecular weight of 1,609 and a fluorine atom content of 54 mass%, which is obtained by reacting a perfluoropolyether compound PFPE6 having one hydroxy group at each end of the molecular chain containing a poly(oxyperfluoroalkylene) group and a number-average molecular weight of 1,550, with an isocyanate compound N1 having the active energy ray-polymerizable group. As shown in Table 3, the curable composition of Comparative Example 13 exhibits excellent homogeneity, and the hard coat film having a hard coat layer obtained from this curable composition has excellent water repellency and scratch resistance, but compared with the hard coat film having a hard coat layer obtained from the curable composition of Example 1 to Example 9, it showed poor results in slipperiness and abrasion resistance.From these results, it was shown that the hard coat film obtained from the curable composition containing perfluoropolyether having active energy ray polymerizable groups at only one end of the molecular chain containing poly (oxyperfluoroalkylene) group as a surface modifier is superior in slipperiness compared with the hard coat film obtained from the curable composition containing only perfluoropolyether having active energy ray polymerizable groups at both ends of the molecular chain containing poly (oxyperfluoroalkylene) group as a surface modifier.

[0124] As shown in Table 2, the curable compositions of Examples 10 and 11 comprise a polyfunctional acrylate PA1 or PA2, and a perfluoropolyether SMA1 having an active energy ray polymerizable group at each end of the molecular chain containing a poly(oxyperfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass; and further comprise a perfluoropolyether compound PFPE3 having a number average molecular weight of 1900 and having one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and a weight average molecular weight of 1908 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group; and also comprise an antistatic agent AN1. And, as shown in Table 4, the curable compositions of Examples 10 and 11 exhibited excellent homogeneity, and the hard coat films having a hard coat layer obtained from the curable compositions exhibited excellent slip properties, scratch resistance, water repellency, and abrasion resistance.

[0125] On the other hand, as shown in Table 2, the curable composition of Comparative Example 14 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having an active energy ray-polymerizable group at each end of a molecular chain containing a poly(oxyperfluoroalkylene) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further contains an antistatic agent AN1. As shown in Table 4, the curable composition of Comparative Example 14 has excellent homogeneity, and a hard coat film having a hard coat layer obtained from the curable composition is excellent in water repellency, scratch resistance, and abrasion resistance, but compared to a hard coat film having a hard coat layer obtained from the curable composition of Example 10 in which SMA3 was added to the curable composition of Comparative Example 14, the hard coat film did not contain SMA3 and therefore showed inferior slipperiness. This is thought to be because SMA1 has eight acrylic groups per molecule, which gives it high immobilization ability in the film, resulting in excellent scratch resistance and abrasion resistance, but low molecular mobility and therefore inferior slipperiness.

[0126] As shown in Table 2, the curable composition of Comparative Example 15 contained SMA3, which had a weight-average molecular weight of 1908 and was obtained by reacting a perfluoropolyether compound PFPE3 having a number-average molecular weight of 1900 and a hydroxy group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group with an isocyanate compound N1 having an active energy ray-polymerizable group, and further contained an antistatic agent AN1. As shown in Table 4, the curable composition of Comparative Example 15 had excellent homogeneity, but the hard coat film having a hard coat layer obtained from this curable composition exhibited excellent slip properties but inferior scratch resistance compared to the hard coat film having a hard coat layer obtained from the curable composition of Example 10, in which SMA1 was added to the curable composition of Comparative Example 15. This is thought to be due to the fact that the use of SMA3, which has an active energy ray-polymerizable group at only one end, alone reduced its immobilization ability in the film.

Claims

1. (a) an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) a perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500 (excluding the perfluoropolyether (c) described below); (c) a perfluoropolyether having the active energy ray-polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,550 to 3,500; and (d) a polymerization initiator that generates radicals when exposed to active energy rays, The (b) perfluoropolyether is a compound represented by the following formula [4]: The curable composition, wherein the perfluoropolyether (c) is a compound represented by the following formula [2]: 【Chemistry 1】 (In the above formula [2], m is the number of repeating units -(CF 2 CF 2 O)-, and n is the number of repeating units -(CF 2 O)-, satisfying 5≦(m+n)≦30, m and n each independently represent an integer of 0 or more, q is the number of oxyethylene groups and represents an integer of 0 to 20, A represents a terminal group having the active energy ray-polymerizable group, and the terminal group A is a group represented by the following formula [A2].) 【Chemistry 2】 (In the above formula [4], r is the number of repeating units -(CF 2 CF 2 O)-, and s is the number of repeating units -(CF 2 O)-, satisfying 5≦(r+s)≦40, r and s each independently represent an integer of 0 or more, and when both repeating units are present, these repeating units are bonded by block bonds, random bonds, or block bonds and random bonds, and A represents a terminal group having the active energy ray-polymerizable group, and the terminal group A is a group represented by the following formula [A2].) 【Chemistry 3】 (In the above formula [A2], R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and * represents a bond to a urethane bond of the compound represented by the formula [2] or the compound represented by the formula [4].)

