A curable composition containing two types of 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

[Technical Field]

[0001] The present invention relates to a curable composition useful as a hard coat layer forming material applied to the surface of various display elements, and more particularly to a homogeneous curable composition that can form a hard coat layer with excellent slipperiness, scratch resistance, abrasion resistance, and water repellency, and is free of suspended and settled matter. In this invention, "perfluoropolyether" refers to a material having an active energy ray polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group. Here, 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 in its hydrocarbon group, etc., with fluorine atoms, a material having an active energy ray polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group is referred to as a "perfluoropolyether." [Background technology]

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

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

[0004] Generally, to impart scratch resistance and abrasion resistance to a hard coat layer, a method is employed that increases the surface hardness of the hard coat layer and provides resistance to external forces by forming a high-density crosslinked structure. Currently, polyfunctional acrylate-based materials that undergo three-dimensional crosslinking by radicals generated by active energy ray irradiation are the most commonly used materials for forming such hard coat layers. Furthermore, fluorine-based surface modifiers added to the coating solution that forms the hard coat layer are generally materials that have active energy ray polymerizable groups in order to impart scratch resistance and abrasion resistance to the hard coat layer (Patent Document 1). From the viewpoint of scratch resistance and abrasion resistance, low molecular weight materials with many active energy ray polymerizable groups that can form a high-density crosslinked structure, so-called materials with a small acrylic equivalent, are preferred.

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

[0006] To improve the aforementioned trade-off relationship, one method involves introducing a crosslinking group to only one end of a molecular chain containing fluorine atoms in order to increase the mobility of the fluorine atom-containing chain. However, compared to the method of introducing crosslinking groups to both ends of the molecular chain containing fluorine atoms, while the slipperiness of the hard coat layer is superior, the durability tends to be inferior. In addition, when a crosslinking group is introduced to only one end of a molecular chain containing fluorine atoms, there is less steric hindrance to the molecular chain containing fluorine atoms compared to when a crosslinking group is introduced to both ends of the molecular chain containing fluorine atoms. As a result, the molecular chain containing fluorine atoms tends to aggregate easily, and the coating solution that forms the hard coat layer tends to become cloudy when prepared.

[0007] From the viewpoint of slipperiness and water repellency, a high proportion of fluorine atoms is generally preferred, but there is a concern that the fluorine-based surface modifier may aggregate in the coating solution. If the fluorine-based surface modifier aggregates in the coating solution used to form the hard coat layer, the molecular chains containing fluorine atoms will not sufficiently segregate on the surface of the hard coat layer when the hard coat layer is formed using that coating solution, and the original slipperiness and water repellency properties will not be exhibited.

[0008] To improve the solubility of fluorine-based surface modifiers, one approach is to reduce the proportion of fluorine atoms in the fluorine-based surface modifier. However, as mentioned above, this would likely result in a decrease in the slipperiness and water repellency of the hard coat layer, making it difficult to achieve high levels of slipperiness and water repellency.

[0009] As a method for improving the solubility of fluorine-based surface modifiers, Patent Document 3 reports the use of a fluorine-containing polyether, which forms aggregates and causes turbidity in the hard coat agent composition, in combination with a fluorine-containing block copolymer that has excellent compatibility with the composition.

[0010] Patent Document 4 reports that by using in combination a linear polymer having a fluoropolyether as the main chain and acrylic groups at one or both ends of the molecular chain with a fluorine content of 48% to 62% by mass, and a linear polymer having a siloxane skeleton with a fluoropolyether as the main chain and multiple acrylic groups at both ends of the molecular chain with 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, regarding abrasion resistance, Patent Document 4 states in paragraph

[0006] that "abrasion resistance is represented by slipperiness," indirectly evaluating abrasion resistance in terms of slipperiness. Therefore, there are no specific examples regarding scratch resistance or abrasion resistance. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] International Publication No. 2016 / 163479 [Patent Document 2] Patent No. 6497449 [Patent Document 3] Japanese Patent Publication No. 2005-179613 [Patent Document 4] International Publication No. 2020 / 170698 [Overview of the project] [Problems that the invention aims to solve]

[0012] Since Patent Document 3 states that the fluorine-containing block copolymer is inferior to fluorine-containing polyether in water repellency and lubricity, it can be easily assumed that the fluorine concentration of the above-mentioned fluorine-containing block copolymer is lower than that of the above-mentioned fluorine-containing polyether, making it difficult to achieve both compatibility with the composition and good lubricity and water repellency. Patent Document 4 describes that, regarding slipperiness, in linear polymers with a fluorine content of 48% to 62% by mass, the slipperiness is equivalent whether the molecular chain has an acrylic group at one end or at both ends. Therefore, it can be assumed that the slipperiness is not at a sufficient level. The present invention aims to provide a homogeneous, curable composition free of suspended and settled matter that can form a hard coat layer that achieves a high level of both durability and slipperiness, which are typically in a trade-off relationship. In addition to these, for practical use, the hard coat layer must also possess high liquid-repellent properties. [Means for solving the problem]

[0013] In other words, the present invention relates to (a) an active energy ray curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule, (b) Perfluoropolyethers having active energy ray polymerizable groups at the end of molecular chains containing poly(oxyperfluoroalkylene) groups, and having a weight-average molecular weight of 1400 to 3500 (excluding perfluoropolyethers described in (c) below), (c) Perfluoropolyethers 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 1550 to 3500, and (d) A curable composition comprising a polymerization initiator that generates radicals by 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 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 1400 to 3500 (excluding the perfluoropolyether described in (c) below), (c) Only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group has the active energy ray-polymerizable group, and 0.05 to 3 parts by mass of a perfluoropolyether having a weight average molecular weight of 1,550 to 3,500, and (d) A curable composition containing 0.5 to 20 parts by mass of a polymerization initiator that generates radicals by 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 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 reaction product of a raw material perfluoropolyether having a number average molecular weight of 1,200 to 3,000 and having a hydroxy group only at 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 0.05 to 3 parts by mass of a perfluoropolyether, and (d) A curable composition containing 0.5 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.

[0016] The perfluoropolyether (c) has the active energy ray-polymerizable group only at 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 perfluoropolyether (c) has an active energy ray-polymerizable group via a urethane bond.

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

[0019] The poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has repeating units -(CF2O)- and / or repeating units -(CF2CF2O)-, and both If it has repeating units, it is a group formed by joining these repeating units by block joining, random joining, or block joining and random joining.

[0020] The molecular chain containing the poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has a structure represented by the following formula [1]. [ka] (In the above formula [1], m is the number of repeating units -(CF2CF2O)- and n is the number of repeating units -(CF2O)-, satisfying 5 ≤ (m + n) ≤ 30, and m and n are each independent (The character represents an integer greater than or equal to 0, and q represents the number of oxyethylene groups, which is an integer between 0 and 20.)

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

[0022] The (c) perfluoropolyether is a compound represented by the following formula [2]. [ka] (In formula [2] above, m, n, and q have the same meanings as in formula [1] above, 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 formula [A2]. [ka] (In the above formulas [A1] and [A2], R 1 and R 2 Each of the symbols independently represents a hydrogen atom or a methyl group, and * represents a bond with a urethane bond in the compound represented by formula [2] above.

[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]. [ka] (In the above formula [3], r is the number of repeating units -(CF2CF2O)- and s is the number of repeating units -(CF2O)-, satisfying 5 ≤ (r + s) ≤ 40, and r and s are each independent If a value is set to represent a non-negative integer and both repeating units exist, these repeating units are joined by block combinations, random combinations, or block combinations and random combinations.

