Curable composition containing two perfluoropolyethers

Abstract

The present invention provides a homogeneous curable composition free from suspended matter and precipitates, which can form a hard coating layer that has both durability and slidability at a high level of properties, and also has high liquid repellency on the basis of actual use. The present invention provides a curable composition comprising: (a) a reactive energy ray-curable multifunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) a perfluoropolyether having a reactive energy ray-polymerizable group at a terminal of a molecular chain including a poly(oxyperfluoroalkylene) group, and a weight average molecular weight of 1400 to 3500 (wherein the perfluoropolyether of (c) described below is excluded); (c) a perfluoropolyether having the reactive energy ray-polymerizable group at only a single terminal of a molecular chain including a poly(oxyperfluoroalkylene) group, and a weight average molecular weight of 1550 to 3500; and (d) a polymerization initiator that generates radicals with a reactive energy ray.

Description

Technical Field

[0001] This invention relates to curable compositions useful as forming materials for hard coatings applied to the surfaces of various display elements, and to homogeneous curable compositions capable of forming hard coatings with excellent slip properties, scratch resistance, abrasion resistance and water repellency, and free from suspended matter and sediment.

[0002] It should be noted that the term "perfluoropolyether" used in this invention refers to a compound having an active energy-emitting polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group. Even if not all hydrogen atoms in the molecular chain containing the poly(perfluoroalkylene oxide) group or the hydrocarbon group containing the active energy-emitting polymerizable group are replaced with fluorine atoms, the term "compound having an active energy-emitting polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group" is still used. Background Technology

[0003] In recent years, touch panels have been introduced into various devices such as portable information terminals like mobile phones and tablet computers, notebook computers, home appliances, and automotive interior and exterior trim. The use of fingers or pens to operate the surfaces of touch panels for display elements such as LCDs and OLEDs has become increasingly common. Assuming finger operation, the touch panel surface requires water and oil repellency to facilitate the removal of fingerprints, and further requires abrasion resistance to maintain water and oil repellency even with repeated finger rubbing. Furthermore, from the tactile perspective of fingers or pens, the surface needs to be slip-resistant when operating the touch panel surface. Additionally, the touch panel surface requires scratch resistance to prevent damage. To impart these properties to the touch panel surface, surface coatings, such as hard coatings, are applied.

[0004] Fluorinated compounds are used as forming materials for hard coatings due to their high sliding and water / oil repellency properties, for example, by methods that involve adding a small amount of fluorine-based surface modifiers to the coating liquid to form the hard coating. It is known that fluorine-based surface modifiers segregate on the surface of the hard coating due to the low surface energy of fluorine atoms.

[0005] Generally, to impart scratch resistance and abrasion resistance to hard coatings, a method is employed to increase the surface hardness of the hard coating by forming a high-density cross-linked structure, thereby providing resistance to external forces. Currently, the most commonly used material for forming such hard coatings is a multifunctional acrylate-based material that undergoes three-dimensional cross-linking using free radicals generated by irradiation with active energy rays. Furthermore, fluorine-based surface modifiers added to the coating liquid for forming the hard coating are also typically materials with active energy ray polymerizable groups (Patent Document 1) to impart scratch resistance and abrasion resistance to the hard coating. From the viewpoint of scratch resistance and abrasion resistance, materials with low molecular weight, a large number of active energy ray polymerizable groups, and a low acrylic equivalent, capable of forming a high-density cross-linked structure, are preferred.

[0006] On the other hand, as described in Patent Document 2, since durable properties such as scratch resistance and abrasion resistance are required for hard coatings, when fluorine-based surface modifiers with crosslinking groups are used, the molecular chains containing fluorine atoms become immobilized, reducing the sliding properties of the hard coating. In other words, there is a trade-off between durable properties such as scratch resistance and abrasion resistance and sliding properties, making it difficult to achieve both high performance levels.

[0007] To improve the aforementioned trade-off, a method exists to introduce crosslinking groups only at one end of the fluorine-containing molecular chain to enhance its mobility. However, compared to introducing crosslinking groups at both ends of the fluorine-containing molecular chain, while the hard coating exhibits excellent sliding properties, its durability tends to be poor. Furthermore, compared to introducing crosslinking groups at both ends of the fluorine-containing molecular chain, introducing crosslinking groups only at one end results in less steric hindrance to the fluorine-containing molecular chain, making it prone to aggregation. Consequently, the coating solution used to prepare the hard coating tends to become cloudy.

[0008] From the perspective of lubrication and water repellency, substances with a high proportion of fluorine atoms are generally considered preferred. However, there is a possibility that fluorine-based surface modifiers may agglomerate in the coating solution. If the fluorine-based surface modifier agglomerates in the coating solution used to form the hard coating, the molecular chains containing fluorine atoms will not fully segregate on the surface of the hard coating, thus failing to exhibit the original lubrication and water repellency properties.

[0009] To improve the solubility of fluorine-based surface modifiers, one could consider reducing the proportion of fluorine atoms in the fluorine-based surface modifier. As mentioned above, it is conceivable that the sliding properties and water repellency of the hard coating will decrease, making it difficult to meet the high performance levels of sliding properties and water repellency.

[0010] As a method for improving the solubility of fluorine-based surface modifiers, Patent Document 3 reports a fluorinated polyether that becomes agglomerate when used to obtain a hard coating agent composition, which is the main cause of the turbidity of the composition, and a fluorinated block copolymer with excellent compatibility with the composition.

[0011] Patent Document 4 reports that by combining a linear polymer having a fluorinated polyether backbone with acrylic groups at one or both ends of the molecular chain and a fluorine content of 48% to 62% by mass, and a linear polymer having a fluorinated polyether backbone with multiple acrylic groups at both ends of the molecular chain and a fluorine content of 25% to less than 45% by mass, a hard coating with improved solubility, excellent water repellency, and excellent sliding properties in a composition of the aforementioned linear polymer with a fluorine content of 48% to 62% by mass, can be obtained. However, regarding abrasion resistance, Patent Document 4 describes it in paragraph 0006 as "abrasion resistance represented by sliding properties," indirectly evaluating abrasion resistance using sliding properties. Therefore, there are no specific examples regarding scratch resistance and abrasion resistance.

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: International Publication No. 2016 / 163479

[0015] Patent Document 2: Japanese Patent No. 6497449

[0016] Patent Document 3: Japanese Patent Application Publication No. 2005-179613

[0017] Patent Document 4: International Publication No. 2020 / 170698 Summary of the Invention

[0018] The problem that the invention aims to solve

[0019] Patent document 3 describes that the fluorinated block copolymer described in the document has poor water repellency and lubricity compared to the fluorinated polyether. Therefore, the fluorine concentration of the fluorinated block copolymer is lower than that of the fluorinated polyether, and it is easy to imagine that it is difficult to simultaneously achieve compatibility with the composition, lubricity, and water repellency.

[0020] Patent document 4 describes the following results regarding slip properties: In the aforementioned linear polymers with a fluorine content of 48% to 62% by mass, the slip properties are the same whether the molecular chain has an acrylic group at one end or at both ends. Therefore, it can be assumed that the slip properties have not reached a sufficient level.

[0021] The problem in this invention is to provide a homogeneous, curable composition free of suspended matter and sediment that can form a hard coating that balances high performance with a trade-off between durability and slipperiness. Furthermore, assuming practical use, the hard coating needs to possess high liquid-repellent properties.

[0022] Solution for solving the problem

[0023] That is, the present invention is a curable composition comprising: (a) an active energy-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) a perfluoropolyether having an active energy-curable polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group and having a weight-average molecular weight of 1400 to 3500 (except for (c) perfluoropolyether described later); (c) a perfluoropolyether having the active energy-curable polymerizable group only at a single end of a molecular chain containing a poly(perfluoroalkylene oxide) group and having a weight-average molecular weight of 1550 to 3500; and (d) a polymerization initiator that generates free radicals using active energy rays.

[0024] A curable composition comprising: (a) 100 parts by mass of an active energy-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) 0.05 to 3 parts by mass of a perfluoropolyether (excluding (c) perfluoropolyether described later) having an active energy-curable polyfunctional group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group and having a weight average molecular weight of 1400 to 3500; (c) 0.05 to 3 parts by mass of a perfluoropolyether having the active energy-curable polyfunctional group only at a single end of a molecular chain containing a poly(perfluoroalkylene oxide) group and having a weight average molecular weight of 1550 to 3500; and (d) 0.5 to 20 parts by mass of a polymerization initiator that generates free radicals using active energy rays.

[0025] A curable composition comprising: (a) 100 parts by mass of an active energy-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-curable polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group and having a weight average molecular weight of 1400 to 3500 (except for (c) the perfluoropolyether described below); (c) 0.05 to 3 parts by mass of a perfluoropolyether as a reaction product of a raw material perfluoropolyether and a compound having a number average molecular weight of 1200 to 3000, wherein the raw material perfluoropolyether has a hydroxyl group only at a single end of a molecular chain containing a poly(perfluoroalkylene oxide) group, and the compound has a functional group that reacts with the hydroxyl group and the active energy-curable polymerizable group; and (d) 0.5 to 20 parts by mass of a polymerization initiator that generates free radicals using active energy rays.

[0026] The (c) perfluoropolyether has the active energy-ray polymerizable group at only one end of the molecular chain containing the poly(perfluoroalkylene oxide) group, and has a weight-average molecular weight of 1550 to 3500.

[0027] The (c) perfluoropolyether has active energy-emitting polymerizable groups via urethane bonds.

[0028] The fluorine content of the perfluoropolyether (c) is from 35% to 65% by mass.

[0029] The poly(perfluoroalkylene oxide) group of the (c) perfluoropolyether has repeating units –(CF2O)- and / or repeating units –(CF2CF2O)-. In the case of having repeating units of both, the poly(perfluoroalkylene oxide) group of the (c) perfluoropolyether is a group formed by bonding these repeating units by block bonding, random bonding, or block bonding and random bonding.

[0030] The molecular chain containing poly(perfluoroalkylene oxide) groups of the (c) perfluoropolyether has the structure shown in the following formula [1].

[0031]

[0032] (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, m and n independently represent integers above 0, and q is the number of oxyethylidene, representing integers from 0 to 20.)

