TWI791603B - Curable composition for extensible and scratch-resistant coating - Google Patents

Abstract

The present invention provides a material for forming a hard coating layer having elongation, excellent scratch resistance, and a transparent appearance. The present invention relates to a hard coating film comprising (a) 100 parts by mass of an active energy ray-curable lactone denatured polyfunctional monomer, (b) a molecule containing a poly(oxyperfluoroalkylene) group Perfluoropolyether having an active energy ray polymerizable group at both ends of the chain via a urethane bond (except for the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond A curable composition consisting of 0.1 to 10 parts by mass of (c) 1 to 20 parts by mass of a polymerization initiator that generates free radicals by active energy rays (except perfluoropolyether having a poly(oxyalkylene) group) and the hard coating film of the hard coating layer formed by the composition.

Description

Curable composition for coating with extensibility and scratch resistance

The present invention relates to a curable composition useful as a material for forming a hard coat layer on the surface of various display elements such as touch panel displays and liquid crystal displays. Specifically, it is a curable composition that has elongation and excellent scratch resistance, and can form a hard coating layer with a transparent appearance.

A large number of resin molded products are used in portable information terminals such as mobile phones and tablet computers, notebook computers, home appliances, and automotive interior and exterior parts. In order to improve the designability of these resin molded products, decoration is usually given to the surface by printing or the like after molding the resin. In recent years, as a decoration method for the three-dimensional surface of the above-mentioned resin molded product, a hard coating layer is used on one side of the film, and a decorative film with a printing layer or an adhesive layer on the other side is used, and these decorative films are adhered through Layers, methods of laminating to resin molded products are being examined.

As the required characteristics of the above-mentioned decorative film, the first formability is necessary. In other words, even if stretched, cracks and the like cannot be generated on the hard coat layer, and stretchability that can follow the three-dimensional surface is required. Second, its scratch resistance is necessary. The hard coat layer of the above-mentioned decorative film is located on the outermost surface in a state of being bonded to the resin molded product, and plays a role of protecting the surface.

Generally, when imparting scratch resistance to a hard coating layer, for example, by forming a highly cross-linked structure, that is, forming a cross-linked structure with low molecular mobility, the method of increasing the surface hardness and imparting resistance to external force is adopted. As these hard coat layer forming materials, polyfunctional acrylate-based materials that undergo three-dimensional crosslinking by radicals are most widely used at present. However, multifunctional acrylate materials have no extensibility at all due to their high crosslink density. On the other hand, for imparting extensibility to the hard coat layer, for example, a polyfunctional acrylate oligomer or a polyfunctional urethane acrylate oligomer having a molecular weight of about 1,000 to 10,000 with an adjusted acrylate group density is used. Oligomer method. These polyfunctional acrylate oligomers have crosslinking sites and extension sites in their molecular structures, and can exhibit moderate extensibility through the molecular mobility of the extension sites. However, the crosslinking density will decrease and its scratch resistance will be poor. In this way, the elongation and scratch resistance of the hard coat layer have a trade-off relationship, and it has been a problem since the past to have both characteristics.

However, for a portable information terminal represented by a mobile phone, a person can grasp it with a palm and perform touch operation with fingers. Therefore, there is a problem that fingerprints are attached to the outer casing when it is held by hand, and the appearance is impaired. Fingerprints contain moisture from sweat and oil from sebum, and in order to prevent these from adhering, it is strongly desired to impart water and oil repellency to the hard coating layer on the surface of the case. From such a point of view, antifouling properties such as fingerprints are expected to be provided on the casing surface of the portable information terminal. However, even if the initial antifouling performance can reach a fairly high level, since people have to touch it every day, the function is often reduced during use. Therefore, the durability of the antifouling property during use becomes a problem.

Conventionally, as a method of imparting antifouling properties to the surface of a hard coat layer, a method of adding a small amount of a fluorine-based surface modifier to a coating solution for forming a hard coat layer has been used. The fluorine-based compound to be added is to impart water repellency and oil repellency by segregating the low surface energy on the surface of the hard coat layer. As the fluorine-based compound, an oligomer having a number average molecular weight of about 1,000 to 5,000 called a perfluoropolyether having a poly(oxyperfluoroalkylene) chain is used from the viewpoint of water repellency and oil repellency. . However, because perfluoropolyether has a better fluorine concentration, it is generally difficult to dissolve in the organic solvent used in the coating solution for forming the hard coating layer. Moreover, the aggregation phenomenon also arises with respect to the formed hard coat layer. In such a perfluoropolyether, in order to impart solubility in an organic solvent and impart dispersibility to a hard coat layer, a method of adding an organic moiety to the perfluoropolyether is used. Furthermore, in order to impart scratch resistance, a method of bonding active energy ray hardening sites represented by (meth)acrylate groups is used. Hitherto, as an antifouling hard coating layer having scratch resistance, a component that imparts antifouling properties to the surface of the hard coating layer has been disclosed on both ends of a poly(oxyperfluoroalkylene) chain, which will have A technique in which a poly(oxyalkylene) group and a (meth)acryl group compound having a urethane bond interposed therebetween are used as a surface modifying agent (Patent Document 1). [Prior Art Literature] [Patent Document]

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

[Problem solved by the invention]

However, for the purpose of imparting scratch resistance to the hard coat layer exhibiting elongation, even if the surface modifying agent of Patent Document 1 is added to a polyfunctional acrylate oligomer, etc., because these oligomers have high molecular weight and hydrophobic The compatibility is deteriorated, and the hard coating layer of the hardened product has the problem of becoming cloudy. [means to solve the problem]

The present inventors, in order to achieve the above-mentioned purpose, repeated detailed examinations and found that on both ends of the molecular chain containing poly(oxyperfluoroalkylene) groups, there is no poly(oxyalkylene) group interposed therebetween. , and through the urethane bond, the perfluoropolyether having the active energy ray polymerizable group has solubility in the coating solution for forming the hard coating layer containing the lactone-modified polyfunctional monomer and is suitable for hard coating Excellent dispersibility in the layer, and the curable composition containing the perfluoropolyether and the lactone-denatured polyfunctional monomer has elongation and excellent scratch resistance, and can form a hard coating layer showing a transparent appearance to complete the present invention. invention.