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

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

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

[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 coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is made of the cured film.

[0032] The aforementioned film substrate is a resin film, having a hard coat layer underneath 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 onto a film substrate to form a coating film, and irradiating the coating film with active energy rays to cure it and form a hard coat layer.

[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 curing the coating film by irradiating it with active energy rays to form a hard coat layer.

[0036] A method for manufacturing a hard coat film, further comprising the step of forming a lower layer of a 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) 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 1400 to 3500 (excluding perfluoropolyether (B) described later), 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 1550 to 3500.

[0038] A surface modifier comprising: perfluoropolyether (A) 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 1400 to 3500 (excluding perfluoropolyether (B) described later); and perfluoropolyether (B) which is a reaction product of a raw material perfluoropolyether having a number-average molecular weight of 1200 to 3000 and having a hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group that reacts with the hydroxyl group and 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 1550 to 3500.

[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 of the perfluoropolyether (A) containing a poly(oxyperfluoroalkylene) group has a structure represented by the following formula [3], and the molecular chain of the perfluoropolyether (B) containing a poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1]. [ka] (In equations [1] and [3] above, m is the number of repeating units -(CF2CF2O)-, and n is the number of repeating units -(CF2O)-, satisfying 5 ≤ (m + n) ≤ 30, and m and n Each of the following independently represents an integer greater than or equal to 0, q is the number of oxyethylene groups and represents an integer from 0 to 20, r is the number of repeating units -(CF2CF2O)- and s is the number of repeating units -(CF2O)-, satisfying 5 ≤ (r + s) ≤ 40, and r and s are each independently Represents an integer greater than or equal to 0, and the repeating units are -(CF2CF2O)- and -(CF2O If both of the above are present, these repeating units are joined by block joins, random joins, or block joins and random joins.

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

[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]. [ka] (In formulas [2] and [4] above, m, n, and q are the same as defined in formula [1], r and s are the same as defined 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 formula [A2].) [ka] (In the above formulas [A1] and [A2], R 1 and R 2 Each of the symbols independently represents a hydrogen atom or a methyl group, and * represents a bond with a urethane bond in the compound represented by formula [2] or formula [4]. [Effects of the Invention]

[0045] According to the present invention, it is possible to provide a curable composition useful for forming cured films and hard coat layers that achieve both excellent scratch resistance, abrasion resistance, and excellent slipperiness, even in thin films with a thickness of 1 μm to 20 μm. Furthermore, according to the present invention, it is possible to provide a hard coat film comprising a cured film obtained from the curable composition or a hard coat layer made of the cured film, thereby providing a hard coat film that excels in both durability properties such as scratch resistance and abrasion resistance and slipperiness, which are in a trade-off relationship. Moreover, according to the present invention, it is possible to provide a curable composition useful for forming cured films and hard coat layers that not only achieve both of the above properties but also impart high water-repellent properties, as well as a hard coat film comprising a hard coat layer that excels in these properties. [Modes for carrying out the invention]

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

[0047] [(a) Active energy ray curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule] (a) A polyfunctional monomer that has two or more (meth)acryloyl groups in one molecule and is curable by active energy rays (hereinafter also simply referred to as "(a) polyfunctional monomer") refers to a monomer that undergoes a polymerization reaction and hardens when irradiated with active energy rays such as ultraviolet light.

[0048] In the curable composition of the present invention, preferred (a) polyfunctional monomers include monomers selected from the group consisting of polyfunctional (meth)acrylate compounds, monomers selected from the group consisting of polyfunctional urethane (meth)acrylate compounds described later, and monomers selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds. In the present invention, as (a) polyfunctional monomer, one or more of the above-mentioned polyfunctional (meth)acrylate compounds can be used alone or in combination. In the present invention, (meth)acrylate compounds include both acrylate compounds and methacrylate compounds, and for example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

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

[0050] In addition, as a preferred (a) polyfunctional monomer in the present invention, examples include polyfunctional monomers having at least three (meth)acryloyl groups in one molecule, for example, at least four in one molecule. In the present invention, as a (a) polyfunctional monomer, examples include monomers 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 above polyfunctional (meth)acrylate compounds (compounds that do not have a urethane bond) include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and 1,3-propanediol di(meth)acrylate. 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tricyclo[5.2.1.0 2,6 Decandimethanol di(meth) Examples include acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, bis[4-(meth)acryloylthiophenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Among these, preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0052] Examples of the oxyalkylene-modified polyfunctional (meth)acrylate compounds mentioned above include (meth)acrylate compounds of polyols modified with oxyalkylene. Examples of the polyols include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0053] The above-mentioned polyfunctional urethane (meth)acrylate compound is a compound having multiple acryloyl groups or methacryloyl groups in one molecule and having one or more urethane bonds [-NHC(=O)O-], and may further have urea bonds [-NHC(=O)NH-]. Examples of the polyfunctional urethane (meth)acrylate compound include compounds obtained by the reaction of a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and compounds obtained by the reaction of a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group and a polyol, but the polyfunctional urethane (meth)acrylate compounds that can be used in the present invention are not limited to these examples.

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

[0055] (a) The polyfunctional monomer may be a lactone-modified polyfunctional (meth)acrylate compound, and ε-caprolactone is preferred as the lactone to be modified. Examples of the lactone-modified polyfunctional (meth)acrylate compound include ε-caprolactone-modified pentaerythritol tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tetra(meth)acrylate, ε-caprolactone-modified dipentaerythritol penta(meth)acrylate, and ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0056] [(b) Perfluoropolyethers having active energy ray polymerizable groups at the ends of molecular chains containing poly(oxyperfluoroalkylene) groups, and having a weight-average molecular weight of 1400 to 3500] A perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group of component (b), and having a weight-average molecular weight of 1400 to 3500, will hereinafter also be simply referred to as "(b) perfluoropolyether". (b) perfluoropolyether excludes the (c) perfluoropolyether described later. A preferred (b) perfluoropolyether in the curable composition of the present invention has an active energy ray polymerizable group via a urethane bond at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group. The ends of the molecular chain containing the poly(oxyperfluoroalkylene) group may be all ends or some ends of the molecular chain. If the molecular chain is linear, all ends and some ends of the molecular chain are both ends and one end of the linear molecular chain, respectively. Examples of linking groups between the poly(oxyperfluoroalkylene) group and the urethane bond include a hydrocarbon group having an ether bond, in which at least one hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. Furthermore, a preferred (b) perfluoropolyether does not have a silicon atom in its chemical structure.

[0057] (b) The perfluoropolyether, together with component (c) described later, plays a role as a surface modifier in the hard coat layer formed from the curable composition of the present invention. Furthermore, because (b) the perfluoropolyether has excellent compatibility with (a) the polyfunctional monomer, clouding is suppressed, enabling the formation of a hard coat layer that exhibits a transparent appearance.

[0058] As the above poly(oxyperfluoroalkylene) group, from the viewpoint of obtaining a cured film with good scratch resistance, -[CF2O]-(oxyperfluoromethylene group) and -[CF2CF2 A group having both O]-(oxyperfluoroethylene group) as repeating units is preferred. In this case, the bonding of these oxyperfluoroalkylene groups may be either block bonding or random bonding.

[0059] (b) Perfluoropolyethers are not limited to those having one active energy ray polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group, but may have two or more active energy ray polymerizable groups. Examples of such active energy ray polymerizable groups include (meth)acryloyl groups and vinyl groups, and examples of terminal groups having such active energy ray polymerizable groups include the group represented by formula [A1] or formula [A2]. Of these terminal groups, the group represented by formula [A2] having two active energy ray polymerizable groups is preferred.

