Cured product of a hard coat composition

Abstract

The present invention provides a hard coat forming material having both excellent durability such as scratch resistance and abrasion resistance and excellent sliding properties. The solution is a curable composition comprising: (a) a reactive energy ray-curable multifunctional monomer; (b) a perfluoropolyether having a reactive energy ray-polymerizable group at the end of a molecular chain comprising a poly(oxyperfluoroalkylene) group (wherein the perfluoropolyether of (c) below is excluded); (c) a perfluoropolyether having a molecular weight of 1000 or more and a group represented by Formula [1], Formula [2] or Formula [3] described below at the end of a molecular chain comprising a poly(oxyperfluoroalkylene) group; and (d) a polymerization initiator that generates radicals by 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, free of suspended matter and sediment. Background Technology

[0002] In recent years, touch panels have been increasingly adopted in various fields, including portable information terminal devices such as mobile phones and tablet computers, notebook computers, home appliances, and automotive interior and exterior parts. The use of touch panels on display elements such as LCDs and OLEDs for operation by touch with fingers or pens has become more common. Assuming finger operation, the touch panel surface requires water and oil repellency to facilitate fingerprint removal, and further, abrasion resistance to maintain water and oil repellency even after repeated finger rubbing. Furthermore, from the tactile perspective of fingers or pens, smoothness is required when operating the touch panel surface. Additionally, scratch resistance is required to prevent damage to the touch panel surface. To impart these properties to the touch panel surface, surface coatings, such as hard coatings, are applied.

[0003] Fluorinated compounds are used as forming materials for hard coatings due to their high sliding and water / oil repellency properties, for example, by adding a small amount of fluorine-based surface modifiers to the coating solution used to form the hard coating. It is known that fluorine-based surface modifiers segregate onto the surface of the hard coating due to the low surface energy of fluorine atoms.

[0004] Generally, to impart scratch resistance and abrasion resistance to hard coatings, a method is employed that increases 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. Fluorine-based surface modifiers added to the coating liquid for forming the hard coating are also generally materials with active energy ray polymerizable groups (Patent Document 1) in order to impart scratch resistance and abrasion resistance to the hard coating.

[0005] 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 a fluorine-based surface modifier with crosslinking groups is used, for example, the molecular chains containing fluorine atoms become immobilized, reducing the slip properties of the hard coating. In other words, durability properties such as scratch resistance and abrasion resistance are trade-offs with slip properties, making it difficult to achieve high levels of both. As a method to improve this trade-off, one approach is to introduce crosslinking groups at a single end of the molecular chain, such as a molecular chain containing fluorine atoms, but this does not provide a satisfactory level of properties.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2016 / 163479

[0009] Patent Document 2: Japanese Patent No. 6497449 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] In this invention, the objective is to provide a curable composition capable of forming a hard coating that combines high performance levels with durable properties and slip properties in a complementary relationship. In addition, for practical applications, the hard coating also needs to possess high liquid-repellent properties.

[0012] Methods for solving problems

[0013] The first aspect of the present invention is a curable composition comprising: (a) 100 parts by mass of an active energy ray curable polyfunctional monomer; (b) 0.05 to 5 parts by mass of a perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly(oxy-perfluoroalkylene) group (except for (c) perfluoropolyether described later); (c) 0.05 to 5 parts by mass of a perfluoropolyether having a molecular weight of 1000 or more having a group represented by the following formula [1], [2] or [3] at the end of a molecular chain containing a poly(oxy-perfluoroalkylene) group; and (d) 1 to 20 parts by mass of a polymerization initiator that generates free radicals by active energy rays.

[0014]

[0015] (In the above equations [1], [2] and [3], R 1 Indicates trifluoromethyl, fluoro, trifluoromethoxy, or nitro, in R 1 In the case of trifluoromethyl, trifluoromethoxy, or nitro groups, m represents an integer from 1 to 5, and in R 1 In the case of fluorine groups, m represents an integer from 2 to 5, and R 2Indicates methyl or methoxy, n represents 1, 2 or 3, R 3 The asterisk (*) indicates an alkyl group having 3 to 10 carbon atoms, and the asterisk (*) indicates a bond to the molecular chain of the perfluoropolyether described in (c) above, which contains a poly(oxy-perfluoroalkylene) group.

[0016] The above-mentioned (c) perfluoropolyether, for example, has groups shown in formula [1], formula [2] or formula [3] at each end of the molecular chain containing the poly(oxyperfluoroalkylene) group.

[0017] The above-mentioned (c) perfluoropolyether, for example, has a group shown in formula [1], formula [2] or formula [3] at a single end of the molecular chain containing the poly(oxyperfluoroalkylene) group.

[0018] The perfluoropolyethers described above (c) do not, for example, have the aforementioned active energy-ray polymerizable groups.

[0019] The poly(oxy-perfluoroalkylene) group of the perfluoropolyether described above (b) and the poly(oxy-perfluoroalkylene) group of the perfluoropolyether described above (c) have, for example, repeating units -[CF2O]- and / or repeating units -[CF2CF2O]-. In the case of having repeating units of both, these repeating units are groups formed by combining these repeating units by block bonding, random bonding, or block bonding and random bonding.

[0020] The molecular chains of the perfluoropolyethers described above (b) containing poly(oxy-perfluoroalkylene) groups and the molecular chains of the perfluoropolyethers described above (c) containing poly(oxy-perfluoroalkylene) groups have, for example, the structures shown in the following formulas [4] or [5].

[0021]

[0022] (In the above formulas [4] and [5], p is the total number of repeating units -[CF2CF2O]- and repeating units -[CF2O]- and represents an integer from 3 to 30. The repeating units -[CF2CF2O]- and repeating units -[CF2O]- are combined by block bonding, random bonding, or block bonding and random bonding. q is the number of oxyethylidene and represents an integer from 0 to 10.)

[0023] The ratio of the content of perfluoropolyether in (b) above to the content of perfluoropolyether in (c) above is, for example, 0.5 to 4.

[0024] The curable composition of the first aspect of the present invention may further include (e) a solvent.

[0025] The second aspect of the present invention is a cured film obtained from the curable composition of the first aspect of the present invention.

[0026] The third aspect of the present invention is a hard coating film, which has a hard coating layer on at least one side of a film substrate, the hard coating layer being composed of the cured film of the second aspect of the present invention.

[0027] The aforementioned hard coating is formed, for example, by a method comprising the steps of: applying the curable composition of the first aspect of the present invention onto a film substrate to form a coating film; and irradiating the coating film with active energy rays for curing.

[0028] The aforementioned hard coating is formed, for example, by a method comprising the steps of: applying the curable composition of the first aspect of the present invention onto a film substrate to form a coating film; removing the solvent from the coating film by heating; and curing the coating film by irradiating it with active energy rays.

[0029] The aforementioned film substrate is composed of multiple layers, for example, a lower layer of the aforementioned hard coating on the surface of the resin film.

