TW202016211A - Curable composition for flexible coating - Google Patents

Abstract

To provide a curable composition, with which it is possible to form a hard coat layer that is extremely scratch-resistant and stretchable and furthermore can also be wear-resistant. Provided are: a curable composition including (a) 100 parts by mass of an oxyethylene-modified polyfunctional monomer that has at least three active energy beam-polymerisable groups, the average oxyethylene modification amount of said monomer being less than 3 mol in relation to 1 mol of said polymerisable groups, (b) 0.1-10 parts by mass of a perfluoropolyether that has an active energy beam-polymerisable group at both ends of the molecular chain, which includes a poly(oxyperfluoroalkylene) group, with a urethane bond therebetween (excluding a perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond), and (c) 1-20 parts by mass of a polymerisation initiator that produces radicals by means of an active energy beam; and a hard coat film comprising a hard coat layer formed by said composition.

Description

Curable composition for flexible coating

The present invention relates to a curable composition useful as a material for forming a hard coating layer applied to the surface of a flexible display or the like. The details relate to a hardenable composition that can form a hard coating layer having extremely high scratch resistance, bending resistance and elongation, and further having abrasion resistance.

Smartphones are widely and popular as indispensable products in our daily lives. In recent years, as displays for smartphones and the like, flexible displays, so-called flexible displays are being developed. Flexible displays, such as those that can be bent and rolled, are expected to be widely used as portable cell phone displays.

On the surface of a smartphone, cover glass is usually used to prevent damage to the display. However, general glass is hard and cannot be bent back, so it cannot be applied to flexible displays. Therefore, an attempt was made to use a plastic film having a hard coating layer having scratch resistance. The plastic film provided with these hard coating layers generates stress in the tensile direction on the hard coating layer when the hard coating layer is bent to the outside. Therefore, the hard coating layer must have certain extensibility.

In general, when imparting scratch resistance to the hard coating layer, for example, a method of forming a highly cross-linked structure, that is, increasing the surface hardness by forming a cross-linked structure with low molecular mobility and imparting resistance to external forces. As these hard coating layer forming materials, multifunctional acrylate-based materials that are crosslinked by three-dimensionally with free radicals are currently used most. However, the polyfunctional acrylate-based material usually has no extensibility because the crosslink density is high. Such a hard coating layer has a trade-off relationship between the extensibility and scratch resistance, and it is a problem to have both characteristics.

As a method of combining the elongation and scratch resistance of a hard coating layer, it has been revealed that a polyfunctional acrylic acid modified with a polyfunctional urethane acrylate oligomer and a high molecular mobility ethylene oxide is used. Ester technology (Patent Document 1).

However, with the above-mentioned flexible display, since the touchpad is carried, the touchpad is operated by finger contact. Therefore, fingerprints will adhere to the touch panel when the fingers are in contact, which may cause damage to the appearance. The fingerprint contains moisture derived from sweat and oil derived from sebum. If it is difficult to adhere the moisture and oil, it is strongly expected to impart water repellency and oil repellency to the hard coating layer. From such a viewpoint, the surface of the hard coating layer is expected to have antifouling properties against fingerprints and the like. However, for the hard coating layer, even if the antifouling property at the initial stage of use reaches a high level, since the person touches it by hand every day, the function of the antifouling property in use is often reduced. Therefore, the durability of the antifouling property during use becomes a problem.

In general, as a method of imparting antifouling properties to the surface of the hard coating layer, there is a method of adding a small amount of a fluorine-based surface modifier to the coating solution used to form the hard coating layer. The added fluorine-based surface modifier imparts water repellency and oil repellency due to the low surface energy segregating on the surface of the hard coating layer. As the fluorine-based surface modifier, from the viewpoint of water repellency and oil repellency, a number average molecular weight of about 1,000 to 5,000 having a poly(oxyperfluoroalkylene) chain called perfluoropolyether is used Of oligomers. However, since this perfluoropolyether has a high fluorine concentration, it is generally difficult to dissolve in the organic solvent used in the coating liquid for forming the hard coating layer. In addition, the formed hard coating layer causes aggregation.

In such a perfluoropolyether, in order to impart solubility to an organic solvent and dispersibility in a hard coating layer, a method for introducing the perfluoropolyether into an organic site is used. Furthermore, in order to impart scratch resistance, a method of bonding an active energy ray hardening site represented by a (meth)acrylate group is used. Up to now, it has been disclosed that as the anti-fouling hard coating layer having scratch resistance, the poly(oxyalkylene) group and one amino group are interposed at both ends of the poly(oxyperfluoroalkylene) chain. A compound having an (meth)acryloyl group with an ester bond is used as a surface modifier (Patent Document 2). [Prior Technical Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2013/191254 [Patent Literature 2] International Publication No. 2016/163479

[Problems solved by the invention]

However, in the method described in Patent Document 1, a polyfunctional urethane acrylate is added to impart scratch resistance, and this stretchability has a problem. In addition, the surface modifier described in Patent Document 2 has a problem with this antifouling property. That is, the present invention aims to provide a curable composition that can form a hard coating layer having extremely high scratch resistance, bending resistance, and elongation, and having more abrasion resistance. [Means to solve the problem]

The inventors of the present invention conducted a detailed review to achieve the above object and found that the curable composition having the following oxyethylated denatured polyfunctional monomer can be formed to have extremely high scratch resistance and bending resistance and elongation, and also The present invention is completed by a hard coating layer having further abrasion resistance. The oxyethylenated denatured multifunctional monomer is that at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, there is no (oxyalkylene) group and an urethane bond is interposed , A perfluoropolyether having an active energy ray polymerizable group, and an oxyethylated polyfunctional monomer having at least 3 active energy ray polymerizable groups, and the average amount of oxyethylated groups for the polymerizable group For 1 mol, less than 3 mol of oxyethylated denatured polyfunctional monomer.