[0060] (b) Perfluoropolyethers are more preferably those having active energy ray polymerizable groups at both ends of the molecular chain containing poly(oxyperfluoroalkylene) groups, and even more preferably those with a large number of such active energy ray polymerizable groups in one molecule, from the viewpoint of obtaining a cured film with good scratch resistance. The number of such polymerizable groups is preferably two or more at each end of the molecular chain containing poly(oxyperfluoroalkylene) groups, and more preferably three or more.

[0061] (b) By having a weight-average molecular weight of 1400 to 3500 perfluoropolyether, a hard coat layer with 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, per 100 parts by mass of the (a) polyfunctional monomer. A content of (b) perfluoropolyether of 0.05 parts by mass or more provides sufficient scratch resistance to the hard coat layer, and a content of (b) perfluoropolyether of 3 parts by mass or less allows for sufficient compatibility with (a) polyfunctional monomer and a hard coat layer with less cloudiness.

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

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

[0065] (c) Perfluoropolyethers are not limited to those having one active energy ray polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, but may also have two or more active energy ray polymerizable groups. Examples of such active energy ray polymerizable groups include (meth)acryloyl groups and vinyl groups, and examples of terminal groups having such active energy ray polymerizable groups include the group represented by formula [A1] or formula [A2]. Of these terminal groups, the group represented by formula [A2] having two active energy ray polymerizable groups is preferred.

[0066] (c) The perfluoropolyether, together with (b) the perfluoropolyether, plays a role as a surface modifier in the hard coat layer formed from the curable composition of the present invention. Furthermore, because (c) the perfluoropolyether has excellent compatibility with (b) the perfluoropolyether, clouding is suppressed, and it is possible to form a hard coat layer that exhibits a transparent appearance. In addition, (c) the perfluoropolyether preferably has a poly(oxyalkylene) group from the viewpoint of compatibility with (a) the polyfunctional monomer. A poly(oxyethylene) group is preferred as the poly(oxyalkylene) group.

[0067] In the curable composition of the present invention, the preferred (c) perfluoropolyether has an active energy ray polymerizable group via a urethane bond at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group. From the viewpoint of obtaining a cured film with good scratch resistance, the poly(oxyperfluoroalkylene) group is -[CF2O]-(oxyperfluoro A group having both a romethylene group and an oxyperfluoroethylene group as repeating units is preferred. In this case, the bonding of these oxyperfluoroalkylene groups may be either block bonding or random bonding.

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

[0069] (c) The weight-average molecular weight of the perfluoropolyether is 1550 to 3500, preferably 1600 to 3500, and more preferably 1700 to 3500. (c) When the weight-average molecular weight of the perfluoropolyether is within the above range, (c) the perfluoropolyether is more likely to remain on the surface of the hard coat layer obtained from the curable composition of the present invention, and the shear stress on the layer surface is sufficiently reduced, so that a hard coat layer with excellent slipperiness can be obtained. In addition, when the weight-average molecular weight of the perfluoropolyether is within the above range, the hardness of the layer surface is appropriately adjusted, and a hard coat layer with excellent durability such as scratch resistance can be obtained. In other words, when the weight-average molecular weight of the 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 (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 per 100 parts by mass of the (a) polyfunctional monomer. When the content of (c) perfluoropolyether is 0.05 parts by mass or more, (c) perfluoropolyether is sufficiently present on the surface of the hard coat layer obtained from the curable composition of the present invention, so that a hard coat layer with excellent slipperiness can be obtained. Also, when the content of (c) perfluoropolyether is 3 parts by mass or less, a hard coat layer that is well compatible with (b) perfluoropolyether and has little turbidity can be obtained. Furthermore, the content of (c) perfluoropolyether per 100 parts by mass of (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) Perfluoropolyethers may be used individually or in combination of two or more types.

[0072] [(d) Polymerization initiator] In the curable composition of the present invention, preferred (d) polymerization initiators are polymerization initiators that generate radicals by active energy rays such as electron beams, ultraviolet rays, and X-rays, particularly by ultraviolet irradiation.

[0073] (d) Examples of polymerization initiators include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinone diazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These polymerization initiators may be used individually or in combination of two or more. In the present invention, from the viewpoint of transparency, surface curability, and thin film curability, it is preferable to use alkylphenones as the polymerization initiator (d). By using alkylphenones, a cured film with improved scratch resistance can be obtained.

[0074] Examples of the alkylphenones mentioned above include α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; α-aminoalkylphenones such as 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one; 2,2-dimethoxy-1,2-diphenylethane-1-one; and methyl phenylglyoxylate.

[0075] In the curable composition of the present invention, the content of (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, per 100 parts by mass of the polyfunctional monomer (a).

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

[0077] As the solvent (e) above, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halides such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and o-dichlorobenzene; esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of solvents include ethers such as propylene glycol mono-n-propyl ether, 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 solvents obtained by mixing two or more of these solvents.

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

[0079] [Other additives] Furthermore, the curable composition of the present invention may optionally contain one or more commonly added additives, such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, adhesion promoters, plasticizers, ultraviolet absorbers, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc., either alone or in combination of two or more, as long as the effects of the present invention are not impaired.

[0080] <Cured film> The curable composition of the present invention can be applied (coated) onto a substrate to form a coating film, and a cured film can be formed by irradiating the coating film with active energy rays to polymerize (cure) it. This cured film is also a subject of the present invention. Furthermore, the hard coat layer in the hard coat film described later can be made of the above cured film.

[0081] Examples of the above-mentioned substrates include various resins (polyesters such as polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetylcellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin), metal, wood, paper, glass, and slate. The shape of these substrates may be in the form of a plate, film, or three-dimensional molded body. Furthermore, on the surface of the above-mentioned substrates, for example, a primer layer, ultraviolet absorption layer, infrared absorption layer, near-infrared absorption layer, electromagnetic wave absorption layer, color correction layer, refractive index adjustment layer, weather-resistant layer, anti-reflective layer, antistatic layer, discoloration prevention layer, gas barrier layer, water vapor barrier layer, light scattering layer, electrode layer, etc. may be formed as a layer beneath the hard coat layer, and multiple layers beneath the hard coat layer may be laminated. The layer formed on the surface of the above-mentioned substrate is not particularly limited as long as it does not impair the effects of the present invention.

[0082] The coating method on the above-mentioned substrate can be appropriately selected from cast coating, spin coating, blade coating, dip coating, roll coating, spray coating, bar coating, die coating, inkjet, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.), with the roll-to-roll method being particularly suitable. From the viewpoint of thin-film coating, it is desirable to use relief printing, especially gravure coating. It is preferable to filter the curable composition of the present invention beforehand using a filter with a pore size of about 0.2 μm before coating. When coating, a solvent may be added to the curable composition as needed. In this case, various solvents listed in [(e) Solvent] above can be used.

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

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

[0085] <Hard coat film> Using the curable composition of the present invention, a hard coat film can be manufactured having a hard coat layer on at least one surface of a film substrate. This hard coat film is also a subject of the present invention and is suitably used, for example, to protect the surface of various display elements such as touch panels and liquid crystal displays.

[0086] The hard coat layer in the hard coat film of the present invention can be formed by a method comprising the steps of applying the curable composition of the present invention onto a film substrate to form a coating film, removing the solvent by heating as necessary, and curing the coating film by irradiating it with active energy rays such as ultraviolet light. A method for manufacturing a hard coat film comprising these steps, in which a hard coat layer is provided on at least one surface of a film substrate, is also subject to the present invention.

