JP7332989B2 - Curable composition for antiglare hard coat - Google Patents

Description

The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display elements such as touch panel displays and liquid crystal displays, and is particularly excellent in scratch resistance and antiglare properties (antiglare function). , relates to a curable composition capable of forming a hard coat layer which is also excellent in initial water repellency.

A large number of products equipped with a touch panel display, such as personal computers, mobile phones, portable game machines, and ATMs, have been commercialized. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels having a multi-touch function is rapidly increasing.

On the surface of these touch panel displays, an anti-glare hard-coated film having a hard-coated layer of about several μm on which unevenness is formed is laminated in order to prevent deterioration of visibility due to reflection of external light on the screen. method is used. As a method for forming unevenness on the surface, a method of incorporating fine particles having a particle diameter of about several μm in the hard coat layer is generally used.

By the way, a capacitive touch panel is operated by touching it with a human finger. As a result, fingerprints adhere to the surface of the touch panel each time an operation is performed, which may cause problems such as significantly impairing the visibility of the image on the display and degrading the appearance of the display. Fingerprints contain water derived from sweat and oil derived from sebum, and in order to make it difficult for both of them to adhere, it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the surface of the display. ing.
However, since people touch the capacitive touch panel with their fingers every day, even if the antifouling property of the capacitive touch panel has reached a considerable level in the initial stage, the visibility of the image on the display and the antifouling property may be affected by scratches during use. Sexual function is often impaired. In particular, since the antiglare hard coat layer has irregularities on its surface, it is likely to be caught and scratched. Therefore, the durability of the antifouling property during use has been a problem.

Until now, in the hard coat layer having antiglare and scratch resistance, poly(oxyperfluoroalkylene) structures and (meth ) A technique using methyl methacrylate-styrene copolymer (MS) resin fine particles as a surface modifier having an acryloyl group and a component that imparts antiglare properties to a hard coat layer is disclosed (Patent Document 1 ). On the other hand, a perfluoropolyether having an active energy ray-polymerizable group is added to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond as a surface modifier, and an antiglare hard coat layer. A technique using polymethyl methacrylate particles is disclosed as a component that imparts (Patent Document 2)

JP 2013-257359 A WO2016/163478

In the method specifically described in Patent Document 1, the fluorine content of the surface modifier having a poly(oxyperfluoroalkylene) structure and (meth)acryloyl group in the molecule is low, and sufficient antifouling properties and resistance are obtained. There was a problem that the abrasion resistance could not be obtained. Further, if the amount of MS resin particles added is reduced in order to obtain scratch resistance, sufficient antiglare properties cannot be obtained. There was a problem that the Another problem is that the dispersibility of the resin particles in the hard coat layer is poor, and the resin particles aggregate to impair the appearance of the coating film. Further, the method specifically described in Patent Document 2 can obtain scratch resistance and sufficient antiglare properties, but has the problem that the initial water contact angle is not sufficient and the water repellency is low. That is, there has been a demand for a hard coat layer that is excellent in antiglare properties and scratch resistance and exhibits high initial water repellency.

As a result of intensive studies to achieve the above object, the present inventors have found a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, in which both ends of the molecular chain have poly(oxyalkylene) By using a perfluoropolyether having an active energy ray-polymerizable group as a fluorine-based surface modifier through a urethane bond instead of through a group, and by adopting a curable composition to which fine particles are added, excellent The inventors have found that it is possible to form a hard coat layer that has antiglare properties and high scratch resistance and exhibits high initial water repellency, and completed the present invention.

（上記式［１］中、
ｎは、繰り返し単位－［ＯＣＦ_２ＣＦ_２］－の数と、繰り返し単位－［ＯＣＦ_２］－の数との総数であって５乃至３０の整数を表し、
前記繰り返し単位－［ＯＣＦ_２ＣＦ_２］－と、前記繰り返し単位－［ＯＣＦ_２］－は、ブロック結合、ランダム結合、又は、ブロック結合及びランダム結合の何れかにて結合してなる。）
第６観点として、前記成分（ｃ）の微粒子が有機微粒子である、第１観点乃至第５観点のうち何れか一つに記載の硬化性組成物に関する。
第７観点として、前記成分（ｃ）の有機微粒子がポリメタクリル酸メチル微粒子である、第６観点に記載の硬化性組成物に関する。
第８観点として、（ｅ）溶媒をさらに含む、第１観点乃至第７観点のうち何れか一つに記載の硬化性組成物に関する。
第９観点として、第１観点乃至第８観点のうち何れか一つに記載の硬化性組成物より得られる硬化膜に関する。
第１０観点として、フィルム基材の少なくとも一方の面にハードコート層を備えるハードコートフィルムであって、該ハードコート層が第９観点に記載の硬化膜からなる、ハードコートフィルムに関する。
第１１観点として、前記ハードコート層が１μｍ乃至２０μｍの層厚を有する、第１０観点に記載のハードコートフィルムに関する。
第１２観点として、前記ハードコート層が３μｍ乃至１５μｍの層厚を有する、第１１観点に記載のハードコートフィルムに関する。
第１３観点として、フィルム基材の少なくとも一方の面にハードコート層を備えるハードコートフィルムの製造方法であって、該ハードコート層が、第１観点乃至第８観点のうち何れか一つに記載の硬化性組成物をフィルム基材上に塗布し塗膜を形成する工程と、該塗膜に活性エネルギー線を照射し硬化する工程とを含む、ハードコートフィルムの製造方法に関する。
第１４観点として、第１０観点乃至第１２観点のうち何れか一つに記載のハードコートフィルムを備えたディスプレイに関する。
第１５観点として、第１０観点乃至第１２観点のうち何れか一つに記載のハードコートフィルムを備えた偏光板に関する。That is, the present invention, as a first aspect,
(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(b) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via a urethane bond (provided that 0.05 parts by mass to 10 parts by mass, excluding perfluoropolyethers having a poly(oxyperfluoroalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond;
(c) 5 parts by mass to 40 parts by mass of fine particles having an average particle diameter of 0.2 μm to 15 μm, and (d) 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. Regarding the composition.
As a second aspect, the curable composition according to the first aspect, wherein the (b) perfluoropolyether has at least two active energy ray-polymerizable groups via urethane bonds at both ends of its molecular chain. Regarding.
As a third aspect, the curable composition according to the second aspect, wherein the (b) perfluoropolyether has at least three active energy ray-polymerizable groups at both ends of its molecular chain via urethane bonds. Regarding.
As a fourth aspect, the poly(oxyperfluoroalkylene) group has both repeating units -[OCF ₂ ]- and repeating units -[OCF ₂ CF ₂ ]-, and these repeating units are block-bonded or random-bonded. , or the curable composition according to any one of the first aspect to the third aspect, which is a group formed by bonding with a block bond and a random bond.
As a fifth aspect, it relates to the curable composition according to the fourth aspect, wherein the (b) perfluoropolyether has a partial structure represented by the following formula [1].