(式中，n為重複單位-[OCF₂ CF₂ ]-的數與重複單位 -[OCF₂ ]-的數之總數，其為5～30的整數) 作為第6觀點，前述(a)多官能單體係關於含有選自由內酯變性多官能(甲基)丙烯酸酯化合物及內酯變性多官能胺基甲酸酯(甲基)丙烯酸酯化合物所成群的至少1個之第1觀點至第5觀點中任一項所記載的硬化性組成物。 作為第7觀點，前述(a)多官能單體為ε-己內酯變性多官能單體，其係關於第1觀點至第6觀點中任一項所記載的硬化性組成物。 作為第8觀點，其係關於進一步含有(d)溶劑之第1觀點至第7觀點中任一項所記載的硬化性組成物。 作為第9觀點，其係關於藉由第1觀點至第8觀點中任一項所記載的硬化性組成物所得之硬化膜。 作為第10觀點，其為於薄膜基材的至少一面上具備硬質塗布層的硬質塗布薄膜，其係關於該硬質塗布層由第9觀點所記載的硬化膜所成的硬質塗布薄膜。 作為第11觀點，其為於薄膜基材的至少一面上具備硬質塗布層的硬質塗布薄膜，其係關於該硬質塗布層為藉由含有將第1觀點至第8觀點中任一項所記載的硬化性組成物塗布於薄膜基材上並形成塗膜的步驟，與於該塗膜照射活性能量線使其硬化的步驟之方法所形成的硬質塗布薄膜。 作為第12觀點，其關於前述硬質塗布層具有1～10μm的膜厚之第10觀點或第11觀點所記載的硬質塗布薄膜。 作為第13觀點，其係關於在含有聚(氧基全氟伸烷基)基的分子鏈之各兩末端上，隔著胺基甲酸酯鍵，具有至少3個活性能量線聚合性基之全氟聚醚化合物(但，除去於前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間具有聚(氧化伸烷基)基的全氟聚醚化合物以外)。 作為第14觀點，其係關於前述聚(氧基全氟伸烷基)基具有作為重複單位的-[OCF₂ ]-及-[OCF₂ CF₂ ]-的第13觀點所記載的全氟聚醚化合物。 作為第15觀點，其係關於具有式[1]所示部分結構的第14觀點所記載的全氟聚醚化合物。

(式中，n為重複單位-[OCF₂ CF₂ ]-的數與重複單位 -[OCF₂ ]-的數之總數，其表示5～30的整數)。 作為第16觀點，其係關於由第13觀點至第15觀點中任一項所記載的全氟聚醚化合物所成的表面改質劑。 作為第17觀點，其係關於使用第13觀點至第15觀點中任一項所記載的全氟聚醚化合物在表面改質上的用途。 [發明之效果]That is, the first aspect of the present invention relates to a curable composition comprising (a) 100 parts by mass of an active energy ray-curable lactone-denatured polyfunctional monomer, (b) poly(oxyperfluoroalkylene) A perfluoropolyether (except for the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned amine) having an active energy ray polymerizable group at both ends of the molecular chain of the urethane bond 0.1-10 parts by mass other than perfluoropolyether having poly(oxyalkylene) groups between urethane bonds, and (c) 1-20 parts by mass of a polymerization initiator that generates free radicals by active energy rays share. As a second viewpoint, the aforementioned (b) perfluoropolyether is a curable composition described in the first viewpoint having at least two active energy ray polymerizable groups at both ends. As a third viewpoint, the aforementioned (b) perfluoropolyether is a curable composition described in the second viewpoint having at least three active energy ray polymerizable groups at both ends. As a fourth viewpoint, the aforementioned poly(oxyperfluoroalkylene) group is any one of the first viewpoint to the third viewpoint that has -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as repeating units. A hardening composition of record. As a fifth viewpoint, the aforementioned (b) perfluoropolyether is the curable composition described in the fourth viewpoint having a partial structure represented by the formula [1].

(In the formula, n is the sum of the number of repeating units -[OCF ₂ CF ₂ ]- and the number of repeating units -[OCF ₂ ]-, which is an integer of 5 to 30.) As a sixth aspect, the aforementioned (a) is more The functional monosystem contains at least one member selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds and lactone-modified polyfunctional urethane (meth)acrylate compounds from the first point of view to The curable composition described in any one of the fifth viewpoints. As a seventh viewpoint, the (a) polyfunctional monomer is an ε-caprolactone-modified polyfunctional monomer, which is the curable composition described in any one of the first viewpoint to the sixth viewpoint. As an eighth viewpoint, it is the curable composition described in any one of the first viewpoint to the seventh viewpoint that further contains (d) a solvent. As a ninth viewpoint, it relates to a cured film obtained from the curable composition described in any one of the first viewpoint to the eighth viewpoint. As a tenth viewpoint, it is a hard coat film provided with a hard coat layer on at least one surface of a film base material, and it is a hard coat film which consists of the cured film as described in a ninth viewpoint about this hard coat layer. As an eleventh viewpoint, it is a hard coat film provided with a hard coat layer on at least one surface of a film substrate, and the hard coat layer is obtained by containing any one of the first viewpoint to the eighth viewpoint. A hard coat film formed by a step of applying a curable composition on a film substrate to form a coating film, and a step of irradiating the coating film with active energy rays to harden it. As a 12th viewpoint, it is about the hard-coat film as described in the 10th viewpoint or the 11th viewpoint that the said hard-coat layer has a film thickness of 1-10 micrometers. As a thirteenth viewpoint, it relates to having at least three active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond. Perfluoropolyether compounds (except for perfluoropolyether compounds having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond). As a 14th viewpoint, it is the perfluoropolyethylene described in the 13th viewpoint that the aforementioned poly(oxyperfluoroalkylene) group has -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as repeating units. Ether compounds. As a 15th viewpoint, it relates to the perfluoropolyether compound described in the 14th viewpoint which has a partial structure represented by formula [1].

(In the formula, n is the total number of the repeating unit -[OCF ₂ CF ₂ ]- and the repeating unit -[OCF ₂ ]-, which represents an integer of 5 to 30). As a 16th viewpoint, it relates to the surface modifying agent which consists of the perfluoropolyether compound described in any one of the 13th viewpoint to the 15th viewpoint. As a 17th viewpoint, it relates to the use for surface modification using the perfluoropolyether compound described in any one of the 13th viewpoint to the 15th viewpoint. [Effect of Invention]

According to the present invention, it is possible to provide a curable composition used for forming a cured film and a hard coat layer that has excellent scratch resistance even on a film having a thickness of about 1 to 10 μm, has an excellent appearance, and has elongation. Also, according to the present invention, there can be provided a cured film obtained from the aforementioned curable composition, or a hard coating film provided on the surface of the hard coating layer formed thereby, which has scratch resistance, excellent appearance, and has extensibility hard coating film.