[0087] As the above-mentioned film substrate, various transparent resin films suitable for optical applications are used from among the substrates listed in the <cured film> section above. Preferred resin films include, for example, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrene, polyolefins, polyamides, polyimides, and triacetylcellulose (TAC).

[0088] The above-mentioned film substrate may be formed by laminating multiple layers. For example, layers different from the resin film, such as a primer layer, ultraviolet absorption layer, infrared absorption layer, near-infrared absorption layer, electromagnetic wave absorption layer, color correction layer, refractive index adjustment layer, weather-resistant layer, anti-reflective layer, antistatic layer, discoloration prevention layer, gas barrier layer, water vapor barrier layer, light scattering layer, and electrode layer, may be laminated on the surface of the resin film as layers beneath the hard coat layer, and multiple layers beneath the hard coat layer may be laminated. The layers laminated on the surface of the above-mentioned resin film are not particularly limited as long as they do not impair the effects of the present invention.

[0089] Furthermore, the method for applying the curable composition of the present invention onto the above-mentioned film substrate (coating film formation step) and the method for irradiating the coating film with active energy rays (curing step) can be the method described above under <Cured Film>. In addition, if the curable composition of the present invention contains a solvent (in the form of a varnish), a step of drying the coating film and removing the solvent may be included after the coating film formation step, if necessary. In that case, the method for drying the coating film (solvent removal step) described above under <Cured Film> can be used.

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

[0091] <Surface modifier> The present invention also applies to surface modifiers comprising perfluoropolyethers (A) 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 1400 to 3500 (excluding perfluoropolyether (B) described later), and perfluoropolyethers (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 1550 to 3500. Furthermore, the present invention also includes a surface modifier comprising a perfluoropolyether (A) 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 1400 to 3500 (excluding perfluoropolyether (B) described later), and a perfluoropolyether (B) which is a reaction product of a raw material perfluoropolyether having a number-average molecular weight of 1200 to 3000 and having a hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a functional group that reacts with the hydroxyl group and the compound having the active energy ray polymerizable group. Note that "perfluoropolyether (A)" is the same as the perfluoropolyether (b) mentioned above, and "perfluoropolyether (B)" is the same as the perfluoropolyether (c) mentioned above. [Examples]

[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. The apparatus and conditions used for sample preparation and analysis of physical properties in the examples are as follows.

[0093] (1) Coating by bar coater Equipment: PM-9050MC manufactured by SMT Co., Ltd. Bar: A-Bar OSP-15 manufactured by OSG System Products Co., Ltd. Maximum wet film thickness 15 μm (film thickness after drying 3 μm) Application speed: 4m / min (2) Film thickness measurement Equipment: F20 film thickness measurement system manufactured by Filmetrics Co., Ltd. (3) Oven Equipment: PO-250-45-D(4) UV curing 2-layer clean oven (upper and lower type) manufactured by Sanki Keisou Co., Ltd. Equipment: Heraeus Corporation CV-110QC-G Lamp: Heraeus H-bulb electrodeless lamp (manufactured by Heraeus Co., Ltd.) (5) Scratch resistance test and abrasion resistance test Equipment: Shinto Scientific Co., Ltd. Reciprocating wear testing machine TRIBOGEAR TYPE:30S Scanning speed: 3200 mm / min Scanning distance: 50mm (6) Contact angle measurement Equipment: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measurement temperature: 23℃ (7) Measurement of the coefficient of dynamic friction Equipment: TRIBOGEAR® TYPE: HHS2000, a load-variable friction and wear testing system manufactured by Shinto Kagaku Co., Ltd. Probe: 0.6mmR sapphire pin Load: 200g Scanning speed: 2 mm / second Scanning distance: 10mm (8) Total light transmittance, haze measurement Equipment: Haze meter NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd. (9) Weight average molecular weight measurement Gel permeation chromatography (GPC) Equipment: HLC-8420GPC manufactured by Tosoh Corporation Columns: TSKgelG2000HXL and TSKgelG3000HXL, manufactured by Tosoh Corporation. Measurement temperature: 40℃ Eluent: Tetrahydrofuran Detection: RI (10) Combustion Ion Chromatography Automatic sample combustion system: AQF-2100 H manufactured by Nitto Seikou Analytech Co., Ltd. (formerly Mitsubishi Chemical Analytech Co., Ltd.) Ion chromatograph: Dionex Integrion, manufactured by Thermo Fisher Scientific Co., Ltd. Sample: 2 mg Absorbent solution: 2.7 mM sodium carbonate + 0.3 mM sodium bicarbonate aqueous solution Eluent: 2.7 mM sodium carbonate + 0.3 mM sodium bicarbonate aqueous solution Column: Thermo Fisher Scientific Co., Ltd. AG-12A / AS-12A Flow rate: 1.5mL / min Detector: Electrical conductivity (with suppressor) Standard sample: Fluoride ion standard solution (F-1000), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (formerly Wako Pure Chemical Industries, Ltd.) If the solvent in the sample did not contain 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 solid content concentration. If the solvent in the sample contained fluorine atoms, the sample solvent was evaporated using a halogen moisture meter at 120°C for 20 minutes. The fluorine concentration was measured using samples where the mass change was constant and it was determined that all the solvent had evaporated.