(in the above formula [1],
n is the total number of repeating units -[OCF ₂ CF ₂ ]- and repeating units -[OCF ₂ ]- and represents an integer of 5 to 30;
The repeating unit -[OCF ₂ CF ₂ ]- and the repeating unit -[OCF ₂ ]- are bound by either block bond, random bond, or block bond and random bond. )
As a sixth aspect, the present invention relates to the curable composition according to any one of the first to fifth aspects, wherein the fine particles of component (c) are organic fine particles.
As a seventh aspect, it relates to the curable composition according to the sixth aspect, wherein the organic fine particles of component (c) are polymethyl methacrylate fine particles.
As an eighth aspect, it relates to the curable composition according to any one of the first to seventh aspects, further comprising (e) a solvent.
A ninth aspect relates to a cured film obtained from the curable composition according to any one of the first to eighth aspects.
A tenth aspect relates to a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to the ninth aspect.
As an eleventh aspect, it relates to the hard coat film according to the tenth aspect, wherein the hard coat layer has a layer thickness of 1 μm to 20 μm.
As a twelfth aspect, it relates to the hard coat film according to the eleventh aspect, wherein the hard coat layer has a layer thickness of 3 μm to 15 μm.
As a thirteenth aspect, a method for producing a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is any one of the first aspect to the eighth aspect. A method for producing a hard coat film, comprising the steps of: applying the curable composition of (1) onto a film substrate to form a coating film; and curing the coating film by irradiating it with active energy rays.
A fourteenth aspect relates to a display comprising the hard coat film according to any one of the tenth to twelfth aspects.
A fifteenth aspect relates to a polarizing plate comprising the hard coat film according to any one of the tenth to twelfth aspects.

According to the present invention, a cured film and a hard coat that not only have excellent scratch resistance and high antiglare properties even in a thin film with a thickness of about 1 μm to 20 μm and have an excellent appearance, but also exhibit high initial water repellency. Curable compositions useful for forming layers can be provided.
In addition, according to the present invention, it is possible to provide a hard coat film having on its surface a cured film obtained from the curable composition or a hard coat layer formed therefrom, which has antiglare properties, scratch resistance and It is possible to provide a hard coat film which is excellent in appearance and initial water repellency.

<Curable composition>
Specifically, the curable composition of the present invention is
(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(b) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via a urethane bond (provided that 0.05 parts by mass to 10 parts by mass, excluding perfluoropolyethers having a poly(oxyperfluoroalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond;
(c) 5 parts by mass to 40 parts by mass of fine particles having an average particle diameter of 0.2 μm to 15 μm, and (d) 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. Regarding the composition.
First, each of the above components (a) to (e) will be described below.

[(a) Active energy ray-curable polyfunctional monomer]
The term "active energy ray-curable polyfunctional monomer" refers to a monomer that undergoes a polymerization reaction and cures when irradiated with an active energy ray such as ultraviolet rays.
Preferred (a) active energy ray-curable polyfunctional monomers in the curable composition of the present invention include monomers selected from the group consisting of polyfunctional (meth)acrylate compounds.
In addition, in this invention, a (meth)acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid refers to acrylic acid and methacrylic acid.

Examples of the polyfunctional (meth)acrylate compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra (meth)acrylates, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate , ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di (Meth)acrylates, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,9-nonane Diol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth) Acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl) isocyanurate di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyl Oxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, bis[4-(meth)acryloylthio phenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, Mention may be made of polypropylene glycol di(meth)acrylate.
Among them, preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

Moreover, a polyfunctional urethane (meth)acrylate compound can be mentioned as a polyfunctional (meth)acrylate compound. The polyfunctional urethane (meth)acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (--NHCOO--).
Examples of the polyfunctional urethane (meth)acrylate compound include those obtained by the reaction of a polyfunctional isocyanate and a (meth)acrylate having a hydroxy group, and a mixture of a polyfunctional isocyanate and a (meth)acrylate having a hydroxy group and a polyol. Examples include those obtained by reaction, but the polyfunctional urethane (meth)acrylate compounds that can be used in the present invention are not limited to these examples.

