JPWO2016163478A1 - Curable composition for antiglare coating - Google Patents

Abstract

An object of the present invention is to provide a material for forming a hard coat layer which is excellent in antiglare property and exhibits high scratch resistance. (A) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (b) via a poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, or poly 0.1 to 10 parts by mass of perfluoropolyether having an active energy ray polymerizable group through an (oxyalkylene) group and one urethane bond in this order, (c) organic fine particles 8 having an average particle diameter of 1 to 10 μm -30 parts by mass, (d) 1-20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and (e) a curable composition containing an organic solvent, and a hard coat layer formed from the composition Hard coat film provided. [Selection figure] None

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 a touch panel display and a liquid crystal display, and more particularly to a hard coat layer excellent in antiglare property (antiglare function). The present invention relates to a curable composition that can be formed.

  A large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a portable game device, and an ATM 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.

  An anti-glare hard coat film having a hard coat layer of about several μm with irregularities formed on the surface is bonded to the surface of these touch panel displays in order to prevent a decrease in visibility due to reflection of external light on the screen. The method is used. As a method for forming irregularities on the surface, a method in which fine particles having a particle size of about several μm are contained in a hard coat layer is generally used.

By the way, the capacitive touch panel is operated by touching it with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time an operation is performed, causing problems that the visibility of the image on the display is remarkably impaired and the appearance of the display is impaired. The fingerprint contains moisture derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the display surface in order to prevent both of them from adhering. ing.
However, since capacitive touch panels are touched by a finger every day, even if the initial antifouling property has reached a considerable level, their functions often deteriorate due to scratches during use. . In particular, the antiglare hard coat layer has irregularities on its surface, so that it tends to be caught and easily damaged. Therefore, the durability of the antifouling property in the process of use has been a problem.

  Up to now, as a hard coat layer having antiglare and scratch resistance, as a component for imparting antifouling and scratch resistance to the surface of the hard coat layer, a poly (oxyperfluoroalkylene) structure and (meth) in the molecule A technique using methyl methacrylate-styrene copolymer (MS) resin fine particles as a surface modifier having an acryloyl group and a component for imparting antiglare properties to the hard coat layer is disclosed (Patent Document 1). .

JP 2013-257359 A

  In the method specifically described in Patent Document 1, the fluorine content of the surface modifier having a poly (oxyperfluoroalkylene) structure and a (meth) acryloyl group in the molecule is low, and sufficient antifouling and antifouling properties are obtained. There was a problem that it was impossible to obtain scratch resistance. Also, if the amount of MS resin particles added is reduced to obtain scratch resistance, sufficient antiglare properties cannot be obtained, and if MS resin particles are added to such an extent that sufficient antiglare properties can be obtained, scratch resistance can be obtained. There was a problem that the remarkably decreased. Furthermore, the dispersibility of the resin particles in the hard coat layer is poor, and it becomes an agglomerate, and the appearance of the coating film is impaired. That is, there has been a demand for a hard coat layer that has excellent antiglare properties and exhibits high scratch resistance.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a poly (oxyalkylene) group is attached to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) structure via a poly (oxyalkylene) group or a poly (oxyalkylene). By using a curable composition in which a compound having an active energy ray-polymerizable group is added as a fluorine-based surface modifier via a group and one urethane bond, and organic fine particles are further added thereto, The inventors have found that a hard coat layer having antiglare properties and high scratch resistance can be formed, and completed the present invention.

That is, the present invention provides the first aspect as follows:
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) Active energy rays through a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of a perfluoropolyether having a polymerizable group,
(C) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm,
(D) It relates to a curable composition containing 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and (e) an organic solvent.
As a second aspect, the curable composition according to the first aspect, in which the poly (oxyperfluoroalkylene) group is a group having — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — as repeating units. About.
As a third aspect, the present invention relates to the curable composition according to the first aspect or the second aspect, in which the poly (oxyalkylene) group is a poly (oxyethylene) group.
As a fourth aspect, the polyfunctional monomer of component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. It relates to the curable composition as described in any one of viewpoints.
As a fifth aspect, the present invention relates to the curable composition according to any one of the first aspect to the fourth aspect, in which the organic fine particles of the component (c) are spherical particles.
As a sixth aspect, the present invention relates to the curable composition according to any one of the first aspect to the fifth aspect, wherein the organic fine particles of the component (c) are polymethyl methacrylate particles.
As a seventh aspect, the present invention relates to the curable composition according to any one of the first aspect to the sixth aspect, in which the polymerization initiator of the component (d) is an alkylphenone.
As an eighth aspect, the present invention relates to a cured film obtained from the curable composition according to any one of the first aspect to the seventh aspect.
As a ninth aspect, the present invention relates to a hard coat film comprising a hard coat layer on at least one surface of a film base material, wherein the hard coat layer comprises the cured film described in the eighth aspect.
As a tenth aspect, a hard coat film including a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is curable according to any one of the first aspect to the seventh aspect. It is related with the hard coat film formed by the method of apply | coating a composition on a film base material, and forming the coating film, and the method of irradiating this coating film with an active energy ray and hardening | curing.
As an eleventh aspect, the hard coat layer according to the ninth aspect or the tenth aspect, wherein the hard coat layer has a thickness of 1 to 10/7 times the average particle diameter of the organic fine particles.
As a twelfth aspect, the hard coat film according to any one of the ninth aspect to the eleventh aspect, wherein the hard coat layer has a thickness of 1 to 20 μm.
As a thirteenth aspect, the present invention relates to the hard coat film according to the twelfth aspect, in which the hard coat layer has a thickness of 3 to 10 μm.