(式[1]中，n表示重複單位-[OCF₂ CF₂ ]-之數與重複單位-[OCF₂ ]-之數的總數)。 作為第6觀點，有關前述(a)氧基伸乙基變性多官能單體含有選自由氧基伸乙基變性多官能(甲基)丙烯酸酯化合物及氧基伸乙基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種之第1觀點至第5觀點中任一所記載的硬化性組成物。 作為第7觀點，有關前述(a)氧基伸乙基變性多官能單體之平均氧基伸乙基變性量對於前述聚合性基1mol而言為2mol以下之第1觀點至第6觀點中任一所記載的硬化性組成物。 作為第8觀點，有關進一步含有(d)溶劑之第1觀點至第7觀點中任一所記載的硬化性組成物。 作為第9觀點，有關藉由如第1觀點至第8觀點中任一所記載的硬化性組成物所得之硬化膜。 作為第10觀點，有關於薄膜基材的至少一面上具備硬質塗佈層之硬質塗佈薄膜，該硬質塗佈層含有如第9觀點所記載的硬化膜而成之硬質塗佈薄膜。 作為第11觀點，有關於薄膜基材的至少一面上具備硬質塗佈層之硬質塗佈薄膜，該硬質塗佈層係由以下方法而形成，該方法含有：將如第1觀點至第8觀點中任一所記載的硬化性組成物塗佈於薄膜基材上而形成塗膜之步驟，與於該塗膜上照射活性能量線而使其硬化的步驟。 作為第12觀點，有關前述硬質塗佈層具有1μm至10μm之膜厚的如第10觀點或第11觀點所記載的硬質塗佈薄膜。 作為第13觀點，有關含有將如第1觀點至第8觀點中任一所記載的硬化性組成物塗佈於薄膜基材上而形成塗膜之步驟，與於該塗膜照射活性能量線而使其硬化的步驟之層合體的製造方法。 [發明之效果]That is, as the first viewpoint in the present invention: (a) An oxyethylated denatured polyfunctional monomer having at least three active energy ray polymerizable groups, the average amount of oxyethylated denature is not greater than 1 mol of the polymerizable group Up to 3 mol of 100 parts by mass of oxyethylated ethylenic polyfunctional monomer, (b) at both ends of the molecular chain containing poly(oxyperfluoroalkylene) group, with active energy through the urethane bond Perfluoropolyether of linear polymerizable group (except for perfluoropolyether having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond) 0.1 parts by mass to 10 parts by mass, and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. As a second aspect, the curable composition described in the first aspect regarding the (b) perfluoropolyether having at least two active energy ray polymerizable groups at both ends. As a third aspect, the curable composition described in the second aspect regarding the (b) perfluoropolyether having at least three active energy ray polymerizable groups at both ends. As a fourth aspect, any one of the first to third aspects regarding the poly(oxyperfluoroalkylene) group as a repeating unit -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- A curable composition as described. As a fifth aspect, the curable composition described in the fourth aspect regarding the (b) perfluoropolyether having a partial structure represented by the following formula [1].

(In formula [1], n represents the total number of repeating units-[OCF ₂ CF ₂ ]-number and repeating units-[OCF ₂ ]-number). As a sixth aspect, the aforementioned (a) oxyethyl-modified polyfunctional monomer contains a compound selected from the group consisting of oxyethyl-modified polyfunctional (meth)acrylate compounds and oxyethyl-modified polyfunctional aminocarbamate ( The curable composition described in any one of the first to fifth points of at least one group consisting of meth)acrylate compounds. As a seventh viewpoint, any one of the first to sixth viewpoints regarding the average (a) oxyethylated polyfunctional monomer as the average oxyethylated amount of the polymerizable group is 1 mol or less to 2 mol of the polymerizable group The curable composition described. As an eighth aspect, the curable composition described in any one of the first to seventh aspects further containing (d) a solvent. As a ninth aspect, it relates to a cured film obtained by the curable composition as described in any one of the first to eighth aspects. As a tenth aspect, there is a hard coating film provided with a hard coating layer on at least one surface of a film substrate, the hard coating layer containing a hard coating film as described in the ninth aspect. As an eleventh viewpoint, there is a hard coating film provided with a hard coating layer on at least one side of a film substrate, the hard coating layer is formed by the following method, the method including: as described in the first to eighth viewpoints The step of applying the curable composition described on any one of the film substrates to form a coating film, and the step of irradiating the coating film with active energy rays to harden it. As a twelfth aspect, the hard coating film as described in the tenth or eleventh aspect relates to the hard coating layer having a film thickness of 1 μm to 10 μm. As a thirteenth aspect, there is a step of applying a curable composition as described in any one of the first to eighth aspects on a film substrate to form a coating film, and irradiating the coating film with active energy rays A method for manufacturing a laminate in the step of hardening it. [Effect of invention]

According to the present invention, it is possible to provide a hardenable composition capable of forming a hard coating layer having extremely high scratch resistance, bending resistance and elongation, and further having abrasion resistance.

[Forms for carrying out the invention] <hardening composition>

The hardenable composition of the present invention contains in detail: (a) An oxyethylated denatured polyfunctional monomer with at least 3 active energy ray polymerizable groups, the average oxyethylated denatured amount is less than 3 mol of oxyethylated denatured multifunctional monomer for 1 mol of the polymerizable group 100 parts by mass, (b) At both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, a perfluoropolyether having an active energy ray polymerizable group via an urethane bond (but, except for the poly (Other than perfluoropolyethers having a poly(oxyalkylene) group between the (oxyperfluoroalkylene) group and the aforementioned urethane bond) 0.1 parts by mass to 10 parts by mass, and (c) by active energy 1 to 20 parts by mass of a polymerization initiator that generates free radicals. First, the components of the above (a) to (c) will be described below.