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

In the present invention, the (a) active energy ray-curable polyfunctional monomer is selected from the group consisting of the polyfunctional (meth)acrylate compound (compound containing no urethane bond) and the polyfunctional urethane (meth)acrylate compound. can be used alone or in combination of two or more. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth)acrylate compound (compound containing no urethane bond) and a polyfunctional urethane (meth)acrylate compound together.
Further, as the polyfunctional (meth)acrylate compound, it is preferable to use a polyfunctional (meth)acrylate compound having a functionality of 5 or more and a polyfunctional (meth)acrylate compound having a functionality of 4 or less in combination (in this case, it contains a urethane bond. It does not matter whether or not the
Further, when the polyfunctional (meth)acrylate compound (compound containing no urethane bond) and the polyfunctional urethane (meth)acrylate compound are used in combination, the polyfunctional (meth)acrylate compound (compound containing no urethane bond ), it is preferable to use 20 to 100 parts by mass, more preferably 30 to 70 parts by mass of the polyfunctional urethane (meth)acrylate compound with respect to 100 parts by mass.
Furthermore, in the polyfunctional (meth)acrylate compound, when using a combination of the pentafunctional or higher polyfunctional (meth)acrylate compound and the tetrafunctional or lower polyfunctional (meth)acrylate compound, a pentafunctional or higher polyfunctional (meth)acrylate compound With respect to 100 parts by mass of the functional (meth)acrylate compound, it is preferable to use 10 to 100 parts by mass of a tetrafunctional or less polyfunctional (meth)acrylate compound, more preferably 20 to 60 parts by mass. preferable.
Further, 20 to 100 parts by mass of a polyfunctional urethane (meth)acrylate compound per 100 parts by mass of a polyfunctional (meth)acrylate compound (a compound containing no urethane bond) and 100 polyfunctional (meth)acrylate compounds having pentafunctional or higher functionality Using 10 parts by mass to 100 parts by mass of a polyfunctional (meth)acrylate compound having tetrafunctionality or less with respect to parts by mass;
20 to 100 parts by mass of a polyfunctional urethane (meth)acrylate compound per 100 parts by mass of a polyfunctional (meth)acrylate compound (compound containing no urethane bond) and 100 parts by mass of a pentafunctional or higher polyfunctional (meth)acrylate compound 20 parts by mass to 60 parts by mass of a polyfunctional (meth)acrylate compound having a tetrafunctionality or less against
30 to 70 parts by mass of a polyfunctional urethane (meth)acrylate compound and 100 parts by mass of a pentafunctional or higher polyfunctional (meth)acrylate compound per 100 parts by mass of a polyfunctional (meth)acrylate compound (compound containing no urethane bond) 10 parts by mass to 100 parts by mass of a polyfunctional (meth)acrylate compound having tetrafunctionality or less against
30 to 70 parts by mass of a polyfunctional urethane (meth)acrylate compound and 100 parts by mass of a pentafunctional or higher polyfunctional (meth)acrylate compound per 100 parts by mass of a polyfunctional (meth)acrylate compound (compound containing no urethane bond) It is preferable to use 20 to 60 parts by mass of a polyfunctional (meth)acrylate compound having a functionality of 4 or less.

[(b) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via a urethane bond (however, , excluding perfluoropolyethers having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.)]
In the present invention, the component (b) is a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, and at both ends of its molecular chain, not through a poly(oxyalkylene) group but through a urethane bond Therefore, a perfluoropolyether having an active energy ray-polymerizable group (hereinafter also simply referred to as "(b) a perfluoropolyether having a polymerizable group at both ends of the molecular chain") is used. Component (b) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied.
In addition, the component (b) has excellent compatibility with the component (a), thereby suppressing clouding of the hard coat layer and making it possible to form a hard coat layer exhibiting a transparent appearance.
The poly(oxyalkylene) group mentioned above 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.

Although the number of carbon atoms in the alkylene group in the poly(oxyperfluoroalkylene) group is not particularly limited, it preferably has 1 to 4 carbon atoms. That is, the poly(oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are alternately linked, and the oxyperfluoroalkylene group is a carbon atom. A group having a structure in which a divalent fluorocarbon group of numbers 1 to 4 and an oxygen atom are linked. Specifically, -[OCF ₂ ]-(oxyperfluoromethylene group), -[OCF ₂ CF ₂ ]-(oxyperfluoroethylene group), -[OCF ₂ CF ₂ CF ₂ ]-(oxyperfluoropropane -1,3-diyl group) and -[OCF ₂ C(CF ₃ )F]-(oxyperfluoropropane-1,2-diyl group).
The above oxyperfluoroalkylene groups may be used singly or in combination of two or more. any of the combinations.

Among these, -[OCF ₂ ]-(oxyperfluoromethylene group) and -[OCF ₂ CF ₂ ] are used as the poly(oxyperfluoroalkylene) group from the viewpoint of obtaining a cured film having good scratch resistance. It is preferable to use a group having both - (oxyperfluoroethylene group) as repeating units.
Among them, as the above poly(oxyperfluoroalkylene) group, the repeating units: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- are in a molar ratio of [repeating unit: -[OCF ₂ ]-]:[repeating The unit:-[OCF ₂ CF ₂ ]-] is preferably a group containing a ratio of 2:1 to 1:2, more preferably a group containing a ratio of approximately 1:1. Bonding of these repeating units may be either block bonding or random bonding.
The total number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21.
Further, the poly(oxyperfluoroalkylene) group has a weight average molecular weight (Mw) of 1,000 to 5,000, preferably 1,500 to 3,000, measured in terms of polystyrene by gel permeation chromatography. .

Examples of the active energy ray-polymerizable group include a (meth)acryloyl group and a vinyl group.

(b) Perfluoropolyethers having polymerizable groups at both ends of the molecular chain are not limited to those having one active energy ray-polymerizable group such as a (meth)acryloyl group at both ends of the molecular chain; It may have one or more active energy ray-polymerizable groups at both ends of the molecular chain. A5], and structures in which acryloyl groups in these structures are substituted with methacryloyl groups.