[0030] The aforementioned hard coating has, for example, a film thickness of 1 μm to 20 μm.

[0031] The fourth aspect of the present invention is a method for manufacturing a laminate of a membrane substrate and a hard coating, comprising the steps of: applying the curable composition of the first aspect of the present invention onto the membrane substrate to form a coating film; and irradiating the coating film with active energy rays for curing.

[0032] The aforementioned film substrate is composed of multiple layers, for example, a lower layer of the aforementioned hard coating on the surface of the resin film.

[0033] The fifth aspect of the present invention is a perfluoropolyether compound having groups represented by formula [1], formula [2] or formula [3] at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group.

[0034] The molecular chains containing poly(oxy-perfluoroalkylene) groups have, for example, the structures shown in formula [4] or formula [5].

[0035] The aforementioned perfluoropolyether compounds, for example, have groups represented by formula [1], formula [2] or formula [3] at each end of the molecular chain containing the poly(oxyperfluoroalkylene) group.

[0036] The aforementioned perfluoropolyether compounds, for example, have groups represented by formula [1], formula [2] or formula [3] at a single end of the molecular chain containing a poly(oxyperfluoroalkylene) group.

[0037] The aforementioned perfluoropolyether compounds, for example, do not have active energy-emitting polymerizable groups.

[0038] The sixth aspect of the present invention is a surface modifier comprising the perfluoropolyether compound of the fifth aspect of the present invention, and a perfluoropolyether compound having the above-described active energy-ray polymerizable groups at the ends of a molecular chain containing a poly(oxy-perfluoroalkylene) group having the structure shown in the above formula [4] or formula [5].

[0039] The effects of the invention

[0040] According to the present invention, a curing composition useful for forming cured films and hard coatings that possess both excellent scratch resistance / abrasion resistance and excellent lubricity, even for films with a thickness of 1 μm to 20 μm. Furthermore, according to the present invention, a hard coating film having a cured film obtained from the above-described curing composition or a hard coating film composed of such a cured film can be provided, and a hard coating film with excellent durability properties such as scratch resistance and abrasion resistance, as well as excellent lubricity, can be provided in a trade-off. Further according to the present invention, a curing composition useful for forming cured films and hard coatings that, in addition to possessing both of the above-described properties, also impart high liquid repellency, and a hard coating film possessing these excellent properties can be provided. Detailed Implementation

[0041] <Curing Composition>

[0042] The components of the curable composition of the present invention will be described below.

[0043] [(a) Active energy radiation-cured multifunctional monomer]

[0044] The so-called active energy ray-curable polyfunctional monomer (hereinafter also simply referred to as "(a) polyfunctional monomer") of component (a) refers to a monomer having two or more active energy ray polymerizable groups that are cured by polymerization reaction through irradiation with active energy rays such as ultraviolet light. Examples of such active energy ray polymerizable groups include, for example, (meth)acryloyl and vinyl groups.

[0045] In the curable compositions of the present invention, preferred (a) polyfunctional monomers include monomers selected from polyfunctional (meth)acrylate compounds, as well as monomers selected from polyfunctional urethane (meth)acrylate compounds described later, and monomers selected from lactone-modified polyfunctional (meth)acrylate compounds. In the present invention, as (a) polyfunctional monomers, one or more from the group consisting of the aforementioned polyfunctional (meth)acrylate compounds may be used alone or in combination. It should be noted that in the present invention, the term "(meth)acrylate compound" includes both acrylate compounds and methacrylate compounds; for example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

[0046] Furthermore, (a) the multifunctional monomer can be an olefin-modified multifunctional monomer. Examples of such olefin modification include oxymethylene modification, ethylene oxide modification, and propylene oxide modification. Examples of such olefin-modified multifunctional monomers include compounds in which the olefin has been modified in the aforementioned multifunctional (meth)acrylate or multifunctional urethane (meth)acrylate compounds are examples. The aforementioned olefin-modified multifunctional monomers can be used alone or in combination of two or more.

[0047] Furthermore, in this invention, as (a) the multifunctional monomer, a multifunctional monomer having at least three, for example, at least four active energy-ray polymerizable groups can be used. In this invention, as (a) the multifunctional monomer, a monomer selected from olefin-modified multifunctional (meth)acrylate compounds having at least three active energy-ray polymerizable groups can be used.

[0048] Examples of the aforementioned polyfunctional (meth)acrylate compounds (however, compounds without carbamate bonds) include, for example, trimethylolpropane tri(meth)acrylate, bis(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-Octadiol 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, Di(2-hydroxyethyl)isocyanurate di(meth)acrylate, Tri(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, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are preferred polyfunctional (meth)acrylate compounds.

[0049] Examples of the above-mentioned olefin-modified polyfunctional (meth)acrylate compounds include, for example, (meth)acrylate compounds of polyols modified with olefins. Examples of the above-mentioned polyols include, for example, glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, decaglycerol, polyglycerol, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, and dipentaerythritol.

[0050] The aforementioned polyfunctional urethane (meth)acrylate compounds are compounds having multiple acryloyl or methacryloyl groups within one molecule and having one or more urethane bonds [-NHC(=O)O-]. Examples of such polyfunctional urethane (meth)acrylate compounds include, for example, 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.

[0051] It should be noted that examples of the aforementioned polyfunctional isocyanates include, for example, toluene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, and 1,6-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. Further examples of the aforementioned polyols include, for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and other diols; polyester polyols as products of the reaction of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, and adipic acid; polyether polyols; and polycarbonate diols.

[0052] (a) The multifunctional monomer may also be a lactone-modified multifunctional (meth)acrylate compound, with ε-caprolactone being the preferred lactone for modification. Examples of the above-mentioned lactone-modified multifunctional (meth)acrylate compounds include, for example, 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.

[0053] [(b) Perfluoropolyethers with active energy-emitting polymerizable groups at the ends of molecular chains containing poly(oxy-perfluoroalkylene) groups]

[0054] Hereinafter, the perfluoropolyether containing an active energy-emitting polymerizable group at the end of the molecular chain containing a poly(oxy-perfluoroalkylene) group, which is component (b), will also be referred to as "(b) perfluoropolyether". (b) perfluoropolyether is any substance other than (c) perfluoropolyether described later. In the curable composition of the present invention, the preferred (b) perfluoropolyether has an active energy-emitting polymerizable group at the end of the molecular chain containing a poly(oxy-perfluoroalkylene) group via a urethane bond. The end of the aforementioned molecular chain containing a poly(oxy-perfluoroalkylene) group can be either all ends or 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 are respectively the two ends and one end of the linear molecular chain. Examples of linking groups between the poly(oxy-perfluoroalkylene) group and the urethane bond include, for example, hydrocarbon groups having ether bonds, wherein at least one hydrogen atom of the hydrocarbon group can be replaced by a fluorine atom.