[0033] In the above formula [1], m and n independently represent integers greater than 1.

[0034] The (c) perfluoropolyether is a compound represented by the following formula [2].

[0035]

[0036] (In the above formula [2], m, n and q have the same meaning as those defined in formula [1], and A represents the terminal group having the active energy ray polymerizable group.)

[0037] The terminal group A is a group represented by formula [A1] or formula [A2].

[0038]

[0039] (In the above equations [A1] and [A2], R) 1 and R 2Each of the above represents a hydrogen atom or a methyl group independently, and * represents a carbamate bond with the compound shown in formula [2].

[0040] The (b) perfluoropolyether has the active energy-ray polymerizable groups at both ends of the molecular chain containing the poly(perfluoroalkylene oxide) group.

[0041] The molecular chain containing poly(perfluoroalkylene oxide) groups of the (b) perfluoropolyether has the structure shown in the following formula [3].

[0042]

[0043] (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. r and s independently represent integers above 0. In the case of repeating units on both sides, these repeating units are bonded together by block bonding, random bonding, or block bonding and random bonding.)

[0044] In the above formula [3], r and s independently represent integers greater than 1.

[0045] The (b) perfluoropolyether is a compound represented by the following formula [4].

[0046]

[0047] (In the above formula [4], r and s have the same meaning as in the above formula [3], and A represents the terminal group having the active energy ray polymerizable group.)

[0048] The terminal group A is a group represented by formula [A1] or formula [A2].

[0049]

[0050] (In the above equations [A1] and [A2], R) 1 and R 2 Each of the above represents a hydrogen atom or a methyl group independently, and * represents a carbamate bond with the compound shown in formula [4].

[0051] The curable composition of the present invention further comprises (e) a solvent.

[0052] A cured film obtained from the curable composition.

[0053] A hard coating film having a hard coating layer on at least one side of a film substrate, the hard coating layer being composed of the cured film.

[0054] The membrane substrate has a lower layer of hard coating between its surface and the hard coating layer, and the membrane substrate is made of resin.

[0055] The hard coating has a film thickness of 1 μm to 20 μm.

[0056] A method for manufacturing a hard coating film includes: a step of coating the curable composition onto a film substrate to form a coating film; and a step of irradiating the coating film with active energy rays to cure it and form a hard coating layer.

[0057] A method for manufacturing a hard coating film includes: a step of coating a curable composition onto a film substrate to form a coating film; a step of removing the solvent from the coating film by heating; and a step of irradiating the coating film with active energy rays to cure it and form a hard coating layer.

[0058] A method for manufacturing a hard coating film further includes: a step of forming a lower layer of a hard coating on the surface of a film substrate, wherein the film substrate is a resin film, and the coating film is formed on the lower layer of the hard coating.

[0059] A surface modifier comprising: a perfluoropolyether (A) having an active energy-ray polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group and having a weight-average molecular weight of 1400 to 3500 (except for a perfluoropolyether (B) described later); and a perfluoropolyether (B) having the active energy-ray polymerizable group only at a single end of a molecular chain containing a poly(perfluoroalkylene oxide) group and having a weight-average molecular weight of 1550 to 3500.

[0060] A surface modifier comprising: a perfluoropolyether (A) having an active energy-ray polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group and having a weight-average molecular weight of 1400 to 3500 (except for perfluoropolyether (B) described later); and a perfluoropolyether (B) as a reaction product of a raw material perfluoropolyether and a compound, wherein the raw material perfluoropolyether has a hydroxyl group at only one end of a molecular chain containing a poly(perfluoroalkylene oxide) group and has a number-average molecular weight of 1200 to 3000, and the compound has a functional group that reacts with the hydroxyl group and the active energy-ray polymerizable group.

[0061] The perfluoropolyether (B) has the active energy-ray polymerizable group only at a single end of the molecular chain containing the poly(perfluoroalkylene oxide) group, and has a weight-average molecular weight of 1550 to 3500.

[0062] The perfluoropolyether (B) contains fluorine atoms in a proportion of 35% to 65% by mass.

[0063] The perfluoropolyether (A) has the active energy-ray polymerizable groups at both ends of the molecular chain containing the poly(perfluoroalkylene oxide) group.

[0064] The perfluoropolyether (A) has a molecular chain containing a poly(perfluoroalkylene oxide) group with the structure shown in the following formula [3], and the perfluoropolyether (B) has a molecular chain containing a poly(perfluoroalkylene oxide) group with the structure shown in the following formula [1].

[0065]

[0066] (In the above formulas [1] and [3], 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 independently represent integers greater than 0, q is the number of oxyethylidene units, representing integers 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, where r and s independently represent integers greater than 0. In the case of having both repeating units -(CF2CF2O)- and repeating units -(CF2O)-, these repeating units are bonded together by block bonding, random bonding, or block bonding and random bonding.)

[0067] In Equation [1], m and n independently represent integers greater than or equal to 1, and in Equation [3], r and s independently represent integers greater than or equal to 1.

[0068] 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].

[0069]

[0070] (In the above formulas [2] and [4], m, n and q have the same meaning as the definition in formula [1], r and s have the same meaning as the definition in formula [3], and A represents the terminal group having the active energy ray polymerizable group, which is the group shown in the following formula [A1] or formula [A2].)

[0071]

[0072] (In the above equations [A1] and [A2], R) 1 and R 2 Each of the above represents a hydrogen atom or a methyl group independently, and * represents a carbamate bond with the compound shown in formula [2] or formula [4].

[0073] Invention Effects

[0074] According to the present invention, a curing composition useful for forming cured films and hard coatings that possess excellent scratch resistance / abrasion resistance and excellent lubricity even in films with a thickness of 1 μm to 20 μm can be provided. Furthermore, according to the present invention, a cured film obtained from the curing composition or a hard coating having a hard coating composed of the cured film can be provided, offering a hard coating with excellent durability properties such as scratch resistance and abrasion resistance, as well as excellent lubricity, representing a trade-off. Moreover, according to the present invention, a curing composition useful for forming cured films and hard coatings that impart high water repellency in addition to possessing the aforementioned two properties, and a hard coating having these excellent properties, can be provided. Detailed Implementation

[0075] <Curing Composition>

[0076] The components of the curable composition of the present invention will be described below.

[0077] [(a) Active energy-curable multifunctional monomers having two or more (meth)acryloyl groups in one molecule]

[0078] (a) Active energy ray-curable polyfunctional monomers (hereinafter also referred to as "(a) polyfunctional monomers") that have two or more (meth)acryloyl groups in one molecule of component refer to monomers that are polymerized and cured by irradiation with active energy rays such as ultraviolet rays.

[0079] In the curable compositions 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 monomers, one of the above-mentioned polyfunctional (meth)acrylate compounds may be used alone, or two or more may be used in combination. It should be noted that in the present invention, (meth)acrylate compounds include both acrylate compounds and methacrylate compounds; for example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

[0080] Furthermore, (a) the polyfunctional monomer can also be an oxoalkylene-modified polyfunctional monomer. Examples of such oxoalkylene modification include oxomethylene modification, oxoethylene modification, and oxopropylene modification. Examples of oxoalkylene-modified polyfunctional monomers include compounds modified with oxoalkylene from the aforementioned polyfunctional (meth)acrylate or polyfunctional urethane (meth)acrylate compounds. The oxoalkylene-modified polyfunctional monomer can be used alone or in combination of two or more.

[0081] Furthermore, in this invention, preferred (a) polyfunctional monomers include polyfunctional monomers having at least three (meth)acryloyl groups in a molecule, for example, polyfunctional monomers having at least four (meth)acryloyl groups in a molecule. In this invention, as (a) polyfunctional monomers, monomers selected from the group consisting of oxoalkylene-modified polyfunctional (meth)acrylate compounds having at least three (meth)acryloyl groups in a molecule are also included.

[0082] Examples of the aforementioned polyfunctional (meth)acrylate compounds (wherein, the compounds do not have urethane bonds) include: trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and 1,3-propanediol di(meth)acrylate. Acrylates, 1,3-Butanediol di(meth)acrylate, 1,4-Butanediol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, 2-Methyl-1,8-Octadecyldiol 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] 2，6Decanediol di(meth)acrylate, dioxanediol 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-adamantanediol 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.

[0083] Examples of the aforementioned oxoalkylene-modified polyfunctional (meth)acrylate compounds include (meth)acrylate compounds of polyols modified with oxoalkylene. Examples of such polyols include: glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, decaglycerol, polyglycerol, trimethylolpropane, di(trimethylolpropane), pentaerythritol, and dipentaerythritol.

[0084] The aforementioned polyfunctional urethane (meth)acrylate compound is a compound having multiple acryloyl or methacryloyl groups in a molecule and having one or more urethane bonds [-NHC(=O)O-], and may further have urea bonds [-NHC(=O)NH-]. Examples of such polyfunctional urethane (meth)acrylate compounds include, for instance, compounds obtained by reacting a polyfunctional isocyanate with a hydroxyl-containing (meth)acrylate, and compounds obtained by reacting a polyfunctional isocyanate with a hydroxyl-containing (meth)acrylate and a polyol; however, the polyfunctional urethane (meth)acrylate compounds that can be used in this invention are not limited to these examples.

[0085] It should be noted that examples of the aforementioned polyfunctional isocyanates include, for example, toluene diisocyanate, isophorone diisocyanate, phenyl dimethyl diisocyanate, and hexamethylene diisocyanate. Furthermore, examples of the aforementioned hydroxyl-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tripentaerythritol hepta(meth)acrylate. Moreover, examples of the aforementioned polyols include, for example, diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; polyester polyols as reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, and adipic acid; polyether polyols; and polycarbonate diols.

[0086] (a) The multifunctional monomer may also be a lactone-modified multifunctional (meth)acrylate compound, with ε-caprolactone being the preferred modified lactone. Examples of such lactone-modified multifunctional (meth)acrylate compounds 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.