According to the present invention, there is provided a curable composition useful for forming a cured film and a hard coat layer having excellent scratch resistance and high antiglare property even in a thin film having a thickness of about 1 to 10 μm and excellent in appearance. can do.
Further, according to the present invention, it is possible to provide a hard coat film obtained by applying the cured film obtained from the curable composition or a hard coat layer formed from the cured film, and having anti-glare and scratch resistance. And the hard coat film excellent in an external appearance can be provided.

<Curable composition>
In detail, the curable composition of the present invention includes:
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) Active energy rays through a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of a perfluoropolyether having a polymerizable group,
(C) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm,
(D) It relates to a curable composition containing 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and (e) an organic solvent.
Hereinafter, the components (a) to (e) will be described first.

[(A) Active energy ray-curable polyfunctional monomer]
The active energy ray-curable polyfunctional monomer refers to a monomer that is cured by a polymerization reaction that proceeds by irradiation with an active energy ray such as ultraviolet rays.
In the curable composition of the present invention, the preferable (a) active energy ray-curable polyfunctional monomer is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
In the present invention, the (meth) acrylate compound refers to 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, and pentaerythritol tetra. (Meth) acrylate, 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 Nord A di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decandiol 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]} de Candimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9 -Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantane Diol di (meth) acrylate, 1, - it can be mentioned adamantane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.
Among them, preferred are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

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—).
For example, the polyfunctional urethane (meth) acrylate is obtained by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group, or by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol. Although what is obtained etc. are mentioned, the polyfunctional urethane (meth) acrylate compound which can be used by this invention is not limited only to this illustration.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth). An acrylate, tripentaerythritol hepta (meth) acrylate, etc. are mentioned.
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; these diols, succinic acid, and malein. Examples include polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as acids and adipic acid; polyether polyols; polycarbonate diols and the like.

In the present invention, as the (a) active energy ray-curable polyfunctional monomer, one kind is selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound, or two or more kinds are used. Can be used in combination. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound in combination. Moreover, it is preferable to use together 5 or more functional polyfunctional (meth) acrylate compound and 4 or less polyfunctional (meth) acrylate compound as said polyfunctional (meth) acrylate compound.
Moreover, when using the said polyfunctional (meth) acrylate compound and the said polyfunctional urethane (meth) acrylate compound in combination, the polyfunctional urethane (meth) acrylate compound 20 with respect to 100 mass parts of polyfunctional (meth) acrylate compounds. It is preferable to use -100 mass parts, and it is more preferable to use 30-70 mass parts.
Furthermore, in the polyfunctional (meth) acrylate compound, when the polyfunctional (meth) acrylate compound having 5 or more functions and the polyfunctional (meth) acrylate compound having 4 or less functions are used in combination, the polyfunctional (meth) acrylate compound has 5 or more functions. It is preferable to use 10 to 100 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functional groups, and more preferable to use 20 to 60 parts by mass with respect to 100 parts by mass of the functional (meth) acrylate compound.
Moreover, polyfunctional urethane (meth) acrylate compound 20-100 mass parts with respect to 100 mass parts of polyfunctional (meth) acrylate compounds, and polyfunctional (functional) 4 or less polyfunctionality with respect to 100 mass parts of polyfunctional (meth) acrylate compounds more than 5 functions. Use at 10 to 100 parts by weight of (meth) acrylate compound,
Polyfunctional (meth) acrylate compound 20 to 100 parts by mass with respect to 100 parts by mass of polyfunctional (meth) acrylate compound and polyfunctional (meth) acrylate compound with a functionality of 4 or less with respect to 100 parts by mass of polyfunctional (meth) acrylate compound having 5 or more functions ) Use at 20-60 parts by mass of acrylate compound,
Polyfunctional (meth) acrylate compound with respect to 100 parts by mass Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass and polyfunctional (meth) acrylate compound with 100 or more parts of polyfunctional (meth) acrylate compound ) Use at 10-100 parts by mass of acrylate compound,
Polyfunctional (meth) acrylate compound with respect to 100 parts by mass Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass and polyfunctional (meth) acrylate compound with 100 or more parts of polyfunctional (meth) acrylate compound ) It is preferable to use it in 20-60 mass parts of acrylate compounds.