[0055] (b) The perfluoropolyether, along with component (c) described below, acts as a surface modifier in the hard coating formed by the curable composition of the present invention. Furthermore, due to its excellent compatibility with the polyfunctional monomer (a), the perfluoropolyether (b) can suppress turbidity and form a hard coating with a transparent appearance.

[0056] From the viewpoint of obtaining a cured film with good scratch resistance, the poly(oxyperfluoroalkylene) group described above is preferably a group having both -[CF2O]-(oxyperfluoromethylene) and -[CF2CF2O]-(oxyperfluoroethylene) as repeating units. In this case, the combination of these oxyperfluoroalkyl groups can be either block or random.

[0057] As the molecular chain containing the above-mentioned poly(oxy-perfluoroalkylene) group, it is preferred to have the structure shown in the following formula [4] or formula [5].

[0058]

[0059] In equations [4] and [5] above, p is the total number of repeating units -[CF2CF2O]- and repeating units -[CF2O]-, and represents, for example, an integer from 3 to 30, preferably from 7 to 21. The combination of repeating units -[CF2CF2O]- and repeating units -[CF2O]- can be either block combination or random combination. In equation [5] above, q is the number of oxyethylenes and represents an integer from 0 to 10.

[0060] Examples of active energy-ray polymerizable groups include (meth)acryloyl groups and vinyl groups. (b) Perfluoropolyethers are not limited to substances having one active energy-ray polymerizable group at the end of a molecular chain containing a poly(oxy-perfluoroalkylene) group, but can be substances having two or more active energy-ray polymerizable groups. Examples of end structures containing active energy-ray polymerizable groups include, for example, structures of formulas [A1] to [A5] shown below, and structures in which the acryloyl group is replaced with a methacryloyl group. Among these structures, structures of formulas [A3], [A4] and [A5] having two or more active energy-ray polymerizable groups, and structures in which the acryloyl group is replaced with a methacryloyl group are preferred.

[0061]

[0062] In the curable composition of the present invention, the content of (b) perfluoropolyether is 0.05 to 5 parts by mass relative to 100 parts by mass of the polyfunctional monomer (a), preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 1 part by mass. By having the content of (b) perfluoropolyether at 0.05 parts by mass or more, sufficient scratch resistance can be imparted to the hard coating. Furthermore, by having the content of (b) perfluoropolyether at 5 parts by mass or less, a hard coating that is sufficiently compatible with the polyfunctional monomer (a) and has minimal whitening can be obtained.

[0063] (b) Perfluoropolyethers may be used alone or in combination of two or more. In the case of combination of two or more, a perfluoropolyether may also be included in which a single end (one end) of a molecular chain containing a poly(oxy-perfluoroalkylene) group has an active energy-ray polymerizable group via a urethane bond, and a hydroxyl group is present at the other end (the other end) of the molecular chain.

[0064] [(c) Perfluoropolyethers with a molecular weight of 1000 or more having groups of formula [1], formula [2] or formula [3] at the end of a molecular chain containing a poly(oxy-perfluoroalkylene) group]

[0065] The perfluoropolyether containing poly(oxyperfluoroalkylene) groups at the end of the molecular chain containing the poly(oxyperfluoroalkylene) group, having a molecular weight of 1000 or more, for example 1000 to 4000, is also referred to as "(c) perfluoropolyether". (c) perfluoropolyether differs from (b) perfluoropolyether in that it has groups at the end of the molecular chain containing the poly(oxyperfluoroalkylene) group as shown in formulas [1], [2], or [3], and has a molecular weight of 1000 or more. On the other hand, the definitions of the molecular chain containing the poly(oxyperfluoroalkylene) group and its end in (c) perfluoropolyether are the same as those in (b) perfluoropolyether. Therefore, the molecular chain containing the poly(oxyperfluoroalkylene) group preferably has the structure shown in formula [4] or [5].

[0066]

[0067] R in the above formula [1] 1 Indicates trifluoromethyl, fluoro, trifluoromethoxy, or nitro, in R 1 In the case of trifluoromethyl, trifluoromethoxy, or nitro groups, m represents an integer from 1 to 5, and in R 1 In the case of a fluorine group, m represents an integer from 2 to 5. R in the above formula [2] 2 R represents methyl or methoxy, preferably methyl, and n represents 1, 2 or 3. In the above formula [3], R... 3The alkyl group represents an alkyl group with 3 to 10 carbon atoms, for example, an alkyl group with 3 to 6 carbon atoms. The asterisk (*) in the above formulas [1], [2] and [3] represents a bond with the molecular chain containing the poly(oxyperfluoroalkylene) group.

[0068] (c) Perfluoropolyether, for example, is obtained by reacting a perfluoropolyether having a hydroxyl group at the end of the structure shown in Formula [4] or Formula [5] with an isocyanate compound shown in Formula [1a], Formula [2a] or Formula [3a].

[0069]

[0070] OCN-R 3 [3a]

[0071] R in the above formula [1a] 1 and m, R in the above formula [2a] 2 and n, and R in the above formula [3a] 3 R in equations [1], [2] and [3] respectively 1 R 2 R 3 The definitions of m and n have the same meaning.

[0072] (c) The perfluoropolyether, along with (b) the perfluoropolyether described above, functions as a surface modifier in the hard coating formed by the curable composition of the present invention. Furthermore, due to its excellent compatibility with (b) the perfluoropolyether, (c) the perfluoropolyether can suppress turbidity and form a hard coating with a transparent appearance.

[0073] By having a molecular weight of (c) perfluoropolyether of 1000 or more, (c) perfluoropolyether easily adheres to the surface of the hard coating obtained from the curable composition of the present invention, resulting in a hard coating with excellent sliding properties. Furthermore, by having a molecular weight of (c) perfluoropolyether of, for example, 4000 or less, a hard coating with good compatibility with (a) multifunctional monomers and minimal whitening can be obtained.

[0074] In the curable composition of the present invention, the content of (c) perfluoropolyether is preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the polyfunctional monomer (a) above, and the ratio of the content of (b) perfluoropolyether to the content of (c) perfluoropolyether is 0.5 to 4. By having a content of (c) perfluoropolyether of 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, by having a content of (c) perfluoropolyether of 5 parts by mass or less, a hard coating that is sufficiently compatible with (b) perfluoropolyether and has minimal whitening can be obtained.

[0075] (c) Perfluoropolyethers may be used alone or in combination of two or more. In the case of combination of two or more, it may also include a perfluoropolyether having a group shown in formula [1], formula [2] or formula [3] at one end of a molecular chain containing a poly(oxy-perfluoroalkylene) group, and having an active energy-ray polymerizable group or hydroxyl group at the other end of the molecular chain. It should be noted that (c) perfluoropolyethers are more preferably free from the active energy-ray polymerizable group present in (b) perfluoropolyethers.

[0076] [(d) Polymerization initiator]

[0077] In the curable compositions 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.