（式［２］中、Ａは前記式［Ａ１］乃至式［Ａ５］で表される構造及びこれらの構造中のアクリロイル基をメタクリロイル基に置換した構造のうちの１つを表し、ＰＦＰＥは前記ポリ（オキシパーフルオロアルキレン）基を表し（ただし、Ｌ^１と直接結合する側がオキシ末端であり、酸素原子と結合する側がパーフルオロアルキレン末端である。）、Ｌ^１は、フッ素原子１個乃至３個で置換された炭素原子数２又は３のアルキレン基を表し、ｍはそれぞれ独立して１乃至５の整数を表し、Ｌ^２は、ｍ＋１価のアルコールからＯＨを除いたｍ＋１価の残基を表す。）Examples of such (b) perfluoropolyethers having polymerizable groups at both ends of the molecular chain include compounds represented by the following formula [2].

(In formula [2], A represents one of the structures represented by the above formulas [A1] to [A5] and the structures in which the acryloyl groups in these structures are substituted with methacryloyl groups, and PFPE is the above represents a poly(oxyperfluoroalkylene) group (wherein the side directly bonded to L ¹ is the oxy terminal, and the side bonded to the oxygen atom is the perfluoroalkylene terminal), and L ¹ has 1 to 3 fluorine atoms; represents an alkylene group having 2 or 3 carbon atoms substituted with , m each independently represents an integer of 1 to 5, L ² is an m + 1 valent residue obtained by removing OH from an m + 1 valent alcohol represent.)

Examples of the alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms include -CH ₂ CHF-, -CH ₂ CF ₂ -, -CHFCF ₂ -, and -CH ₂ CH ₂ CHF. -, -CH ₂ CH ₂ CF ₂ -, and -CH ₂ CHFCF ₂ -, and -CH ₂ CF ₂ - is preferred.

（式［Ｂ１］乃至式［Ｂ１２］中、Ａは前記式［Ａ１］乃至式［Ａ５］で表される構造及びこれらの構造中のアクリロイル基をメタクリロイル基に置換した構造のうちの１つを表す。）
上記式［Ｂ１］乃至式［Ｂ１２］で表される構造の中で、式［Ｂ１］及び式［Ｂ２］がｍ＝１の場合に相当し、式［Ｂ３］乃至式［Ｂ６］がｍ＝２の場合に相当し、式［Ｂ７］乃至式［Ｂ９］がｍ＝３の場合に相当し、式［Ｂ１０］乃至式［Ｂ１２］がｍ＝５の場合に相当する。
これらの中でも、式［Ｂ３］で表される構造が好ましく、特に式［Ｂ３］と式［Ａ３］の組合せが好ましい。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 formulas [B1] to [B12]. mentioned.

(In the formulas [B1] to [B12], A is one of the structures represented by the formulas [A1] to [A5] and the structures in which the acryloyl groups in these structures are substituted with methacryloyl groups. represent.)
Among the structures represented by the above formulas [B1] to [B12], formulas [B1] and [B2] correspond to the case where m = 1, and formulas [B3] to [B6] correspond to m = 2, equations [B7] to [B9] correspond to m=3, and equations [B10] to [B12] correspond to m=5.
Among these, the structure represented by formula [B3] is preferable, and the combination of formula [B3] and formula [A3] is particularly preferable.

式［１］で表される部分構造は、前記式［２］で表される化合物から、Ａ－ＮＨＣ（＝Ｏ）を除いた部分に相当する。
式［１］中のｎは、繰り返し単位－［ＯＣＦ_２ＣＦ_２］－の数と、繰り返し単位－［ＯＣＦ_２］－の数との総数を表し、５乃至３０の範囲の整数が好ましく、７乃至２１の範囲の整数がより好ましい。また、繰り返し単位－［ＯＣＦ_２ＣＦ_２］－の数と、繰り返し単位－［ＯＣＦ_２］－の数との比率は、２：１乃至１：２の範囲であることが好ましく、およそ１：１の範囲とすることがより好ましい。これら繰り返し単位の結合は、ブロック結合及びランダム結合の何れであってもよい。Among (b) perfluoropolyethers having polymerizable groups at both ends of the molecular chain, compounds having a partial structure represented by the following formula [1] are particularly preferred.

The partial structure represented by formula [1] corresponds to the portion of the compound represented by formula [2] excluding A-NHC(=O).
n in formula [1] represents the total number of repeating units -[OCF ₂ CF ₂ ]- and repeating units -[OCF ₂ ]-, and is preferably an integer in the range of 5 to 30; Integers in the range to 21 are more preferred. 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, approximately 1:1. is more preferable. Bonding of these repeating units may be either block bonding or random bonding.

In the present invention, the (b) perfluoropolyether having a polymerizable group at both ends of the molecular chain is 0.05 parts by mass to 10 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Parts by weight, for example 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.
(b) By using 0.05 parts by mass or more of perfluoropolyether having polymerizable groups at both ends of the molecular chain, sufficient scratch resistance can be imparted to the hard coat layer. In addition, by using (b) a perfluoropolyether having a polymerizable group at both ends of the molecular chain in a proportion of 10 parts by mass or less, (a) the active energy ray-curable polyfunctional monomer is sufficiently compatible. , a hard coat layer with less cloudiness can be obtained.

（式［３］中、ＰＦＰＥ、Ｌ^１、Ｌ^２及びｍは、前記式［２］と同じ意味を表す。）で表される化合物の両末端に存在するヒドロキシ基に対して、重合性基を有するイソシアネート化合物、即ち、前記式［Ａ１］乃至式［Ａ５］で表される構造及びこれらの構造中のアクリロイル基をメタクリロイル基に置換した構造における結合手にイソシアナト基が結合した化合物（例えば、２－（メタ）アクリロイルオキシエチルイソシアネート、１，１－ビス（（メタ）アクリロイルオキシメチル）エチルイソシアネート）を反応させてウレタン結合を形成することにより得ることができる。The (b) perfluoropolyether having a polymerizable group at both ends of the molecular chain is, for example, the following formula [3]

(In Formula [3], PFPE, L ¹ , L ² and m have the same meanings as in Formula [2] above.) To the hydroxy groups present at both ends of the compound represented by Formula [2], polymerizable groups i.e., a compound in which an isocyanato group is bonded to the bond in the structures represented by the above formulas [A1] to [A5] and the structure in which the acryloyl group in these structures is substituted with a methacryloyl group (e.g., It can be obtained by reacting 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate) to form a urethane bond.