[(B) Active energy via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group Perfluoropolyether having a linear polymerizable group]
In the present invention, as component (b), a poly (oxyalkylene) group and one urethane bond are bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group. In order, perfluoropolyether having an active energy ray polymerizable group (hereinafter, also referred to simply as “(b) perfluoropolyether having a polymerizable group at both ends”) is used. The component (b) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied.

The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but preferably 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 oxygen atoms are alternately connected, and the oxyperfluoroalkylene group is a carbon atom. This refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked. Specifically, - [OCF _2] - (oxy perfluoromethylene _{group), - [OCF 2 CF 2} ] - ( oxy perfluoroethylene _{group), - [OCF 2 CF 2} CF 2] - ( oxy perfluoropropane -1,3-diyl group),-[OCF ₂ C (CF ₃ ) F]-(oxyperfluoropropane-1,2-diyl group) and the like.
The above oxyperfluoroalkylene groups may be used alone or in combination of two or more. In such a case, the bonds of plural types of oxyperfluoroalkylene groups are block bonds and random bonds. Any of these may be used.

Among these, from the viewpoint of obtaining a cured film having good scratch resistance, as the poly (oxyperfluoroalkylene) group,-[OCF ₂ ]-(oxyperfluoromethylene group) and-[OCF ₂ CF ₂ ]. It is preferable to use a group having both of-(oxyperfluoroethylene group) as repeating units.
Among them, as the poly (oxyperfluoroalkylene) group, the repeating unit: — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — are represented by a molar ratio of [repeating unit: — [OCF ₂ ] —]: [repeating]. Unit:-[OCF ₂ CF ₂ ]-] = 2: It is preferably a group that is included in a ratio of 1 to 1: 2, more preferably a group that is included in a ratio of approximately 1: 1. The bond of these repeating units may be either a block bond or a random bond.
The number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30 and more preferably in the range of 7 to 21 as the total number of repeating units.
Moreover, the weight average molecular weight (Mw) measured by polystyrene conversion by the gel permeation chromatography of the said poly (oxyperfluoroalkylene) group is 1,000-5,000, Preferably it is 1,500-2,000. .

The number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyalkylene) group refers to a group having a structure in which an alkylene group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyalkylene group is a divalent alkylene having 1 to 4 carbon atoms. A group having a structure in which a group and an oxygen atom are linked. Examples of the alkylene group include an ethylene group, a 1-methylethylene group, a trimethylene group, and a tetramethylene group.
The oxyalkylene groups may be used singly or in combination of two or more. In that case, the bonds of the plural oxyalkylene groups may be either block bonds or random bonds. May be.
Among these, the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.
The number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is, for example, in the range of 1 to 15, and more preferably in the range of 5 to 12, for example, 7 to 12.

  Examples of the active energy ray polymerizable group that bonds the poly (oxyalkylene) group or the poly (oxyalkylene) group and one urethane bond in this order include a (meth) acryloyl group and a urethane (meth) acryloyl group. And vinyl group.

  The active energy ray polymerizable group is not limited to one having one active energy ray polymerizable portion such as a (meth) acryloyl moiety, and may have two or more active energy ray polymerizable portions, For example, the following structures A1 to A5 and structures obtained by substituting acryloyl groups in these structures with methacryloyl groups are exemplified.

As the perfluoropolyether having a polymerizable group at both ends (b), the following compounds and compounds obtained by substituting acryloyl groups in these compounds with methacryloyl groups from the viewpoint of easy industrial production Can be mentioned as a preferred example. In the structural formula, A represents one of the structures represented by the formulas [A1] to [A5], PFPE represents the poly (oxyperfluoroalkylene) group, and n is independent of each other. Represents the number of repeating units of the oxyethylene group, preferably 1-15, more preferably 5-12, and even more preferably 7-12.

  Among them, the (b) perfluoropolyether having a polymerizable group at both ends of the present invention has a poly (oxyalkylene) group and one urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group. In this order, that is, a poly (oxyalkylene) group is bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, and a urethane bond is bonded to each poly (oxyalkylene) group at both ends. It is preferably a perfluoropolyether having one bonded and an active energy ray polymerizable group bonded to each urethane bond at both ends. Further, in the perfluoropolyether, the active energy ray polymerizable group is preferably a perfluoropolyether which is a group having at least two active energy ray polymerizable moieties.

  In the present invention, (b) the perfluoropolyether having a polymerizable group at both ends is 0.1 to 10 parts by mass, preferably 100 parts by mass of the aforementioned (a) active energy ray-curable polyfunctional monomer, It is desirable to use it in the ratio of 0.2-5 mass parts.