[0094] Furthermore, the abbreviations represent the following meanings. Polyfunctional acrylate PA1: Dipentaerythritol pentaacrylate / hexaacrylate mixture [Manufactured by Toagosei Co., Ltd., Aronics® M-403] Polyfunctional Acrylate PA2: Oxyethylene-modified polyfunctional acrylate [Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., New Frontier® MF-001] Polyfunctional Acrylate PA3: Polyfunctional Urethane Acrylate [Manufactured by Negami Kogyo Co., Ltd., Art Resin (Registered Trademark) UN-3320HS] Polyfunctional acrylate PA4: Pentaerythritol triacrylate / Pentaerythritol tetraacrylate [Manufactured by Nippon Kayaku Co., Ltd., PET30] PFPE1: A perfluoropolyether with the following structure, having two hydroxyl groups at each end without a poly(oxyalkylene) group interposed therein [Fomblin® T4, manufactured by Solvay Specialty Polymers].19 The number-average molecular weight of 2,200 calculated from the analysis results by 1 19F-NMR and 1H-NMR [Chemical formula] (In the above formula, r is the number of repeating units -(CF2CF2O)-, and s is the number of repeating units -(CF2O)-, satisfying 5 ≤ (r + s) ≤ 40, and r and s are each independently integers of 0 or more.) PFPE2: A perfluoropolyether having one hydroxy group without a poly(oxyalkylene) group only at one end, with the following structure [manufactured by Solvay Specialty Polymers, 7324X 19 The number-average molecular weight of 1,750 to 1,950 calculated from the analysis results by 1 19F-NMR and 1H-NMR [Chemical formula] (In the above formula, m is the number of repeating units -(CF2CF2O)-, and n is the number of repeating units -(CF2O)-, satisfying 5 ≤ (m + n) ≤ 30, and m and n are each independently integers of 0 or more.) PFPE3: A perfluoropolyether having one hydroxy group via a poly(oxyethylene) group only at one end, with the following structure [manufactured by Solvay Specialty Polymers, Fomblin (registered trademark) 4102X 19 The number-average molecular weight of 1,900 calculated from the analysis results by 1 19F-NMR and 1H-NMR [Chemical formula] (In the above formula, m is the number of repeating units -(CF2CF2O)-, and n is the number of repeating units -(CF2O)-, satisfying 5 ≤ (m + n) ≤ 30, and m and n are each independently integers of 0 or more, and q is the number of oxyethylene groups, representing an integer of 2 to 20.) PFPE4: A perfluoropolyether with the following structure, having one hydroxyl group at only one end without a poly(oxyalkylene) group [manufactured by Apollo Scientific]. FO2 molecular weight 978.15] [ka] PFPE5: A perfluoropolyether with the following structure, having one hydroxyl group at only one end without a poly(oxyalkylene) group (1H,1H-perfluoro-3,6,9-tri Oxatridecane-1-ol [Exfluor Research, C10GOL, Molecular weight 548.1] [ka] PFPE6: A perfluoropolyether with the following structure, having one hydroxyl group at each end without a poly(oxyalkylene) group [Fomblin® D2, manufactured by Solvay Specialty Polymers]. 19 F-NMR and 1 The results of the H-NMR analysis were calculated [Number average molecular weight: 1550] [ka] (In the above formula, m is the number of repeating units -(CF2CF2O)- and n is the number of repeating units -(CF2O)-, satisfying 5 ≤ (m + n) ≤ 30, and m and n are independent of each other.) (Represents a non-negative integer.) N1: 1,1-Bis(acryloyloxymethyl)ethyl isocyanate [Manufactured by Showa Denko K.K., Karenz® BEI] N2:2-Acryloyloxyethyl isocyanate [Kalenz® AOI, manufactured by Showa Denko K.K.] SMA6: A perfluoropolyether having active energy ray polymerizable groups at the ends of molecular chains containing poly(oxyperfluoroalkylene) groups [Opttool® DAC-HP, manufactured by Daikin Industries, Ltd., 20% by mass non-volatile content solution, weight-average molecular weight (Mw) measured in polystyrene equivalent by GPC is 1521, dispersion degree (Mw / Mn) is 1.1 (Mn is number-average molecular weight), fluorine atom content in the perfluoropolyether compound calculated by combustion ion chromatography is 35% by mass]. SMA7: A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, with a total of four active energy ray polymerizable groups at both ends of the molecular chain. [Solvay Specialty Polymers Fluorolink® AD-1700, 70% by mass non-volatile content solution, weight-average molecular weight (Mw) measured in polystyrene equivalent by GPC: 3973, dispersion degree (Mw / Mn): 2.1, fluorine atom content in the perfluoropolyether compound calculated by combustion ion chromatography: 29% by mass] DOTDD: Dioctyl tin dieodecanate [Manufactured by Nitto Chemical 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® 2959, manufactured by IGM Resins] AN1: PEDOT-PSS aqueous dispersion [Sigma-Aldrich PEDOT-PSS 3.0% to 4.0% by mass aqueous dispersion High conductivity grade Product number 655201]

[0095] [Manufacturing Example 1] Manufacturing of SMA1, a component of surface modifiers A screw-cap tube was filled with 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. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA1. The weight-average molecular weight (Mw) of the obtained SMA1, measured in polystyrene equivalent by GPC, was 2494, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA1, calculated by combustion ion chromatography, was 42% by mass.

[0096] [Manufacturing Example 2] Manufacturing of SMA2, a component of surface modifiers A screw-cap tube was filled with 2.20 g (1.2 mmol) of PFPE2, 0.28 g (1.2 mmol) of N1, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N1), and 0.6 g of MEK. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain an 80% by mass MEK solution of the target perfluoropolyether compound SMA2. The weight-average molecular weight (Mw) of the obtained SMA2, measured in polystyrene equivalent by GPC, was 1710, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA2, calculated by combustion ion chromatography, was 63% by mass.

[0097] [Manufacturing Example 3] Manufacturing of SMA3, a component of surface modifiers A screw-cap tube was filled with 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. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA3. The weight-average molecular weight (Mw) of the obtained SMA3, measured in polystyrene equivalent by GPC, was 1908, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA3, calculated by combustion ion chromatography, was 47% by mass.

[0098] [Manufacturing Example 4] Manufacturing of SMA4, a component of surface modifiers A screw-cap tube was filled with 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. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA4. The weight-average molecular weight (Mw) of the obtained SMA4, measured in polystyrene equivalent by GPC, was 1299, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA4, calculated by combustion ion chromatography, was 51% by mass, which is comparable to the 51% fluorine atom content theoretically calculated from the structure of SMA4.

[0099] [Manufacturing Example 5] Manufacturing of SMA5, a component of surface modifiers A screw-cap tube was filled with 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. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA5. The weight-average molecular weight (Mw) of the obtained SMA5, measured in polystyrene equivalent by GPC, was 1029, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA5, calculated by combustion ion chromatography, was 46% by mass, which is comparable to the theoretically calculated fluorine atom content of 47% by mass from the structure of SMA5.

[0100] [Manufacturing Example 6] Manufacturing of SMA8, a component of surface modifiers A screw-cap tube was filled with 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. This mixture was stirred using a stirrer tip at room temperature (approximately 23°C) for 72 hours to obtain a 50% PGMEA solution of the target perfluoropolyether compound SMA8. The weight-average molecular weight (Mw) of the obtained SMA8, measured in polystyrene equivalent by GPC, was 1609, and the dispersion ratio (Mw / Mn) was 1.0. Furthermore, the fluorine atom content in SMA8, calculated by combustion ion chromatography, was 54% by mass.

[0101] [Examples 1 to 9, Comparative Examples 1 to 13] Each component listed in Table 1 was mixed to prepare a curable composition with the solid content concentration listed in Table 1. Here, solid content refers to components other than the solvent. In Table 1, [parts] represents [parts by mass] and [%] represents [mass%]. In Table 1, the polyfunctional acrylate and surface modifier each represent solid content.

[0102] [Table 1]

[0103] These curable compositions were applied by bar coating onto an A4-sized PET film [Toray Industries, Inc., Lumirror® U403 (also known as U40), 100 μm thick] with a primer layer formed on both sides by easy-adhesion treatment, to obtain a coating film. This coating film was dried in a 60°C oven for 8 minutes to remove the solvent. The obtained film was exposed to a nitrogen atmosphere at an exposure of 300 mJ / cm². 2 By irradiating and exposing with UV light, a hard coat layer (cured film) is formed. I made a film.

[0104] [Examples 10 to 11, Comparative Examples 14 to 15] Each component listed in Table 2 was mixed to prepare a curable composition with the solid content concentration listed in Table 2. Here, solid content refers to components other than the solvent. In Table 2, [parts] represents [parts by mass] and [%] represents [mass%]. In Table 2, the polyfunctional acrylate and surface modifier each represent solid content.

[0105] [Table 2]

[0106] These curable compositions were applied by bar coating onto an A4-sized PET film [Toray Industries, Inc., Lumirror® U403 (also known as U40), 100 μm thick] with a primer layer formed on both sides by easy-adhesion treatment, to obtain a coating film. This coating film was dried in a 65°C oven for 3 minutes to remove the solvent. The obtained film was exposed to a nitrogen atmosphere at an exposure of 300 mJ / cm². 2 By irradiating and exposing with UV light, a hard coat layer (cured film) is formed. I made a film.