[(a) An oxyethylated denatured polyfunctional monomer having at least 3 active energy ray polymerizable groups, the average oxyethylated denatured amount is less than 3 mol of oxyethylated denatured polyfunctional for the polymerizable group of 1 mol Monomers (also only describe oxyethylated polyfunctional monomers having at least three (a) active energy ray polymerizable groups)] An oxyethylidene-modified multifunctional mono-system having at least 3 active energy ray polymerizable groups refers to a polyfunctional monomer modified with oxyethylidene groups having at least 3 active energy ray polymerizable groups, the average oxygen The amount of ethyl denaturation is less than 3 mol of oxyethylated polyfunctional monomer for 1 mol of the polymerizable group. For the curable composition of the present invention, as the preferred (a) oxyethylated denatured multifunctional monomer having at least 3 active energy ray polymerizable groups, it has at least 3 active energy ray polymerizable groups, and the average oxygen The amount of ethylenyl denaturation less than 3 mol for 1 mol of the polymerizable group is selected from the group consisting of oxyethylenated polyfunctional (meth)acrylate compounds and oxyethylenated polyfunctional aminocarbamate (methyl) Monomers of acrylate compounds. In addition, in the present invention, the (meth)acrylate compound means both the acrylate compound and the methacrylate compound, and for example, (meth)acrylic acid means acrylic acid and methacrylic acid.

(a) The average oxyethylated denatured amount in an oxyethylated denatured polyfunctional monomer having at least 3 active energy ray polymerizable groups is not Up to 3 mol, preferably 2 mol or less for 1 mol of the active energy ray polymerizable group possessed by the monomer. In addition, (a) the average amount of oxyethylated denaturation in an oxyethylated polyfunctional monomer having at least 3 active energy ray polymerizable groups is 1 mol of active energy ray polymerized groups in the monomer When it is larger than 0 mol, it is preferably 0.1 mol or more and preferably 0.5 mol or more for 1 mol of the active energy ray polymerizable group possessed by the monomer.

Examples of the oxyethylated polyfunctional (meth)acrylate compound include (meth)acrylate compounds of polyols modified with oxyethylated groups. Examples of the polyhydric alcohol include glycerin, diglycerin, triglyceride, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and diglycerin. Pentaerythritol.

The (a) active energy ray polymerizable group in the oxyethylated denatured polyfunctional monomer having at least three active energy ray polymerizable groups includes, for example, (meth)acryloyl, vinyl, epoxy base.

For (a) an oxyethylated denatured polyfunctional monomer having at least 3 active energy ray polymerizable groups, the number of additions of oxyethylated 1 molecule is 1 to 30, preferably 1 to 12.

In the present invention, the above (a) oxyethylated polyfunctional monomer having at least three active energy ray polymerizable groups may be used alone, or two or more types may be used in combination.

[(b) At both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, a perfluoropolyether having an active energy ray polymerizable group via an urethane bond (but, except for the above (Other than perfluoropolyethers having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the aforementioned urethane bond)] In the present invention, it is used as the component (b) at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, without the poly(oxyalkylene) group but through the amino group An ester bond, a perfluoropolyether having an active energy ray polymerizable group (hereinafter simply referred to as "(b) perfluoropolyether having a polymerizable group at both ends"). (b) The component plays the role of a surface modifier in the hard coating layer using the curable composition of the present invention. In addition, the compatibility between the component (b) and the component (a) is excellent, whereby the hard coating layer can be suppressed from becoming cloudy, and the formation of the hard coating layer exhibiting a transparent appearance can be made possible. In addition, the above-mentioned poly(oxyalkylene) group means that 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 of the alkylene group in the poly(oxyperfluoroalkylene) group is not particularly limited, but preferably has 1 to 4 carbon atoms. That is, the above-mentioned poly(oxyperfluoroalkylene) group refers to a group having a structure in which a bivalent fluorinated carbon group having 1 to 4 carbon atoms and oxygen atoms are alternately linked, and oxyperfluoroalkylene group refers to , A group having a structure in which a bivalent fluorinated carbon group having 1 to 4 carbon atoms and an oxygen atom are connected. Specific examples include -[OCF ₂ ]-(oxyperfluoromethylene), -[OCF ₂ CF ₂ ]-(oxyperfluoroethylidene), -[OCF ₂ CF ₂ CF ₂ ]-(oxygen Groups such as perfluoropropane-1,3-diyl), -[OCF ₂ C(CF ₃ )F]-(oxyperfluoropropane-1,2-diyl). The above-mentioned oxyperfluoroalkylene groups may be used alone or in combination of two or more. In this case, the bonding of plural oxyperfluoroalkylene groups may be block binding (block binding) and no Any one of the standard bonding.

Among these, from the viewpoint of obtaining a cured film that can improve scratch resistance, as the poly(oxyperfluoroalkylene) group, -[OCF ₂ ]-(oxygen having a repeating unit is used The radicals of both groups (perfluoromethylene) and -[OCF ₂ CF ₂ ]-(oxyperfluoroethylidene) are preferred. Among them, as the above-mentioned poly(oxyperfluoroalkylene) group, the repeating units: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- become [repeating units: -[OCF ₂ ]-] at a molar ratio: [Repeat unit: -[OCF ₂ CF ₂ ]-]=2:1 to 1:2 is preferably contained in the ratio of the base, preferably in a ratio of about 1:1. The bonding of these repeating units may be any of block bonding and random bonding. The number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30 as the total number of repeating units, and preferably in the range of 7 to 21. In addition, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the above poly(oxyperfluoroalkylene) group in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 3,000, or 1,500 to 2,000.

Examples of the active energy ray polymerizable group bonded through the urethane bond include (meth)acryloyl group and vinyl group.

(b) Perfluoropolyethers having polymerizable groups at both ends are not limited to those having active energy ray polymerizable groups such as (meth)acryl acetyl groups at both ends, and may also have at both ends Two or more active energy ray polymerizable groups, for example, as the terminal structure containing an active energy ray polymerizable group, the structures shown below [A1] to [A5], and the propylene amide group in these structures A structure substituted by methacryloyl.