In addition, the curable composition of the present invention includes (b) a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, and at both ends of its molecular chain, via urethane bonds, active energy ray polymerization. In addition to perfluoropolyether having a functional group (provided that it does not have a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond), poly (oxyperfluoroalkylene ) group, having an active energy ray-polymerizable group at one end (one end) of the molecular chain via a urethane bond, and the other end of the molecular chain (the other end terminal) with a hydroxy group (however, between the poly (oxyperfluoroalkylene) group and the urethane bond and between the poly (oxyperfluoroalkylene) group and the hydroxy group) (oxyalkylene) group) or a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, as represented by the above formula [3], at both ends of its molecular chain perfluoropolyether having a hydroxy group (provided that it does not have a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the hydroxy group) [having an active energy ray-polymerizable group compound] may be included.

[(c) fine particles having an average particle diameter of 0.2 μm to 15 μm]
In the curable composition of the present invention, fine particles having an average particle diameter of 0.2 μm to 15 μm (hereinafter also simply referred to as “(c) fine particles”) are formed on the surface of the hard coat layer formed from the curable composition. is made into an uneven shape to impart antiglare properties.
In the present invention, organic fine particles, inorganic fine particles, and organic-inorganic composite fine particles can be used as the (c) fine particles. Among these fine particles, it is preferable to use organic fine particles from the viewpoint of transparency. The organic fine particles can also play a role in controlling the haze value of the hard coat layer by controlling the difference between the refractive index thereof and the refractive index of the curable composition, which is the material for forming the hard coat layer.
The shape of the fine particles (c) is not particularly limited. For example, it may be approximately spherical in the form of beads, or may be irregular in shape such as powder. , an aspect ratio of 1.5 or less, and most preferably spherical particles.

Examples of the organic fine particles include polymethyl methacrylate fine particles (PMMA fine particles), silicone fine particles, polystyrene fine particles, polycarbonate fine particles, acrylic styrene fine particles, benzoguanamine fine particles, melamine fine particles, polyolefin fine particles, polyester fine particles, polyamide fine particles, polyimide fine particles, polyfluoride fine particles. Examples include ethylene oxide fine particles. One type of these organic fine particles may be used alone, or two or more types may be used in combination.
Among these organic fine particles, polymethyl methacrylate fine particles can be preferably used.

The average particle size of the (c) fine particles used in the present invention is in the range of 0.2 μm to 15 μm, preferably in the range of 1 μm to 10 μm. Here, the average particle diameter (μm) is a 50% volume diameter (median diameter) obtained by measurement by a laser diffraction/scattering method based on Mie theory. If the average particle size of the fine particles (c) is larger than the above numerical range, the image sharpness of the display is reduced. becomes more likely to occur. Although the particle size distribution of the fine particles (c) is not particularly limited, they are preferably monodisperse fine particles having a uniform particle size.
The fine particles (c) are preferably fine particles having a refractive index different from the cured product of the active energy ray-curable polyfunctional monomer (a) in a range of 0 to 0.20. The refractive index difference is preferably 0 to 0.10.
In addition, the fine particles (c) have an average particle diameter of 0.1 with respect to the film thickness of the cured film obtained from the curable composition of the present invention, which will be described later. It is preferably chosen to satisfy the range of .to 1.0.

Commercially available organic fine particles can be suitably used, for example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, ARX series, AFX series, MB series, MBP series, MB-C series, ACX series, ACP series [manufactured by Sekisui Plastics Co., Ltd.]; Tospearl (registered trademark) series [Momentive Performance Materials Japan (same)]; Eposter (registered trademark) series, MA series, ST series, MX series [manufactured by Nippon Shokubai Co., Ltd.]; Optobeads (registered trademark) series [ Nissan Chemical Co., Ltd.]; Flowbead series [Sumitomo Seika Co., Ltd.]; Trepal (registered trademark) PPS, PAI, PES, EP [all manufactured by Toray Industries]; 3M (registered trademark) ) Dynion TF micro powder series [manufactured by 3M]; Chemisnow (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, SGP series Soken Chemical Co., Ltd.]; C series, WS series [manufactured by Toyobo Co., Ltd.]; Artpearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, BE series , manufactured by Neagari Kogyo Co., Ltd.]; Shin-Etsu Silicone (registered trademark) KMP series [manufactured by Shin-Etsu Chemical Co., Ltd.].

In the present invention, the fine particles (c) are 5 parts by mass to 40 parts by mass, for example 5 parts by mass to 30 parts by mass, preferably 8 parts by mass, with respect to 100 parts by mass of the active energy ray-curable polyfunctional monomer (a). parts to 25 parts by mass.

[(d) Polymerization Initiator that Generates Radicals by Active Energy Rays]
A preferred polymerization initiator that generates radicals by active energy rays in the curable composition of the present invention (hereinafter also simply referred to as "(d) polymerization initiator") is, for example, an active energy such as an electron beam, an ultraviolet ray, or an X-ray. It is a polymerization initiator that generates radicals when exposed to radiation, particularly when exposed to ultraviolet rays.
Examples of the polymerization initiator (d) include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenone, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These may be used singly or in combination of two or more.
Among them, in the present invention, it is preferable to use alkylphenones as the polymerization initiator (d) from the viewpoint of transparency, surface curability, and thin film curability. By using alkylphenones, a cured film with improved scratch resistance can be obtained.