＜Hardening composition＞ The curable composition of the present invention contains the following (a) to (c) in detail. (a) 100 parts by mass of an active energy ray-curable lactone-denatured polyfunctional monomer, (b) Perfluoropolyethers having active energy ray polymerizable groups at both ends of molecular chains containing poly(oxyperfluoroalkylene) groups via urethane bonds (except for the aforementioned poly 0.1 to 10 parts by mass other than perfluoropolyethers having a poly(oxyalkylene) group between the (oxyperfluoroalkylene) group and the aforementioned urethane linkage), and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. First, each component of said (a)-(c) is demonstrated below.

[(a) Active energy ray-curing lactone denatured polyfunctional monomer] The active energy ray-curable lactone-denatured polyfunctional monomer system refers to a lactone-denatured polyfunctional monomer that is polymerized and cured by irradiating active energy rays such as ultraviolet rays. Preferred (a) active energy ray-curing lactone-modified polyfunctional monomers for the curable composition of the present invention are selected from lactone-modified polyfunctional (meth)acrylate compounds and lactone-modified polyfunctional amine groups A monomer in which formate (meth)acrylate compounds are grouped. In addition, the (meth)acrylate compound of this invention means both of an acrylate compound and a methacrylate compound. For example (meth)acrylic acid means acrylic acid and methacrylic acid.

Examples of the above-mentioned lactone-denatured polyfunctional (meth)acrylate compound include denaturation with lactones such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone (that is, the development of lactones). (cycloaddition or ring-opening addition polymerization) polyol or polythiol (meth)acrylate compound. Examples of the polyhydric alcohol include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, glycerin, bisphenol A, ethoxylated trimethylolpropane, ethoxylated pentaerythritol, ethyl Oxylated dipentaerythritol, ethoxylated glycerin, ethoxylated bisphenol A, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol alcohol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, tricyclo[5.2.1.0 ^2,6 ]decanedimethanol, 1, 3-Adamantanediol, 1,3-Adamantanedimethanol, Ethylene Glycol, Diethylene Glycol, Triethylene Glycol, Tetraethylene Glycol, Polyethylene Glycol, Propylene Glycol, Dipropylene Glycol, Polypropylene Glycol, Neopentyl Glycol Diol, dioxane glycol, bis(2-hydroxyethyl)isocyanurate, ginseng(2-hydroxyethyl)isocyanurate, 9,9-bis(4-hydroxyphenyl)fluorene , 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, etc. Moreover, examples of the mercaptan include bis(2-mercaptoethyl)sulfide, bis(4-mercaptophenyl)sulfide, and the like.

Examples of such lactone-denatured polyfunctional (meth)acrylate compounds include lactone-denatured trimethylolpropane tri(meth)acrylate, lactone-denatured ditrimethylolpropane tetra(meth)acrylate Esters, lactone-denatured pentaerythritol di(meth)acrylate, lactone-denatured pentaerythritol tri(meth)acrylate, lactone-denatured pentaerythritol tetra(meth)acrylate, lactone-denatured dipentaerythritol penta(meth)acrylate , Lactone-denatured dipentaerythritol hexa(meth)acrylate, lactone-denatured 2-hydroxy-1,3-bis(meth)acryloxypropane, lactone-denatured 2-hydroxy-1-acryloxy- 3-Methacryloxypropane, lactone-denatured glycerol tri(meth)acrylate, lactone-denatured bisphenol A di(meth)acrylate, lactone-denatured ethoxylated trimethylolpropane tri(meth)acrylate base) acrylates, lactone-denatured ethoxylated pentaerythritol tetra(meth)acrylate, lactone-denatured ethoxylated dipentaerythritol hexa(meth)acrylate, lactone-denatured ethoxylated tri(methyl)glycerol ) acrylate, lactone-denatured ethoxylated bisphenol A di(meth)acrylate, lactone-denatured 1,3-propanediol di(meth)acrylate, lactone-denatured 1,3-butanediol Di(meth)acrylate, lactone-denatured 1,4-butanediol di(meth)acrylate, lactone-denatured 1,6-hexanediol di(meth)acrylate, lactone-denatured 2-methacrylate 1,8-octanediol di(meth)acrylate, lactone-denatured 1,9-nonanediol di(meth)acrylate, lactone-denatured 1,10-decanediol di(meth)acrylate base) acrylate, lactone-denatured tricyclo[5.2.1.0 ^2,6 ]decanedimethanol di(meth)acrylate, lactone-denatured 1,3-adamantanediol di(meth)acrylate, lactone-denatured Ester denatured 1,3-adamantane dimethanol di(meth)acrylate, lactone denatured ethylene glycol di(meth)acrylate, lactone denatured diethylene glycol di(meth)acrylate, lactone denatured Triethylene glycol di(meth)acrylate, lactone-denatured tetraethylene glycol di(meth)acrylate, lactone-denatured polyethylene glycol di(meth)acrylate, lactone-denatured propylene glycol di(meth)acrylate ) acrylate, lactone-denatured dipropylene glycol di(meth)acrylate, lactone-denatured polypropylene glycol di(meth)acrylate, lactone-denatured neopentyl glycol di(meth)acrylate, lactone-denatured dioxin Alkyl glycol di(meth)acrylate, lactone denatured bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, lactone denatured ginseng(2-hydroxyethyl)isocyanurate Ester tri(meth)acrylate, lactone-denatured 9,9-bis(4-(meth)acryloxyphenyl)fluorene, lactone-denatured 9,9-bis[4-(2-(methyl) )acryloxyethoxy)phenyl]fluorene, lactone denatured bis[2-(meth)acrylthioethyl]sulfide, lactone denatured bis[4-(meth)acryl Thienyl] sulfide, etc.