[0087] [(b) Perfluoropolyethers with active energy-emitting polymerizable groups at the ends of molecular chains containing poly(perfluoroalkylene oxide) groups and a weight-average molecular weight of 1400 to 3500]

[0088] Hereinafter, the perfluoropolyether of component (b) having active energy-emitting polymerizable groups at the ends of the molecular chain containing the poly(perfluoroalkylene oxide) group and having a weight-average molecular weight of 1400 to 3500 will also be referred to as "(b) perfluoropolyether". (b) perfluoropolyether excludes (c) perfluoropolyether described later. In the curable composition of the present invention, the preferred (b) perfluoropolyether has active energy-emitting polymerizable groups at the ends of the molecular chain containing the poly(perfluoroalkylene oxide) group via urethane bonds. The ends of the molecular chain containing the poly(perfluoroalkylene oxide) group can be any of all ends and a portion of the ends of the molecular chain. In the case where the molecular chain is linear, all ends and a portion of the ends of the linear molecular chain are respectively the two ends and one end of the linear molecular chain. As the linking group between the poly(perfluoroalkylene oxide) group and the urethane bond, examples include hydrocarbon groups having ether bonds, at least one of the hydrogen atoms of the hydrocarbon group optionally being replaced by a fluorine atom. Furthermore, the preferred (b) perfluoropolyether does not have silicon atoms in its chemical structure.

[0089] (b) The perfluoropolyether, along with component (c) described later, acts as a surface modifier in the hard coating formed by the curable composition of the present invention. Furthermore, (b) the perfluoropolyether exhibits excellent compatibility with the polyfunctional monomer (a), thus suppressing turbidity and enabling the formation of a hard coating with a transparent appearance.

[0090] From the viewpoint of obtaining a cured film with good scratch resistance, it is preferable that the poly(perfluoroalkylene oxide) group has both -[CF2O]- (perfluoromethylene oxide) and -[CF2CF2O]- (perfluoroethylene oxide) as repeating units. In this case, the bonding of these perfluoroalkyl oxides can be either block bonding or random bonding.

[0091] (b) Perfluoropolyethers are not limited to having one active energy-emitting polymerizable group at the end of the molecular chain containing a poly(perfluoroalkylene oxide) group, but may also have two or more active energy-emitting polymerizable groups. Examples of such active energy-emitting polymerizable groups include (meth)acryloyl and vinyl groups, and examples of end groups having such active energy-emitting polymerizable groups include groups represented by formula [A1] or [A2]. Among these end groups, the group represented by formula [A2] having two active energy-emitting polymerizable groups is preferred.

[0092] From the viewpoint of obtaining a cured film with good scratch resistance, (b) the perfluoropolyether more preferably has active energy-ray polymerizable groups at both ends of the molecular chain containing the poly(perfluoroalkylene oxide) group, and even more preferably, the number of such active energy-ray polymerizable groups in a molecule is large. The number of such polymerizable groups is preferably two or more at each end of the molecular chain containing the poly(perfluoroalkylene oxide) group, and more preferably three or more at each end.

[0093] By using (b) perfluoropolyethers with a weight-average molecular weight of 1400 to 3500, a hard coating with excellent scratch resistance, abrasion resistance and lubrication can be obtained.

[0094] In the curable composition of the present invention, the content of (b) perfluoropolyether relative to 100 parts by weight of the (a) polyfunctional monomer is, for example, 0.05 parts by weight to 10 parts by weight, 0.05 parts by weight to 5 parts by weight, or 0.05 parts by weight to 3 parts by weight, preferably 0.1 parts by weight to 3 parts by weight, more preferably 0.1 parts by weight to 1 part by weight. By having a content of (b) perfluoropolyether of 0.05 parts by weight or more, sufficient scratch resistance can be imparted to the hard coating. Furthermore, by having a content of (b) perfluoropolyether of 3 parts by weight or less, sufficient compatibility with (a) polyfunctional monomer can be achieved, resulting in a hard coating with less turbidity.

[0095] (b) Perfluoropolyethers may be used alone or in combination of two or more. In the case of a combination of two or more, a perfluoropolyether may also contain a group having an active energy-emitting polymerizable group via a urethane bond at one end (one end) of a molecular chain containing a poly(perfluoroalkylene oxide) group, and a hydroxyl group at the other end (the other end) of its molecular chain.

[0096] [(c) Perfluoropolyethers having the active energy-emitting polymerizable group at only one end of the molecular chain containing the poly(perfluoroalkylene oxide) group, and having a weight-average molecular weight of 1550 to 3500]

[0097] Hereinafter, the perfluoropolyether of component (c) having the active energy-emitting polymerizable group at only one end of the molecular chain containing the poly(perfluoroalkylene oxide) group, and having a weight-average molecular weight of 1550 to 3500, will also be referred to as "(c) perfluoropolyether". (c) perfluoropolyether is obtained, for example, by reacting a raw material perfluoropolyether with a compound having a hydroxyl group at only one end of the molecular chain containing the poly(perfluoroalkylene oxide) group, having a number-average molecular weight of 1200 to 3000, and the compound having a functional group that reacts with the hydroxyl group and the active energy-emitting polymerizable group. Examples of functional groups that react with the hydroxyl group include, for example, hydroxyl, carboxyl, and isocyanate groups.

[0098] "Furthermore, it is preferable that the single end of the raw material perfluoropolyether has a fluorine-containing group on the side opposite to the single end having a hydroxyl group, and more preferably a trifluoromethoxy group. (c) Perfluoropolyether with a group containing the fluorine atom on the single end opposite to the single end having the active energy ray polymerizable group can be sufficiently transferred to the surface of the hard coating, exhibiting excellent water repellency and sliding properties."

[0099] (c) Perfluoropolyethers are not limited to having only one active energy-emitting polymerizable group at a single end of the molecular chain containing a poly(perfluoroalkylene oxide) group, but may also have two or more active energy-emitting polymerizable groups. Examples of such active energy-emitting polymerizable groups include (meth)acryloyl and vinyl groups, and examples of end groups having such active energy-emitting polymerizable groups include groups represented by formula [A1] or [A2]. Among these end groups, the group represented by formula [A2] having two active energy-emitting polymerizable groups is preferred.

[0100] (c) The perfluoropolyether, along with (b) the perfluoropolyether, functions as a surface modifier in the hard coating formed by the curable composition of the present invention. Furthermore, the perfluoropolyether (c) exhibits excellent compatibility with (b) the perfluoropolyether, thus suppressing turbidity and enabling the formation of a hard coating with a transparent appearance. Moreover, from the viewpoint of compatibility with the polyfunctional monomer (a), the perfluoropolyether (c) preferably has a poly(oxyalkylene) group. As this poly(oxyalkylene) group, a poly(oxyethylene) group is preferred.

[0101] In the curable composition of the present invention, the preferred (c) perfluoropolyether has an active energy-ray polymerizable group at the single end of a molecular chain containing only a poly(perfluoroalkylene oxide) group via a urethane bond. As the aforementioned poly(perfluoroalkylene oxide) group, from the viewpoint of obtaining a cured film with good scratch resistance, it is preferable to have a group having both -[CF₂O]-(perfluoromethylene oxide) and -[CF₂CF₂O]-(perfluoroethylene oxide) as repeating units. In this case, the bonding of these perfluoroalkylene oxides can be either block bonding or random bonding.

[0102] (c) The fluorine content of the perfluoropolyether is, for example, 35% by mass or more and 65% by mass or less, preferably 40% by mass or more and 65% by mass or less, more preferably 45% by mass or more and 65% by mass or less. When the fluorine content is 35% by mass or more, a hard coating with excellent water repellency and lubricity can be obtained. When it exceeds 65% by mass, there is a possibility that it is not sufficiently compatible with (a) the multifunctional monomer and cannot obtain sufficient properties.

[0103] (c) The weight-average molecular weight of the perfluoropolyether is from 1550 to 3500, preferably from 1600 to 3500, and more preferably from 1700 to 3500. With the weight-average molecular weight of (c) the perfluoropolyether being within the above range, (c) the perfluoropolyether easily remains on the surface of the hard coating obtained from the curable composition of the present invention, and the shear stress on the layer surface is sufficiently reduced, thus resulting in a hard coating with excellent sliding properties. Furthermore, with the weight-average molecular weight of (c) the perfluoropolyether being within the above range, a hard coating with excellent durability, such as scratch resistance, can be obtained after appropriate adjustment of the surface hardness. In other words, with the weight-average molecular weight of (c) the perfluoropolyether being within the above range, both sliding properties and durability can be achieved.

[0104] 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 relative to 100 parts by mass of the polyfunctional monomer (a). 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 coating obtained from the curable composition of the present invention, thus obtaining a hard coating with excellent sliding properties. Furthermore, when the content of (c) perfluoropolyether is 3 parts by mass or less, it is sufficiently compatible with (b) perfluoropolyether, resulting in a hard coating with less turbidity. Furthermore, the content of (c) perfluoropolyether is, for example, 10 to 800 parts by mass relative to 100 parts by mass of the perfluoropolyether (b), more preferably 10 to 500 parts by mass, and even more preferably 10 to 400 parts by mass.

[0105] (c) Perfluoropolyethers may be used alone or in combination of two or more.

[0106] [(d) Polymerization initiator]

[0107] In the curable composition of the present invention, the preferred polymerization initiator (d) is, for example, a polymerization initiator that generates free radicals by active energy rays such as electron beams, ultraviolet rays, and X-rays, especially by ultraviolet irradiation.

[0108] Examples of polymerization initiators for (d) include: benzoin derivatives, alkylphenyl ketones, thioxanone derivatives, azo derivatives, azido derivatives, diazo derivatives, o-quinone diazido derivatives, acylphosphine oxides, oxime esters, organic peroxides, benzophenone derivatives, dicumarol derivatives, diimidazole derivatives, titanium oxide derivatives, thiols, halogenated hydrocarbons, trichloromethyltriazine derivatives, and ononium salts such as iodonium salts and sulfonium salts. These polymerization initiators can be used alone or in combination of two or more. In this invention, from the viewpoints of transparency, surface curability, and film curability, alkylphenyl ketones are preferred as polymerization initiators for (d). By using alkylphenyl ketones, a cured film with further improved scratch resistance can be obtained.