The perfluoropolyether having a polymerizable group at both ends (b) is, for example, a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group. A urethanization reaction of an isocyanate compound having a polymerizable group such as 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate with respect to the hydroxy group of (meth) It can be obtained by a method of dehydrochlorinating acrylic acid chloride or chloromethylstyrene, a method of dehydrating (meth) acrylic acid, a method of esterifying itaconic anhydride, and the like.
Among them, in a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, 2- (meth) acryloyloxyethyl isocyanate or 1 , 1-bis ((meth) acryloyloxymethyl) ethyl isocyanate and other isocyanate compounds having a polymerizable group, or (meth) acrylic acid chloride or chloromethylstyrene is removed from the hydroxy group. The method of reacting with hydrochloric acid is particularly preferable because the reaction is easy.

  In addition, the curable composition of the present invention includes (b) a poly (oxyalkylene) group or one poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group. Through the urethane bond in this order, in addition to the perfluoropolyether having an active energy ray-polymerizable group, the poly (oxyperalkylene) group is attached to one end of the molecular chain containing the poly (oxyperfluoroalkylene) group or the poly (oxyalkylene) group. A perfluoropolyether having an active energy ray-polymerizable group via a (oxyalkylene) group and one urethane bond in this order and having a hydroxy group at the other end via a poly (oxyalkylene) group; (Oxyperfluoroalkylene) A hydroxyl group is bonded to both ends of a molecular chain containing a group via a poly (oxyalkylene) group. Perfluoropolyethers [not having an active energy ray-polymerizable group compound] it may contain.

[(C) Organic fine particles having an average particle diameter of 1 to 10 μm]
In the curable composition of the present invention, the organic fine particles having an average particle diameter of 1 to 10 μm (hereinafter, also simply referred to as “(c) organic fine particles”) are the surface of the hard coat layer formed from the curable composition. Is made uneven to impart antiglare properties.
The organic fine particles can also play a role of controlling the haze value of the hard coat layer by controlling the difference between the refractive index and the refractive index of the curable composition that is the hard coat layer forming material.

  The shape of the organic fine particles is not particularly limited, but may be, for example, a bead-like substantially spherical shape or an irregular shape such as a powder, but is preferably substantially spherical, more preferably an aspect. A substantially spherical particle having a ratio of 1.5 or less, and most preferably a true spherical particle.

Examples of the organic fine particles include polymethyl methacrylate particles (PMMA particles), silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, polyfluoride particles. And ethylene oxide particles. These organic fine particles may be used alone or in combination of two or more.
Among them, polymethyl methacrylate particles can be suitably used as the organic fine particles.

The average particle size of the organic fine particles used in the present invention is in the range of 1 to 10 μm, preferably in the range of 3 to 8 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 the Mie theory. When the average particle size of the organic fine particles is larger than the above numerical range, the image sharpness of the display is deteriorated, and when the average particle size is smaller than the above numerical range, sufficient antiglare property cannot be obtained and glare increases. It becomes easy. The organic fine particles are not particularly limited in terms of particle size distribution, but are preferably monodispersed fine particles having a uniform particle size.
The organic fine particles are preferably organic fine particles having a refractive index having a refractive index difference of 0 to 0.20 with respect to the cured product of the active energy ray-curable polyfunctional monomer (a). The refractive index difference is preferably 0 to 0.10.
The organic fine particles have an average particle size of the average particle size b / film thickness a = 0.7 to 0.7 of the cured film obtained from the curable composition of the present invention described later. It is preferable to select so as to satisfy the range of 1.0.

  Commercially available products can be suitably used as the organic fine particles. For example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, Same ARX series, Same AFX series, Same MB series, Same MBP series, Same MB-C series, Same ACX series, Same ACP series [Sekisui Plastics Co., Ltd.]; Tospearl (registered trademark) series [Momentive・ Performance Materials Japan (same)]; Eposter (registered trademark) series, MA series, ST series, MX series [above, Nippon Shokubai Co., Ltd.]; Opt Beads (registered trademark) series [ Nissan Chemical Industries, Ltd.]; Flow beads series [Sumitomo Seika Co., Ltd.]; Lepal (registered trademark) PPS, PAI, PES, EP (above, manufactured by Toray Industries, Inc.); 3M (registered trademark) Dionion TF micro powder series (manufactured by 3M); Chemisnow (registered trademark) MX series, MZ series, MR series, same KMR series, same KSR series, same MP series, same SX series, same SGP series [above, manufactured by Soken Chemical Co., Ltd.]; Tuftic (registered trademark) AR650 series, same AR-750 series , FH-S series, A-20, YK series, AK series, ASF series, HU series, F series, C series, WS series [above, manufactured by Toyobo Co., Ltd.]; Art Pearl (registered trademark) ) GR series, SE series, G series, GS series, J series, MF series, BE series Over's [more, Negami Chemical Industrial Co., Ltd.]; Shin-Etsu Silicone can be used (registered trademark) KMP series [Shin-Etsu Chemical Co., Ltd.] or the like.