Among them, ε-caprolactone is preferred as the denatured lactone, for example, the compound in which the lactone of the above-mentioned lactone-denatured polyfunctional (meth)acrylate compound is ε-caprolactone is preferred. Examples of preferable lactone-modified polyfunctional (meth)acrylate compounds include ε-caprolactone-denatured pentaerythritol tri(meth)acrylate, ε-caprolactone-denatured pentaerythritol tetra(meth)acrylate, ε-caprolactone-denatured dipentaerythritol penta(meth)acrylate, ε-caprolactone-denatured dipentaerythritol hexa(meth)acrylate, etc.

The above-mentioned lactone-modified polyfunctional urethane (meth)acrylate compound has a plurality of (meth)acryl groups in one molecule, has a urethane bond (-NHCOO-), and has, for example, γ - Compounds with ring-opened structures of lactones such as butyrolactone, δ-valerolactone, and ε-caprolactone. For example, as the above-mentioned lactone-denatured polyfunctional urethane (meth)acrylate, those obtained by the reaction of a polyfunctional isocyanate and a (meth)acrylate having a hydroxyl group denatured with a lactone can be mentioned. The lactone-modified polyfunctional urethane (meth)acrylate that can be used in the present invention is obtained by reacting polyfunctional isocyanate, hydroxyl-containing (meth)acrylate, and lactone-denatured polyol, etc. The compound is not limited to this relevant illustration.

In addition, as said polyfunctional isocyanate, for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, etc. are mentioned. Moreover, examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, di Pentaerythritol penta(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and the like. On the other hand, examples of the aforementioned polyhydric alcohols include glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these Polyester polyols produced by the reaction of diols with succinic acid, maleic acid, adipic acid and other aliphatic dicarboxylic acids or dicarboxylic anhydrides; polyether polyols; polycarbonate diols, etc.

In the present invention, as the above-mentioned (a) active energy ray-curable lactone-denatured polyfunctional monomer, the above-mentioned lactone-denatured polyfunctional (meth)acrylate compound and the above-mentioned lactone-denatured polyfunctional carbamic acid can be used. A single type of ester (meth)acrylate compound or a combination of two or more types.

[(b) Perfluoropolyether (except for the above-mentioned Other than perfluoropolyethers having a poly(oxyperfluoroalkylene) group between the poly(oxyperfluoroalkylene) group and the aforementioned urethane bond)] In the present invention, as the component (b), it is used on both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, and the aminomethyl group is not interposed between the poly(oxyalkylene) group. A perfluoropolyether having an active energy ray polymerizable group having an ester bond (hereinafter referred to as "(b) a perfluoropolyether having a polymerizable group at both terminals" only sometimes). The component (b) functions as a surface modifier in the hard coat layer of the curable composition to which the present invention is applied. Moreover, (b) component is excellent in compatibility with (a) component, and the cloudiness phenomenon of a hard-coat layer can be suppressed by this, and the hard-coat layer which shows a transparent appearance can be formed. In addition, the poly(oxyalkylene) group means a group in which the number of repeating units of the oxyalkylene group is 2 or more and the alkylene group in the oxyalkylene group is an unsubstituted alkylene group.

The number of carbon atoms in the alkylene group in the above poly(oxyperfluoroalkylene) group is not particularly limited, but those with 1 to 4 carbon atoms are preferred. That is, the above-mentioned poly(oxyperfluoroalkylene) group means a group having a structure in which a divalent carbon fluoride group having 1 to 4 carbon atoms and an oxygen atom are alternately linked, and the oxyperfluoroalkylene group means a group having a carbon atom The base of the structure in which the divalent fluorinated carbon group of the number 1 to 4 is connected to an oxygen atom. Specific examples include -[OCF ₂ ]-(oxyperfluoromethyl), -[OCF ₂ CF ₂ ]-(oxyperfluoroethyl), -[OCF ₂ CF ₂ CF ₂ ]-(oxyperfluoro propane-1,3-diyl), -[OCF ₂ C(CF ₃ )F]-(oxyperfluoropropane-1,2-diyl) and the like. The above-mentioned oxyperfluoroalkylene groups can be used singly or in combination of two or more kinds, and the bonding of plural kinds of oxyperfluoroalkylene groups can be any of chimeric bonding and random bonding depending on the need.

Among them, from the viewpoint of obtaining a cured film with good scratch resistance, as the poly(oxyperfluoroalkylene) group, -[OCF ₂ ]-(oxyperfluoroalkylene) having as a repeating unit is used. Both groups of fluoromethyl) and -[OCF ₂ CF ₂ ]-(oxyperfluoroethyl) are preferred. Wherein it is also used as the above-mentioned poly(oxy perfluoroalkylene) group, and the molar ratio of the repeating unit: -[OCF ₂ ]- to -[OCF ₂ CF ₂ ]- is [repeating unit: -[OCF ₂ ]- ]: [repeating unit: -[OCF ₂ CF ₂ ]-]=2:1 to 1:2 are preferred, and about 1:1 is preferred. The linkage of these repeating units may be any of chimeric linkage and random linkage. The total number of repeating units in the above-mentioned oxyperfluoroalkylene group is preferably in the range of 5-30, more preferably in the range of 7-21. Furthermore, the poly(oxyperfluoroalkylene) group has a weight average molecular weight (Mw) of 1,000 to 5,000, preferably 1,500 to 2,000 as measured in terms of polystyrene by gel permeation chromatography.

Examples of the active energy ray polymerizable group to be bonded via a urethane bond include a (meth)acryl group, a urethane (meth)acryl group, a vinyl group, and the like.

(b) The perfluoropolyether having a polymerizable group at both ends is not limited to one having an active energy ray polymerizable group such as a (meth)acryl group at both ends, and may have 2 at both ends. For those with more than one active energy ray polymerizable group, for example, as the terminal structure containing the active energy ray polymerizable group, the structures of A1 to A5 shown below, and the acryl group and methacryl group in these structures can be mentioned. The replaced structure.

(式中，A表示前述式[A1]～式[A5]所示結構及將這些結構中之丙烯醯基以甲基丙烯醯基所取代的結構中之1者，PFPE表示前述聚(氧基全氟伸烷基)基(但，與L¹ 直接鍵結的側為氧末端，與氧原子鍵結的側為全氟伸烷基末端。)，L¹ 表示以氟原子1～3個所取代的碳原子數2～3的伸烷基，m各獨立表示1～5的整數，L² 表示自m+1價醇除去OH的m+1價殘基)。Examples of the perfluoropolyether having a polymerizable group at both terminals (b) in this way include compounds represented by the following formula [2].