[0109] Examples of the aforementioned alkyl phenyl ketones include, for instance, α-hydroxyalkyl phenyl ketones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropane-1-one, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one; α-aminoalkyl phenyl ketones such as 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylpropane-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one; 2,2-dimethoxy-1,2-diphenylethane-1-one; and methyl phenylglyoxylate.

[0110] In the curable composition of the present invention, the content of (d) polymerization initiator relative to 100 parts by mass of the (a) polyfunctional monomer is, for example, 0.5 parts by mass to 20 parts by mass, preferably 1 part by mass to 20 parts by mass, and more preferably 2 parts by mass to 10 parts by mass.

[0111] [(e) solvent]

[0112] The curable composition of the present invention may also contain solvent (e) as an arbitrary component, i.e., it may also be formulated as a varnish. As solvent (e), it may be appropriately selected by taking into account the solubility / dispersibility of components (a) to (d), as well as the workability of the curable composition during application and the drying properties before and after curing, which are related to the formation of the cured film (hard coating) described later.

[0113] Examples of solvents used in (e) above include: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral oil, and cyclohexane; halides such as chloromethane, bromomethane, iodomethane, 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); and diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether. Ethers such as propylene glycol monoethyl ether (PGME), 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, isopropanol, n-butanol, isobutanol, tert-butanol, 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 formed by mixing two or more of these solvents.

[0114] In the curable composition of the present invention, the content of solvent (e) is not particularly limited, for example, the solid component concentration of the curable composition of the present invention is from 1% by mass to 70% by mass, preferably from 5% by mass to 50% by mass. Here, solid component concentration (also referred to as non-volatile component concentration) means the content of solid component (the portion from all components after removing the solvent component) of the curable composition of the present invention relative to the total mass (total mass) of components (a) to (e) and other additives.

[0115] [Other Additives]

[0116] Furthermore, in the curable composition of the present invention, as long as the effect of the present invention is not impaired, it is also possible to appropriately combine one or more of the commonly added additives, such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, adhesion promoters, plasticizers, ultraviolet absorbers, storage stabilizers, anti-static agents, inorganic fillers, pigments, dyes, etc., as needed.

[0117] <Cured film>

[0118] The curable composition of the present invention can be coated onto a substrate to form a coating film, and then irradiated with active energy rays to polymerize (cur) the coating film to form a cured film, which is also the subject of the present invention. Furthermore, a hard coating layer composed of the above-described cured film can be used as the hard coating layer in the hard coating film described later.

[0119] Examples of substrates include various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc., polyesters, polyurethanes, thermoplastic polyurethanes (TPU), polyolefins, polyamides, polyimides, epoxy resins, melamine resins, cellulose triacetate (TAC), acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-styrene copolymers (AS), norbornene resins), metals, wood, paper, glass, and slate. These substrates can be in the form of plates, films, or three-dimensional molded bodies. Furthermore, 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, anti-static layer, anti-discoloration layer, gas barrier layer, water vapor barrier layer, light scattering layer, electrode layer, etc., can be formed on the surface of these substrates as a lower layer of the hard coating, or multiple layers of this lower layer of the hard coating can be stacked. As for the layer formed on the surface of the aforementioned substrate, there are no particular limitations as long as it does not impair the effect of the present invention.

[0120] The coating method applied to the aforementioned substrate can be appropriately selected from cast coating, spin coating, blade coating, dip coating, roller coating, spray coating, bar coating, mold coating, inkjet coating, and printing methods (relief printing, gravure printing, offset printing, screen printing, etc.). Among these, relief printing is ideal from the perspective of utilizing a roll-to-roll method, and from the viewpoint of film coating properties, gravure printing is particularly ideal. It should be noted that the curable composition of the present invention is preferably filtered beforehand using a filter with a pore size of approximately 0.2 μm before coating. It should also be noted that, during coating, a solvent may be further added to the curable composition as needed. Various solvents listed in [(e) solvents] can be used as solvents in this case.

[0121] After coating a substrate with the curable composition of the present invention to form a coating film, the coating film is pre-dried using a heating unit such as a heating plate or oven to remove the solvent (solvent removal process). The heating and drying conditions at this time are preferably set at 40°C to 120°C for approximately 30 seconds to 10 minutes. After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet light. Examples of active energy rays include ultraviolet light, electron beams, and X-rays, with ultraviolet light being particularly preferred. As a light source for ultraviolet irradiation, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs can be used, for example. Furthermore, polymerization can be completed by post-baking, specifically by heating using a heating unit such as a heating plate or oven.

[0122] It should be noted that the thickness of the cured film after drying and curing is typically 0.1 μm to 20 μm, preferably 0.5 μm to 10 μm.

[0123] <Hard Coating>

[0124] The curable composition of the present invention can be used to manufacture a hard coating film having a hard coating layer on at least one side (surface) of a film substrate. This hard coating film is also the subject of the present invention, and is preferably used, for example, to protect the surfaces of various display elements such as touch panels and liquid crystal displays.

[0125] The hard coating layer in the hard coating film of the present invention can be formed by a method comprising: a step of coating a film substrate with the curable composition of the present invention to form a coating film; a step of removing the solvent by heating as needed; and a step of curing the coating film by irradiating it with active energy rays such as ultraviolet light. A method for manufacturing a hard coating film having a hard coating layer on at least one side of a film substrate, including these steps, is also the subject of the present invention.

[0126] As the aforementioned film substrate, various transparent resin films suitable for optical applications can be used from the substrates listed in the <Curing Film> section. Preferred resin films include, for example, films made of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polycarbonate, polymethacrylate, polystyrene, polyolefins, polyamides, polyimides, and cellulose triacetate (TAC).

[0127] As the aforementioned film substrate, multiple layers can be stacked together. 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-reflection layer, anti-static layer, anti-discoloration layer, gas barrier layer, water vapor barrier layer, light scattering layer, and electrode layer, can be stacked on the surface of the resin film as the lower layer of the hard coating. Multiple layers of this lower layer of the hard coating can also be stacked. There are no particular limitations on the layers stacked on the surface of the resin film, as long as they do not impair the effects of the present invention.

[0128] Furthermore, the coating method (coating film forming step) for applying the curable composition of the present invention to the above-mentioned film substrate and the method for irradiating the coating film with active energy rays (curing step) can use the methods listed in the "Curing Film" section. Additionally, in the case where the curable composition of the present invention contains a solvent (in varnish form), a step of drying the coating film to remove the solvent can be included as needed after the coating film forming step. In this case, the coating film drying method (solvent removal step) listed in the "Curing Film" section can be used.

[0129] The thickness (film thickness) of the hard coating thus obtained is, for example, 1 μm to 20 μm, preferably 1 μm to 10 μm.

[0130] <Surface Modifier>

[0131] The following surface modifiers are also the subject of this invention, comprising: a perfluoropolyether (A) having an active energy-ray polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group and a weight-average molecular weight of 1400 to 3500 (except for the perfluoropolyether (B) described later); and a perfluoropolyether (B) having the active energy-ray polymerizable group only at a single end of a molecular chain containing a poly(perfluoroalkylene oxide) group and a weight-average molecular weight of 1550 to 3500.

[0132] Furthermore, the following surface modifiers are also included in this invention, comprising: a perfluoropolyether (A) having an active energy-ray polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group and a weight-average molecular weight of 1400 to 3500 (except for the perfluoropolyether (B) described later); and a perfluoropolyether (B) as a reaction product of a raw material perfluoropolyether and a compound, wherein the raw material perfluoropolyether has a hydroxyl group only at a single end of a molecular chain containing a poly(perfluoroalkylene oxide) group and a number-average molecular weight of 1200 to 3000, and the compound has a functional group that reacts with the hydroxyl group and the active energy-ray polymerizable group.

[0133] It should be noted that "perfluoropolyether (A)" is the same as the perfluoropolyether in (b), and "perfluoropolyether (B)" is the same as the perfluoropolyether in (c).

[0134] Example

[0135] The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to the embodiments described below. It should be noted that, in the embodiments, the apparatus and conditions for preparing samples and analyzing physical properties are as follows.

[0136] (1) Coating using a bar coater

[0137] Device: PM-9050MC manufactured by SMT Corporation.

[0138] Rod: A-Bar OSP-15 manufactured by OSG SYSTEM PRODUCTS, with a maximum wet film thickness of 15 μm (3 μm after drying).

[0139] Coating speed: 4m / min.

[0140] (2) Film thickness measurement

[0141] Apparatus: F20 film thickness measurement system manufactured by Filmetrics Co., Ltd.

[0142] (3) Oven

[0143] Equipment: Sanji Keisoku Co., Ltd. double-layer cleanroom drying oven (top and bottom type) PO-250-45-D.

[0144] (4) UV curing

[0145] Device: Heraeus Corporation CV-110QC-G.

[0146] Lamp: Heraeus Corporation's electrodeless lamp H-bulb.

[0147] (5) Scratch resistance test and abrasion resistance test

[0148] Apparatus: TRIBOGEAR TYPE: 30S reciprocating wear tester manufactured by Shin-Tung Science Co., Ltd.

[0149] Scanning speed: 3200 mm / minute.

[0150] Scanning distance: 50mm.

[0151] (6) Contact angle measurement

[0152] Device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd.

[0153] Measurement temperature: 23℃.

[0154] (7) Measurement of dynamic friction coefficient

[0155] Apparatus: TRIBOGEAR (registered trademark) HHS2000 load-variable friction and wear testing system manufactured by Shin-Tung Science Co., Ltd.

[0156] Probe: 0.6mmR sapphire needle.

[0157] Load: 200g.

[0158] Scanning speed: 2 mm / second.

[0159] Scanning distance: 10mm.

[0160] (8) Measurement of total transmittance and haze

[0161] Device: NDH5000 haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0162] (9) Determination of weight-average molecular weight

[0163] Gel permeation chromatography (GPC).

[0164] Device: Tosoh Corporation HLC-8420GPC.

[0165] Chromatographic columns: TSKgel G2000HXL and TSKgel G3000HXL manufactured by Tosoh Co., Ltd.

[0166] Measurement temperature: 40℃.

[0167] Eluent: Tetrahydrofuran.

[0168] Detection: RI.