  In the present invention, the organic fine particles (c) are used in a proportion of 8 to 30 parts by mass, preferably 8 to 20 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. desirable.

[(D) Polymerization initiator that generates radicals by active energy rays]
In the curable composition of the present invention, a preferred polymerization initiator that generates radicals by active energy rays (hereinafter also simply referred to as “(d) polymerization initiator”) is, for example, active energy such as electron beam, ultraviolet ray, and X-ray. It is a polymerization initiator that generates radicals by irradiation with ultraviolet rays, in particular.
Examples of the above (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones. Biscumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, or onium salts such as iodonium salts and sulfonium salts. You may use these individually by 1 type or in mixture of 2 or more types.
Among them, in the present invention, it is preferable to use alkylphenones as the polymerization initiator (d) from the viewpoints of transparency, surface curability, and thin film curability. By using alkylphenones, a cured film with improved scratch resistance can be obtained.

  Examples of the alkylphenones include 1-hydroxycyclohexyl = phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) Α) such as phenyl) -2-methylpropan-1-one, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one, etc. 2-hydroxyalkylphenones; 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 Α-aminoalkylphenones such as -one; 2,2-dimethoxy-1,2-diphenylethane-1-one; And methyl oxylate.

  In this invention, (d) a polymerization initiator is 1-20 mass parts with respect to 100 mass parts of above-mentioned (a) active energy ray-curable polyfunctional monomers, Preferably it is used in the ratio of 2-10 mass parts. Is desirable.

[(E) Solvent]
The curable composition of the present invention further includes (e) a solvent, that is, can be in the form of a varnish (film forming material).
As said solvent, the said (a)-(d) component is melt | dissolved and disperse | distributed, and the workability | operativity at the time of the application concerning the cured film (hard coat layer) formation mentioned later, the drying property before and behind hardening, etc. are considered. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane; Halides such as methyl, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether Esters or ester ethers such as cetate; 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 Ethers such as glycol monoisopropyl ether and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, isopropyl alcohol, n- Butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, ben Alcohols such as alcohol, ethylene glycol; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; heterocyclic compounds such as N-methyl-2-pyrrolidone; Moreover, these 2 or more types of mixed solvents are mentioned.

In addition, a solvent having a high boiling point can 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, 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 Methyl 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, etc. Can be mentioned.

  Although the usage-amount of these (e) solvent is not specifically limited, For example, it uses by the density | concentration from which solid content concentration in the curable composition of this invention is 1-70 mass%, Preferably it is 5-50 mass%. Here, the solid content concentration (also referred to as the non-volatile content concentration) is the solid content relative to the total mass (total mass) of the components (a) to (e) (and other additives as required) of the curable composition of the present invention. The content of (all solvent components are removed) is expressed.

[Other additives]
In addition, to the curable composition of the present invention, additives that are generally added as necessary, for example, polymerization inhibitors, photosensitizers, leveling agents, surface activity, unless the effects of the present invention are impaired. An agent, an adhesion-imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like may be appropriately blended.
Moreover, you may mix | blend inorganic fine particles, such as a titanium oxide, in order to control the haze value of a cured film.

<Curing film>
The curable composition of this invention can form a cured film by apply | coating (coating) on a base material, forming a coating film, and irradiating an active energy ray to this coating film and superposing | polymerizing (hardening). The cured film is also an object of the present invention. Moreover, the hard coat layer in the hard coat film mentioned later can consist of this cured film.
Examples of the base material in this case include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, Acetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass, slate, and the like. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.

The coating method on the base material is 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, a die coating method, an ink jet method, a printing method (a relief plate, an intaglio plate). , Lithographic printing, screen printing, etc.) can be selected as appropriate. Among them, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating, a relief printing method, particularly a gravure coating method is used. It is desirable. It is preferable that the curable composition is filtered in advance using a filter having a pore diameter of about 0.2 μm or the like and then used for coating. In addition, when apply | coating, you may further add a solvent to this curable composition as needed. Examples of the solvent in this case include the various solvents mentioned in [(e) Solvent].
After the curable composition is applied on the substrate to form a coating film, the coating film is pre-dried with a hot plate or an oven as necessary to remove the solvent (solvent removal step). In this case, the heat drying conditions are preferably 40 to 120 ° C. and about 30 seconds to 10 minutes, for example.
After drying, the coating film is cured by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
Furthermore, after that, polymerization may be completed by performing post-baking, specifically by heating using a hot plate, an oven or the like.
In addition, the thickness of the cured film formed is 0.01-50 micrometers normally after drying and hardening, Preferably it is 0.05-20 micrometers.

<Hard coat film>
A hard coat film provided with a hard coat layer on at least one surface (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 elements such as a touch panel and a liquid crystal display.

  The hard coat layer in the hard coat film of the present invention comprises a step of applying the curable composition of the present invention on a film substrate to form a coating film, and irradiating the coating film with active energy rays such as ultraviolet rays. It can be formed by a method including a step of curing the coating film.