[0078] Examples of polymerization initiators (d) include, for example, benzoin derivatives, alkylbenzophenone derivatives, thioxanone derivatives, azo derivatives, azido derivatives, diazo derivatives, o-quinone diazo derivatives, acylphosphine oxides, oxime esters, organic peroxides, benzophenone derivatives, dicumarol derivatives, biimidazole derivatives, dicerotitanium derivatives, thiols, halogenated hydrocarbons, trichloromethyltriazine derivatives, and iodine. Salt, matte salt, etc. Salts. These polymerization initiators can be used alone or in combination of two or more. In this invention, from the viewpoints of transparency, surface curing, and film curing properties, alkyl phenyl ketones are preferred as polymerization initiators (d). By using alkyl phenyl ketones, a cured film with improved scratch resistance can be obtained.

[0079] Examples of the aforementioned alkyl phenyl ketones include, for instance, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropane-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one and other α-hydroxyalkyl phenyl ketones; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one and other α-aminoalkyl phenyl ketones; 2,2-dimethoxy-1,2-diphenylethane-1-one; and methyl benzoylformate.

[0080] In the curable composition of the present invention, the content of (d) polymerization initiator is 1 to 20 parts by mass relative to 100 parts by mass of the above-mentioned (a) multifunctional monomer, preferably 2 to 10 parts by mass.

[0081] [(e) solvent]

[0082] The curable composition of the present invention may contain solvent (e) as an optional component, i.e., it may be in the form of a varnish. As solvent (e), it may be appropriately selected by taking into account the solubility / dispersibility of components (a) to (d) above, the workability of the curable composition during application related to the formation of the cured film (hard coating) described later, and the drying properties before and after curing.

[0083] Examples of solvents used in (e) above include, for instance, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral oil, and cyclohexane; halogenated compounds 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 cellosol acetate, ethyl cellosol acetate, and propylene glycol monomethyl ether acetate (PGMEA); and diethyl ether, tetrahydrofuran (THF), and 1,4-diethylfuran. Ethers such as alkanes, methyl cellosolves, ethyl cellosolves, butyl cellosolves, propylene glycol monomethyl ether, 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, 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 obtained by mixing two or more of these solvents.

[0084] In the curable composition of the present invention, the content of solvent (e) is not particularly limited. For example, the solid content concentration of the curable composition of the present invention is 1% to 70% by mass, preferably 5% to 50% by mass. Here, the solid content concentration (also called the non-volatile component concentration) refers to the content of solid content (the component after removing the solvent component from all components) of the curable composition of the present invention relative to the total mass (total mass) of components (a) to (e) and other additives.

[0085] [Other Additives]

[0086] Furthermore, in the curable composition of the present invention, as long as the effect of the present invention is not impaired, one or more of the commonly added additives, such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, adhesion promoters, plasticizers, ultraviolet absorbers, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc., can be appropriately mixed as needed, either alone or in combination of two or more.

[0087] <Cured film>

[0088] The curable composition of the present invention forms a coating film by coating (applying) it onto a substrate, and then polymerizes (cures) the coating film by irradiating it with active energy rays, thereby forming a cured film, which is also the subject of the present invention. Furthermore, a hard coating layer composed of the aforementioned cured film can be used as the hard coating layer in the hard coating film described later.

[0089] Examples of substrates include various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) and other polyesters, polyurethanes, thermoplastic polyurethanes (TPU), polyolefins, polyamides, polyimides, epoxy resins, melamine resins, triacetyl cellulose (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 3D molded bodies. Furthermore, for example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near-infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather-resistant layer, an anti-reflective layer, an antistatic layer, a discoloration prevention layer, a gas barrier layer, a water vapor blocking layer, a light scattering layer, an electrode layer, etc., can be formed on the surface of the substrate as a lower layer of the hard coating, or multiple such lower layers of the hard coating can be stacked. As a layer formed on the surface of the aforementioned substrate, there are no particular limitations as long as it does not impair the effects of the present invention.

[0090] The coating method applied to the aforementioned substrate can be appropriately selected from casting coating, spin coating, blade coating, dip coating, roller coating, spray coating, bar coating, mold coating, inkjet coating, and printing methods (letterpress printing, gravure printing, offset printing, screen printing, etc.). Among these, roll-to-roll methods can be utilized, and from the viewpoint of film coating properties, letterpress printing, especially gravure printing, is desirable. 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 can be further added to the curable composition as needed. Various solvents listed in [(e) solvents] above can be used as solvents in this case.

[0091] After forming a coating film by applying the curable composition of the present invention onto a substrate, the coating film is pre-dried using a heating means such as a hot plate or oven to remove the solvent (solvent removal process). The preferred heating and drying conditions at this time are, for example, 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. Examples of light sources used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. Further, a post-baking process is performed, specifically by heating using a heating means such as a hot plate or oven, thereby ending the polymerization.

[0092] It should be noted that the thickness of the cured film after drying and curing is typically 0.1 μm to 50 μm, preferably 0.5 μm to 20 μm.

[0093] <Hard Coating>

[0094] 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 suitable for use in protecting the surfaces of various display elements, such as touch panels and liquid crystal displays.

[0095] The hard coating layer in the hard coating film of the present invention can be formed by a method comprising the steps of: applying the curable composition of the present invention onto a film substrate to form a coating film; removing the solvent by heating as needed; and irradiating the coating film with active energy rays such as ultraviolet light to cure the coating film. A method for manufacturing a hard coating film having a hard coating layer on at least one side of a film substrate, comprising these steps, is also the subject of the present invention.

[0096] As the aforementioned film substrate, various transparent resin films suitable for optical applications can be used among the substrates mentioned 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 triacetyl cellulose (TAC).

[0097] As the aforementioned film substrate, multiple layers can be stacked together. For example, layers different from the resin film, such as a primer layer, an ultraviolet absorption layer, an infrared absorption layer, a near-infrared absorption layer, an electromagnetic wave absorption layer, a color correction layer, a refractive index adjustment layer, a weather-resistant layer, an anti-reflective layer, an antistatic layer, a discoloration prevention layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, and an electrode layer, can be stacked on the surface of the resin film as the lower layer of the hard coating. Multiple lower layers 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.

[0098] Furthermore, the coating method (coating film forming step) for applying the curable composition of the present invention to the aforementioned film substrate, and the method for irradiating the coating film with active energy rays (curing step), can use the methods described in the above-mentioned <cured 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) described in the above-mentioned <cured film> section can be used.

[0099] The thickness (film thickness) of the hard coating obtained by this operation is, for example, 1 μm to 20 μm, preferably 1 μm to 10 μm.