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 3 parts by mass of a perfluoropolyether (excluding the perfluoropolyether (c) described below) having an active energy ray-polymerizable group at an end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500, (c) 0.05 to 3 parts by mass of a perfluoropolyether having the active energy ray-polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,550 to 3,500, and (d) 0.5 to 20 parts by mass of a polymerization initiator that generates radicals when exposed to active energy rays, The (b) perfluoropolyether is a compound represented by the following formula [4]: The curable composition, wherein the (c) perfluoropolyether is a compound represented by the following formula [2]: 【Chemistry 4】 (In the above formula [2], m is the number of repeating units -(CF 2 CF 2 O)-, and n is the number of repeating units -(CF 2 O)-, and 5≦(m+n)≦30 is satisfied, and m and n are each Each independently represents an integer of 0 or more, q is the number of oxyethylene groups and represents an integer of 0 to 20, A represents a terminal group having the active energy ray-polymerizable group, and the terminal group A is a group represented by the following formula [A2]. 【Chemistry 5】 (In the above formula [4], r is the number of repeating units -(CF 2 CF 2 O)-, and s is the number of repeating units -(CF 2 O)-, satisfying 5≦(r+s)≦40, r and s each independently represent an integer of 0 or more, and when both repeating units are present, these repeating units are bonded by block bonds, random bonds, or block bonds and random bonds, and A represents a terminal group having the active energy ray-polymerizable group, and the terminal group A is a group represented by the following formula [A2].) 【Chemistry 6】 (In the above formula [A2], R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and * represents a bond to a urethane bond of the compound represented by the formula [2] or the compound represented by the formula [4].)

3. (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 3 parts by mass of a perfluoropolyether (excluding the perfluoropolyether (c) described below) having an active energy ray-polymerizable group at an end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500, (c) 0.05 to 3 parts by mass of a perfluoropolyether which is a reaction product between a raw material perfluoropolyether having a number average molecular weight of 1,200 to 3,000 and a hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group reactive with the hydroxyl group and the active energy ray-polymerizable group, and (d) 0.5 to 20 parts by mass of a polymerization initiator that generates radicals when exposed to active energy rays, The (b) perfluoropolyether is a compound represented by the following formula [4]: The curable composition, wherein the perfluoropolyether (c) is a compound represented by the following formula [2]: 【Chemistry 7】 (In the above formula [2], m is the number of repeating units -(CF 2 CF 2 O)-, and n is the number of repeating units -(CF 2 O)-, satisfying 5≦(m+n)≦30, m and n each independently represent an integer of 0 or more, q is the number of oxyethylene groups and represents an integer of 0 to 20, A represents a terminal group having the active energy ray-polymerizable group, and the terminal group A is a group represented by the following formula [A2].) 【Chemistry 8】 (In the above formula [4], r is the number of repeating units -(CF 2 CF 2 O)-, and s is the number of repeating units -(CF 2 O)-, satisfying 5≦(r+s)≦40, r and s each independently represent an integer of 0 or more, and when both repeating units are present, these repeating units are bonded by block bonds, random bonds, or block bonds and random bonds, and A represents a terminal group having the active energy ray-polymerizable group, and the terminal group A is a group represented by the following formula [A2].) 【Chemistry 9】 (In the above formula [A2], R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and * represents a bond to a urethane bond of the compound represented by the formula [2] or the compound represented by the formula [4].)

4. The curable composition according to claim 1 , wherein the perfluoropolyether (c) has a fluorine atom content of 35% by mass to 65% by mass.

5. The curable composition according to claim 1 , wherein in the formula [2], m and n each independently represent an integer of 1 or more.

6. The curable composition according to claim 1 , wherein in the formula [4], r and s each independently represent an integer of 1 or more.