(式中，A表示，前述式[A1]至式[A5]所示結構及使此等結構中之丙烯醯基由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(但除與L¹ 鍵結之側為氧基末端，且與L² 鍵結之側為全氟伸烷基末端)，L¹ 及L² 表示由1至3個氟原子進行取代的碳原子數2或3之伸烷基或伸烷基羰基，n各獨立表示1至5的整數，L³ 表示由n+1價醇去除OH之n+1價的殘基)。As (b) a perfluoropolyether having a polymerizable group at both ends, for example, a perfluoropolyether having at least 2 active energy ray polymerizable groups at each end, or at least 3 active energy rays at each end Perfluoropolyethers with polymerizable groups are preferred. As such (b) perfluoropolyether having a polymerizable group at both ends, for example, a compound represented by the following formula [2] can be mentioned.

(In the formula, A represents one of the structures represented by the aforementioned formulas [A1] to [A5] and the structure in which the acryloyl group in these structures is replaced with a methacryloyl group, and PFPE represents the aforementioned poly( Oxyperfluoroalkylene) group (but the side bonded to L ¹ is an oxy terminal and the side bonded to L ² is a perfluoroalkyl terminal), L ¹ and L ² represent from 1 to 3 Alkyl or alkylcarbonyl groups with 2 or 3 carbon atoms substituted by fluorine atoms, n each independently represents an integer of 1 to 5, and L ³ represents the n+1 valent residue of OH removed by n+1 valent alcohol base).

Examples of the C 2 or C 3 alkylene or alkylcarbonyl group substituted with 1 to 3 fluorine atoms include -CH ₂ CHF-, -CH ₂ CF ₂ -, -CHFCF ₂ -, -CH ₂ CH ₂ CHF-, -CH ₂ CH ₂ CF ₂ -, -CH ₂ CHFCF ₂ -, -C(=O)CF ₂ -, preferably CH ₂ CF ₂ .

(式中，A表示前述式[A1]至式[A5]所示結構，及使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1個)。 在上述式[B1]至式[B12]所示結構之中，式[B1]及式[B2]相當於n=1之情況，式[B3]至式[B6]相當於n=2之情況，式[B7]至式[B9]相當於n=3之情況，式[B10]至式[B12]相當於n=5之情況。 此等中亦以式[B3]所示結構為佳，特佳為式[B3]與式[A3]之組合。Examples of the partial structure (A-NHC(=O)O) _n L ³ -in the compound represented by the above formula [2] include structures represented by the following formulae [B1] to [B12].

(In the formula, A represents one of the structures represented by the aforementioned formulas [A1] to [A5], and a structure in which the acryloyl group in these structures is replaced with a methacryloyl group). Among the structures shown in the above formulas [B1] to [B12], formulas [B1] and [B2] correspond to the case of n=1, and formulas [B3] to [B6] correspond to the case of n=2 , Equations [B7] to [B9] correspond to the case of n=3, and equations [B10] to [B12] correspond to the case of n=5. Among these, the structure represented by formula [B3] is also preferable, and a combination of formula [B3] and formula [A3] is particularly preferable.

上述式[1]所示部分結構相當於由前述式[2]所示化合物中除去A-NHC(=O)-的部分。 前述式[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至30之範圍為佳，以7至21之範圍為較佳。又，重複單位-[OCF₂ CF₂ ]-之數與重複單位-[OCF₂ ]-之數的比率以2：1至1：2之範圍者為佳，成為約1：1之範圍者為較佳。這些重複單位的鍵結可為嵌段鍵結及無規鍵結中任一種。Preferred (b) perfluoropolyethers having polymerizable groups at both ends include compounds having a partial structure represented by the following formula [1].

The partial structure represented by the above formula [1] corresponds to the portion where A-NHC(=O)- is removed from the compound represented by the aforementioned formula [2]. In the above formula [1], n represents the total number of repeating units-[OCF ₂ CF ₂ ]- and repeating units-[OCF ₂ ]-, preferably in the range of 5 to 30, and in the range of 7 to 21. Is better. In addition, 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. The bonding of these repeating units may be any of block bonding and random bonding.

For the present invention, (b) in perfluoropolyether having polymerizable groups at both ends, 100 parts by mass of oxyethylated denatured polyfunctional monomer having at least 3 active energy ray polymerizable groups in (a) In other words, it is preferably used in a ratio of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass.

(式中，PFPE、L¹ 、L² 、L³ 及n表示與前述相同意思)所示化合物之兩末端上所存在的羥基而言，具有聚合性基之異氰酸酯化合物，即使前述式[A1]至式[A5]所示結構及此等結構中之丙烯醯基由甲基丙烯醯基所取代的結構中之結合鍵上，鍵結著異氰酸酯基之化合物(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)進行反應而形成胺基甲酸酯鍵而得。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 , L ³ and n represent the same meaning as described above.) The hydroxyl groups present at both ends of the compound shown are isocyanate compounds having a polymerizable group even if the aforementioned formula [A1] To the structure shown in formula [A5] and the structure in which the acryl group in the structure is replaced by a methacryl group, a compound (for example, 2-(meth)acryl) bonded to an isocyanate group Oxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl) ethyl isocyanate) are reacted to form urethane bonds.

In addition, the curable composition of the present invention contains (b) at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, and has an active energy ray polymerizable group through an urethane bond. Perfluoropolyether (however, there is no poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond), it may also be Perfluoroalkylene group) is a perfluoropolyether with an active energy ray polymerizable group at one end of the molecular chain through an urethane bond, and a hydroxyl group at the other end of the molecular chain (but (There is no poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond, and between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned hydroxyl group) Or as shown in the above formula [3], a perfluoropolyether having a hydroxyl group at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group (but, in the aforementioned poly(oxyperfluoroalkylene) Between the group and the aforementioned hydroxyl group, there is no poly(oxyalkylene)) [compound without active energy ray polymerizable group].

The present invention also relates to a perfluoropolyether having at least 3 active energy ray polymerizable groups at each end of a molecular chain containing a poly(oxyperfluoroalkylene) group via an urethane bond at each end Compounds (except perfluoropolyethers having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond). As the perfluoropolyether compound having polymerizable groups at both ends, a compound having a partial structure represented by the above formula [1] is preferred. As described above, the perfluoropolyether compound of the present invention can achieve excellent compatibility with the component (a), thereby suppressing the white turbidity of the hard coating layer, and enabling the formation of a transparent coating hard coating layer. . The present invention also relates to a surface modifier containing the above-mentioned perfluoropolyether compound and the use of the perfluoropolyether compound for surface modification.