[0100] <Surface Modifier>

[0101] Surface modifiers of perfluoropolyether compounds containing groups of formula [1], [2], or [3] at the ends of molecular chains containing poly(oxy-perfluoroalkylene) groups, and perfluoropolyether compounds having active energy-ray polymerizable groups at the ends of molecular chains containing poly(oxy-perfluoroalkylene) groups having structures of formula [4] or [5], are also objects of the present invention. The aforementioned active energy-ray polymerizable groups are those possessed by the perfluoropolyether in (b) above. Preferably, the former perfluoropolyether compound does not possess the aforementioned active energy-ray polymerizable groups. Furthermore, the former perfluoropolyether compound itself is also an object of the present invention.

[0102] Example

[0103] The present invention will be described in more detail below with examples, but the present invention is not limited to the following examples. It should be noted that, in the examples, the apparatus and conditions used for sample preparation and property analysis are as described below.

[0104] (1) Coating using a rod coater

[0105] Device: PM-9050MC manufactured by Esutech Co., Ltd.

[0106] Bar: A-Bar OSP-30, manufactured by Irotech Co., Ltd., maximum wet film thickness: 30 μm

[0107] Coating speed: 4m / min

[0108] (2) Oven

[0109] Equipment: Sanki Co., Ltd. 2-layer cleanroom drying oven (top and bottom type) PO-250-45-D

[0110] (3) UV curing

[0111] Device: CV-110QC-G manufactured by ヘレウス Co., Ltd.

[0112] Lamp: H-bulb electrodeless lamp manufactured by Herus Corporation

[0113] (4) Scratch resistance test and abrasion resistance test

[0114] Apparatus: TriboGear Type: 30S reciprocating wear testing machine manufactured by Shin-Tung Science Co., Ltd.

[0115] Scanning speed: 3200 mm / min

[0116] Scanning distance: 50mm

[0117] (5) Contact angle

[0118] Device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd.

[0119] Measurement temperature: 23℃

[0120] (6) Determination of dynamic friction coefficient μk

[0121] Apparatus: TRIBOGEAR (registered trademark), a load-variable friction and wear testing system manufactured by Shin-Tung Science Co., Ltd. TYPE: HHS2000

[0122] Probe: 0.6mmR sapphire needle

[0123] Load: 200g

[0124] Scanning speed: 2mm / second

[0125] Scanning distance: 10mm

[0126] (7) Total light transmittance, haze

[0127] Device: NDH5000 haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0128] In addition, abbreviations have the following meanings.

[0129] Multifunctional acrylate PA1: Dipentaerythritol pentaacrylate / hexaacrylate mixture [Toa Synthetic Co., Ltd. Alonix (registered trademark) M-403, pentaacrylate ratio 50%~60% (catalog value)]

[0130] Multifunctional acrylate PA2: Ethylene oxide modified multifunctional acrylate [Daiichi Kogyo Pharmaceutical Co., Ltd. New Florian (registered trademark) MF-001]

[0131] Polyfunctional acrylate PA3: Polyfunctional carbamate acrylate [Kenjo Kogyo Co., Ltd. Art Regimen (Registered Trademark) UN-3320HS]

[0132] Multifunctional acrylate PA4: Caprolactone-modified dipentaerythritol hexaacrylate [Nippon Kayaku Co., Ltd. DPCA30]

[0133] PFPE1: A perfluoropolyether containing two hydroxyl groups at each end of a molecular chain comprising a poly(oxyalkylene) group, without the presence of a poly(oxyalkylene) group. [Fomblin (registered trademark), manufactured by Solbeys Co., Ltd., T4. Number-average molecular weight calculated from NMR analysis results: 2200]

[0134] PFPE2: A perfluoropolyether containing two hydroxyl groups at each end of a molecular chain comprising a poly(oxyalkylene) group [Fluorolink (registered trademark) E10H, manufactured by Solbeys Corporation; number-average molecular weight calculated from NMR analysis results: 1818].

[0135] PFPE3: A perfluoropolyether containing a poly(oxyalkylene) group at each end of a molecular chain, each having one hydroxyl group instead of a poly(oxyalkylene) group. [Fomblin (registered trademark), manufactured by Solbeys Corporation. D2, number-average molecular weight calculated from NMR analysis results: 1500]

[0136] PFPE4: A perfluoropolyether (1H,1H-perfluoro-3,6,9-trioxatridecane-1-ol) with one hydroxyl group at a single end without a poly(oxyalkylene) group [Exfluor Research, C10GOL, molecular weight 548.1 (catalog value)].

[0137] N1: 1,1-Bis(acryloyloxymethyl)ethyl isocyanate [Showa Denko Corporation (registered trademark) BEI]

[0138] N2: Propyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0139] N3: Butyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0140] N4: Hexyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0141] N5: 2,4-Difluorophenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0142] N6: 4-(trifluoromethyl)phenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0143] N7: 3-(trifluoromethyl)phenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0144] N8: 3-(trifluoromethoxy)phenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0145] N9: p-Toluenesulfonyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0146] N10: 4-Nitrophenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0147] N11: 4-Fluorophenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0148] N12: Phenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0149] N13: p-Tolyl Isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0150] N14: p-Methoxyphenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0151] N15: 3,5-Dimethylphenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0152] N16: 2,6-Dimethylphenyl isocyanate [Tokyo Chemical Industry Co., Ltd.]

[0153] DOTDD: Dioctyltin dineodecaate [Nitto Kasei Corporation Neostar (Registered Trademark) U-830]

[0154] SMA2: A perfluoropolyether containing a total of four active energy-emitting polymerizable groups at both ends of a molecular chain containing a poly(oxy-perfluoroalkylene) group [Fluorolink (registered trademark) AD-1700, 70% by mass solution of non-volatile components, manufactured by Solbeys Corporation]

[0155] SMA3: A perfluoropolyether with active energy-ray polymerizable groups at the single end of a molecular chain containing a poly(oxy-perfluoroalkylene) group [DAC-HP, 20% by mass solution of non-volatile components]

[0156] O2959: 2-Hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropane-1-one [OMNIRAD (registered trademark) 2959 manufactured by IGM Resins]

[0157] MEK: Methyl Ethyl Ketone

[0158] PGME: Propylene Glycol Monomethyl Ether

[0159] [Manufacturing Example 1] Manufacturing of SMA1, a component of a surface modifier

[0160] 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 MEK were added to a screw-in tube. The mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMA1. The resulting SMA1 corresponds to component (b) of the curable composition of this invention.

[0161] [Example 1] Manufacturing of SMB1, a component of the surface modifier

[0162] 2.22 g (1.5 mmol) of PFPE2, 0.25 g (3.0 mmol) of N2, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N2), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB1. The resulting SMB1 corresponds to component (c) of the curable composition of the present invention.

[0163] [Example 2] Manufacturing of SMB2, a component of the surface modifier

[0164] 2.19 g (1.5 mmol) of PFPE2, 0.29 g (3.0 mmol) of N3, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N3), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB2. The resulting SMB2 corresponds to component (c) of the curable composition of the present invention.

