TW201708426A - Anti-glare coating curable composition - Google Patents

Abstract

To provide a material for forming a hard coat layer which has excellent antiglare properties and exhibits high scratch resistance. This curable composition contains (a) 100 parts by mass of an active energy beam-curable multifunctional monomer, (b) 0.1-10 parts by mass of a perfluoropolyether which has an active energy beam-polymerizable group on both terminals of a poly(oxyperfluoroalkylene) group-containing molecular chain, with a poly(oxyalkylene) group, or a poly(oxyalkylene) group and one urethane bond, in that order, interposed therebetween, (c) 8-30 parts by mass of inorganic particles containing having an average particle diameter of 1-10 [mu]m, (d) 1-20 parts by mass of a polymerization initiator that generates radicals by means of active energy rays, and (e) an organic solvent. A hard coat film has a hard coat layer formed from said composition.

Description

Anti-glare coating curable composition

The present invention relates to a curable composition which is useful as a material for forming a hard coat layer which is applied to the surface of various display elements such as a touch panel display, a liquid crystal display, etc., and particularly relates to an anti-glare property (anti-glare (Anti -glare) Functional) a hardenable composition of an excellent hard coat.

Most of the products equipped with touch panels for flat panel displays such as personal computers, mobile phones, portable game devices, and ATMs are commercially available. In particular, with the advent of smart phones or tablets, the capacitive touch panel with multi-touch capability has increased the number of mounts in one breath.

In order to prevent deterioration of visibility due to reflection of external light on the screen of the touch panel display, an anti-glare hard coat film having a hard coat layer having a surface roughness of several μm is formed. The method. As a method of forming irregularities on the surface, a method of containing fine particles having a particle diameter of about several μm in a hard coat layer is generally used.

Moreover, the electrostatic capacitance type touch panel is operated by being touched by a human finger. Therefore, each time an operation is performed, the attachment finger The surface of the touch panel significantly impairs the visibility of the image of the display or the appearance of the display. In the case where the fingerprint contains moisture derived from sweat and oil derived from sebum, in order to make it difficult to adhere to any of these, it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the surface of the display.

However, in the electrostatic capacitance type touch panel, since the person touches the finger every day, even if the initial antifouling property reaches a considerable level, the function can be reduced by increasing the scratch during use. In particular, in the anti-glare hard coat layer, since the surface has irregularities, hook marks are easily generated and scratches are easily caused. Therefore, there is a problem of durability against the antifouling property of the use process.

As a hard coat layer having anti-glare property and scratch resistance, it has been disclosed as a component which imparts antifouling property and scratch resistance to the surface of a hard coat layer, and has a poly(oxyperfluorocyclohexane) structure in the molecule. And a technique of using a methyl methacrylate-styrene copolymer (MS) resin fine particle as a component of a (meth) acrylonitrile-based surface modifier, and a component which imparts anti-glare property to a hard-coat layer (patent document 1) ).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-257359

The method specifically described in Patent Document 1 is in the molecule The surface modifier having a poly(oxyperfluoroalkylene) structure and a (meth)acrylonitrile group has a low fluorine content, and a problem of sufficient antifouling property and scratch resistance cannot be obtained. In addition, when the amount of the MS resin particles to be added is reduced, the anti-glare property is not obtained, and when the MS resin particles are added until the degree of sufficient anti-glare property is obtained, the scratch resistance is remarkable. Reduced issues. Further, the dispersibility of the resin particles in the hard coat layer is deteriorated, and the aggregate has a problem of impairing the appearance of the coating film. That is, a hard coat layer which is excellent in anti-glare property and exhibits high scratch resistance is sought.

As a result of repeated efforts by the present inventors to achieve the above object, it has been found that a poly(oxyalkylene) group or a permeate polymer is transmitted through both ends of a molecular chain to be composed of a poly(oxyperfluoroalkylene) structure. The compound having an active energy ray-polymerizable group and a compound having an active energy ray-polymerizable group are used as a fluorine-based surface modifier, and further, a curable composition to which organic fine particles are added is formed. The present invention has been completed by an excellent anti-glare property and a highly scratch-resistant hard coat layer.

In other words, the present invention relates to a curable composition comprising the following (a) to (e), (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, and (b) The two ends of the molecular chain comprising a poly(oxyperfluoroalkylene) group are active through a poly(oxyalkylene) group or sequentially through a poly(oxyalkylene) group and a urethane bond. 0.1 to 10 parts by mass of the perfluoropolyether of the energy ray polymerizable group, (c) 8 to 30 parts by mass of the organic fine particles having an average particle diameter of 1 to 10 μm, (d) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray, and (e) an organic solvent.