As the film substrate, various transparent resin films that can be used for optical applications among the substrates mentioned in the above-mentioned <cured film> are used. Preferably, for example, a resin selected from polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose, etc. A film is mentioned.
Moreover, the application method (coating film formation process) of the curable composition on the film substrate and the active energy ray irradiation method (curing process) to the coating film use the method described in the above <cured film>. Can do. Moreover, the process of drying this coating film and removing a solvent can be included after a coating-film formation process as needed. In that case, the drying method (solvent removal process) of the coating film quoted to the above-mentioned <cured film> can be used.
The hard coat layer thus obtained is preferably set to have a thickness of 1 to 10/7 times the average particle size of the organic fine particles. For example, the thickness of the hard coat layer is preferably 1 to 20 μm, more preferably 3 to 10 μm.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) Bar coat application device: PM-9050MC manufactured by SMT Co., Ltd.
Bar 1: OSG System Products Co., Ltd. A-Bar OSP-30, maximum wet film thickness 30 μm (corresponding to wire bar # 12)
Bar 2: OSG System Products A-Bar OSP-22, maximum wet film thickness 22 μm (corresponding to wire bar # 9)
Application speed: 4 m / min (2) Oven Equipment: Dust dryer DRC433FA manufactured by Advantech Toyo Co., Ltd.
(3) UV curing device: CV-110QC-G manufactured by Heraeus Co., Ltd.
Lamp: Heraeus high pressure mercury lamp H-bulb
(4) Film thickness Equipment: Nikon Digital Length Measuring Machine Digimicro MH-15M + Counter TC-101
(5) Glossiness device: Gloss meter GM-268Plus manufactured by Konica Minolta Co., Ltd.
Measurement angle: 60 degrees (6) Scratch test Device: Reciprocating wear tester manufactured by Shinto Kagaku Co., Ltd. TRIBOGEAR TYPE: 30S
Scanning speed: 3,000 mm / min Scanning distance: 50 mm
(7) Total light transmittance, haze Device: Nippon Denshoku Industries Co., Ltd. Haze meter NDH5000
(8) Contact angle device: DropMaster DM-501, manufactured by Kyowa Interface Science Co., Ltd.
Measurement temperature: 20 ° C

Abbreviations represent the following meanings.
PFPE1: Perfluoropolyether having a hydroxy group via a poly (oxyalkylene) group (repeating unit number 8 to 9) at both ends [Fluorolink 5147X manufactured by Solvay Specialty Polymers]
PFPE2: Perfluoropolyether having a hydroxy group via a poly (oxyalkylene) group (with 5 to 6 repeating units) at both ends [Fluorolink 5158X manufactured by Solvay Specialty Polymers]
PFPE3: Perfluoropolyether having hydroxy groups at both ends [Fluorolink D manufactured by Solvay Specialty Polymers]
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko KK]
DBTDL: Dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]
DPHA: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [KAYALAD (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.]
PETA: Pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture [Shin Nakamura Chemical Co., Ltd. NK ester A-TMM-3LM-N]
UA: Hexafunctional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129, manufactured by Daicel Ornex Co., Ltd.]
SM4: UV-reactive fluorine-based surface modifier having a perfluoropolyether structure [manufactured by DIC Corporation, MegaFac (registered trademark) RS-75, active ingredient 40 mass% MEK / MIBK solution]
FP1: Cross-linked polymethyl methacrylate true spherical particle [Techpolymer (registered trademark) SSX-105 manufactured by Sekisui Plastics Co., Ltd., average particle size: 5 μm]
FP2: Cross-linked polymethyl methacrylate true spherical particle [Techpolymer (registered trademark) SSX-103, manufactured by Sekisui Plastics Co., Ltd., average particle size: 3 μm]
FP3: Melamine resin / silica composite true spherical particle [manufactured by Nissan Chemical Industries, Ltd. Optobeads (registered trademark) 2000M, average particle size 2 μm]
FP4: Cross-linked silicone true spherical particles [Mostivive Performance Materials Co., Ltd. Tospearl (registered trademark) 120, average particle size 2 μm]
FP5: Cross-linked silicone true spherical particles [Tospearl (registered trademark) 145 manufactured by Momentive Performance Materials Co., Ltd., average particle size: 4.5 μm]
FP6: Polyorganosilsesquioxane true spherical particles [Shin-Etsu Chemical Co., Ltd., Shin-Etsu Silicone (registered trademark) KMP-590, average particle size 2 μm]
IP1: Rutile type titanium oxide particles [JR-600E manufactured by Teika Co., Ltd., average particle size 0.27 μm]
I2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [IRGACURE (registered trademark) 2959, manufactured by BASF Japan Ltd.]
EPA: ethyl p-dimethylaminobenzoate [KAYACURE (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.]
PET: Polyethylene terephthalate (PET) film with easy adhesion on both sides [Lumirror (registered trademark) U403, manufactured by Toray Industries, Inc., thickness 100 μm]
PC: Double-sided easy adhesion polycarbonate (PC) film [Mitsubishi Gas Chemical Co., Ltd. Iupilon (registered trademark) film FE-2000, thickness 100 μm]
TAC: Double-sided easy-adhesion-treated cellulose triacetate (TAC) film [Fuji Film Co., Ltd. Fujitac (registered trademark) TD80ULM, thickness 80 μm]
AcOPr: propyl acetate MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone PGME: propylene glycol monomethyl ether