[0165] [Example 3] Manufacturing of SMB3, a component of the surface modifier

[0166] 2.12 g (1.4 mmol) of PFPE2, 0.36 g (2.8 mmol) of N4, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N4), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB3. The resulting SMB3 corresponds to component (c) of the curable composition of the present invention.

[0167] [Example 4] Manufacturing of SMB4, a component of the surface modifier

[0168] 2.05 g (1.4 mmol) of PFPE2, 0.42 g (2.8 mmol) of N5, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N5), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB4. The resulting SMB4 corresponds to component (c) of the curable composition of the present invention.

[0169] [Example 5] Manufacturing of SMB5, ​​a component of the surface modifier

[0170] 1.98 g (1.3 mmol) of PFPE2, 0.49 g (2.6 mmol) of N6, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N6), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB5. The resulting SMB5 corresponds to component (c) of the curable composition of the present invention.

[0171] [Example 6] Manufacturing of SMB6, a component of the surface modifier

[0172] 1.98 g (1.3 mmol) of PFPE2, 0.49 g (2.6 mmol) of N7, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N7), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB6. The resulting SMB6 corresponds to component (c) of the curable composition of the present invention.

[0173] [Example 7] Manufacturing of SMB7, a component of the surface modifier

[0174] 2.34 g (1.6 mmol) of PFPE2, 0.63 g (3.2 mmol) of N8, 0.030 g (0.01 times the total mass of PFPE2 and N8), and 3.0 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB7. The resulting SMB7 corresponds to component (c) of the curable composition of the present invention.

[0175] [Example 8] Manufacturing of SMB8, a component of the surface modifier

[0176] 4.09 g (2.2 mmol) of PFPE2, 1.10 g (4.4 mmol) of N9, 0.052 g of DOTDD (0.01 times the total mass of PFPE2 and N9), and 5.3 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB8. The resulting SMB8 corresponds to component (c) of the curable composition of the present invention.

[0177] [Example 9] Manufacturing of SMB9, a component of the surface modifier

[0178] 2.44 g (1.6 mmol) of PFPE2, 0.53 g (3.2 mmol) of N10, 0.030 g of DOTDD (0.01 times the total mass of PFPE2 and N10), and 3.0 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB9. The resulting SMB9 corresponds to component (c) of the curable composition of the present invention.

[0179] [Example 10] Manufacturing of SMB10, a component of the surface modifier

[0180] 1.87 g (0.8 mmol) of PFPE1, 0.41 g (3.2 mmol) of N6, 0.025 g of DOTDD (0.01 times the total mass of PFPE1 and N6), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB10. The resulting SMB10 corresponds to component (c) of the curable composition of the present invention.

[0181] [Example 11] Manufacturing of SMB11, a component of the surface modifier

[0182] 4.17 g (2.1 mmol) of PFPE3, 1.01 g (4.2 mmol) of N6, 0.052 g of DOTDD (0.01 times the total mass of PFPE3 and N6), and 5.2 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB11. The resulting SMB11 corresponds to component (c) of the curable composition of the present invention.

[0183] [Example 12] Manufacturing of SMB12, a component of the surface modifier

[0184] 4.34 g (2.2 mmol) of PFPE3, 0.86 g (4.4 mmol) of N9, 0.052 g of DOTDD (0.01 times the total mass of PFPE3 and N9), and 5.3 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB12. The resulting SMB12 corresponds to component (c) of the curable composition of the present invention.

[0185] [Example 13] Manufacturing of SMB13, a component of the surface modifier

[0186] 4.11 g (2.7 mmol) of PFPE2, 0.51 g (2.7 mmol) of N6, 0.66 g (2.7 mmol) of N1, 0.053 g of DOTDD (0.01 times the total mass of PFPE2, N6, and N1), and 4.67 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23°C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB13. The resulting SMB13 corresponds to component (c) of the curable composition of the present invention.

[0187] [Example 14] Manufacturing of SMB14, a component of the surface modifier

[0188] 4.85 g (3.4 mmol) of PFPE4, 0.63 g (3.4 mmol) of N6, 0.025 g of DOTDD (0.01 times the total mass of PFPE4 and N6), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB14.

[0189] [Comparative Example 1] Manufacturing of SMB15

[0190] 2.09 g (1.4 mmol) of PFPE2, 0.38 g (2.8 mmol) of N11, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N11), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB15.

[0191] [Comparative Example 2] Manufacturing of SMB16

[0192] 2.14 g (1.4 mmol) of PFPE2, 0.34 g (2.8 mmol) of N12, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N12), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB16.

[0193] [Comparative Example 3] Manufacturing of SMB17

[0194] 2.10 g (1.4 mmol) of PFPE2, 0.37 g (2.8 mmol) of N13, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N13), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB17.

[0195] [Comparative Example 4] Manufacturing of SMB18

[0196] 2.48 g (1.7 mmol) of PFPE2, 0.49 g (3.4 mmol) of N14, 0.030 g of DOTDD (0.01 times the combined mass of PFPE2 and N14), and 3.0 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB18.

[0197] [Comparative Example 5] Manufacturing of SMB19

[0198] 2.07 g (1.4 mmol) of PFPE2, 0.41 g (2.8 mmol) of N15, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N15), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB19.

[0199] [Comparative Example 6] Manufacturing of SMB20

[0200] 2.07 g (1.4 mmol) of PFPE2, 0.41 g (2.8 mmol) of N16, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N16), and 2.5 g of MEK were added to a screw-in tube. The resulting mixture was stirred with a stir bar at room temperature (approximately 23 °C) for 72 hours to obtain a 50% by mass MEK solution of the target perfluoropolyether compound SMB20.

[0201] [Examples 1-14, Comparative Examples 1-6]

[0202] The homogeneity of 50% (w / w) MEK solutions of various perfluoropolyether compounds was evaluated. The evaluation procedures are shown below. The results are presented in Table 1.

[0203] [Homogeneity of the solution]

[0204] The appearance of the 50% by mass MEK solutions of each of the obtained perfluoropolyether compounds was visually confirmed and evaluated according to the following criteria.

[0205] A: Clear solution (no suspended matter or sediment)

[0206] C: Both suspended solids and settled solids are present.

[0207] [Table 1]

[0208] Table 1

[0209]

[0210] As shown in Table 1, the perfluoropolyether compounds SMB1 to SMB14 obtained by reacting at least one of the following isocyanate compounds N2 to N10 with any one of the perfluoropolyethers PFPE1 to PFPE4 (Example 13 further reacted isocyanate compound N1) have relatively weak agglomeration power and therefore high solubility.

[0211]

[0212] On the other hand, as shown in Table 1, the perfluoropolyether compounds SMB15 to SMB20 obtained by reacting any one of the following isocyanate compound groups N11 to N16 with perfluoropolyether PFPE2 resulted in high coagulation power and low solubility.

[0213]

[0214] [Examples 15-38, Comparative Examples 7-15]

[0215] Mix the components listed in Table 2 to prepare a curable composition with the solid component concentrations listed in Table 2. Here, "solid component" refers to components other than the solvent. 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.