According to a second aspect, the curable composition of the first aspect, wherein the poly(oxyperfluoroalkylene) group has -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as a repeating unit The basis.

The third aspect is the curable composition according to the first aspect or the second aspect, wherein the poly(oxyalkylene) group is a poly(oxyethylene) group.

The curable composition according to any one of the first aspect to the third aspect, wherein the polyfunctional single system of the component (a) is selected from the group consisting of polyfunctional (meth) acrylate compounds and At least one of the group consisting of polyfunctional urethane (meth) acrylate compounds.

The curable composition according to any one of the first aspect to the fourth aspect, wherein the organic fine particles of the component (c) are true spherical particles.

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.

The sclerosing composition according to any one of the first aspect to the sixth aspect, wherein the polymerization initiation of the component (d) The agent is an alkyl phenone.

The eighth aspect relates to a cured film obtained by the curable composition according to any one of the first to seventh aspects.

According to a ninth aspect, a hard coat film comprising a hard coat film having a hard coat layer on a surface of at least one side of a film substrate, wherein the hard coat layer is formed of a cured film of the eighth aspect.

According to a tenth aspect, a hard coat film comprising a hard coat film having a hard coat layer on at least one side of a film substrate, wherein the hard coat layer comprises: from the first viewpoint to the seventh The step of applying the curable composition of any one of the viewpoints to a film substrate to form a coating film, and the step of curing the coating film by irradiating an active energy ray.

The hard coat film according to the ninth aspect or the tenth aspect, wherein the hard coat layer has a thickness of 1 to 10/7 times larger than an average particle diameter of the organic fine particles.

The hard coat film according to any one of the ninth aspect, wherein the hard coat layer has a film thickness of 1 to 20 μm.

The hard coat film according to the twelfth aspect, wherein the hard coat layer has a film thickness of 3 to 10 μm.

According to the present invention, it is possible to provide a hardenable composition for forming a cured film and a hard coat layer which are excellent in scratch resistance and high anti-glare property even in a film having a thickness of about 1 to 10 μm. Things.

Moreover, according to the present invention, it is possible to provide a hard coat film obtained by the above-mentioned curable composition or a hard coat film formed by the hard coat layer formed thereon, which can provide hardness, anti-glare property, and excellent appearance. Apply film.

<Sclerosing composition>

The curable composition of the present invention relates in detail to a curable composition comprising (a) to (e), (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, and (b) comprising The both ends of the molecular chain of the poly(oxyperfluoroalkylene) group pass through the poly(oxyalkylene) group or sequentially pass through the poly(oxyalkylene) group and one urethane bond to have active energy. 0.1 to 10 parts by mass of the perfluoropolyether of the linear polymerizable group, (c) 8 to 30 parts by mass of the organic fine particles having an average particle diameter of 1 to 10 μm, and (d) polymerization initiation of radical generation by the active energy ray 1 to 20 parts by mass of the agent, and (e) an organic solvent.

Hereinafter, each component of the above (a) to (e) will be described.

[(a) Active energy ray-curable polyfunctional monomer]

The active energy ray-curable polyfunctional monomer refers to a monomer which is cured by a polymerization reaction by irradiation with an active energy ray such as ultraviolet rays.

In the curable composition of the present invention, preferred (a) active energy ray-curable polyfunctional monomer is selected from the group consisting of polyfunctional (meth) acrylate compounds and polyfunctional urethane (meth) acrylates. a monomer in the group consisting of ester compounds.

Further, the term "(meth)acrylate compound" as used in the present invention means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic means acrylic acid and methacrylic acid.

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri(meth) acrylate, ditrimethylolpropane tetra(meth) acrylate, and pentaerythritol di(meth) acrylate. , pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, ethoxy Trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerol Acrylate, ethoxylated bisphenol 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-decanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate Two two Alcohol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylic acid Ester, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane dimethanol di(meth)acrylate, dioxanediol di(meth)acrylate, 2-hydroxy-1-propenyloxy-3-methylpropenyloxypropane, 2-hydroxy-1,3-bis(methyl)propenyloxypropane, 9,9-bis[4-(2-(methyl)propenyloxyethoxy)phenyl]anthracene, bis[4 -(Meth)acryloylphenylthio]sulfide, bis[2-(methyl)acrylamidoethylthio]sulfide, 1,3-adamantanediol di(meth)acrylate, 1 3-adamantane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and the like.