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

In the present invention, the polymerization initiator (d) is 1 part by mass to 20 parts by mass, preferably 2 parts by mass to 10 parts by mass, relative to 100 parts by mass of the active energy ray-curable polyfunctional monomer (a). use in

[(e) solvent]
The curable composition of the present invention may further contain (e) a solvent, ie, it may be in the form of a varnish (film-forming material).
The above solvent dissolves and disperses the above components (a) to (d), and also takes into account the workability during coating for forming a cured film (hard coat layer) described later, the drying property before and after curing, and the like. can be selected as appropriate. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits and cyclohexane; methyl chloride, methyl bromide, Halides such as methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Esters or ester ethers such as glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl Ethers such as ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclohexanone Ketones such as; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, alcohols such as ethylene glycol; N,N-dimethylformamide ( DMF), N,N-dimethylacetamide (DMAc), amides such as N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethylsulfoxide (DMSO), and mixtures of two or more of these solvents Solvents can be mentioned.

A solvent having a high boiling point may also be used for the purpose of controlling the dispersibility of the fine particles during drying after coating.
Examples of such solvents include cyclohexyl acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, and ethylene glycol monobutyl ether acetate. , diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, Diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, 3-methoxybutanol, dipropylene glycol dimethyl ether, dipropylene glycol- Methyl-propyl-ether may be mentioned.

(e) The amount of the solvent to be used is not particularly limited, but for example, it is used at a concentration such that the solid content concentration in the curable composition of the present invention is 1% to 70% by mass, preferably 5% to 50% by mass. Here, the solid content concentration (also referred to as non-volatile content concentration) refers to the total mass (total mass) of the components (a) to (d) (and optionally other additives) of the curable composition of the present invention. It represents the content of minutes (all components minus the solvent component).

[Other additives]
In addition, the curable composition of the present invention generally contains additives, such as polymerization accelerators, polymerization inhibitors, photosensitizers, leveling agents, which are generally added as necessary as long as they do not impair the effects of the present invention. Agents, surfactants, adhesion imparting agents, plasticizers, ultraviolet absorbers, light stabilizers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, and dyes may be blended as appropriate.
In addition, inorganic fine particles such as titanium oxide may be blended for the purpose of controlling the haze value of the cured film.
Furthermore, for the purpose of increasing the hardness and scratch resistance of the cured film, for example, inorganic fine particles such as silicon dioxide (silica) and silicon dioxide (silica) having a reactive group such as an active energy ray-curable group may be blended. good. Nanoparticles having an average particle size of less than 0.2 μm can be used as the inorganic fine particles of the other additives.

<Cured film>
The curable composition of the present invention can be applied (coated) onto a substrate to form a coating film, and the coating film is irradiated with an active energy ray to polymerize (cure) to form a cured film. The cured film is also an object of the present invention. Further, the hard coat layer in the hard coat film to be described later can be made of the cured film.
Examples of the base material in this case include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass , slate. The shape of these substrates may be plate-like, film-like or three-dimensional molded body.

Examples of coating methods on the substrate include cast coating, spin coating, blade coating, dip coating, roll coating, spray coating, bar coating, die coating, inkjet, printing ( Relief printing method, intaglio printing method, lithographic printing method, screen printing method, etc.) can be appropriately selected, and among these methods, roll-to-roll method can be used, and thin film coating From this point of view, it is desirable to use the letterpress printing method, particularly the gravure coating method. It is preferable that the curable composition is filtered in advance using a filter having a pore size of about 0.2 μm, and then subjected to application. When applying, a solvent may be added to the curable composition, if necessary. As the solvent in this case, various solvents listed in the above [(e) solvent] can be used.
After the curable composition is applied on the substrate to form a coating film, the coating film is pre-dried with a heating means such as a hot plate or an oven, if necessary, to remove the solvent (solvent removal step). At this time, the heat drying conditions are preferably, for example, 40° C. to 120° C. and about 30 seconds to 10 minutes.
After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. As a light source for ultraviolet irradiation, for example, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs can be used.
Furthermore, after that, the polymerization may be completed by performing post-baking, specifically by heating using a heating means such as a hot plate or an oven.
The thickness of the formed cured film after drying and curing is usually 0.01 μm to 50 μm, for example 0.05 μm to 20 μm, preferably 1 μm to 20 μm, more preferably 3 μm to 15 μm.

<Hard coat film>
A hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced using the curable composition of the present invention. The hard coat film is also an object of the present invention, and the hard coat film is suitably used for protecting the surface of various display devices such as touch panels and liquid crystal displays.

The hard coat layer in the hard coat film of the present invention is formed by applying the curable composition of the present invention on a film substrate to form a coating film, and irradiating the coating film with an active energy ray such as ultraviolet rays. It can be formed by a method including a step of curing the coating film. The present invention also includes a method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, including these steps.

As the film substrate, various transparent resin films that can be used for optical purposes are used among the substrates mentioned in <Cured film> above. Preferred resin films include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrenes, polyolefins, and polyamides. , polyimide, triacetyl cellulose (TAC) and the like.
In addition, the method of applying the curable composition onto the film substrate (coating film forming step) and the method of irradiating the active energy ray to the coating film (curing step) are the methods listed in the above-mentioned <cured film>. can be done. Further, when the curable composition of the present invention contains a solvent (in the form of a varnish), a step of drying the coating film to remove the solvent can be included after the coating film forming step, if necessary. In that case, the method of drying the coating film (solvent removal step) described in <Cured film> above can be used.
The layer thickness (film thickness) of the hard coat layer thus obtained is preferably set to be 1 to 10 times the average particle diameter of the (c) fine particles. For example, the thickness of the hard coat layer is preferably 1 μm to 20 μm, more preferably 3 μm to 15 μm.