[0169] (10) Combustion ion chromatography

[0170] Automatic sample combustion device system: Nitto Seiko Analytical Technology Co., Ltd. (formerly Mitsubishi Chemical Analytical Technology Co., Ltd.) AQF-2100H.

[0171] Ion chromatograph: Dionex Integrion, manufactured by ThermoFisher Scientific Co., Ltd.

[0172] Sample size: 2 mg.

[0173] Absorbent solution: 2.7 mM sodium carbonate + 0.3 mM sodium bicarbonate aqueous solution.

[0174] Eluent: 2.7 mM sodium carbonate + 0.3 mM sodium bicarbonate aqueous solution.

[0175] Chromatographic column: ThermoFisher Scientific Co., Ltd. AG-12A / AS-12A.

[0176] Flow rate: 1.5 mL / min.

[0177] Detector: Conductivity (using a suppressor).

[0178] Standard sample: Fluoride ion standard solution (F-1000) made by Fujifilm and Wako Pure Chemical Industries, Ltd. (formerly Wako Pure Chemical Industries, Ltd.).

[0179] If the solvent in the sample does not contain fluorine atoms, the fluorine concentration is determined while the sample is still containing the solvent, and the fluorine concentration is calculated by converting the concentration of the solid component to the fluorine concentration of the solute. If the solvent in the sample contains fluorine atoms, a halogen moisture meter is used to evaporate the solvent in the sample at 120°C for 20 minutes. The fluorine concentration is then determined using a sample whose mass change is considered constant and whose solvent has completely evaporated.

[0180] In addition, abbreviations have the following meanings.

[0181] Multifunctional acrylate PA1: Dipentaerythritol pentaacrylate / hexaacrylate mixture [ARONIX (registered trademark) M-403 manufactured by Toa Synthetic Co., Ltd.].

[0182] Polyfunctional acrylate PA2: Oxyethylidene modified polyfunctional acrylate [NewFrontier (registered trademark) MF-001 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.].

[0183] Polyfunctional acrylate PA3: Polyfunctional urethane acrylate [ART RESIN (registered trademark) UN-3320HS manufactured by Nekami Kogyo Co., Ltd.].

[0184] Multifunctional acrylate PA4: Pentaerythritol triacrylate / Pentaerythritol tetraacrylate [Nippon Kayaku Co., Ltd. PET30].

[0185] PFPE1: A perfluoropolyether with two hydroxyl groups at each end, without poly(oxyalkylene) groups, having the following structure [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers, based on...] 19 F-NMR and 1 The number-average molecular weight calculated from the H-NMR analysis results is 2200.

[0186]

[0187] (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, where r and s independently represent integers greater than 0.)

[0188] PFPE2: A perfluoropolyether with the following structure, having only one hydroxyl group at a single end without being via a poly(oxyalkylene) group [Solvay Specialty Polymers 7324X, based on...]. 19 F-NMR and 1 The number-average molecular weight calculated from the H-NMR analysis results is 1750–1950.

[0189]

[0190] (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, where m and n independently represent integers greater than 0.)

[0191] PFPE3: A perfluoropolyether with the following structure, having only one hydroxyl group at a single end via a poly(oxyethylene) group [Fomblin (registered trademark) 4102X, manufactured by Solvay Specialty Polymers, based on...] 19 F-NMR and 1 The number-average molecular weight calculated from the H-NMR analysis results is 1900.

[0192]

[0193] (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. m and n independently represent integers above 0, and q is the number of oxyethylidene units, representing integers from 2 to 20.)

[0194] PFPE4: A perfluoropolyether with the following structure [FO2 manufactured by Apollo Scientific, molecular weight 978.15] having only one hydroxyl group at a single end without being via a poly(oxyalkylene) group.

[0195]

[0196] PFPE5: A perfluoropolyether with the following structure (1H,1H-perfluoro-3,6,9-trioxadecan-1-ol) [C10GOL, Exfluor Research, molecular weight 548.1] having only one hydroxyl group at a single end without the presence of a poly(oxoalkyl) group.

[0197]

[0198] PFPE6: A perfluoropolyether with a hydroxyl group at each end, without poly(oxyalkylene) groups, having the following structure [Fomblin (registered trademark) D2 manufactured by Solvay Specialty Polymers, based on...] 19 F-NMR and 1 The number-average molecular weight calculated from the H-NMR analysis results is 1550.

[0199]

[0200] (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, where m and n independently represent integers greater than 0.)

[0201] N1: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Showa Denko Co., Ltd. Karenz (registered trademark) BEI].

[0202] N2: 2-Acryloyloxyethyl isocyanate [Showa Denko Co., Ltd. Karenz (registered trademark) AOI].

[0203] SMA6: A perfluoropolyether with active energy-ray polymerizable groups at the ends of molecular chains containing poly(perfluoroalkylene oxide) groups [DAIKIN Kogyo Co., Ltd. OPTOOL (registered trademark) DAC-HP, 20% by mass solution of non-volatile components, weight-average molecular weight based on GPC converted to polystyrene: Mw is 1521, dispersity: Mw / Mn is 1.1 (Mn is number-average molecular weight), fluorine content in the perfluoropolyether compound calculated by combustion ion chromatography is 35% by mass].

[0204] SMA7: A perfluoropolyether with a total of four active energy-emitting polymerizable groups at both ends of a molecular chain containing a poly(perfluoroethylene oxide) group [Solvay Specialty Polymers Fluorolink (registered trademark) AD-1700, 70% by mass solution of non-volatile components, weight-average molecular weight based on GPC converted to polystyrene: Mw is 3973, dispersity: Mw / Mn is 2.1, and the fluorine content in the perfluoropolyether compound is 29% by mass as calculated by combustion ion chromatography].

[0205] DOTDD: Dioctyltin dinedecanoate [NEOSTANN (registered trademark) U-830 manufactured by Nitto Kasei Corporation].

[0206] MEK: Methyl ethyl ketone.

[0207] PGME: Propylene glycol monomethyl ether.

[0208] PGMEA: Propylene glycol monomethyl ether acetate.

[0209] MeOH: Methanol.

[0210] O2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropane-1-one [OMNIRAD (registered trademark) 2959 manufactured by IGMresins].

[0211] AN1: PEDOT-PSS aqueous dispersion [Sigma-Aldrich PEDOT-PSS 3.0% to 4.0% by mass aqueous dispersion, high conductivity grade, product number 655201].

[0212] [Manufacturing Example 1] Manufacturing of SMA1, a component of a surface modifier

[0213] 1.19 g (0.5 mmol) of PFPE1, 0.52 g (2.0 mmol) of N1, 0.017 g of DOTDD (0.01 times the total mass of PFPE1 and N1), and 1.67 g of PGMEA were added to a screw-type tube. The mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA1. The weight-average molecular weight (Mw) of the obtained SMA1, determined by GPC based on polystyrene conversion, was 2494, and the dispersity (Mw / Mn) was 1.0. Furthermore, the fluorine content in SMA1, calculated by combustion ion chromatography, was 42% by mass.

[0214] [Manufacturing Example 2] Manufacturing of SMA2, a component of a surface modifier

[0215] 2.20 g (1.2 mmol) of PFPE2, 0.28 g (1.2 mmol) of N1, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N1), and 0.6 g of MEK were added to a screw-type tube. The mixture was stirred with a stir bar 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, determined by GPC based on polystyrene conversion, was 1710, and the dispersity (Mw / Mn) was 1.0. Furthermore, the fluorine content in SMA2, calculated by combustion ion chromatography, was 63% by mass.

[0216] [Manufacturing Example 3] Manufacturing of SMA3, a component of a surface modifier

[0217] 3.08 g (1.6 mmol) of PFPE3, 0.39 g (1.6 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE3 and N1), and 3.5 g of PGMEA were added to a screw-type tube. The mixture was stirred at room temperature (approximately 23 °C) for 72 hours using a stir bar to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA3. The weight-average molecular weight (Mw) of the obtained SMA3, determined by GPC conversion to polystyrene, was 1908, and the dispersity (Mw / Mn) was 1.0. Furthermore, the fluorine content in SMA3, calculated by combustion ion chromatography, was 47% by mass.

[0218] [Manufacturing Example 4] Manufacturing of SMA4, a component of the surface modifier

[0219] 2.78 g (2.9 mmol) of PFPE4, 0.68 g (2.9 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE4 and N1), and 3.5 g of PGMEA were added to a screw-type tube. The mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA4. The weight-average molecular weight (Mw) of the obtained SMA4, determined by GPC to polystyrene conversion, was 1299, and the dispersity (Mw / Mn) was 1.0. Furthermore, the fluorine content in SMA4, calculated by combustion ion chromatography, was 51% by mass, showing a value similar to the 51% by mass fluorine content calculated theoretically based on the structure of SMA4.

[0220] [Manufacturing Example 5] Manufacturing of SMA5, a component of a surface modifier

[0221] 2.41 g (4.4 mmol) of PFPE5, 1.05 g (4.4 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE5 and N1), and 3.5 g of PGMEA were added to a screw-type tube. The mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA5. The weight-average molecular weight (Mw) of the obtained SMA5, determined by GPC to polystyrene conversion, was 1029, and the dispersity (Mw / Mn) was 1.0. Furthermore, the fluorine content in SMA5, calculated by combustion ion chromatography, was 46% by mass, showing a value similar to the 47% by mass fluorine content calculated theoretically based on the structure of SMA5.

[0222] [Manufacturing Example 6] Manufacturing of SMA8, a surface modifier

[0223] 3.66 g (2.4 mmol) of PFPE6, 0.67 g (4.8 mmol) of N2, 0.054 g of DOTDD (0.01 times the total mass of PFPE6 and N2), and 4.4 g of PGMEA were added to a screw-type tube. The mixture was stirred at room temperature (approximately 23 °C) for 72 hours using a stir bar to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA8. The weight-average molecular weight (Mw) of the obtained SMA8, determined by GPC based on polystyrene conversion, was 1609, and the dispersity (Mw / Mn) was 1.0. Furthermore, the fluorine content in SMA8, calculated by combustion ion chromatography, was 54% by mass.