(In the formula, A represents one of the structures represented by the aforementioned formula [A1] to formula [A5] and a structure in which the acryl group in these structures is replaced by a methacryl group, and PFPE represents the aforementioned poly(oxyl group) Perfluoroalkylene) group (However, the side directly bonded to ^L1 is an oxygen terminal, and the side bonded to an oxygen atom is a perfluoroalkylene terminal.), ^L1 means that it is substituted with 1 to 3 fluorine atoms Alkylene groups with 2 to 3 carbon atoms, each of m independently represents an integer of 1 to 5, and ^L2 represents an m+1-valent residue obtained by removing OH from an m+1-valent alcohol).

Examples of the alkylene group having 2 to 3 carbon atoms which may be substituted by 1 to 3 fluorine _atoms include _{CH2CHF , CH2CF2 , CHFCF2 , CH2CH2CHF} , _CH2CH2CF2 , CH ₂ CHFCF _{2 ,} etc., preferably CH ₂ CF ₂ .

(式中，A表示前述式[A1]～式[A5]所示結構及將於這些結構中之丙烯醯基由甲基丙烯醯基所取代的結構中之一者) 在上述式[B1]～式[B12]所示結構之中，式[B1]及式[B2]相當於m＝1之情況，式[B3]～式[B6]相當於m＝2之情況，式[B7]～式[B9]相當於m＝3之情況，式[B10]～式[B12]相當於m＝5之情況。 彼等之中，亦以式[B3]所示結構為佳，特別以式[B3]與式[A3]的組合為佳。Examples of the partial structure (A-NHC(=O)O) _m L ² - in the compound represented by the above formula [2] include structures represented by the following formula [B1] to formula [B12].

(In the formula, A represents one of the structures represented by the above-mentioned formula [A1] to formula [A5] and the structure in which the acryl group in these structures is replaced by a methacryl group) In the above-mentioned formula [B1] ~ Among the structures shown in formula [B12], formula [B1] and formula [B2] correspond to the case of m=1, formula [B3] to formula [B6] correspond to the case of m=2, formula [B7] to Formula [B9] corresponds to the case of m=3, and formula [B10] to formula [B12] correspond to the case of m=5. Among them, the structure represented by the formula [B3] is also preferable, and the combination of the formula [B3] and the formula [A3] is particularly preferable.

式[1]所示部分結構相當於自式[2]所示化合物除去 A-NHC(＝O)的部分。 式[1]中之n表示重複單位-[OCF₂ CF₂ ]-之數與重複單位-[OCF₂ ]-之數的總數，以5～30的範圍之整數為佳，以7～21的範圍之整數為較佳。又，重複單位-[OCF₂ CF₂ ]-之數與重複單位-[OCF₂ ]-之數的比率在2：1～1：2之範圍者為佳，約1：1的範圍者為較佳。這些重複單位之鍵結可為嵌合鍵結及無規鍵結中任一種。As preferable (b) perfluoropolyether which has a polymeric group at both terminals, the compound which has a partial structure represented by a formula [1] is mentioned.

The partial structure represented by the formula [1] corresponds to a portion in which A-NHC (=O) is removed from the compound represented by the formula [2]. The n in the formula [1] represents the total number of the repeating unit -[OCF ₂ CF ₂ ]- and the repeating unit -[OCF ₂ ]-, preferably an integer in the range of 5-30, preferably 7-21 Integers in the range are preferred. Also, the ratio of the number of repeating units -[OCF ₂ CF ₂ ]- to the number of repeating units -[OCF ₂ ]- is preferably in the range of 2:1 to 1:2, and the range of about 1:1 is better good. The linkage of these repeating units may be any of chimeric linkage and random linkage.

The proportion of the perfluoropolyether having a polymerizable group at both ends of the present invention (b) is 0.1 to 10 parts by mass for 100 parts by mass of the active energy ray-curable lactone-denatured polyfunctional monomer of (a), Preferably it is a ratio of 0.2 to 5 parts by mass.

(式中，PFPE、L¹ 、L² 及m與前述相同意義)所示化合物的兩末端上所存在的羥基，將具有聚合性基的異氰酸酯化合物，即將前述式[A1]～式[A5]所示結構及這些結構中之丙烯醯基以甲基丙烯醯基進行取代的結構中之結合鍵上鍵結異氰酸酯基的化合物(例如，2-(甲基)丙烯醯氧基乙基異氰酸酯、1,1-雙((甲基)丙烯醯氧基甲基)乙基異氰酸酯等)進行反應後形成胺基甲酸酯鍵而得到。The above (b) perfluoropolyether having a polymerizable group at both ends can be obtained by, for example, the following formula [3]

(In the formula, PFPE, L ¹ , L ² and m have the same meanings as described above) The hydroxyl groups present at both ends of the compound represented by the polymerizable isocyanate compound, that is, the aforementioned formula [A1] to formula [A5] Compounds in which an isocyanate group is bonded to a bond in the structures shown and those structures in which the acryl group is substituted with a methacryl group (for example, 2-(meth)acryloxyethyl isocyanate, 1 , 1-bis ((meth) acryloxymethyl) ethyl isocyanate, etc.) are reacted to form urethane bonds.

In addition, in the curable composition of the present invention, in addition to containing (b) a poly(oxyperfluoroalkylene) group-containing molecular chain having active energy ray polymerization via a urethane bond at both ends In addition to the perfluoropolyether of the radical (however, there is no poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond), it may also be contained in A perfluoropolyether (but , there is no poly(oxyalkylene) between the aforementioned poly(oxygen perfluoroalkylene) group and the aforementioned urethane bond and between the aforementioned poly(oxygen perfluoroalkylene) group and the aforementioned hydroxyl group base) group), or a perfluoropolyether having hydroxyl groups at both ends of the molecular chain containing a poly(oxy perfluoroalkylene) group as shown in the above formula [3] (however, in the aforementioned poly(oxygen There is no poly(oxyalkylene) group between the perfluoroalkylene) group and the aforementioned hydroxyl group) [a compound without an active energy ray polymerizable group].