The hard coat film of the present invention can be used as a hard coat film for a display or a polarizing plate, and a display and a polarizing plate comprising the hard coat film are also objects of the present invention.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
In the examples, the equipment and conditions used for sample preparation and physical property analysis are as follows.

(1) Coating device by bar coater: Automatic Filmapplicator AB3125 manufactured by TQC Sheen
Bar 1: OSG System Products Co., Ltd. A-Bar OSP-42, maximum wet film thickness 42 μm (equivalent to wire bar #16)
Bar 2: OSG System Products Co., Ltd. A-Bar OSP-22, maximum wet film thickness 22 μm (equivalent to wire bar #9)
Bar 3: OSG System Products Co., Ltd. A-Bar OSP-52, maximum wet film thickness 52 μm (equivalent to wire bar #20)
Coating speed: 4 m/min (2) Oven equipment: 2-layer clean oven (upper and lower type) PO-250-45-D manufactured by Sanki Keiso Co., Ltd.
(3) UV curing device: CV-110QC-G manufactured by Heraeus Co., Ltd.
Lamp: High-pressure mercury lamp H-bulb manufactured by Heraeus Co., Ltd.
(4) Film thickness (layer thickness)
Equipment: Digital length measuring machine Digimicro MH-15M + counter TC-101 manufactured by Nikon Corporation
(5) Gloss measurement Device: Gloss meter GM-268 Plus manufactured by Konica Minolta Co., Ltd.
Measurement angle: 60 degrees (6) Scratch resistance test Equipment: Reciprocating wear tester TRIBOGEAR TYPE: 30H manufactured by Shinto Kagaku Co., Ltd.
Scanning speed: 4,500 mm/min Scanning distance: 50 mm
(7) Total light transmittance, haze Apparatus: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
(8) Contact angle measurement device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd.
Measurement temperature: 20°C

Abbreviations have the following meanings.
PFPE1: Perfluoropolyether having two hydroxy groups at both ends of the molecular chain without intervening poly(oxyalkylene) group [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers]
PFPE2: Perfluoropolyether having hydroxy groups at both ends of the molecular chain via poly(oxyalkylene) groups (8 or 9 repeating units) [Fluorolink 5147X manufactured by Solvay Specialty Polymers]
BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Kalenz (registered trademark) BEI manufactured by Showa Denko K.K.]
DOTDD: dioctyl tin dineodecanoate [Nitto Kasei Co., Ltd. Neostan (registered trademark) U-830]
DBTDL: dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]
DPHA: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [KAYALAD (registered trademark) DN-0075 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.]
UA: Hexafunctional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 manufactured by Daicel-Ornex Co., Ltd.]
FP1: Crosslinked polymethyl methacrylate spherical particles [Techpolymer (registered trademark) SSX-105 manufactured by Sekisui Plastics Co., Ltd., average particle size 5 μm]
FP2: Crosslinked polymethyl methacrylate spherical particles [Techpolymer (registered trademark) SSX-108 manufactured by Sekisui Plastics Co., Ltd., average particle size 8 μm]
FP3: Crosslinked polymethyl methacrylate spherical particles [Techpolymer (registered trademark) SSX-110 manufactured by Sekisui Plastics Co., Ltd., average particle size 10 μm]
FP4: Crosslinked polymethyl methacrylate spherical particles [Techpolymer (registered trademark) SSX-103 manufactured by Sekisui Plastics Co., Ltd., average particle size 3 μm]
O2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [OMNIRAD® 2959 from IGM Resins]
EPA: ethyl p-dimethylaminobenzoate [KAYACURE (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.]
PET: double-sided easy-adhesive polyethylene terephthalate (PET) film [Lumirror (registered trademark) U403 manufactured by Toray Industries, Inc., thickness 100 μm]
TAC: double-sided easy-adhesion treated cellulose triacetate (TAC) film [FUJIFILM Corporation Fuji Tac (registered trademark) TD80ULP, thickness 80 μm]
MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone PGME: propylene glycol monomethyl ether

[Production Example 1] Production of perfluoropolyether (SM1) having four acryloyl groups at both ends of the molecular chain via urethane bonds (not via poly(oxyalkylene) groups). 0.19 g (0.5 mmol), 0.52 g (2.0 mmol) BEI, 0.017 g DOTDD (0.01 times the combined mass of PFPE1 and BEI), and 1.67 g MEK were charged. This mixture was stirred at room temperature (approximately 23° C.) for 24 hours using a stirrer tip to obtain a 50 mass % MEK solution of the target compound SM1.
The weight average molecular weight Mw of the resulting SM1 measured in terms of polystyrene by GPC was 3,000, and the degree of dispersion Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Production Example 2] Production of perfluoropolyether (SM2) having acryloyl groups at both ends of the molecular chain via poly(oxyalkylene) groups. 26 g (1.0 mmol), 0.01 g (0.02 mmol) of DBTDL, and 1.30 g of MEK were charged. The mixture was stirred with a stirrer tip at room temperature (approximately 23° C.) for 24 hours. This reaction mixture was diluted with 3.93 g of MEK to obtain a 20 mass % MEK solution of the target compound SM2.

[Examples 1 to 9, Comparative Examples 1 to 4]
The following components were mixed according to Table 1 to prepare a curable composition having a solid concentration of 40% by mass. In addition, solid content refers to components other than a solvent here. Moreover, in Table 1, [parts] represents [parts by mass], and [%] represents [% by mass].
(1) Polyfunctional monomer: 50 parts by mass of DPHA, 30 parts by mass of UA, and 20 parts by mass of PETA (2) Surface modifier: Add the surface modifier described in Table 1 to the amount described in Table 1 (solid content or active ingredient conversion)
(3) Organic fine particles: Organic fine particles shown in Table 1 in the amount shown in Table 1 (4) Polymerization initiator: 5 parts by mass of O2959 (5) Polymerization accelerator: EPA The amount shown in Table 1 (6) Solvent: The solvent shown in Table 1 and the amount shown in Table 1 This curable composition is applied to an A4 size film shown in Table 2 using a bar coater using the bar shown in Table 2 to form a coating film. Obtained. This coating film was dried in an oven under the conditions shown in Table 2 to remove the solvent. A hard coat film having a hard coat layer (cured film) having a thickness shown in Table 2 was produced by exposing the obtained film to UV light having an exposure amount shown in Table 2 under a nitrogen atmosphere. did.