[0224] [Examples 1 to 9, Comparative Examples 1 to 13]

[0225] The components listed in Table 1 are mixed to prepare a curable composition with the solid component concentrations listed in Table 1. Here, solid components refer to components other than solvents. Furthermore, in Table 1, [parts] represents [parts by mass], and [%] represents [% by mass]. It should be noted that the polyfunctional acrylates and surface modifiers in Table 1 represent solid components.

[0226] [Table 1]

[0227]

[0228] These curable compositions were applied to an A4-sized PET film [Toray Lumirror U403 (also known as U40), 100 μm thick] with a primer layer formed on both sides after easy-bonding treatment using a rod coater, resulting in a coating film. The coating film was then dried in an oven at 60°C for 8 minutes to remove the solvent. The resulting film was then exposed to nitrogen atmosphere at an exposure dose of 300 mJ / cm². 2 The UV light is used to expose the film, thereby creating a hard coating with a hard coating layer (cured film).

[0229] [Examples 10 to 11, Comparative Examples 14 to 15]

[0230] The components listed in Table 2 are mixed to prepare a curable composition with the solid component concentrations listed in Table 2. Here, solid components refer to components other than solvents. Furthermore, in Table 2, [parts] indicates [parts by mass], and [%] indicates [% by mass]. It should be noted that the polyfunctional acrylates and surface modifiers in Table 2 represent solid components.

[0231] [Table 2]

[0232]

[0233] These curable compositions were applied to an A4-sized PET film [Toray Lumirror U403 (also known as U40), 100 μm thick] with a primer layer formed on both sides after easy-bonding treatment using a rod coater, resulting in a coating film. The coating film was then dried in an oven at 65°C for 3 minutes to remove the solvent. The resulting film was then exposed to a nitrogen atmosphere at an exposure dose of 300 mJ / cm². 2 The UV light is used to expose the film, thereby creating a hard coating with a hard coating layer (cured film).

[0234] The homogeneity of each curing composition, as well as the scratch resistance, water repellency, abrasion resistance, slip properties, and haze of the resulting hard coatings, were evaluated. The evaluation steps are shown below. The results are presented in Tables 3 and 4.

[0235] [Composition homogeneity]

[0236] The appearance of each prepared curable composition was visually confirmed and evaluated according to the following criteria.

[0237] A: Transparent solutions (without suspended matter, precipitate, or phase separation).

[0238] C: Any of the following: suspended matter, precipitate, or phase separation.

[0239] [Abrasion Resistance]

[0240] The surface of the hard coating obtained was rubbed 5000 times with steel wool [BONSTAR (registered trademark) #0000 (ultra-fine)] mounted on a reciprocating abrasion tester with a load of 1 kg and a stroke of 50 mm. The extent of scratches in the area excluding the 5 mm width at both ends of the 50 mm stroke was then visually assessed. Furthermore, scratches on the hard coating surface were confirmed using a microscope (KEYENCE Co., Ltd.), and evaluated according to the following criteria A, B, and C. It should be noted that, assuming actual use as a hard coating, a minimum requirement of B and an aspiration of A are expected.

[0241] A: No damage (0 damages).

[0242] B: Scratches are produced (1 to 4 scratches with a length of 1mm to 9mm).

[0243] C: There are 5 or more scars with a length of 1mm to 9mm, or 1 or more scars with a length of 1cm or more.

[0244] Water repellency

[0245] 1 μL of water was applied to the hard coating surface, and the contact angle θ was measured five times after 5 seconds. The average value was evaluated according to the following criteria. It should be noted that this assumes actual use as a hard coating, with an expected value of A. It should also be noted that if the contact angle is measured immediately after water application, the value is high and unstable; therefore, in this measurement, the contact angle was measured 5 seconds after water application.

[0246] A: θ > 105°.

[0247] B: 100°≤θ≤105°.

[0248] C: θ < 100°.

[0249] [Abrasion Resistance]

[0250] The hard-coated surface was rubbed 2500 times with a 1kg load using a cylindrical eraser [Minoan Rubberstick, φ6.0mm] mounted on a reciprocating abrasion tester. 1μL of water was applied to the rubbed area, and the contact angle θ at five points was measured after 5 seconds. The average of these measurements was taken as the contact angle value, and the surface was evaluated according to the following criteria. It should be noted that, assuming practical use as a hard coating, a minimum value of B is required, with an ideal value of A.

[0251] A: θ≥90°.

[0252] B: 85°≤θ<90°.

[0253] C: 85° < θ.

[0254] [Slippery]

[0255] The coefficient of kinetic friction was measured at five points on the hard-coated surface, and the average value was used for evaluation. It should be noted that the smaller the coefficient of kinetic friction value, the less friction occurs with the probe, serving as a standard for sliding performance. A smaller coefficient of kinetic friction value indicates better sliding performance during contact; therefore, a smaller coefficient of kinetic friction value is preferred.

[0256] [Haze]

[0257] As a reference value, the haze at three locations on the hard coating surface was measured, and the average value was calculated. It should be noted that the PET film used as the substrate [Toray Corporation Lumirror U403 (also known as U40), 100μm thick] has a haze of 1.6.

[0258] [Table 3]

[0259]

[0260] [Table 4]

[0261]

[0262] As shown in Table 1, the curable compositions of Examples 1 to 8 comprise polyfunctional acrylates PA1 to PA4 and the following: a perfluoropolyether SMA1 with active energy-ray polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass; further comprising: an isocyanate compound N1 having the aforementioned active energy-ray polymerizable groups reacted with a perfluoropolyether compound PFPE2 or PFPE3 having a number-average molecular weight of 1750 to 1950 and a hydroxyl group at only one end of a molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in an SMA2 with a weight-average molecular weight of 1710 or an SMA3 with a weight-average molecular weight of 1908. Furthermore, as shown in Table 3, the curable compositions of Examples 1 to 8 exhibit excellent homogeneity, and the hard coating film having the hard coating obtained from the curable compositions exhibits excellent slip properties, scratch resistance, water repellency, and abrasion resistance.

[0263] As shown in Table 1, the curable composition of Example 9 comprises a polyfunctional acrylate PA1, a perfluoropolyether SMA6 having an active energy-ray polymerizable group at the end of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 1521, and a fluorine atom content of 35% by mass, and further comprises an isocyanate compound N1 having the aforementioned active energy-ray polymerizable group, and a perfluoropolyether compound PFPE2 having a number-average molecular weight of 1750 to 1950 with a hydroxyl group at only one end of a molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in an SMA2 with a weight-average molecular weight of 1710. Furthermore, as shown in Table 3, the curable composition of Example 9 exhibits excellent homogeneity, and the hard coating film having the hard coating obtained from this curable composition exhibits excellent slip properties, water repellency, and abrasion resistance. Regarding the hard coating film having the hard coating obtained by the curable composition of Example 9, its scratch resistance is slightly worse than that of the hard coating film having the hard coating obtained by the curable compositions of Examples 1 to 8, but the other items shown in Table 2 show excellent performance levels.

[0264] On the other hand, as shown in Table 1, the curable composition of Comparative Example 1 comprises a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having active energy-ray polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass. It further comprises an isocyanate compound N1 having the aforementioned active energy-ray polymerizable groups, reacted with a perfluoropolyether compound PFPE4 having a molecular weight of 978.15 and a hydroxyl group at only one end of a molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in an SMA4 with a weight-average molecular weight of 1299 and a fluorine atom content of 51% by mass. Furthermore, as shown in Table 3, although the curable composition of Comparative Example 1 exhibits excellent homogeneity, the hard coating film having the hard coating obtained from this curable composition shows poorer sliding properties and scratch resistance compared to the hard coating films obtained from the curable compositions of Examples 1 to 9. The results show that even when using perfluoropolyethers with a high proportion of fluorine atoms and active energy-ray polymerizable groups only at the single end of the molecular chain containing (perfluoroalkylene oxide) groups, the sliding and scratch resistance are poor, indicating that the weight-average molecular weight of the perfluoropolyether is important for sliding and scratch resistance.

[0265] Furthermore, as shown in Table 1, the curable composition of Comparative Example 2 comprises a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having active energy-ray polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass. It further comprises an isocyanate compound N1 having the aforementioned active energy-ray polymerizable groups, and a perfluoropolyether compound PFPE5 having a molecular weight of 548.10 and a hydroxyl group at only one end of a molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in an SMA5 with a weight-average molecular weight of 1029 and a fluorine atom content of 47% by mass. Moreover, as shown in Table 3, although the curable composition of Comparative Example 2 exhibits excellent homogeneity, the hard coating film having the hard coating obtained from this curable composition exhibits poor slip resistance, scratch resistance, and abrasion resistance. The results also show that even when using perfluoropolyethers with a high proportion of fluorine atoms and active energy-ray polymerizable groups only at the single end of the molecular chain containing (perfluoroalkylene oxide) groups, the sliding properties, scratch resistance, and abrasion resistance are not necessarily excellent. This indicates that the weight-average molecular weight of the perfluoropolyether is important for sliding properties, scratch resistance, and abrasion resistance.

[0266] Furthermore, as shown in Table 1, the curable compositions of Comparative Examples 3 to 4 comprise a polyfunctional acrylate PA1 and the following substance: SMA4 or SMA5 with a weight average molecular weight of 1299 obtained by reacting an isocyanate compound N1 having the aforementioned active energy-ray polymerizable group with a perfluoropolyether compound PFPE4 having a molecular weight of 978.15 or a perfluoropolyether compound PFPE5 having a molecular weight of 548.10 having only one hydroxyl group at the single end of the molecular chain containing a poly(perfluoroalkylene oxide) group; and further comprising the following substance: SMA2 with a weight average molecular weight of 1710 obtained by reacting an isocyanate compound N1 having the aforementioned active energy-ray polymerizable group with a perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 having only one hydroxyl group at the single end of the molecular chain containing a poly(perfluoroalkylene oxide) group. Furthermore, as shown in Table 3, the curable compositions of Comparative Examples 3 to 4 exhibited poor homogeneity, and the hard coating films obtained from these curable compositions showed poor sliding properties, scratch resistance, and abrasion resistance. This is believed to be because SMA4 and SMA5 have low weight-average molecular weights, thus failing to disrupt the aggregated structure of SMA2 and hindering its solubility in the coating solution. Therefore, it is considered that SMA2 aggregates in the coating solution, and SMA2 cannot sufficiently segregate on the surface of the hard coating, resulting in poor sliding properties, scratch resistance, and abrasion resistance.