[0216] [Table 2]

[0217] Table 2

[0218]

[0219] These curable compositions were coated onto A4-sized PET films [Tore Co., Ltd. Lumira (registered trademark) U403 (alias U40), 100 μm thick] with a primer layer formed on both sides using an easy-bond treatment, to obtain a coating film. The coating film was dried in an oven at 60°C for 8 minutes to remove the solvent. The resulting film was then exposed to a nitrogen atmosphere with an exposure dose of 300 mJ / cm². 2 Expose the material to UV light to create a hard coating film with a hard coating layer (cured film).

[0220] 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 Table 3.

[0221] [Composition homogeneity]

[0222] The appearance of each cured composition was visually confirmed and evaluated according to the following criteria.

[0223] A: Clear solution (no suspended matter, sediment, or phase separation)

[0224] C: Contains any of the following: suspended solids, sediments, and phase separation.

[0225] [Abrasion Resistance]

[0226] 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 degree of damage in the area excluding the 5 mm width at both ends of the 50 mm stroke was then visually assessed 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 required.

[0227] A: No damage (0 damages)

[0228] B: Causes 1 to 4 wounds (1mm to 9mm in length)

[0229] C: Injuries (5 or more wounds with a length of 1mm to 9mm, or 1 or more wounds with a length of 1cm or more)

[0230] Water repellency

[0231] 1 μL of water was applied to the hard coating surface, and the contact angle θ after 10 seconds was measured five times. The average value was evaluated according to the following criteria. It should be noted that, assuming practical use as a hard coating, a minimum requirement of B and an aspiration of A are required.

[0232] A: θ≥105°

[0233] B: 90°≤θ<105°

[0234] C: θ < 90°

[0235] [Abrasion Resistance]

[0236] The hard-coated surface was rubbed 2,500 times with a 1 kg load using a cylindrical eraser [Minoan Rubber Stile, φ6.0 mm] mounted on a reciprocating abrasion tester. 1 μL of water was applied to the rubbed area, and the contact angle θ at 5 points after 5 seconds was measured. The average value was taken as the contact angle value, and the evaluation was performed according to the following criteria. It should be noted that, assuming practical use as a hard coating, a minimum requirement of B and an aspiration of A are required.

[0237] A: θ≥90°

[0238] B: 80°≤θ<90°

[0239] C: 80° < θ

[0240] [Slippery]

[0241] The kinetic friction coefficient μk at five points on the hard-coated surface was measured, and its average value was evaluated according to the following criteria. It should be noted that a smaller kinetic friction coefficient indicates less friction with the probe, serving as a standard for sliding performance. Since a smaller kinetic friction coefficient indicates better sliding performance during contact, a smaller kinetic friction coefficient is preferred.

[0242] A: μk≤0.05

[0243] B: 0.05 < μk ≤ 0.07

[0244] C: μk > 0.07

[0245] [Haze]

[0246] As a reference value, the haze was measured at three locations on the hard coating surface, and its average value was calculated. It should be noted that the PET film used as the substrate [Tore Co., Ltd. Lumira (registered trademark) U403 (alias U40), thickness 100μm] had a haze of 1.6. [Table 3]

[0247] Table 3

[0248]

[0249] As shown in Table 2, the curable compositions of Examples 15 to 36 comprise polyfunctional acrylates PA1 to PA4, perfluoropolyether compounds SMA1 to SMA3, and perfluoropolyether compounds SMB1 to SMB12 obtained by reacting any one of the above-mentioned isocyanate compound groups N2 to N10 with any one of the perfluoropolyethers PFPE1 to PFPE3. Furthermore, as shown in Table 3, the curable compositions of Examples 15 to 36 exhibit excellent homogeneity, and the hard coating film having the hard coating obtained from the curable compositions exhibits excellent sliding properties, scratch resistance, water repellency, and abrasion resistance.

[0250] As shown in Table 2, the curable compositions of Examples 37 and 38 comprise a polyfunctional acrylate PA1, a perfluoropolyether compound SMA1, and a perfluoropolyether compound SMB13 obtained by reacting the aforementioned isocyanate compounds N6 and N1 with a perfluoropolyether PFPE2. Furthermore, as shown in Table 3, the curable compositions of Examples 37 and 38 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.

[0251] On the other hand, as shown in Table 2, the curable compositions of Comparative Examples 7 to 9 contain polyfunctional acrylate PA1 and perfluoropolyether compounds SMA1 to SMA3, but do not contain components (c) such as SMB1 to SMB13 mentioned above. Furthermore, as shown in Table 3, the curable compositions of Comparative Examples 7 to 9 exhibit the same level of homogeneity as the curable compositions of Examples 15 to 38, and the hard coating films having the hard coating obtained from the curable compositions of Comparative Examples 7 to 9 exhibit the same level of scratch resistance and water repellency as the hard coating films having the hard coating obtained from the curable compositions of Examples 15 to 38, but result in poor sliding properties.

[0252] Furthermore, as shown in Table 2, the curable compositions of Comparative Examples 10 and 11 contain polyfunctional acrylate PA1 and perfluoropolyether compounds SMB6 or SMB7 obtained by reacting the above-mentioned isocyanate compounds N7 or N8 with perfluoropolyether PFPE2, and do not contain components (b) such as SMA1 to SMA3. Moreover, as shown in Table 3, the curable compositions of Comparative Examples 10 and 11 exhibit turbidity due to the formation of suspended matter, and have poor homogeneity compared to the curable compositions of Examples 15 to 38. Furthermore, the hard coating films having the hard coating obtained from Comparative Examples 10 and 11 have poorer sliding properties, scratch resistance, water repellency, and abrasion resistance compared to the hard coating films having the hard coating obtained from the curable compositions of Examples 15 to 38.

[0253] Furthermore, as shown in Table 2, the curable compositions of Comparative Examples 12 to 14 contain polyfunctional acrylate PA1, perfluoropolyether compound SMA1, and perfluoropolyethers PFPE1 to PFPE3. Moreover, as shown in Table 3, the curable compositions of Comparative Examples 12 to 14 exhibited turbidity and phase separation due to the low solubility of the aforementioned perfluoropolyethers PFPE1 to PFPE3, resulting in poor homogeneity compared to the curable compositions of Examples 15 to 38.

[0254] Furthermore, as shown in Table 2, the curable composition of Comparative Example 15 contains a polyfunctional acrylate PA1, a perfluoropolyether compound SMA1, and a perfluoropolyether compound SMB14 obtained by reacting the above-mentioned isocyanate compound N6 with a perfluoropolyether PFPE4 with a molecular weight of 548.1. Furthermore, as shown in Table 3, the curable composition of Comparative Example 15 exhibits the same level of homogeneity as the curable compositions of Examples 15 to 38, and the hard coating film having the hard coating obtained from the curable composition of Comparative Example 15 exhibits the same level of scratch resistance, water repellency, and abrasion resistance as the hard coating film having the hard coating obtained from the curable compositions of Examples 15 to 38, but results in poor sliding properties. The perfluoropolyether compound SMB14 has a molecular weight of less than 1000, which is low compared to other perfluoropolyether compounds SMB1 to SMB13. Therefore, it can be considered that the high mobility of the SMB14 molecules makes it difficult to remain on the surface of the hard coating, resulting in poor sliding properties.