Preferred examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

The above polyfunctional urethane (meth) acrylate compound is a compound having a propylene fluorenyl group or a methacryl fluorenyl group and having one or more urethane linkages (-NHCOO-) in one molecule.

For example, examples of the polyfunctional urethane (meth) acrylate include those obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, and a polyfunctional isocyanate having a hydroxyl group ( a reaction of a methyl group acrylate with a polyol, etc., but the polyfunctional urethane (meth) acrylate compound which can be used in the present invention is not It is only limited to this illustration.

Further, examples of the polyfunctional isocyanate include toluene diisocyanate, isophorone diisocyanate, benzodimethyl diisocyanate, and hexamethylene diisocyanate.

Further, examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. Penta(meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like.

Further, examples of the polyhydric alcohol include glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; A polyester polyol such as a reaction product of a diol and an aliphatic dicarboxylic acid or a dicarboxylic acid anhydride such as succinic acid, maleic acid or adipic acid; a polyether polyol; a polycarbonate diol or the like.

In the present invention, the (a) active energy ray-curable polyfunctional monomer may be composed of the above polyfunctional (meth) acrylate compound and the above polyfunctional urethane (meth) acrylate compound. One type or a combination of two or more types will be used in the group. From the viewpoint of the scratch resistance of the obtained cured product, a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound are preferably used in combination. Moreover, as the polyfunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound having 5 or more functional groups and a polyfunctional (meth) acrylate compound having 4 or less functional groups are preferably used in combination.

Further, when the above polyfunctional (meth) acrylate compound is used in combination with the above polyfunctional urethane (meth) acrylate compound, In 100 parts by mass of the polyfunctional (meth) acrylate compound, it is preferred to use 20 to 100 parts by mass of the polyfunctional urethane (meth) acrylate compound, and more preferably 30 to 70 parts by mass.

Further, when the above-mentioned polyfunctional (meth) acrylate compound is used in combination with the above-described pentafunctional or higher polyfunctional (meth) acrylate compound and the above-described tetrafunctional or lower polyfunctional (meth) acrylate compound, 100 parts by mass of the polyfunctional (meth) acrylate compound having a functional or higher functional group is preferably 10 to 100 parts by mass, more preferably 20 to 60 parts by mass, based on the polyfunctional (meth) acrylate compound having 4 or less functional groups.

Further, it is preferred to use a polyfunctional urethane (meth) acrylate compound in an amount of 20 to 100 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate compound, and to have a polyfunctional function with respect to 5 or more functional groups. 100 parts by mass of the acrylate compound, 10 to 100 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functional groups, and a polyfunctional urethane for 100 parts by mass of the polyfunctional (meth) acrylate compound. 20 to 100 parts by mass of the (meth) acrylate compound, and 20 to 60 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functional groups, based on 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functional groups. The polyfunctional urethane (meth) acrylate compound is used in an amount of 30 to 70 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate compound, and is polyfunctional (meth) acrylate with respect to 5 or more functional groups. 100 parts by mass of the compound is used in an amount of 10 to 100 parts by mass based on the polyfunctional (meth) acrylate compound having 4 or less functional groups. The polyfunctional urethane (meth) acrylate compound is used in an amount of 30 to 70 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate compound, and is a polyfunctional (meth) acrylate compound with respect to 5 or more functional groups. 100 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functional groups is used in an amount of 20 to 60 parts by mass.

[(b) at both ends of a molecular chain comprising a poly(oxyperfluoroalkylene) group, through a poly(oxyalkylene) group or sequentially through a poly(oxyalkylene) group and a urethane a perfluoropolyether having a bond and having an active energy ray polymerizable group]

In the present invention, as component (b), it is used at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, through a poly(oxyalkylene) group or sequentially through a poly(oxyalkylene) group and A perfluoropolyether having one urethane bond and having an active energy ray polymerizable group (hereinafter also referred to simply as "(b) a perfluoropolyether having a polymerizable group at both terminals"). The component (b) functions as a surface modifier for applying a hard coat layer of the curable composition of the present invention.