The present invention also relates to a perfluoropolyether compound having at least 3 active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond. (However, perfluoropolyether compounds having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond are excluded). As the perfluoropolyether compound having polymerizable groups at both terminals, a compound having a partial structure represented by the above formula [1] is preferable. As mentioned above, the perfluoropolyether compound of the present invention has excellent compatibility with component (a), thereby suppressing the cloudiness of the hard coat layer and achieving the excellent effect of forming a hard coat layer with a transparent appearance. The present invention also relates to a surface modifying agent made of the above-mentioned perfluoropolyether compound, and a surface modifying agent intended to be used for the perfluoropolyether compound.

[(c) Polymerization initiator that generates free radicals by active energy rays] In the curable composition of the present invention, preferable polymerization initiators that generate radicals by active energy rays (hereinafter sometimes simply referred to as "(c) polymerization initiators") are, for example, those that generate radicals by electron rays, Active energy rays such as ultraviolet rays and X-rays, especially polymerization initiators that generate free radicals by ultraviolet irradiation. Examples of the above (c) polymerization initiator include benzoins, alkylacetophenones, thioxanthones, azos, azides, diazides, and o-quinonediazides. , Acylphosphine oxides, oxime esters, organic peroxides, benzophenones, dicoumarins, biimidazoles, titanocenes, mercaptans, halogenated hydrocarbons, trichloromethyl Triazines, or onium salts such as iodine salts and permeic acid salts, and the like. One type may be used alone, or two or more types may be used in combination. Among them, in the present invention, it is preferable to use alkyl acetophenones as the (c) polymerization initiator from the viewpoint of transparency, surface hardening properties, and film hardening properties. By using alkyl acetophenones, a cured film having improved scratch resistance can be obtained.

Examples of the above-mentioned alkylacetophenones include 1-hydroxycyclohexyl=phenyl=ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-( 4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzene α-Hydroxyalkylacetophenones such as methyl)phenyl)-2-methylpropan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2-mol α-aminoalkylacetophenones such as phenopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, etc. ; 2,2-dimethoxy-1,2-diphenylethan-1-one; methyl phenylglyoxylate, etc.

In the present invention, the ratio of the (c) polymerization initiator to be used is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, relative to 100 parts by mass of the aforementioned (a) active energy ray-curable lactone-denatured polyfunctional monomer. share.

[(d) Solvent] The curable composition of the present invention may further contain (d) a solvent, that is, it may also be in the form of a paint (film forming material). As the above-mentioned solvent, if it is to dissolve the above-mentioned (a) to (c) components, and consider the workability of the coating when the cured film (hard coat layer) is formed later, or the drying properties before and after curing, etc., it can only be selected appropriately. That is, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral oil, and cyclohexane Hydrocarbons; methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylenyl, perchloroethylene, o-dichlorobenzene and other halogenated compounds; acetic acid Ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and other esters or ester ethers; Diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone and other ketones ; Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol and other alcohols; N , Amides such as N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; Acids such as dimethylsulfide, and these two kinds The above mixed solvents. The amount of these (d) solvents used is not particularly limited. For example, the solid content concentration in the curable composition of the present invention is 1 to 70% by mass, preferably used at a concentration of 5 to 50% by mass. Here, the so-called solid content concentration (also referred to as non-volatile matter concentration) refers to the total mass (total mass) of the aforementioned (a) to (d) components (and other additives depending on the desired) of the curable composition of the present invention. The content of solid content (the solvent content is removed from the whole content).

[other additions] Also, for the curable composition of the present invention, without impairing the effect of the present invention, additives generally added can be appropriately added as necessary, such as polymerization inhibitors, photosensitizers, leveling agents, and surface active agents. agent, adhesion imparting agent, plasticizer, ultraviolet absorber, antioxidant, storage stabilizer, antistatic agent, inorganic filler, pigment, dye, etc.

＜Cured film＞ The curable composition of the present invention is coated on a substrate to form a coating film, and the coating film is polymerized (cured) by irradiating active energy rays to form a cured film. This cured film is also made into the object of this invention. Moreover, the hard coat layer in the hard coat film mentioned later can be made of this cured film. As the aforementioned base material in this case, various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) or polyethylene naphthalate) can be mentioned, for example. (PEN) and other polyesters, polyolefins, polyamides, polyimides, epoxy resins, melamine resins, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile- Styrene copolymer (AS), norbornene-based resin, etc.), metal, wood, paper, glass, slate, etc. The shapes of these substrates may be plate-like, film-like, or three-dimensional molded bodies.

For the coating method on the aforementioned substrate, cast coating method, spin coating method, knife coating method, dip coating method, roll coating method, spray coating method, rod coating method, die coating method, inkjet method, printing method, etc. method (letterpress, gravure, lithography, screen printing, etc.), among which roll-to-roll (roll-to-roll) method can be used, and from the viewpoint of film coatability, it is expected to use letterpress printing method, especially gravure printing method coating method. Furthermore, it is preferable to provide the applicator after filtering the curable composition in advance using a filter with a pore size of about 0.2 μm or the like. In addition, when coating, adding a solvent to the curable composition as necessary can also be used as a form of painting. As a solvent in this case, various solvents mentioned in said [(d) solvent] are mentioned. After coating the curable composition on the substrate to form a coating film, the coating film is pre-dried with a hot plate or an oven if necessary to remove the solvent (solvent removal step). As the conditions of heat drying at this time, it is preferable to perform, for example, at 40 to 120°C for about 30 seconds to 10 minutes. After drying, the coating is cured by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron rays, X-rays, and the like, and ultraviolet rays are particularly preferred. As a light source used for ultraviolet irradiation, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs, and the like can be used. And thereafter, polymerization is completed by performing post-baking, specifically, heating using a hot plate, an oven, or the like. In addition, the thickness of the formed cured film is usually 0.01 to 50 μm after drying and curing, preferably 0.05 to 20 μm.

＜Hard Coating Film＞ Using the curable composition of the present invention, a hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced. The hard coating film is also the object of the present invention, and the hard coating film is suitable for protecting the surfaces of various display elements such as touch panels or liquid crystal displays.

The hard coat layer in the hard coat film of the present invention can be formed by applying the curable composition of the present invention to a film substrate to form a coating film, irradiating the coating film with active energy rays such as ultraviolet rays to make the coating layer Formed by the method of film hardening step.