[(c) Polymerization initiator that generates free radicals by active energy rays] The curable composition of the present invention is preferably a polymerization initiator that generates free radicals by active energy rays (hereinafter simply referred to as "(c) polymerization initiator"), for example, by electron rays, ultraviolet rays, Active energy rays such as X-rays are especially polymerization initiators that generate free radicals by ultraviolet irradiation. Examples of the (c) polymerization initiator include benzoin, alkyl ketones, thioxanthones, azos, azides, diazos, o-quinone diazides, Acylphosphine oxides, oxime esters, organic peroxides, benzophenones, bis-coumarins, diimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyl tris Azines, and onium salts such as iodonium salts and sulfonium salts. These can be used alone or in combination of two or more. Among the aforementioned (c) polymerization initiators, also in the present invention, from the viewpoint of transparency, surface curability, and film curability, alkyl ketones are used as (c) polymerization initiators The better. By using alkyl ketones, a cured film with improved scratch resistance can be obtained.

Examples of the alkyl ketones include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 2-hydroxy-1-(4-( 2-hydroxyethoxy)phenyl)-2-methylpropane-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl) Phenyl)-2-methylpropane-1-one and other α-hydroxyalkyl phenones; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane- Α-aminoalkyl benzophenones such as 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one; 2,2- Dimethoxy-1,2-diphenylethane-1-one; phenylglyoxylic acid methyl.

In the present invention, (c) the polymerization initiator is 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the aforementioned (a) oxyethylated modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, It is preferably used at a ratio of 2 parts by mass to 10 parts by mass.

[(d) Solvent] The curable composition of the present invention may further contain (d) a solvent, which may be in the form of paint (film forming material). As the above-mentioned solvent, only dissolving the aforementioned components (a) to (c), and considering the workability when forming a coating layer related to the formation of a hardened film (hard coating layer) to be described later or the drying property before and after curing, etc., is appropriately selected. . As the solvent, for example, 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 methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; 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 Ethers such as monoisopropyl ether, propylene glycol mono-n-butyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, Alcohols such as ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol; N, N- Dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides; dimethyl sulfoxide and other sulfonylates and two kinds of these mixed solvents The above solvent. (d) The amount of the solvent 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 5 to 50% by mass. The solid content concentration (also referred to as non-volatile content concentration) here means 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 the solid component (the solvent component is removed from all components).

[Other additives] In addition, in the curable composition of the present invention, as long as the effect of the present invention is not impaired, additives that are generally added can be appropriately added as necessary, for example, polymerization inhibitors, light sensitizers, and leveling agents can be appropriately added , Surfactants, adhesion-imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes.

<hardened film> The curable composition of the present invention is formed by coating (coating) on a substrate to form a coating film, and irradiating the coating film with active energy rays to perform polymerization (curing) to form a cured film. The hardened film is also an object of the present invention. In addition, the hard coating layer in the hard coating film to be described later may be formed from the cured film. Examples of the aforementioned substrate at this time include various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN ) Etc. polyester, polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triethyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene Copolymer (AS), norbornene-based resin, thermoplastic polyurethane (TPU), etc.), metal, wood, paper, glass, slate. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.

For the coating method on the aforementioned substrate, for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, and a die can be appropriately selected Coating method, inkjet method, printing method (for example, relief printing method, gravure printing method, lithographic printing method, screen printing method), among these methods, can also be used for roll-to-roll method From the viewpoint of film coatability, it is preferable to use a relief printing method, particularly a gravure coating method. In addition, it is preferable to provide it to the applicator after previously filtering the curable composition with a filter having a pore diameter of about 0.2 μm. In addition, at the time of coating, if necessary, a solvent may be added to the curable composition as a form of coating. As the solvent at this time, various solvents mentioned in the aforementioned [(d) solvent] can be mentioned. After the curable composition is applied to the substrate to form a coating film, the coating film is preliminarily dried by a heating means such as a hot plate or an oven, and then the solvent is removed (solvent removal step). As the condition of the heating and drying at this time, for example, it is preferably performed at 40°C to 120°C for about 30 seconds to 10 minutes. After drying, active energy rays such as ultraviolet rays are irradiated to harden the coating film. As the active energy rays, for example, ultraviolet rays, electron rays, and X rays can be used, and ultraviolet rays are particularly preferable. As a light source used for ultraviolet irradiation, for example, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halogen lamps, xenon lamps, and UV-LEDs can be used. Then, by performing post-baking, specifically by heating using a heating means such as a hot plate or an oven, the polymerization is completed. In addition, the thickness of the formed cured film after drying and curing is usually 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm.

<Hard Coated Film> Using the curable composition of the present invention, it is possible to produce a hard coating film having a hard coating layer on at least one surface (surface) of a film substrate. The hard coating film is also an object of the present invention. The hard coating film can be applied to the surface of various display elements to be protected, such as a flexible display.

The hard coating layer in the hard coating film of the present invention can be completed by a method including the step of forming the coating film by applying the aforementioned curable composition of the present invention on a film substrate, The step of irradiating the coating film with active energy rays such as ultraviolet rays to harden the coating film.

As the film substrate, various transparent resin films that can be used for optical applications among the substrates mentioned in the aforementioned <cured film> can be used. Examples of preferred resin films include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). Ester, polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triethyl cellulose, thermoplastic polyurethane (TPU). In addition, the coating method (coating film forming step) for the curable composition on the film substrate and the active energy ray irradiation method (curing step) for the coating film can be applied to the aforementioned <cured film>. method. In addition, when the curable composition of the present invention contains a solvent (paint form), after the coating film forming step, a step of drying the coating film and removing the solvent may be included as necessary. At this time, the method for drying the coating film (solvent removal step) mentioned in the aforementioned <cured film> can be used. The film thickness of the hard coating layer thus obtained is preferably 1 μm to 20 μm, and preferably 1 μm to 10 μm.