[0267] Furthermore, as shown in Table 1, the curable composition of Comparative Example 5 comprises a polyfunctional acrylate PA1 and a perfluoropolyether SMA7 having active energy-ray polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 3973, and a fluorine atom content of 29% by mass. It further comprises an isocyanate compound N1 having the aforementioned active energy-ray polymerizable groups, and a perfluoropolyether compound PFPE2 having a number-average molecular weight of 1750 to 1950 with a hydroxyl group only at one end of a molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in an SMA2 with a weight-average molecular weight of 1710. Also, as shown in Table 3, although the curable composition of Comparative Example 5 exhibits excellent homogeneity and excellent sliding properties, the hard coating film having the hard coating obtained from this curable composition shows poor scratch resistance and abrasion resistance. Based on this result, good sliding properties are not necessarily related to good scratch resistance and abrasion resistance. The hard coating film with the hard coating obtained from the curable composition of Comparative Example 5 exhibits poor scratch resistance and abrasion resistance compared to the hard coating films with the hard coatings obtained from the curable compositions of Examples 1 to 9. This is believed to be because the weight-average molecular weight of SMA7 is higher than that of SMA1 and SMA6, resulting in lower immobilization ability in the film. Furthermore, it is believed that the proportion of fluorine atoms in SMA7 is lower than that in SMA1 and SMA6, leading to poor compatibility between SMA2 and SMA7, and a phase-separated state between SMA2 and SMA7 on the hard coating surface.

[0268] Furthermore, as shown in Table 1, the curable composition of Comparative Example 6 comprises a polyfunctional acrylate PA1 and an isocyanate compound N1 having the aforementioned active energy-ray polymerizable group, and a perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 with a molecular weight of 1710 obtained by reacting a perfluoropolyether compound N1 having a number average molecular weight of 1750 to 1950 with a hydroxyl group only at the single end of a molecular chain containing a poly(perfluoroalkylene oxide) group. Moreover, as shown in Table 3, the curable composition of Comparative Example 6 exhibits poor homogeneity compared to the curable composition of Example 1, which is obtained by adding SMA1 to the curable composition of Comparative Example 6. Furthermore, the hard coating film having the hard coating obtained from the curable composition of Comparative Example 6 shows poorer sliding properties, scratch resistance, water repellency, and abrasion resistance compared to the hard coating film having the hard coating obtained from the curable composition of Example 1. This is believed to be because it does not contain perfluoropolyethers that act as solubilizing aids for SMA2, but instead have active energy-emitting polymerizable groups at the ends of molecular chains containing poly(perfluoroethylene oxide) groups, and have a weight-average molecular weight of 1400 to 3500, thus causing SMA2 to condense in the coating solution.

[0269] Furthermore, as shown in Table 1, the curable composition of Comparative Example 7 contains a polyfunctional acrylate PA1 and an isocyanate compound N1 having the aforementioned active energy-ray polymerizable group, and a perfluoropolyether compound PFPE3 having a number-average molecular weight of 1900 with a molecular weight of 1900 having only one hydroxyl group at a single end of the molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in SMA3 with a weight-average molecular weight of 1908. Also, as shown in Table 3, although the curable composition of Comparative Example 7 exhibits excellent homogeneity, the hard coating film having the hard coating layer obtained from this curable composition shows poor scratch resistance and water repellency compared to the hard coating films having the hard coating layers obtained from the curable compositions of Examples 2 to 4, which were formed by adding SMA1 to the curable composition of Comparative Example 7. This is believed to be because, since SMA3 is used alone, its strong cohesiveness makes it easy to aggregate inside the film, preventing sufficient segregation of SMA3 on the surface of the hard coating. In addition, SMA3 has an active energy-ray polymerizable group only at a single end, resulting in low immobilization ability in the film.

[0270] Furthermore, as shown in Table 1, the curable composition of Comparative Example 8 contains a polyfunctional acrylate PA1 and an isocyanate compound N1 having the aforementioned active energy-ray polymerizable groups, and a perfluoropolyether compound PFPE4 with a molecular weight of 978.15 having a hydroxyl group at only one end of the molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in SMA4 with a weight-average molecular weight of 1299. Also, as shown in Table 3, compared to the curable composition of Comparative Example 1, which was obtained by adding SMA1 to the curable composition of Comparative Example 8, the homogeneity was poor, and the hard coating film with the hard coating obtained from the curable composition of Comparative Example 8 showed poor sliding properties, scratch resistance, and abrasion resistance. This is believed to be because SMA4 aggregates inside the film, preventing sufficient segregation of SMA4 on the surface of the hard coating. In addition, the molecular chains of SMA4 containing poly(perfluoroalkylene oxide) groups are short.

[0271] Furthermore, as shown in Table 1, the curable composition of Comparative Example 9 comprises a polyfunctional acrylate PA1 and an isocyanate compound N1 having the aforementioned active energy-ray polymerizable group, and a perfluoropolyether compound PFPE5 with a molecular weight of 548.1 having a hydroxyl group at only one end of the molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in SMA5 with a weight average molecular weight of 1029. Moreover, as shown in Table 3, although the curable composition of Comparative Example 9 exhibits excellent homogeneity, the hard coating film having the hard coating obtained from this curable composition has a short molecular chain containing a poly(perfluoroalkylene oxide) group, thus showing poor sliding properties, water repellency, scratch resistance, and abrasion resistance.

[0272] Furthermore, as shown in Table 1, the curable composition of Comparative Example 10 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 with active energy-ray polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass. Also, as shown in Table 3, although the curable composition of Comparative Example 10 exhibits excellent homogeneity and the hard coating film with the hard coating obtained from this curable composition demonstrates excellent water repellency, scratch resistance, and abrasion resistance, compared to the hard coating film with the hard coating obtained from the curable composition of Example 1, which is formed by adding SMA2 to the curable composition of Comparative Example 10, it exhibits poor sliding properties because it does not contain SMA2. This is believed to be because SMA1 has eight acryloyl groups in one molecule, thus exhibiting high immobilization ability in the film, resulting in excellent scratch resistance and abrasion resistance. However, on the other hand, due to its high immobilization ability, SMA1 has low molecular mobility and poor sliding properties.

[0273] When judging based on the evaluation results of the hard coatings obtained from the curable compositions of Comparative Example 5 and Comparative Example 10 as shown in Table 3, it is revealed that there is a trade-off between slip properties and scratch resistance.

[0274] Furthermore, as shown in Table 1, the curable composition of Comparative Example 12 contains a polyfunctional acrylate PA1 and a perfluoropolyether SMA7 with active energy-emitting polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 3973, and a fluorine atom content of 29% by mass. Also, as shown in Table 3, although the curable composition of Comparative Example 12 exhibits excellent homogeneity, the hard coating film having the hard coating layer obtained from this curable composition shows poor sliding properties compared to the hard coating film having the hard coating layer obtained from the curable composition of Comparative Example 5 (which is formed by adding SMA2 to the curable composition of Comparative Example 12), since it does not contain SMA2. Based on these results, it is suggested that a hard coating film obtained by using a curable composition containing a perfluoropolyether with active energy-ray polymerizable groups only at one end of the molecular chain containing a poly(perfluoroethylene oxide) group as a surface modifier exhibits superior sliding properties compared to a hard coating film obtained by using a curable composition containing a perfluoropolyether with active energy-ray polymerizable groups only at both ends of the molecular chain containing a poly(perfluoroethylene oxide) group as a surface modifier.

[0275] Furthermore, as shown in Table 1, the curable composition of Comparative Example 13 comprises a polyfunctional acrylate PA1 and a perfluoropolyether SMA1 having active energy-ray polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass. It further comprises an isocyanate compound N1 having the aforementioned active energy-ray polymerizable groups and a perfluoropolyether compound PFPE6 having a number-average molecular weight of 1550 and a hydroxyl group at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in an SMA8 having a weight-average molecular weight of 1609 and a fluorine atom content of 54% by mass. Furthermore, as shown in Table 3, although the curable composition of Comparative Example 13 exhibits excellent homogeneity, and the hard coating film having the hard coating obtained from this curable composition has excellent water repellency and scratch resistance, it shows poorer sliding properties and wear resistance compared to the hard coating films having the hard coatings obtained from the curable compositions of Examples 1 to 9. Based on these results, it is shown that the hard coating film obtained from a curable composition containing a perfluoropolyether having an active energy-ray polymerizable group at only one end of the molecular chain containing a poly(perfluoroethylene oxide) group as a surface modifier has superior sliding properties compared to the hard coating film obtained from a curable composition containing a perfluoropolyether having an active energy-ray polymerizable group at both ends of the molecular chain containing a poly(perfluoroethylene oxide) group as a surface modifier.

[0276] As shown in Table 2, the curable compositions of Examples 10 and 11 comprise polyfunctional acrylates PA1 or PA2 and the following: a perfluoropolyether SMA1 with active energy-emitting polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass; further comprising: an isocyanate compound N1 having the aforementioned active energy-emitting polymerizable groups reacted with a perfluoropolyether compound PFPE3 having a number-average molecular weight of 1900 and a hydroxyl group at only one end of a molecular chain containing a poly(perfluoroalkylene oxide) group, resulting in an SMA3 with a weight-average molecular weight of 1908; and comprising an anti-static agent AN1. Furthermore, as shown in Table 4, the curable compositions of Examples 10 and 11 exhibit excellent homogeneity, and the hard coating film having the hard coating obtained from the curable compositions exhibits excellent slip properties, scratch resistance, water repellency, and abrasion resistance.

[0277] 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 with active energy-emitting polymerizable groups at both ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, a weight-average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further contains an anti-static agent AN1. Furthermore, as shown in Table 4, although the curable composition of Comparative Example 14 exhibits excellent homogeneity and the hard coating film with the hard coating obtained from this curable composition shows excellent water repellency, scratch resistance, and abrasion resistance, compared to the hard coating film with the hard coating obtained from the curable composition of Example 10, which is formed by adding SMA3 to the curable composition of Comparative Example 14, it exhibits poor sliding properties because it does not contain SMA3. This is believed to be because SMA1 has eight acryloyl groups in one molecule, thus exhibiting high immobilization ability in the film, resulting in excellent scratch resistance and abrasion resistance, but on the other hand, it has low molecular mobility and poor sliding properties.