[0107] The homogeneity of each curable composition, as well as the scratch resistance, water repellency, abrasion resistance, slipperiness, and haze of the resulting hard coat films, were evaluated. The evaluation procedure is described below. The results are also shown in Tables 3 and 4. [Composition homogeneity] The appearance of each prepared curable composition was visually inspected and evaluated according to the following criteria. A: Clear solution (no suspended solids, settled solids, or phase separation) C: Presence of any of the following: suspended solids, settled solids, or phase separation. [Scratch resistance] The hard coat layer surface of the obtained hard coat film was rubbed 5000 times back and forth with a 1kg load using steel wool [BONSTAR (registered trademark) #0000 (ultra-fine)] attached to a reciprocating abrasion tester, with a stroke of 50mm. Afterwards, the degree of scratches in the area excluding the 5mm wide areas at both ends of the 50mm stroke was visually inspected, and in addition, it was confirmed using a microscope (KEYENCE Corporation) that the scratches were on the hard coat layer surface. The evaluation was conducted according to the following criteria A, B, and C. When considering actual use as a hard court layer, at least a B rating is required, and an A rating is desirable. A: No scratches (0 scratches) B: Injury (1 to 4 scratches, 1 mm to 9 mm in length) C: Injury (five or more injuries between 1 mm and 9 mm in length, or one or more injuries of 1 cm or longer) [Water repellency] 1 μL of water was applied to the surface of the hard coat layer, and the contact angle θ was measured five times after 5 seconds. The average value was then evaluated according to the following criteria. In actual use as a hard coat layer, a value of A is desirable. Note that measuring the contact angle immediately after water application yields high and unstable values; therefore, in this measurement, the contact angle was measured 5 seconds after water application. A:θ>105° B: 100°≦θ≦105° C:θ<100° [Abrasion resistance] The surface of the hard coat layer is tested on a cylindrical eraser attached to a reciprocating abrasion testing machine [manufactured by Minoan]. A 6.0mm diameter rubber stick was used to rub the surface 2,500 times with a 1kg load applied. 1μL of water was then applied to the rubbed area, and the contact angle θ was measured at 5 points after 5 seconds. The average value was used as the contact angle value and evaluated according to the following criteria. For actual use as a hard coat layer, a value of at least B is required, and A is desirable. A: θ≧90° B: 85°≦θ<90° C:85°<θ [Slippery] The coefficient of dynamic friction was measured at five points on the surface of the hard coat layer, and the average value was used for evaluation. A smaller coefficient of dynamic friction indicates less friction with the probe used, serving as an indicator of slipperiness. A smaller coefficient of dynamic friction is preferable because it results in better slipperiness when touched. [Hayes] For reference, the haze was measured at three locations on the surface of the hard coat layer, and the average value was calculated. The haze of the PET film used as the substrate in this study [Lumirror® U403 (also known as U40), manufactured by Toray Industries, Inc., with a thickness of 100 μm] was 1.6.

[0108] [Table 3]

[0109] [Table 4]

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

[0111] As shown in Table 1, the curable composition of Example 9 contains a polyfunctional acrylate PA1, a perfluoropolyether SMA6 having an active energy ray polymerizable group at the end of a 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 contains SMA2 having a weight-average molecular weight of 1710, obtained by reacting a perfluoropolyether compound PFPE2, which has a number-average molecular weight of 1750 to 1950 and has one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having the active energy ray polymerizable group. As shown in Table 3, the curable composition of Example 9 showed excellent homogeneity, and the hard coat film having a hard coat layer obtained from this curable composition showed excellent slipperiness, 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 terms of scratch resistance compared to the hard coat films having hard coat layers obtained from the curable compositions of Examples 1 to 8, but showed excellent performance levels in other aspects as shown in Table 2.

[0112] On the other hand, as shown in Table 1, the curable composition of Comparative Example 1 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 which has active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, has a weight-average molecular weight of 2494, and contains 42% by mass of fluorine atoms. Furthermore, it contains SMA4 which has a weight-average molecular weight of 1299 and contains 51% by mass of fluorine atoms, obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with a perfluoropolyether compound PFPE4 which has one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and a molecular weight of 978.15. As shown in Table 3, although the curable composition of Comparative Example 1 shows excellent homogeneity, the hard coat film having a hard coat layer obtained from this curable composition showed inferior slipperiness and scratch resistance compared to the hard coat films obtained from the curable compositions of Examples 1 to 9. These results indicate that even when using a perfluoropolyether containing a high proportion of fluorine atoms (oxyperfluoroalkylene) groups and having an active energy ray polymerizable group at only one end of the molecular chain, the slipperiness and scratch resistance are poor, suggesting that the weight-average molecular weight of the perfluoropolyether is important for its slipperiness and scratch resistance.

[0113] Furthermore, as shown in Table 1, the curable composition of Comparative Example 2 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends 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. It also contains SMA5, which has a weight-average molecular weight of 1029 and a fluorine atom content of 47% by mass, obtained by reacting a perfluoropolyether compound PFPE5, which has a molecular weight of 548.10 and has one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having the aforementioned active energy ray polymerizable groups. As shown in Table 3, although the curable composition of Comparative Example 2 showed excellent homogeneity, the hard coat film having a hard coat layer obtained from this curable composition showed poor slipperiness, scratch resistance, and abrasion resistance. These results also indicate that even when using perfluoropolyethers that have active energy ray polymerizable groups only at one end of a molecular chain containing a high proportion of fluorine atoms (oxyperfluoroalkylene), superior lubricity, scratch resistance, and abrasion resistance are not necessarily achieved. This suggests that the weight-average molecular weight of the perfluoropolyether is important for lubricity, scratch resistance, and abrasion resistance.

[0114] Furthermore, as shown in Table 1, the curable compositions of Comparative Examples 3 to 4 contain a polyfunctional acrylate PA1 and a perfluoropolyether compound PFPE4 with a molecular weight of 978.15 or a perfluoropolyether compound PFPE5 with a molecular weight of 548.10, which has one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and are obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with an isocyanate compound N1 having the active energy ray polymerizable group, and further contain an SMA2 with a weight-average molecular weight of 1710, which has a number-average molecular weight of 1750 to 1950, which has one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group. As shown in Table 3, the curable compositions of Comparative Examples 3 to 4 lacked homogeneity, and the hard coat films equipped with the hard coat layer obtained from these curable compositions showed poor slipperiness, scratch resistance, and abrasion resistance. This is thought to be because the weight-average molecular weights of SMA4 and SMA5 were small, which prevented them from breaking down the aggregated structure of SMA2 and thus could not assist in solubility in the coating solution. As a result, SMA2 aggregated in the coating solution, and SMA2 could not be sufficiently segregated on the surface of the hard coat layer, resulting in poor slipperiness, scratch resistance, and abrasion resistance.

[0115] Furthermore, as shown in Table 1, the curable composition of Comparative Example 5 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA7 having active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, a weight-average molecular weight of 3973, and a fluorine atom content of 29% by mass. It also contains SMA2, which has a weight-average molecular weight of 1710, obtained by reacting a perfluoropolyether compound PFPE2, which has a number-average molecular weight of 1750 to 1950 and has one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having the aforementioned active energy ray polymerizable group. As shown in Table 3, although the curable composition of Comparative Example 5 showed excellent homogeneity and excellent slipperiness, the hard coat film having a hard coat layer obtained from this curable composition showed poor scratch resistance and abrasion resistance. This result indicates that good slipperiness does 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 exhibited inferior scratch resistance and abrasion resistance compared 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 that of SMA1 and SMA6, resulting in lower immobilization ability within the film. In addition, the fluorine atom content of SMA7 was smaller than that of SMA1 and SMA6, leading to poor compatibility between SMA2 and SMA7, and causing a phase separation-like state between SMA2 and SMA7 on the hard coat layer surface.