Examples of the film base material include various transparent resin films that can be used for optical applications among the base materials listed in the aforementioned <cured film>. Preferred examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like. Polyester, polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose and other resin films. Also, the methods mentioned above in <cured film> can be used for the method of coating the curable composition on the film substrate (coating film forming step) and the method of irradiating the coating film with active energy rays (curing step). Also, when the curable composition of the present invention contains a solvent (in the form of a paint), after the coating film forming step, a step of drying the coating film to remove the solvent may be included if necessary. At this time, the drying method (solvent removal step) of the coating film mentioned above in <cured film> can be used. The film thickness of the hard coat layer thus obtained is preferably 1 to 20 μm, more preferably 1 to 10 μm. [Example]

Examples are given below, and the present invention can be described more specifically, but the present invention is not limited to the following examples. In addition, in Examples, the apparatus and conditions used for preparation of samples and analysis of physical properties are as follows.

(1) Bar coating Device: PM-9050MC made by SMT Rod: A-Bar OSP-22 manufactured by OSG System Products Co., Ltd., with a maximum wet film thickness of 22 μm (equivalent to wire spindle #9) Coating speed: 4m/min (2) Oven Device: Dust-free dryer DRC433FA manufactured by Advantech Oriental Co., Ltd. (3) UV hardening Device: CV-110QC-G manufactured by Heraeus Co., Ltd. Lighting: Heraeus Co., Ltd. high-pressure mercury lamp H-bulb (4) Gel Permeation Chromatography (GPC) Device: HLC-8220GPC manufactured by Tosoh Co., Ltd. String: Shodex (registered trademark) GPC K-804L, GPC K-805L manufactured by Showa Denko Co., Ltd. Column temperature: 40°C Eluent: Tetrahydrofuran Detector: RI (5) Scratch test Device: Shinto Science Co., Ltd. reciprocating abrasion tester TRIBOGEAR TYPE: 30S Scanning speed: 3,000mm/min Scanning distance: 50mm (6) Total light transmittance, haze Device: Nippon Denshoku Industry Co., Ltd. haze tester NDH5000 (7) Contact angle Device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measuring temperature: 20°C (8) Tensile test Device: Takumi Precision Universal Testing Machine Autograph AGS - 10 kNX manufactured by Shimadzu Corporation Gripper: 1kN manual torsion flat gripper Teeth gripping: high-strength rubberized gripping teeth Tensile speed: 20mm/min Measuring temperature: 20°C

Also, the abbreviated numbers indicate the following meanings. PFPE1: perfluoropolyether [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers, Inc.] having two hydroxyl groups without a poly(oxyalkylene) group interposed between both ends PFPE2: Perfluoropolyether having a hydroxyl group via a poly(oxyalkylene) group (number of repeating units: 8 to 9) at both ends [Solvay Specialty Polymers, Inc. Fluorolink 5147X] SM2: Perfluoropolyether having two methacryl groups at both ends via a urethane bond [Solvay Specialty Polymers, Inc. Fomblin (registered trademark) MT70, 80% by mass MEK solution] BEI: 1,1-bis(acryloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.] DOTDD: Dioctyltin dineodecanoate [Neostan (registered trademark) U-830 manufactured by Nitto Kasei Co., Ltd.] DPCL: Caprolactone-denatured dipentaerythritol hexaacrylate [KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd.] DPHA: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.] PETA: Pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture [NK Ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.] I2959: 2-Hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [IRGACURE (registered trademark) 2959 manufactured by BASF Japan Co., Ltd.] MEK: methyl ethyl ketone PGME: Propylene Glycol Monomethyl Ether

[Example 1] Production of perfluoropolyether (SM1) having 4 acryl groups via urethane bonds at both ends 1.19g (0.5mmol) of PFPE1, 0.52g (2.0mmol) of BEI, 0.017g of DOTDD (0.01 times the total mass of PFPE1 and BEI) and 1.67g of MEK were placed in the screw tube. This mixture was stirred at room temperature (about 23° C.) for 24 hours using a stirrer blade to obtain a 50% by mass MEK solution of SM1 of the target compound. The weight average molecular weight measured by GPC of the obtained SM1 in terms of polystyrene: Mw was 3,000, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Manufacturing example 1] Preparation of 50% by mass MEK solution of SM2 Put SM2 2.5g and MEK 1.5g into the screw tube. This mixture was stirred at room temperature (about 23° C.) for 24 hours using a stirrer blade to obtain a 50% by mass MEK solution of SM2.

[Comparative Production Example 1] Production of perfluoropolyether (SM3) having two acryl groups via poly(oxyalkylene) groups and one urethane bond at both ends PFPE2 1.05g (0.5mmol), BEI 0.26g (1.0mmol), DOTDD 0.013g (0.01 times the total mass of PFPE2 and BEI) and MEK 1.30g were placed in the screw tube. This mixture was stirred using a stirrer blade at room temperature (about 23° C.) for 24 hours to obtain a 50% by mass MEK solution of SM3 of the target compound. The weight average molecular weight measured by GPC of the obtained SM3 in terms of polystyrene: Mw was 3,100, and the degree of dispersion: Mw/Mn was 1.1.

[Examples 2, 3, Comparative Examples 1-3] Based on the description in Table 1, the following components were mixed to prepare curable compositions with solid content concentrations described in Table 1. In addition, the term "solid content" here refers to components other than the solvent. In addition, [parts] in the table represent [parts by mass]. (1) Multifunctional monomer: 100 parts by mass of the multifunctional monomer listed in Table 1 (2) Surface modifying agent: The surface modifying agent listed in Table 1 is expressed in the amount listed in Table 1 (in terms of solid content) Indicates (3) Polymerization initiator: I2959 5 parts by mass (4) Solvent: 158 parts by mass of PGME This curable composition is coated on both sides of an A4 size easy-to-adhesive PET film [Toray Co., Ltd. Lumirror by bar coating] (trademark registration) U403, thickness 100 μm] to obtain a coating film. The coating film was dried in a 120° C. oven for 3 minutes to remove the solvent. The obtained film was exposed to UV light at an exposure dose of 300 mJ/cm ² in a nitrogen atmosphere, and then a hard coat film having a hard coat layer (cured film) with a film thickness of about 5 μm was produced.