[0278] Furthermore, as shown in Table 2, the curable composition of Comparative Example 15 contains a polyfunctional acrylate PA1 and an isocyanate compound N1 having the aforementioned active energy-ray polymerizable group, and a perfluoropolyether compound PFPE3 having a number-average molecular weight of 1900 with a molecular weight of 1900 having only one hydroxyl group at a single end of the molecular chain containing a poly(perfluoroalkylene oxide) group, and further contains an anti-static agent AN1. Also, as shown in Table 4, although the curable composition of Comparative Example 15 exhibits excellent homogeneity, the hard coating film having the hard coating obtained from this curable composition shows excellent sliding properties compared to the hard coating film having the hard coating obtained from the curable composition of Example 10, which is formed by adding SMA1 to the curable composition of Comparative Example 15, but on the other hand, it shows poor scratch resistance. This is believed to be because the immobilization ability in the film is lower due to the use of SMA3 alone, which has an active energy-ray polymerizable group at only a single end.

Claims

1. A curable composition comprising: (a) An active energy-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) A perfluoropolyether having active energy-emitting polymerizable groups at the ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, and having a weight-average molecular weight of 1400 to 3500, wherein, Except for (c) perfluoropolyethers mentioned below; (c) A perfluoropolyether having the active energy-ray polymerizable group only at one end of a molecular chain containing a poly(perfluoroalkylene oxide) group, and having a trifluoromethoxy group at one end opposite to the single end having the active energy-ray polymerizable group, and having a weight-average molecular weight of 1550 to 3500; and (d) Polymerization initiators that utilize active energy rays to generate free radicals. The (b) perfluoropolyether is a compound represented by the following formula [4]. The (c) perfluoropolyether is a compound represented by the following formula [2]. In 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 independently represent integers greater than or equal to 0, q is the number of oxyethylidenes, representing integers from 0 to 20, and A represents a terminal group having the active energy-ray polymerizable group, wherein the terminal group A is the group shown in the following formula [A2]. In formula [4], 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 independently represent integers greater than 0. In the case of repeating units on both sides, these repeating units are bonded together by block bonding, random bonding, or a combination of block bonding and random bonding. A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group shown in formula [A2] below. In the formula [A2], R 2 * indicates a hydrogen atom or a methyl group, and * indicates a carbamate bond with the compound represented by formula [2] or the compound represented by formula [4].

2. A curable composition comprising: (a) 100 parts by mass of an active energy-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) 0.05 to 3 parts by weight of a perfluoropolyether having active energy-emitting polymerizable groups at the ends of molecular chains containing poly(perfluoroalkylene oxide) groups, and having a weight-average molecular weight of 1400 to 3500, wherein, Except for (c) perfluoropolyethers mentioned below; (c) 0.05 to 3 parts by weight of a perfluoropolyether having the active energy-ray polymerizable group only at one end of a molecular chain containing a poly(perfluoroalkylene oxide) group, and having a trifluoromethoxy group at one end opposite to the single end having the active energy-ray polymerizable group, and having a weight-average molecular weight of 1550 to 3500; and (d) 0.5 to 20 parts by mass of a polymerization initiator that generates free radicals using active energy rays. The (b) perfluoropolyether is a compound represented by the following formula [4]. The (c) perfluoropolyether is a compound represented by the following formula [2]. In 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 independently represent integers greater than or equal to 0, q is the number of oxyethylidenes, representing integers from 0 to 20, and A represents a terminal group having the active energy-ray polymerizable group, wherein the terminal group A is the group shown in the following formula [A2]. In formula [4], 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 independently represent integers greater than 0. In the case of repeating units on both sides, these repeating units are bonded together by block bonding, random bonding, or a combination of block bonding and random bonding. A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group shown in formula [A2] below. In the formula [A2], R 2 * indicates a hydrogen atom or a methyl group, and * indicates a carbamate bond with the compound represented by formula [2] or the compound represented by formula [4].

3. A curable composition comprising: (a) 100 parts by mass of an active energy-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) 0.05 to 3 parts by weight of a perfluoropolyether having active energy-emitting polymerizable groups at the ends of molecular chains containing poly(perfluoroalkylene oxide) groups, and having a weight-average molecular weight of 1400 to 3500, wherein, Except for (c) perfluoropolyethers mentioned below; (c) 0.05 to 3 parts by mass of the perfluoropolyether as the product of the reaction of the following raw material perfluoropolyether with the following compound, wherein the raw material perfluoropolyether has a hydroxyl group only at a single end of a molecular chain containing a poly(perfluoroalkylene oxide) group, and a trifluoromethoxy group at a single end opposite to the single end having the hydroxyl group, and has a number average molecular weight of 1200 to 3000, wherein the compound has a functional group that reacts with the hydroxyl group and the active energy-ray polymerizable group; as well as (d) 0.5 to 20 parts by mass of a polymerization initiator that generates free radicals using active energy rays. The (b) perfluoropolyether is a compound represented by the following formula [4]. The (c) perfluoropolyether is a compound represented by the following formula [2]. In 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 independently represent integers greater than or equal to 0, q is the number of oxyethylidenes, representing integers from 0 to 20, and A represents a terminal group having the active energy-ray polymerizable group, wherein the terminal group A is the group shown in the following formula [A2]. In formula [4], 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 independently represent integers greater than 0. In the case of repeating units on both sides, these repeating units are bonded together by block bonding, random bonding, or a combination of block bonding and random bonding. A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group shown in formula [A2] below. In the formula [A2], R 2 * indicates a hydrogen atom or a methyl group, and * indicates a carbamate bond with the compound represented by formula [2] or the compound represented by formula [4].

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

5. The curable composition according to any one of claims 1 to 3, wherein, In the above formula [2], m and n independently represent integers greater than 1.

6. The curable composition according to any one of claims 1 to 3, wherein, In the above formula [4], r and s independently represent integers greater than 1.

7. The curable composition according to any one of claims 1 to 3, wherein, The curable composition further comprises (e) a solvent.

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

9. A hard coating film having a hard coating layer on at least one side of a film substrate, the hard coating layer being composed of the cured film as described in claim 8.

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

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

12. A method for manufacturing a hard coating film, comprising: The process of coating a film onto a film substrate with the curable composition as described in any one of claims 1 to 7; as well as The process of irradiating the coating with active energy rays to cure it and form a hard coating.

13. A method for manufacturing a hard coating film, comprising: The process of coating a film onto a film substrate with the curable composition as described in claim 7; The process of removing the solvent from the coating by heating; as well as The process of irradiating the coating with active energy rays to cure it and form a hard coating.

14. The method for manufacturing a hard coating film according to claim 12 or 13, wherein, The method for manufacturing the hard coating film further includes a step of forming a lower layer of hard coating 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 coating.

15. A surface modifier comprising: A perfluoropolyether (A) having active energy-emitting polymerizable groups at the ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, and having a weight-average molecular weight of 1400 to 3500, wherein... Except for the perfluoropolyether (B) described later; as well as The perfluoropolyether (B) has the active energy-ray polymerizable group only at one end of the molecular chain containing the poly(perfluoroalkylene oxide) group, and has a trifluoromethoxy group at one end opposite to the single end having the active energy-ray polymerizable group, and has a weight-average molecular weight of 1550 to 3500. The perfluoropolyether (A) is a compound represented by the following formula [4]. The perfluoropolyether (B) is a compound represented by the following formula [2]. In 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 independently represent integers greater than or equal to 0, q is the number of oxyethylidenes, representing integers from 0 to 20, and A represents a terminal group having the active energy-ray polymerizable group, wherein the terminal group A is the group shown in the following formula [A2]. In formula [4], 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 independently represent integers greater than 0. In the case of repeating units on both sides, these repeating units are bonded together by block bonding, random bonding, or a combination of block bonding and random bonding. A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group shown in formula [A2] below. In the formula [A2], R 2 * indicates a hydrogen atom or a methyl group, and * indicates a carbamate bond with the compound represented by formula [2] or the compound represented by formula [4].

16. A surface modifier comprising: A perfluoropolyether (A) having active energy-emitting polymerizable groups at the ends of a molecular chain containing a poly(perfluoroalkylene oxide) group, and having a weight-average molecular weight of 1400 to 3500, wherein... Except for the perfluoropolyether (B) described later; and Perfluoropolyether (B) is a reaction product of a perfluoropolyether as a raw material and a compound as described below, wherein the raw material perfluoropolyether has a hydroxyl group only at a single end of a molecular chain containing a poly(perfluoroalkylene oxide) group, and a trifluoromethoxy group at a single end opposite to the single end containing the hydroxyl group, and has a number average molecular weight of 1200 to 3000; the compound has a functional group that reacts with the hydroxyl group and the active energy-emitting polymerizable group. The perfluoropolyether (A) is a compound represented by the following formula [4]. The perfluoropolyether (B) is a compound represented by the following formula [2]. In 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 independently represent integers greater than or equal to 0, q is the number of oxyethylidenes, representing integers from 0 to 20, and A represents a terminal group having the active energy-ray polymerizable group, wherein the terminal group A is the group shown in the following formula [A2]. In formula [4], 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 independently represent integers greater than 0. In the case of repeating units on both sides, these repeating units are bonded together by block bonding, random bonding, or a combination of block bonding and random bonding. A represents the terminal group having the active energy ray polymerizable group, and the terminal group A is the group shown in formula [A2] below. In the formula [A2], R 2 * indicates a hydrogen atom or a methyl group, and * indicates a carbamate bond with the compound represented by formula [2] or the compound represented by formula [4].

17. The surface modifier according to claim 15 or 16, wherein, The perfluoropolyether (B) contains fluorine atoms in a proportion of 35% to 65% by mass.

18. The surface modifier according to claim 15 or 16, wherein, In Equation [2], m and n independently represent integers greater than or equal to 1, and in Equation [4], r and s independently represent integers greater than or equal to 1.

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