[0116] Furthermore, as shown in Table 1, the curable composition of Comparative Example 6 contains a polyfunctional acrylate PA1 and a perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 and having one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, to which an isocyanate compound N1 having the active energy ray polymerizable group has been reacted with SMA2 having a weight average molecular weight of 1710. As shown in Table 3, the curable composition of Comparative Example 6 was inferior in homogeneity to the curable composition of Example 1, which was obtained by adding SMA1 to the curable composition of Comparative Example 6. Moreover, the hard coat film having a hard coat layer obtained from the curable composition of Comparative Example 6 showed 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 SMA2 aggregated in the coating solution because it did not contain perfluoropolyethers, which have active energy ray polymerizable groups at the ends of molecular chains containing poly(oxyperfluoroalkylene) groups that act as a solubility aid for SMA2, and have a weight-average molecular weight of 1400 to 3500.

[0117] Furthermore, as shown in Table 1, the curable composition of Comparative Example 7 contains a polyfunctional acrylate PA1 and a perfluoropolyether compound PFPE3 with a number-average molecular weight of 1900, which has one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and SMA3 with a weight-average molecular weight of 1908, obtained by reacting it with the isocyanate compound N1 having the active energy ray polymerizable group. As shown in Table 3, although the curable composition of Comparative Example 7 exhibited excellent homogeneity, the hard coat film having a hard coat layer obtained from this curable composition showed inferior scratch resistance and water repellency compared to the hard coat films having hard coat layers obtained from the curable compositions of Examples 2 to 4, which added SMA1 to the curable composition of Comparative Example 7. This is thought to be because the use of SMA3 alone resulted in strong cohesive force of SMA3, making it prone to aggregation within the film, and preventing sufficient segregation of SMA3 on the surface of the hard coat layer. In addition, SMA3 has an active energy ray polymerizable group at only one end, resulting in low immobilization ability within the film.

[0118] Furthermore, as shown in Table 1, the curable composition of Comparative Example 8 contains polyfunctional acrylate PA1 and SMA4, which has a weight-average molecular weight of 1299, obtained by reacting a perfluoropolyether compound PFPE4, which has a molecular weight of 978.15 and has one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having the active energy ray polymerizable group. As shown in Table 3, the hard coat film obtained from the curable composition of Comparative Example 8, which had SMA1 added to the curable composition of Comparative Example 1, was inferior in homogeneity, and showed inferior results in terms of slipperiness, scratch resistance, and abrasion resistance. This is thought to be because SMA4 aggregates inside the film, preventing sufficient segregation of SMA4 on the surface of the hard coat layer, as well as because the molecular chain containing the poly(oxyperfluoroalkylene) group of SMA4 is short.

[0119] Furthermore, as shown in Table 1, the curable composition of Comparative Example 9 contains polyfunctional acrylate PA1 and SMA5, which has a weight-average molecular weight of 1029, obtained by reacting a perfluoropolyether compound PFPE5, which has a molecular weight of 548.1 and has one hydroxyl group at only one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having the active energy ray polymerizable group. As shown in Table 3, although the curable composition of Comparative Example 9 had excellent homogeneity, the hard coat film having a hard coat layer obtained from this curable composition showed poor slipperiness, water repellency, scratch resistance, and abrasion resistance because the molecular chain containing the poly(oxyperfluoroalkylene) group was short.

[0120] Furthermore, as shown in Table 1, the curable composition of Comparative Example 10 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 which has active energy ray polymerizable groups at both ends of a molecular chain containing poly(oxyperfluoroalkylene) groups, has a weight-average molecular weight of 2494, and contains 42% by mass of fluorine atoms. As shown in Table 3, the curable composition of Comparative Example 10 exhibits excellent homogeneity, and the hard coat film having a hard coat layer obtained from this curable composition exhibits excellent water repellency, scratch resistance, and abrasion resistance. However, compared to the hard coat film having a hard coat layer obtained from the curable composition of Example 1, which adds SMA2 to the curable composition of Comparative Example 10, it showed inferior slipperiness because it does not contain SMA2. This is thought to be because SMA1 has eight acrylic groups in one molecule, resulting in high immobilization ability in the film, thus providing excellent scratch resistance and abrasion resistance, but also low molecular mobility due to its high immobilization ability, resulting in poor slipperiness.

[0121] Based on the evaluation results of hard coat films equipped with hard coat layers obtained from the curable compositions of Comparative Examples 5 and 10, as shown in Table 3, it was suggested that there is a trade-off relationship between slipperiness and scratch resistance.

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

[0123] Furthermore, as shown in Table 1, the curable composition of Comparative Example 13 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends 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. It also contains SMA8, which has a weight-average molecular weight of 1609 and a fluorine atom content of 54% by mass, obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with a perfluoropolyether compound PFPE6 having one hydroxyl group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group and a number-average molecular weight of 1550. As shown in Table 3, the curable composition of Comparative Example 13 exhibited excellent homogeneity, and the hard coat film having a hard coat layer obtained from this curable composition showed excellent water repellency and scratch resistance, but inferior slipperiness and abrasion resistance compared to the hard coat films having hard coat layers obtained from the curable compositions of Examples 1 to 9. From these results, it was shown that a hard coat film obtained from a curable composition containing a perfluoropolyether having an active energy ray polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group as a surface modifier has superior slipperiness compared to a hard coat film obtained from a curable composition containing only a perfluoropolyether having active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group as a surface modifier.

[0124] As shown in Table 2, the curable compositions of Examples 10 to 11 contain a polyfunctional acrylate PA1 or PA2, and a perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends 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. Furthermore, it contains SMA3, which has a weight-average molecular weight of 1908, obtained by reacting a perfluoropolyether compound PFPE3, which has a number-average molecular weight of 1900 and has one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, with the isocyanate compound N1 having the active energy ray polymerizable group, and also contains an antistatic agent AN1. As shown in Table 4, the curable compositions of Examples 10 to 11 showed excellent homogeneity, and the hard coat film having a hard coat layer obtained from the curable composition showed excellent slipperiness, 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 which has active energy ray polymerizable groups at both ends of a molecular chain containing poly(oxyperfluoroalkylene) groups, has a weight-average molecular weight of 2494, and contains 42% by mass of fluorine atoms, and further contains the antistatic agent AN1. As shown in Table 4, the curable composition of Comparative Example 14 exhibits excellent homogeneity, and the hard coat film having a hard coat layer obtained from this curable composition exhibits excellent water repellency, scratch resistance, and abrasion resistance. However, compared to the hard coat film having a hard coat layer obtained from the curable composition of Example 10, which adds SMA3 to the curable composition of Comparative Example 14, it showed inferior slipperiness because it does not contain SMA3. This is thought to be because SMA1 has eight acrylic groups in one molecule, resulting in high immobilization ability in the film, thus exhibiting excellent scratch resistance and abrasion resistance, but with low molecular mobility and poor slipperiness.

[0126] Furthermore, as shown in Table 2, the curable composition of Comparative Example 15 contains a polyfunctional acrylate PA1 and a perfluoropolyether compound PFPE3 with a number average molecular weight of 1900, which has one hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and SMA3 with a weight average molecular weight of 1908, obtained by reacting it with the isocyanate compound N1 having the active energy ray polymerizable group, and further contains the antistatic agent AN1. As shown in Table 4, although the curable composition of Comparative Example 15 has excellent homogeneity, the hard coat film having a hard coat layer obtained from this curable composition showed excellent slipperiness but inferior scratch resistance compared to the hard coat film having a hard coat layer obtained from the curable composition of Example 10, which added SMA1 to the curable composition of Comparative Example 15. This is thought to be because the immobilization ability in the film was reduced due to the use of SMA3, which has an active energy ray polymerizable group at only one end, alone.