[Synthesis Example 1] Production of perfluoropolyether SM1 having acryloyl groups via poly (oxyalkylene) groups at both ends PFPE1 1.05 g (0.5 mmol), BEI 0.26 g (1.0 mmol) ), DBTDL 0.01 g (0.02 mmol), and MEK 1.30 g. The mixture was stirred for 24 hours at room temperature (approximately 23 ° C.) using a stirrer tip. This reaction mixture was diluted with 3.93 g of MEK to obtain a 20 mass% MEK solution of SM1, which is the target compound.

[Synthesis Example 2] Production of perfluoropolyether SM2 having an acryloyl group via a poly (oxyalkylene) group at both ends In a screw tube, 1.89 g (1.0 mmol) of PFPE2 and 0.52 g (2.0 mmol) of BEI ), 0.01 g (0.02 mmol) of DBTDL, and 2.41 g of MEK. This mixture was stirred at room temperature (approximately 23 ° C.) for 24 hours using a stirrer chip to obtain a 50 mass% MEK solution of SM2 as the target compound.

[Synthesis Example 3] Production of perfluoropolyether SM3 having an acryloyl group at both ends In a screw tube, 2.0 g (1.0 mmol) of PFPE3, 0.52 g (2.0 mmol) of BEI, 0.01 g of DBTDL (0. 02 mmol) and 2.52 g of MEK were charged. This mixture was stirred at room temperature (approximately 23 ° C.) for 24 hours using a stirrer chip to obtain a 50% by mass MEK solution of SM3 as the target compound.

[Examples 1-5, Comparative Examples 1-6]
According to the description of Table 1, the following components were mixed to prepare a curable composition having a solid content concentration shown in Table 1. In addition, solid content refers to components other than a solvent here. In the table, [part] represents [part by mass].
(1) Polyfunctional monomer: DPHA 50 parts by mass, UA 30 parts by mass, and PETA 20 parts by mass (2) Surface modifier: The amount of the surface modifier described in Table 1 described in Table 1 (solid content or (Active ingredient conversion)
(3) Organic fine particles: The amount of organic fine particles described in Table 1 described in Table 1 (4) Polymerization initiator: I2959 5 parts by mass (5) Solvent: PGME The amount described in Table 1 On the A4 size double-sided easy-adhesion-treated PET film [Lumirror (registered trademark) U403, manufactured by Toray Industries, Inc., thickness: 100 μm], a bar coating was applied using the bars shown in Table 2 to obtain a coating film. This 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 having an exposure amount of 500 mJ / cm ^{2 in} a nitrogen atmosphere to expose a hard coat film having a hard coat layer (cured film) having the thickness shown in Table 2. .

[Examples 6 to 12]
According to the description in Table 1, the following components were mixed to prepare a curable composition having a solid content of 40% by mass.
(1) Polyfunctional monomer: DPHA 50 parts by mass, UA 30 parts by mass, and PETA 20 parts by mass (2) Surface modifier: SM1 1 part by mass (in terms of solid content)
(3) Organic fine particles: The amount of organic fine particles described in Table 1 as described in Table 1 (4) Inorganic fine particles: The amount of inorganic fine particles described in Table 1 as described in Table 1 (5) Polymerization initiator: I2959 5 mass Part (6) Polymerization accelerator: EPA 0.1 part by mass (7) Solvent: amount of the solvent described in Table 1 as described in Table 1 This curable composition was placed on the film described in Table 2 of A4 size. Bar 1 was applied using bar 1 to obtain a coating film. This coating film was dried in an oven under the conditions described in Table 2 to remove the solvent. The obtained film was exposed to UV light having an exposure amount of 500 mJ / cm ^{2 in} a nitrogen atmosphere to expose a hard coat film having a hard coat layer (cured film) having the thickness shown in Table 2. .