Claims

1. A curable composition comprising: (a) 100 parts by mass of active energy ray-cured multifunctional monomer; (b) 0.05 to 5 parts by mass of a perfluoropolyether having an active energy-ray polymerizable group at the end of a molecular chain containing a poly(oxy-perfluoroalkylene) group, excluding the perfluoropolyether described below (c); (c) 0.05 to 5 parts by mass of a perfluoropolyether with a molecular weight of 1000 or more, having at each end of a molecular chain containing a poly(oxy-perfluoroalkylene) group and a group represented by formula [1], [2] or [3] respectively; and (d) 1 to 20 parts by mass of a polymerization initiator that generates free radicals via active energy rays. In equations [1], [2] and [3], R 1 Indicates trifluoromethyl, fluoro, trifluoromethoxy, or nitro, in R 1 In the case of trifluoromethyl, trifluoromethoxy, or nitro groups, m represents an integer from 1 to 5, and in R 1 In the case of fluorine groups, m represents an integer from 2 to 5, and R 2 Indicates methyl or methoxy, n represents 1, 2 or 3, R 3 Indicates alkyl groups having 3 to 10 carbon atoms. The term refers to the bonding bond with the molecular chain containing the poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether.

2. The curable composition according to claim 1, wherein the (c) perfluoropolyether does not have the active energy-ray polymerizable group.

3. The curable composition according to claim 1, wherein the poly(oxy-perfluoroalkylene) group of the perfluoropolyether (b) and the poly(oxy-perfluoroalkylene) group of the perfluoropolyether (c) have repeating units - [CF2O]- and / or repeating units - [CF2CF2O]-, and in the case of having both repeating units, the repeating units are groups formed by combining these repeating units by block bonding, random bonding, or block bonding and random bonding.

4. The curable composition according to claim 3, wherein the molecular chain of the (b) perfluoropolyether containing poly(oxy-perfluoroalkylene) groups and the molecular chain of the (c) perfluoropolyether containing poly(oxy-perfluoroalkylene) groups have the structure shown in formula [4] or formula [5]. In equations [4] and [5], p is the total number of repeating units - [CF2CF2O]- and repeating units - [CF2O]- and represents an integer from 3 to 30. The repeating units - [CF2CF2O]- are combined with each other by block bonding, random bonding, or block bonding and random bonding. q is the number of oxyethylidene and represents an integer from 0 to 10.

5. The curable composition according to any one of claims 1 to 4, wherein the content of (b) perfluoropolyether is in the ratio of the content of (c) perfluoropolyether to 0.5 to 4.

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

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

8. 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 of claim 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 formed by a method comprising the steps of: applying a curable composition according to any one of claims 1 to 6 onto a film substrate to form a coating film; and irradiating the coating film with active energy rays for curing.

10. A hard coating film having a hard coating layer on at least one side of a film substrate, the hard coating layer being formed by a method comprising the steps of: applying the curable composition of claim 6 onto a film substrate to form a coating film; removing the solvent from the coating film by heating; and curing the coating film by irradiating it with active energy rays.

11. The hard coating film according to any one of claims 8 to 10, wherein the film substrate is composed of a plurality of layers.

12. The hard coating film according to any one of claims 8 to 10, wherein the film substrate has a lower layer of the hard coating film on the surface of the resin film.

13. The hard coating film according to any one of claims 8 to 10, wherein the hard coating film has a film thickness of 1 μm to 20 μm.

14. A method for manufacturing a laminate of a membrane substrate and a hard coating, comprising the steps of: applying a curable composition according to any one of claims 1 to 6 onto a membrane substrate to form a coating film; and irradiating the coating film with active energy rays for curing.

15. The method for manufacturing a laminate according to claim 14, wherein the film substrate is composed of multiple layers.

16. The method for manufacturing a laminate according to claim 14 or 15, wherein the film substrate has a lower layer of the hard coating on the surface of the resin film.

17. A perfluoropolyether compound with a molecular weight of 1000 or more, wherein each end of a molecular chain containing a poly(oxyperfluoroalkylene) group has a group represented by formula [1] or formula [2]. In equations [1] and [2], R 1 Indicates trifluoromethyl, fluoro, trifluoromethoxy, or nitro, in R 1 In the case of trifluoromethyl, trifluoromethoxy, or nitro groups, m represents an integer from 1 to 5, and in R 1 In the case of fluorine groups, m represents an integer from 2 to 5, and R 2 Indicates methyl or methoxy, n represents 1, 2 or 3. This indicates the bond with the molecular chain containing the poly(oxyperfluoroalkylene) group.

18. The perfluoropolyether compound according to claim 17, wherein the molecular chain comprising the poly(oxyperfluoroalkylene) group has the structure shown in formula [4] or formula [5]. In equations [4] and [5], p is the total number of repeating units - [CF2CF2O]- and repeating units - [CF2O]- and represents an integer from 3 to 30. The repeating units - [CF2CF2O]- are combined with each other by block bonding, random bonding, or block bonding and random bonding. q is the number of oxyethylidene and represents an integer from 0 to 10.

19. The perfluoropolyether compound according to claim 17 or 18, wherein the perfluoropolyether compound does not have an active energy-ray polymerizable group.

20. A surface modifier comprising: a perfluoropolyether compound with a molecular weight of 1000 or more having groups of formula [1], [2] or [3] at each end of a molecular chain containing a poly(oxy-perfluoroalkylene) group; and a perfluoropolyether compound having active energy-ray polymerizable groups at the ends of a molecular chain containing a poly(oxy-perfluoroalkylene) group having a structure of formula [4] or [5]. In equations [1], [2] and [3], R 1 Indicates trifluoromethyl, fluoro, trifluoromethoxy, or nitro, in R 1 In the case of trifluoromethyl, trifluoromethoxy, or nitro groups, m represents an integer from 1 to 5, and in R 1 In the case of fluorine groups, m represents an integer from 2 to 5, and R 2 Indicates methyl or methoxy, n represents 1, 2 or 3, R 3 Indicates alkyl groups having 3 to 10 carbon atoms. This indicates the bond with the molecular chain containing the poly(oxyperfluoroalkylene) group. In equations [4] and [5], p is the total number of repeating units - [CF2CF2O]- and repeating units - [CF2O]- and represents an integer from 3 to 30. The repeating units - [CF2CF2O]- are combined with each other by block bonding, random bonding, or block bonding and random bonding. q is the number of oxyethylidene and represents an integer from 0 to 10.

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