The present invention also relates to a method for producing a laminate including a step of applying the curable composition to a film substrate to form a coating film, and a step of curing the coating film by irradiation with active energy rays. The step of coating on the film substrate to form a coating film and the step of curing the coating film by irradiating with active energy rays can be performed under the same operation and conditions as described above. [Example]

The following examples are given to explain the present invention more specifically, but the present invention is not limited to the following examples. In addition, for the examples, the equipment and conditions used for sample preparation and physical property analysis are as follows.

(1) Coating by bar coating Device: (share) SMT PM-9050MC Bar: A-Bar OSP-22 manufactured by OSG system products (shares), with a maximum wet film thickness of 22 μm (equivalent to wire ingot #9) Coating speed: 4m/min (2) Oven Device: Advantech Toyo Co., Ltd. dust-free dryer DRC433FA (3) UV hardening Device: Heraeus (stock) system CV-110QC-G Lamp: High-pressure mercury lamp H-bulb made by Heraeus (4) Gel permeation chromatography (GPC) Device: HLC-8220GPC manufactured by Tosoh Corporation Pipe column: Shodex (registered trademark) GPC K-804L, GPC K-805L manufactured by Showa Denko Co., Ltd. Column temperature: 40℃ Dissolution solution: tetrahydrofuran Detector: RI (5) Scratch resistance test Device: New East Scientific Co., Ltd. TRIBOGEAR TYPE: 30S Scanning speed: 3,000mm/min Scanning distance: 50mm (6) Contact angle Device: Concordia Interface Science (share) system DropMaster DM-501 Measuring temperature: 20℃ (7) Bending test Device: All good (share) cylindrical mandrel bending tester (8) Tensile test Device: (share) Shimadzu Corporation desktop precision universal testing machine automatic drawing AGS-10kNX Gripper: 1kN manual screw type flat gripper Claws: High-strength rubber jacket claws Stretching speed: 50mm/min Measuring temperature: 23℃ (9) Abrasion resistance test Device: New East Scientific Co., Ltd. TRIBOGEAR TYPE: 30S Scanning speed: 4,500mm/min Scanning distance: 50mm

In addition, the abbreviation means the following. a-1: Ethylene oxide modified trimethylolpropane triacrylate [Aronix (registered trademark) M-350, 3 mol of oxyethylidene] a-2: Ethylene oxide denatured pentaerythritol tetraacrylate [KAYALAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., oxyethyl 4mol] a-3: Ethylene oxide-modified diglycerin tetraacrylate [Aronix (registered trademark) M-460 manufactured by East Asia Synthetic Co., Ltd., 4 mol of oxyethyl group] a-4: Ethylene oxide-modified tetraglycerol polyacrylate [SA-TE6 made by Sakamoto Pharmaceutical Co., Ltd., number of functional groups 6, oxyethyl 6mol] a-5: Modified decaglycerin polyacrylate of ethylene oxide [SA-ZE12 made by Sakamoto Pharmaceutical Co., Ltd., number of functional groups 12, oxyethyl 12mol] a-6: Ethylene oxide denatured dipentaerythritol hexaacrylate [KAYALAD DPEA-12 manufactured by Nippon Kayaku Co., Ltd., oxyethyl 12mol] a-51: Trimethylolpropane triacrylate [NK ester A-TMPT manufactured by Shin Nakamura Chemical Industry Co., Ltd.] a-52: Glycerin triacrylate [Aronix (registered trademark) MT-3547 manufactured by East Asia Synthetic Co., Ltd.] a-53: Pentaerythritol triacrylate/Pentaerythritol tetraacrylate mixture [KAYALAD PET-30 manufactured by Nippon Kayaku Co., Ltd.] a-54: Dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [KAYALAD DPHA manufactured by Nippon Kayaku Co., Ltd.] a-55: Modified trimethylolpropane triacrylate of propylene oxide [Aronix (registered trademark) M-310 manufactured by East Asia Synthetic Co., Ltd., 3 oxy (methyl ethoxy) group] a-56: Propylene oxide denatured glycerin triacrylate [OTA480 produced by Daicel and Ornex Co., Ltd., 3 mol of oxy (methyl ethylidene) group] a-57: Ethylene oxide modified glycerol triacrylate [NK ester A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd., and oxyethyl 9mol] PFPE1: Perfluoropolyether with two hydroxyl groups without poly(oxyalkylene) groups at both ends [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers] BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Showa Denko Co., Ltd. Karenz (registered trademark) BEI] AOI: 2-Acryloyloxyethyl isocyanate [Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.] DOTDD: Dioctyltin dineodecanoate [Nitto Chemical Co., Ltd. Neostan (registered trademark) U-830] I2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropane-1-one [BASF Japan Co., Ltd. IRGACURE (registered trademark) 2959] MEK: methyl ethyl ketone PGME: propylene glycol monomethyl ether MeOH: methanol