The resulting hard coat film was evaluated for appearance, antiglare property, scratch resistance, total light transmittance, haze, and contact angles of water and oleic acid. The procedure for evaluating the appearance, antiglare property, scratch resistance, and contact angle is shown below. The results are also shown in Table 3.
[appearance]
The appearance of the hard coat film was visually confirmed and evaluated according to the following criteria.
A: There is no unevenness over the entire surface of the hard coat layer. C: Aggregates are deposited on the entire surface of the hard coat layer, and spotted unevenness is conspicuous.
The obtained hard coat film was placed on a black base having a gloss Gs (60 °) of 11.8, and the gloss Gs (60 °) of the hard coat layer surface was measured and evaluated according to the following criteria. In addition, when an actual use is assumed as a hard-coat layer, it is calculated | required that it is at least B, and A is desirable.
A: Gs (60 °) ≦ 120
B: 120 <Gs (60 °) ≦ 125
C: Gs (60 °)> 125
[Abrasion resistance]
The hard coat layer surface was rubbed back and forth 1,000 times with a load of 1 kg / cm ² with steel wool [Bonster Sales Co., Ltd. Bonstar (registered trademark) # 0000 (super extra fine)] attached to a reciprocating wear tester. A line was drawn on the rubbed portion with an oil-based marker [Mckey extra fine (blue), using fine side made by Zebra Co., Ltd.]. The line drawn in succession was wiped off with a non-woven wiper [BEMOT M-1 manufactured by Asahi Kasei Fibers Co., Ltd.], and the degree of scratches was visually confirmed and evaluated according to the following criteria. In addition, when an actual use is assumed as a hard-coat layer, it is calculated | required that it is at least B, and it is desirable that it is A.
A: The line drawn with the oil-based marker can be wiped clean without scratching B: The line drawn with the oil-based marker can be wiped off cleanly C: The ink of the oil-based marker enters the scratch and cannot be wiped [Contact angle]
1 μL of water or oleic acid was adhered to the surface of the hard coat layer, the contact angle θ after 5 seconds was measured at 5 points, and the average value was taken as the contact angle value.

  As shown in Tables 1 to 3, perfluoropolyethers SM1 and SM2 having acryloyl groups via poly (oxyalkylene) groups at both ends are used as surface modifiers in the hard coat layer, and organic fine particles are blended Each of the hard coat films produced using the curable compositions of Examples 1 to 12 was excellent in scratch resistance at a film thickness of 4 to 6 μm and was able to obtain a uniform appearance. In addition, the anti-glare property also satisfied all the criteria in consideration of actual use as compared with Comparative Examples described later.

On the other hand, in Comparative Examples 1 and 2 in which the addition amount of the organic fine particles was less than the numerical range defined in the present invention, and in Comparative Example 6 in which the organic fine particles were not added, the desired antiglare property could not be obtained.
In addition, as a surface modifier for the hard coat layer, instead of perfluoropolyether having acryloyl groups via poly (oxyalkylene) groups at both ends, acryloyl groups can be used without poly (oxyalkylene) groups at both ends. Comparative Example 3 using perfluoropolyether SM3 having an inferior surface was inferior to the scratch resistance as compared with Examples, and had an appearance in which aggregates were deposited on the entire surface of the hard coat layer and spotted unevenness was conspicuous.
Furthermore, Comparative Example 4 and Comparative Example 5 using the UV-reactive fluorine-based surface modifier SM4 having a perfluoropolyether structure as the surface modifier resulted in a very poor scratch resistance.

  As described above, as shown in the results of the examples, it is difficult to obtain satisfactory results in the scratch resistance and appearance of the hard coat layer only by slightly different terminal structures of the perfluoropolyether used as the surface modifier. Moreover, when the addition amount of the organic fine particles is out of the predetermined range, the antiglare property cannot be obtained, and only the curable composition of the present invention can obtain a hard coat film satisfying all these performances.

Claims (13)

(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) Active energy ray polymerization via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of perfluoropolyether having a functional group,
(C) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm,
(D) A curable composition containing 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and (e) an organic solvent. The curable composition according to claim 1, wherein the poly (oxyperfluoroalkylene) group is a group having — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — as repeating units. The curable composition according to claim 1 or 2, wherein the poly (oxyalkylene) group is a poly (oxyethylene) group. The polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. The curable composition according to one item. The curable composition according to any one of claims 1 to 4, wherein the organic fine particles of the component (c) are true spherical particles. The curable composition according to any one of claims 1 to 5, wherein the organic fine particles of the component (c) are polymethyl methacrylate particles. The curable composition according to any one of claims 1 to 6, wherein the polymerization initiator of the component (d) is an alkylphenone. The cured film obtained from the curable composition as described in any one of Claims 1 thru | or 7. 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 8. A hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises a film base comprising the curable composition according to any one of claims 1 to 7. A hard coat film formed by a method comprising a step of coating on a material to form a coating film and a step of irradiating the coating film with an active energy ray and curing. The hard coat film according to claim 9 or 10, wherein the hard coat layer has a thickness of 1 to 10/7 times the average particle diameter of the organic fine particles. The hard coat film according to claim 9, wherein the hard coat layer has a thickness of 1 to 20 μm. The hard coat film according to claim 12, wherein the hard coat layer has a thickness of 3 to 10 μm.