7. The curable composition according to claim 1 , further comprising: (e) a solvent.

8. A cured film obtained from the curable composition according to any one of claims 1 to 7.

9. A hard coat film comprising a hard coat layer on at least one surface of a film substrate, the hard coat layer comprising the cured film according to claim 8.

10. 10. The hard coat film according to claim 9, further comprising a lower layer of the hard coat layer between the surface of the film substrate and the hard coat layer, the film substrate being a resin film.

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

12. 8. A method for producing a hard coat film, comprising: applying the curable composition according to claim 1 onto a film substrate to form a coating film; and irradiating the coating film with active energy rays to cure the coating film, thereby forming a hard coat layer.

13. 8. A method for producing a hard coat film, comprising the steps of: applying the curable composition according to claim 7 onto a film substrate to form a coating film; removing the solvent from the coating film by heating; and irradiating the coating film with active energy rays to cure the coating film to form a hard coat layer.

14. The method for producing a hard coat film according to claim 12 or 13, further comprising a step of forming a lower layer of the hard coat layer on a surface of the film substrate, the film substrate being a resin film, and the coating film being formed on the lower layer of the hard coat layer.

15. A perfluoropolyether (A) (excluding the perfluoropolyether (B) described later) having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500, and a perfluoropolyether (B) having the active energy ray-polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,550 to 3,500; The surface modifier, wherein the perfluoropolyether (A) is a compound represented by the following formula [4], and the perfluoropolyether (B) is a compound represented by the following formula [2]: 【Chemistry 10】 (In the above formulas [2] and [4], m is the number of repeating units -(CF 2 CF 2 O)-, and n is the number of repeating units -(CF 2 O)-, and satisfy 5≦(m+n)≦30, m and n each independently represent an integer of 0 or more, q is the number of oxyethylene groups and represents an integer of 0 to 20, r is the number of repeating units -(CF 2 CF 2 O)-, and s is the number of repeating units -(CF 2 O)-, and satisfy 5≦(r+s)≦40, and r and s each independently represent an integer of 0 or more, when both the repeating unit -(CF 2 CF 2 O)- and the repeating unit -(CF 2 O)- are present, these repeating units are bonded by block bonds, random bonds, or block bonds and random bonds, A is the active energy ray weight ratio. The terminal group A is a group represented by the following formula [A2]. 【Chemistry 11】 (In the above formula [A2], R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and * represents a bond to a urethane bond of the compound represented by the formula [2] or the compound represented by the formula [4].)

16. A perfluoropolyether (A) (excluding the perfluoropolyether (B) described later) having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500, and The present invention comprises a perfluoropolyether (B) which is a reaction product between a raw material perfluoropolyether having a number average molecular weight of 1,200 to 3,000 and a hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group reactive with the hydroxyl group and the active energy ray-polymerizable group, The surface modifier, wherein the perfluoropolyether (A) is a compound represented by the following formula [4], and the perfluoropolyether (B) is a compound represented by the following formula [2]: 【Chemistry 12】 (In the above formula [2] and formula [4], m is the number of repeating units -(CF 2 CF 2 O)-, and n is the number of repeating units -(CF 2 O)-, satisfying 5≦(m+n)≦30, m and n each independently represent an integer of 0 or more, q is the number of oxyethylene groups and represents an integer of 0 to 20, r is the number of repeating units -(CF 2 CF 2 O)-, and s is the number of repeating units -(CF 2 O)-, satisfying 5≦(r+s)≦40, r and s each independently represent an integer of 0 or more, the repeating units -(CF 2 CF 2 O)- and the repeating units -(CF When both of the repeating units have the repeating units (A1, A2, A3, A4, A5, A6) and (B1, B1, B2)-, these repeating units are bonded by block bonds, random bonds, or block bonds and random bonds, and A represents a terminal group having the active energy ray-polymerizable group, and the terminal group A is a group represented by the following formula [A2]. 【Chemistry 13】 (In the above formula [A2], R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and * represents a bond to a urethane bond of the compound represented by the formula [2] or the compound represented by the formula [4].)

17. The surface modifier according to claim 15 or 16, wherein the perfluoropolyether (B) has a fluorine atom content of 35% by mass to 65% by mass.

18. In the formula [2], m and n each independently represent an integer of 1 or more, and in the formula [4], r and s each independently represent an integer of 1 or more. The surface modifier according to any one of claims 15 to 17.

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