[Production Example 1] Production of perfluoropolyether (SM1) having four acryl groups at both ends via an urethane bond PFPE1 1.19g (0.5mmol), BEI0.52g (2.0mmol), DOTDD0.017g (0.01 times the total mass of PFPE1 and BEI) and MEK1.67g were charged into the screw tube. This mixture was stirred at room temperature (about 23° C.) for 24 hours using a stirrer chip to obtain a 50% by mass MEK solution of SM1 of the target compound. The weight average molecular weight of the obtained SM1 measured in terms of polystyrene conversion of GPC: Mw was 3,000, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Production Example 2] A perfluoropolyether (SM2) having two acryl groups on one of the two ends and four acryl groups on the other ends of the two ends via an urethane bond Manufacturing Put 1.19 g (0.5 mmol) of PFPE1, 0.36 g (1.5 mmol) of BEI, 0.015 g of DOTDD (0.01 times the total mass of PFPE1 and BEI) and 1.56 g of MEK into the screw tube. The mixture was stirred at room temperature (about 23° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of SM2 of the target compound. The weight average molecular weight of the obtained SM2 measured in terms of polystyrene conversion of GPC: Mw was 2,750, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Production Example 3] A perfluoropolyether (SM3) having 3 acryl groups at one end of both ends and 4 acryl groups at the other ends of the two ends via an urethane bond Manufacturing Put PFPE1 1.19g (0.5mmol), BEI0.36g (1.5mmol), AOI0.07g (0.5mmol), DOTDD0.016g (0.01 times the total mass of PFPE1, BEI, AOI) and MEK1.64g in the screw tube . This mixture was stirred at room temperature (about 23° C.) for 72 hours using a stirrer chip to obtain a 50% by mass MEK solution of SM3 of the target compound. The weight average molecular weight of the obtained SM3 measured in terms of polystyrene conversion of GPC: Mw was 2,900, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Example 1 to Example 9, Comparative Example 1 to Comparative Example 8] The components of the following (1) to (4) were mixed to prepare a curable composition having a solid content concentration described in Table 1. In addition, the solid content here means a component other than a solvent. In Table 1, [parts] represents [parts by mass], EO represents an oxyethylidene group, and PO represents an oxy(methylethylidene) group. (1) Polyfunctional monomer: 100 parts by mass of the polyfunctional monomer described in Table 1 (2) Surface modifier: Surface modifier shown in Table 1 The amount described in Table 1 (solid content conversion) (3 ) Polymerization initiator: I2959 3 parts by mass (4) Solvent: PGME The amount described in Table 1 This hardenable composition is easily adhered on both sides of A4 size PET film [Lumirror (registered trademark) U403 manufactured by Toray Co., Ltd. U403 , Thickness 100 μm] is applied by bar coating to obtain a coating film. The coating film was dried in an oven at 120°C for 3 minutes to remove the solvent. The obtained film was exposed to UV light at an exposure amount of 300 mJ/cm ² under a nitrogen environment, and a hard coating film containing a hard coating layer (hardened film) having a film thickness of about 5 μm was produced.

The resulting hard coating film was evaluated for scratch resistance (appearance, stain resistance), bending resistance, and elongation. The procedure for each evaluation is shown below. The results are combined in Table 2.

[Scratch resistance: Appearance] The surface of the hard coating layer was loaded with 250 g/cm ² of steel wool [Bonster (registered trademark) #0000 (ultra-fine) manufactured by Bonster Sales Co., Ltd. attached to the reciprocating abrasion tester. After 2,000 round trips, the degree of injury was visually confirmed and evaluated based on the following criteria A, B, and C. In addition, when it is assumed that the hard coating layer is actually used, at least B is achieved, and A is preferred. A: Not hurt B: Some were hurt C: All were hurt

[Scratch resistance: Smudge resistance] For the abrasion resistance test before and after, the water contact angle on the surface of the hard coating layer is measured, and the difference between the contact angle value before the test and the contact angle value before and after the test (contact angle before the test-contact angle after the test) is based on the following Benchmarks A and C are evaluated. In addition, the contact angle is such that 1 μl of water is attached to the surface of the hard coating layer, and the contact angle θ after 5 seconds is measured in a 5-point manner, and the average value is used as the contact angle value. In addition, when it is assumed that the hard coating layer is actually used, A is preferable. A: The contact angle value before the test is more than 90 degrees and the difference between the contact angle values before and after the test is less than 10 degrees C: The contact angle value before the test is 90 degrees or more and the difference between the contact angle values before and after the test is 10 degrees or more, or the contact angle value before the test does not reach 90 degrees

[Bending resistance] The hard coating film was cut into a rectangle with a length of 80 mm and a width of 20 mm to prepare a test piece. In a tester provided with a mandrel, the short side of the test piece is fixed, and a 180-degree bend is made between 1 second and 2 seconds to make the hard coating layer outward. The hard coating layer after bending was visually observed to confirm the presence or absence of cracks. The test was conducted under a mandrel with a radius of curvature of 1 mmR, 2 mmR, 3 mmR, 5 mmR, and 10 mmR. The minimum radius of curvature where no cracks occurred was regarded as the bending resistance, and the evaluation was performed according to the following criteria A, B, and C. In addition, when it is assumed that the hard coating layer is actually used, at least B is achieved, and A is preferred. A: Less than 3mmR B: Less than 10mmR above 3mmR C: 10mmR or more

[Extensible] The hard coating film was cut into a rectangle with a length of 60 mm and a width of 10 mm to prepare a test piece. The gripper of the universal testing machine grabs 20mm at both ends of the longitudinal direction of each test piece, and performs a tensile test until the elongation (= (the increase in distance between grippers) ÷ (distance between grippers) × 100) becomes 2.5% , 7.5%, 10%. The hard coating layer of the test piece was visually observed, and the maximum elongation at which no cracks were generated was regarded as the extensibility, and the evaluation was performed based on the following criteria A, B, and C. Moreover, when it is assumed that the hard coating layer is actually used, at least B is achieved, and A is preferable. A: 10% or more B: Less than 2.5% and less than 10% C: less than 2.5%

As shown in Tables 1 and 2, as the multifunctional monomer, an oxyethylated denatured acrylate having a functional group number of 3 or more and 1 mol to 2 mol of oxyethylidene groups for 1 mol of functional groups is used as a surface modifier Using a perfluoropolyether SM1 having four acryl groups at both ends via an urethane bond, and a hard coating film prepared using a curable composition prepared by mixing the two (Examples 1 to 1) Example 7) While having excellent scratch resistance, it also has bending resistance and moderate elongation. Furthermore, it was found that the use of a curable composition in which perfluoropolyether SM2 or SM3 was added instead of the above SM1 as a surface modifier, and the produced hard coating film (Example 8 and Example 9) had excellent scratch resistance. At the same time, it also has bending resistance and moderate elongation.