The antiglare property, scratch resistance, water contact angle, haze, and total light transmittance of the obtained hard coat film were evaluated. The procedures for evaluating antiglare properties, scratch resistance, and water contact angles are shown below. The results are also shown in Table 3.
[Anti-glare]
The resulting hard coat film was placed on a black stand having a glossiness Gs (60°) of 11.8, and the glossiness Gs (60°) of the hard coat layer surface of the hard coat film was measured. Evaluation according to A, B and C. Assuming actual use as a hard coat layer, at least B is required, and A is desirable.
A: Gs (60°) ≤ 120
B: 120 < Gs (60°) ≤ 125
C: Gs (60°)>125
[Scratch resistance]
The hard coat layer surface of the hard coat film was rubbed 2,000 times with steel wool [Liberon #0000 manufactured by Liberon Co.] attached to the reciprocating abrasion tester under a load of 500 g/cm ² . The degree of damage was visually confirmed under a three-color light source and evaluated according to the following criteria A, B and C. Assuming actual use as a hard coat layer, at least B is required, and A is desirable.
A: No scratches B: Several fine scratches C: Scratches on the entire surface [contact angle]
1 μL of water was applied to the surface of the hard coat layer of the hard coat film, and the contact angle θ after 5 seconds was measured at 5 points. Assuming actual use as a hard coat layer, the water contact angle (initial water repellency) is required to be A (108° or more).
A: Water contact angle value ≥ 108°
C: Water contact angle value <108°

As shown in Tables 1 to 3, perm having four acryloyl groups via urethane bonds (not via poly(oxyalkylene) groups) at both ends of the molecular chain is used as a surface modifier in the hard coat layer. Each hard coat film having a hard coat layer prepared using the curable compositions of Examples 1 to 9, which uses fluoropolyether SM1 and contains organic fine particles, has a layer thickness of 10 μm to 14 μm. A hard coat film having a hard coat layer with excellent scratch resistance and antiglare properties could be obtained. In addition, the initial water repellency was 108° or more, which satisfied all the criteria in consideration of actual use, as compared with Comparative Examples described later.

On the other hand, the hard coat film of Comparative Example 1, which has a hard coat layer prepared using a perfluoropolyether SM2 having acryloyl groups at both ends of the molecular chain via a poly(oxyalkylene) group as a surface modifier, The desired initial water repellency was not obtained.
Moreover, in Comparative Examples 2 and 3, which do not contain organic fine particles, desired anti-glare properties could not be obtained. Further, in Comparative Example 4 containing 50 parts by mass of organic fine particles, high antiglare properties were obtained, but the scratch resistance was poor.

Claims (12)

(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer (excluding component (b) below) , (b) a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, both of its molecular chains A perfluoropolyether having an active energy ray-polymerizable group at the end via a urethane bond (however, a perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond) excluding fluoropolyether) 0.05 to 10 parts by mass,
(c) 5 parts by mass to 40 parts by mass of organic fine particles having an average particle diameter of 0.2 μm to 15 μm; a sexual composition,
The poly(oxyperfluoroalkylene) group has both repeating units -[OCF ₂ ]- and repeating units -[OCF ₂ CF ₂ ]-, and these repeating units are block-bonded, random-bonded, or block-bonded. and a group formed by bonding with a random bond,
The curable composition, wherein the (b) perfluoropolyether is a compound represented by the following formula [2].

(in the above formula [2],
A represents one of the structures represented by the following formulas [A1] to [A5] and the structures in which the acryloyl groups in these structures are substituted with methacryloyl groups, and PFPE is the poly(oxyperfluoroalkylene) (where the side directly bonded to L ¹ is the oxy terminal, and the side bonded to the oxygen atom is the perfluoroalkylene terminal), and L ¹ is a carbon atom substituted with 1 to 3 fluorine atoms represents an alkylene group of number 2 or 3, and the partial structure (A-NHC(=O)O) _m L ² - represents a structure represented by the following formula [B3]. )

2. The curable composition according to claim 1 , wherein the (b) perfluoropolyether has at least three active energy ray-polymerizable groups via urethane bonds at both ends of its molecular chain. In the compound represented by the formula [2], in the formula [2], A is the structure represented by the formula [A3] or a structure in which the acryloyl group in the structure is substituted with a methacryloyl group. 3. The curable composition of claim 1 or claim 2 . 4. The curable composition according to any one of claims 1 to 3, wherein the organic fine particles of component (c) are polymethyl methacrylate fine particles. 5. The curable composition of any one of claims 1-4 , further comprising (e) a solvent. A cured film obtained from the curable composition according to any one of claims 1 to 5 . A hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to claim 6 . 8. The hard coat film according to claim 7 , wherein said hard coat layer has a layer thickness of 1 μm to 20 μm. The hard coat film according to claim 8 , wherein the hard coat layer has a layer thickness of 3 µm to 15 µm. A method for producing a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the curable composition according to any one of claims 1 to 5 . onto a film substrate to form a coating film; and a step of irradiating the coating film with active energy rays to cure it. A display comprising the hard coat film according to any one of claims 7 to 9 . A polarizing plate comprising the hard coat film according to any one of claims 7 to 9 .