The homogeneity of each curable composition and the appearance, scratch resistance, elongation, total light transmittance, haze and water contact angle of the obtained hard coating film were evaluated. Evaluation procedures for composition homogeneity, appearance, scratch resistance, elongation, and contact angle are as follows. The results are combined and shown in Table 2. [Composition Homogeneity] The appearance of the curable composition after 2 hours of preparation was visually confirmed and evaluated based on the following criteria. A: Transparent solution C: Cloudy [Appearance] The appearance of the hard coat film was visually confirmed and evaluated based on the following criteria. A: The hard coating layer is completely transparent and has no spots. C: The hard coating layer is spotty and white and makes the spots eye-catching. [Scratch resistance] The surface of the hard coating layer is made of stainless steel wool with a reciprocating abrasion tester [Bonther Bonther (registered trademark) #0000 (ultra-fine)] manufactured by Sales Co., Ltd. was rubbed 2,000 times with a load of 250 g/cm ² , and the degree of damage was visually confirmed and evaluated according to the following criteria. And, assuming actual use as a hard coating layer, at least B can be obtained, and A is preferable. A: No scratches B: Slight scratches C: Full-scale scratches [Extensibility] The hard coating film was taken out into a rectangle with a length of 80 mm and a width of 10 mm to prepare a test piece. From the two ends of the longitudinal direction of the test piece, take out each 20mm with the gripper of the universal testing machine, so that the elongation (= (the increase in the distance between the grippers) ÷ (the distance between the grippers) × 100 ) becomes 5%, 10%, 15%, and 20% to carry out the tensile test. The maximum elongation at which cracks did not occur on the hard coat layer of the test piece was evaluated as elongation. [Contact Angle] 1 μL of water was attached to the surface of the hard coat layer, and the contact angle θ was measured at 5 points after 5 seconds, and the average value was taken as the contact angle value.

【Table 1】

【Table 2】

As shown in Table 1, in the hard coat layer, lactone-modified acrylate is used as a multifunctional monomer, and as a surface modifier, acrylates having 4 acryl groups at both ends via urethane bonds are used. The curable composition of perfluoropolyether SM1 (Example 2) or perfluoropolyether SM2 (Example 3) having two methacryl groups via urethane bonds at each end is transparent solution, and the hard coating film produced by using the curable composition has excellent scratch resistance and moderate extensibility, and can obtain a transparent and spot-free appearance.

On the other hand, comparative example 2 in which perfluoropolyether SM3 having two acryl groups having two acryl groups interposed between poly(oxyalkylene) groups and one urethane bond at both ends was used as a surface modifying agent , the composition was cloudy and poor in homogeneity, and the hard coating layer obtained from the composition had worse haze and a cloudy appearance than those in Examples. In addition, as a result of Comparative Example 1 using the above-mentioned SM1 as a surface modifying agent, acrylate which is a polyfunctional monomer and which has not been denatured by lactone, none of them had elongation.

As shown in the results of the above examples, combining the polyfunctional monomer modified by lactone and the curable composition of specific perfluoropolyether can obtain a scratch resistance, elongation and appearance satisfactory for the first time. Hard coated film.

Claims (11)

A curable composition characterized by containing (a) 100 parts by mass of an active energy ray-curable lactone denatured polyfunctional monomer, (b) two of the molecular chains containing poly(oxyperfluoroalkylene) groups A perfluoropolyether having an active energy ray polymerizable group via a urethane bond at the terminal (except for the poly(oxyperfluoroalkylene) group having a 0.1 to 10 parts by mass of a poly(oxyalkylene)-based perfluoropolyether), and (c) 1 to 20 parts by mass of a polymerization initiator that generates free radicals by active energy rays, wherein the aforementioned poly(oxygen The perfluoroalkylene) group is a group having -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as repeating units, and the aforementioned (b) perfluoropolyether is a compound represented by formula [2];

(In formula [2], A represents the structure shown in the following formula [A3] or a structure in which the acryl group in the structure is substituted with a methacryl group, and PFPE represents the aforementioned poly(oxyperfluoroalkylene) (However, the side directly bonded to ^L1 is an oxygen terminal, and the side bonded to an oxygen atom is a perfluoroalkylene terminal), and ^L1 represents 2 to 3 carbon atoms replaced by 1 to 3 fluorine atoms The alkylene group, the partial structure (A-NHC(=O)O) _m L ² -is the structure shown in the following formula [B3])

The curable composition according to claim 1, wherein the aforementioned (a) multifunctional monomer contains a polyfunctional (meth)acrylate compound selected from lactone-denatured polyfunctional (meth)acrylate compounds and lactone-denatured polyfunctional urethane (meth)acrylic acid At least one ester compound grouped. The curable composition according to claim 1 or 2, wherein the aforementioned (a) polyfunctional monomer is ε-caprolactone denatured polyfunctional monomer. The curable composition according to claim 1 or 2, which further contains (d) a solvent. A cured film, characterized by being obtained by the curable composition according to any one of claims 1 to 4. A hard coating film, which is equipped with a hard coating layer on at least one side of the film substrate, and is characterized in that the hard coating layer is composed of as claimed in item 5 It is made of hardened film. A hard coating film, which is a hard coating film with a hard coating layer on at least one side of the film substrate, characterized in that the hard coating layer is composed of a hardening composition containing any one of claims 1 to 4 It is formed by the step of coating a substance on a film substrate to form a coating film, and the step of irradiating the coating film with active energy rays to harden it. The hard-coated film according to claim 6 or 7, wherein the hard-coated layer has a film thickness of 1-10 μm. A perfluoropolyether compound having at least 3 active energy ray polymerizable groups ( However, except for perfluoropolyether compounds having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond), wherein the aforementioned poly(oxygen The perfluoroalkylene) group is a group having -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as repeating units, and is a compound represented by formula [2];

(In formula [2], A represents the structure shown in the following formula [A3] or a structure in which the acryl group in the structure is substituted with a methacryl group, and PFPE represents the aforementioned poly(oxyperfluoroalkylene) (However, the side directly bonded to ^L1 is an oxygen terminal, and the side bonded to an oxygen atom is a perfluoroalkylene terminal), and ^L1 represents 2 to 3 carbon atoms replaced by 1 to 3 fluorine atoms The alkylene group, the partial structure (A-NHC(=O)O) _m L ² -is the structure shown in the following formula [B3])

A performance modifier, characterized by being made of the perfluoropolyether compound as claimed in claim 9. A use of the perfluoropolyether compound as claimed in Claim 9 for surface modification.