Claims

1. (a) Active energy ray curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule, (b) Perfluoropolyethers having active energy ray polymerizable groups at the end of molecular chains containing poly(oxyperfluoroalkylene) groups, and having a weight-average molecular weight of 1400 to 3500 (excluding perfluoropolyethers of (c) described later), (c) Perfluoropolyethers 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 1550 to 3500, (d) comprising a polymerization initiator that generates radicals by active energy rays, The (b) perfluoropolyether is a compound represented by the following formula [4], A curable composition wherein the (c) perfluoropolyether is a compound represented by the following formula [2]. 【Chemistry 1】 (In the above formula [2], m is the number of repeating units -(CF₂CF₂O)-, and n is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (m + n) ≤ 30, where m and n are independent integers of 0 or more, q is the number of oxyethylene groups and is an integer from 0 to 20, and A is the terminal group having the active energy ray polymerizable group, and the terminal group A is the group represented by the following formula [A2].) 【Chemistry 2】 (In the above formula [4], r is the number of repeating units -(CF₂CF₂O)-, and s is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (r + s) ≤ 40, where r and s each independently represent integers of 0 or more, and when both repeating units are present, these repeating units are connected by block bonds, random bonds, or block bonds and random bonds, where A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group represented by the following formula [A2].) 【Transformation 3】 (In formula [A2] above, R1 and R2 each independently represent a hydrogen atom or a methyl group, and * represents a bond between the compound represented by formula [2] or the compound represented by formula [4] and a urethane bond.)

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 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 1400 to 3500 (excluding the perfluoropolyether described in (c) below), (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 1550 to 3500, and (d) comprising 0.5 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, The (b) perfluoropolyether is a compound represented by the following formula [4], A 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)-, satisfying 5 ≤ (m + n) ≤ 30, where m and n are respectively (Each independently represents an integer greater than or equal to 0, q is the number of oxyethylene groups and represents an integer from 0 to 20, and A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group represented by the following formula [A2].) 【Transformation 5】 (In the above formula [4], r is the number of repeating units -(CF₂CF₂O)-, and s is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (r + s) ≤ 40, where r and s each independently represent integers of 0 or more, and when both repeating units are present, these repeating units are connected by block bonds, random bonds, or block bonds and random bonds, where A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group represented by the following formula [A2].) 【Transformation 6】 (In formula [A2] above, R1 and R2 each independently represent a hydrogen atom or a methyl group, and * represents a bond between the compound represented by formula [2] or the compound represented by formula [4] and a urethane bond.)

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 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 1400 to 3500 (excluding the perfluoropolyether described in (c) below), (c) 0.05 to 3 parts by mass of a perfluoropolyether which is a reaction product of a raw material perfluoropolyether having a number average molecular weight of 1200 to 3000 having a hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group that reacts with the hydroxyl group and the active energy ray polymerizable group, and (d) comprising 0.5 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, The (b) perfluoropolyether is a compound represented by the following formula [4], A curable composition wherein the (c) perfluoropolyether is a compound represented by the following formula [2]. 【Transformation 7】 (In the above formula [2], m is the number of repeating units -(CF₂CF₂O)-, and n is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (m + n) ≤ 30, where m and n are independent integers of 0 or more, q is the number of oxyethylene groups and is an integer from 0 to 20, and A is the terminal group having the active energy ray polymerizable group, and the terminal group A is the group represented by the following formula [A2].) 【Transformation 8】 (In the above formula [4], r is the number of repeating units -(CF₂CF₂O)-, and s is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (r + s) ≤ 40, where r and s each independently represent integers of 0 or more, and when both repeating units are present, these repeating units are connected by block bonds, random bonds, or block bonds and random bonds, where A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group represented by the following formula [A2].) 【Chemistry 9】 (In formula [A2] above, R1 and R2 each independently represent a hydrogen atom or a methyl group, and * represents a bond between the compound represented by formula [2] or the compound represented by formula [4] and a urethane bond.)

4. The curable composition according to any one of claims 1 to 3, wherein the (c) perfluoropolyether has a fluorine atom content of 35% to 65% by mass.

5. The curable composition according to any one of claims 1 to 4, wherein in formula [2], m and n each independently represent an integer of 1 or more.

6. The curable composition according to any one of claims 1 to 5, wherein in formula [4], r and s each independently represent an integer of 1 or more.

7. (e) The curable composition according to any one of claims 1 to 6, further comprising 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, wherein the hard coat layer is made of the cured film described in claim 8.

10. The hard coat film according to claim 9, wherein the film substrate is a resin film, and the hard coat layer has a lower hard coat layer between the surface of the film substrate and the hard coat layer.

11. The hard coat film according to claim 9 or claim 10, wherein the hard coat layer has a thickness of 1 μm to 20 μm.

12. A method for producing a hard coat film, comprising the steps of: applying a curable composition according to any one of claims 1 to 7 onto a film substrate to form a coating film; and irradiating the coating film with active energy rays to cure it and form a hard coat layer.

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

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

15. Perfluoropolyethers (A) having active energy ray polymerizable groups at the ends of molecular chains containing poly(oxyperfluoroalkylene) groups, and having a weight-average molecular weight of 1400 to 3500 (excluding perfluoropolyether (B) described later), and The present invention comprises 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 1550 to 3500. A surface modifier in which 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 formulas [2] and [4] above, m is the number of repeating units -(CF₂CF₂O)-, n is the number of repeating units -(CF₂O)-, 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 from 0 to 20, r is the number of repeating units -(CF₂CF₂O)-, and s is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (r + s) ≤ 40, r and s each independently represent an integer of 0 or more, if both repeating units -(CF₂CF₂O)- and repeating units -(CF₂O)- are present, these repeating units are connected by block bonds, random bonds, or block bonds and random bonds, and A is the activation energy linear gravity This represents a terminal group having a compatible group, and the terminal group A is a group represented by the following formula [A2]. 【Chemistry 11】 (In formula [A2] above, R1 and R2 each independently represent a hydrogen atom or a methyl group, and * represents a bond between the compound represented by formula [2] or the compound represented by formula [4] and a urethane bond.)

16. Perfluoropolyethers (A) having active energy ray polymerizable groups at the ends of molecular chains containing poly(oxyperfluoroalkylene) groups, and having a weight-average molecular weight of 1400 to 3500 (excluding perfluoropolyether (B) described later), and The present invention comprises a perfluoropolyether (B) which is a reaction product of a starting material perfluoropolyether having a number average molecular weight of 1200 to 3000, having a hydroxyl group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and a compound having a functional group that reacts with the hydroxyl group and the active energy ray polymerizable group, A surface modifier in which 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 formulas [2] and [4] above, m is the number of repeating units -(CF₂CF₂O)-, n is the number of repeating units -(CF₂O)-, 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 from 0 to 20, r is the number of repeating units -(CF₂CF₂O)-, and s is the number of repeating units -(CF₂O)-, satisfying 5 ≤ (r + s) ≤ 40, r and s each independently represent an integer of 0 or more, repeating units -(CF₂CF₂O)- and repeating units -(CF₂ When both O) and - are present, these repeating units are formed by block bonds, random bonds, or block bonds and random bonds, where A represents the 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 formula [A2] above, R1 and R2 each independently represent a hydrogen atom or a methyl group, and * represents a bond between the compound represented by formula [2] or the compound represented by formula [4] and a urethane bond.)

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

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

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