On the other hand, as a polyfunctional monomer, when a hard coating film of 3-functional to 6-functional acrylate that is not modified by oxyethylidene (Comparative Example 1 to Comparative Example 4) is used, bending resistance and elongation are obtained. Poor results. In addition, the hard coating film (Comparative Example 5 and Comparative Example 6) using an oxy (methylethylidene) modified trifunctional acrylate has a scratch resistance of 1 mol for 1 mol of the functional group. The result of deterioration. Furthermore, even if it is an oxyethylated denatured acrylate, a hard coating film (Comparative Example 7) using an acrylate of 3 mol with respect to 1 mol of oxyethylated functional groups becomes the result of deterioration of the antifouling property. In addition, the hard coating film (Comparative Example 8) of perfluoropolyether that does not contain a surface modifier becomes the result of deterioration of scratch resistance and stain resistance.

[Examples 10 to 12, and Comparative Example 9] The components of the following (1) to (4) were mixed to prepare a curable composition having a solid content concentration described in Table 3. In addition, the solid content here means a component other than a solvent. In Table 3, [parts] represents [parts by mass], and EO represents oxyethylidene. (1) Polyfunctional monomer: 100 parts by mass of polyfunctional monomer described in Table 3 (2) Surface modifier: 0.2 parts by mass of surface modifier described in Table 3 (solid content conversion) (3) Polymerization Starting agent: I2959 3 parts by mass (4) Solvent: MeOH The amount described in Table 3 This curable composition can be easily adhered to both sides of A4 size PET film [Lumirror (registered trademark) U403 made by Toray Co., Ltd., thickness 100 μm ] A coating film is applied by bar coating. The coating film was dried in an oven at 65°C for 3 minutes and the solvent was removed. The resulting film was irradiated with UV light at an exposure amount of 300 mJ/cm ² under a nitrogen environment and exposed to produce a hard coating film containing a hard coating layer (hardened film) having a film thickness of approximately 5 μm.

For the obtained hard coating film, in addition to the aforementioned evaluations of [abrasion resistance], [bendability] and [extensibility], abrasion resistance was evaluated. The procedure for abrasion resistance evaluation is shown below. The results are shown in Table 4.

[Abrasion resistance] The surface of the hard coating layer was applied with a cylindrical rubber wipe [RUBBER STICK manufactured by Minoan Co., Ltd., φ6.0 mm] attached to a reciprocating abrasion tester under a load of 1 kg to perform 3,000 reciprocating wipes. 1 μL of water was attached to the wiping portion, and the contact angle θ after 5 seconds at 5 points was measured, and the average value was used as the contact angle value, and the evaluation was performed based on the following criteria A, B, and C. In addition, when it is assumed that the hard coating layer is actually used, at least B is achieved, and A is preferred. A: θ≧80° B: 70°≦θ＜80° C: θ<70°

As shown in Table 3 and Table 4, as the multifunctional monomer, an oxyethylated denatured acrylate having a functional group number of 3 or more and 1 mol of oxyethylated groups for 1 mol of functional groups is used as a surface modifier. Perfluoropolyether SM1, SM2 or SM3, the hard coating film (Example 10 to Example 12) made of the hardening composition prepared by the two has excellent scratch resistance, bending resistance and elongation In addition to resistance, it also has good abrasion resistance.

On the other hand, a perfluoropolyether hard coating film (Comparative Example 9) that does not contain a surface modifier becomes the result of deterioration of abrasion resistance.

Claims (13)

A hardening composition characterized by containing: (a) An oxyethylated denatured polyfunctional monomer having at least 3 active energy ray polymerizable groups, the average oxyethylated denatured amount is less than 3 mol of oxyethylated denatured polyfunctional for the polymerizable group of 1 mol 100 parts by mass of monomer, (b) At both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, a perfluoropolyether having an active energy ray polymerizable group via an urethane bond (but, except for the poly (Other than perfluoropolyethers having a poly(oxyalkylene) group between the (oxyperfluoroalkylene) group and the aforementioned urethane bond) 0.1 parts by mass to 10 parts by mass, and (c) by active energy 1 to 20 parts by mass of a polymerization initiator that generates free radicals. The hardenable composition according to claim 1, wherein the aforementioned (b) perfluoropolyether has at least two active energy ray polymerizable groups at both ends. The hardenable composition according to claim 2, wherein the aforementioned (b) perfluoropolyether has at least 3 active energy ray polymerizable groups at each of both ends. The hardenable composition according to any one of claim 1 to claim 3, wherein the poly(oxyperfluoroalkylene) group has -[OCF ₂ ]- and -[OCF ₂ CF ₂ ] as repeating units -The base. The hardenable composition according to claim 4, wherein the aforementioned (b) perfluoropolyether has a partial structure represented by the following formula [1];

(In formula [1], n represents the total number of repeating units-[OCF ₂ CF ₂ ]-number and repeating units-[OCF ₂ ]-number). The curable composition according to any one of claim 1 to claim 5, wherein the aforementioned (a) oxyethyl-modified polyfunctional monomer contains a compound selected from the group consisting of oxyethyl-modified polyfunctional (meth)acrylate compounds and At least one type of oxyethylated polyfunctional urethane (meth)acrylate compound. The hardenable composition according to any one of claim 1 to claim 6, wherein the average amount of oxyethylation of the aforementioned (a) oxyethylated polyfunctional monomer is 2 mol for 1 mol of the aforementioned polymerizable group the following. The hardenable composition according to any one of claim 1 to claim 7, which further contains (d) a solvent. A cured film characterized by being obtained by the curable composition according to any one of claim 1 to claim 8. A hard coating film is a hard coating film having a hard coating layer on at least one surface of a film substrate, and is characterized in that the hard coating layer contains the cured film according to claim 9. A hard coating film, which is a hard coating film provided with a hard coating layer on at least one side of a film substrate, characterized in that the hard coating layer is formed by the following method, which includes: The step of applying the curable composition of any one of claims 1 to 8 to 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 coating film according to claim 10 or claim 11, wherein the aforementioned hard coating layer has a film thickness of 1 μm to 10 μm. A method for manufacturing a laminate, characterized by comprising the steps of applying a curable composition as described in any one of claim 1 to claim 8 on a film substrate to form a coating film, and forming a coating film on the coating film Step of irradiating active energy rays to harden them.