The number of carbon atoms of the alkyl group of the poly(oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the above poly(oxyperfluoroalkylene) group means a group having a structure in which a divalent fluorinated carbon group having 1 to 4 carbon atoms and an oxygen atom are bonded to each other, and an oxyperfluoroalkylene group means having A structural group in which a divalent fluorinated carbon group having 1 to 4 carbon atoms is bonded to an oxygen atom. Specifically, -[OCF ₂ ]-(oxyperfluoromethylene), -[OCF ₂ CF ₂ ]-(oxyperfluorovinyl), -[OCF ₂ CF ₂ CF ₂ ]-( A group such as oxyperfluoropropane-1,3-diyl), -[OCF ₂ C(CF ₃ )F]-(oxyperfluoropropane-1,2-diyl).

The above-mentioned oxyperfluoroalkylene group may be used singly or in combination of two or more. In this case, the bonding of the plurality of oxyperfluoroalkylene groups may be block bonding and random bonding. Anything is fine.

Among these, from the viewpoint of obtaining a cured film having excellent scratch resistance, it is preferred to use -[OCF ₂ ]-(oxyperfluoromethylene) as the poly(oxyperfluoroalkylene) group. And -[OCF ₂ CF ₂ ]-(oxyperfluorovinyl) both as a repeating unit.

Wherein, as the poly(oxyperfluoroalkylene) group, it is preferred that the repeating unit: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]-in terms of molar ratio [repeating unit: -[OCF ₂ ]-]: [Repeat unit: -[OCF ₂ CF ₂ ]-]=2:1~1:2 The ratio includes a base, and more preferably a base included in a ratio of about 1:1. The bonding of these repeating units can be any of block bonding and random bonding.

The total number of repeating units of the above-mentioned 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.

Further, the poly(oxyperfluoro-cyclohexane) group has a weight average molecular weight (Mw) of 1,000 to 5,000, preferably 1,500 to 2,000, as measured by polystyrene conversion by gel permeation chromatography.

The number of carbon atoms of the alkyl group of the poly(oxyalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the above poly(oxyalkylene) group means a group having a structure in which an alkylene group having 1 to 4 carbon atoms and an oxygen atom are bonded to each other, and an oxygen-extended alkyl group means a valence of 2 to 4 carbon atoms. The base of the structure in which an alkyl group is bonded to an oxygen atom. As Examples of the alkylene group include a vinyl group, a 1-methylvinyl group, a trimethylene group, and a tetramethylene group.

The above-mentioned oxygen alkyl group may be used singly or in combination of two or more. In this case, the bonding of the plurality of oxygen alkyl groups may be either a block bond or a random bond.

Among them, the above poly(oxyalkylene) group is preferably a poly(oxyethylene) group.

The number of repeating units of the oxygen-alkylene group in the poly(oxyalkylene) group is more preferably in the range of, for example, 1 to 15, for example, in the range of 5 to 12, for example, in the range of 7 to 12.

Examples of the active energy ray-polymerizable group which is permeable to a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane bond, and a (meth) acrylonitrile group, Amino (meth) acrylonitrile, vinyl, and the like.

The active energy ray polymerizable group is not limited to an active energy ray polymerizable portion having one (meth) acrylonitrile group or the like, and may have two or more active energy ray polymerizable portions, and examples thereof include the following The structure of A1 to A5 and the structure in which the acryl fluorenyl group in the structure is substituted with a methacryl fluorenyl group.

As such a (b) perfluoropolyether having a polymerizable group at both terminals, from the viewpoint of industrial production, the compounds shown below and the propylene thiol groups in the compounds are substituted. A methacrylic acid group-based compound is preferred. Further, in the structural formula, the A system represents one of the structures represented by the above formula [A1] to the formula [A5], the PFPE means the poly(oxyperfluoroalkylene) group, and n each independently represents the repetition of the oxyethylene group. The number of units is preferably from 1 to 15, more preferably from 5 to 12, and even more preferably from 7 to 12.

Wherein (b) a perfluoropolyether having a polymerizable group at both terminals, which is at both ends of a molecular chain comprising a poly(oxyperfluoroalkylene) group, sequentially passes through a poly(oxyalkylene) And a urethane bond, that is, preferably a poly(oxyalkylene) group bonded to both ends of the molecular chain comprising a poly(oxyperfluoroalkylene) group, respectively Each poly(oxyalkylene) group at the end is bonded to a urethane bond, and each of the urethane bonds at the two ends is bonded to an active energy ray-polymerizable perfluoropolyether. Further, in the perfluoropolyether, the active energy ray-polymerizable group is preferably a perfluoropolyether having at least two or more active energy ray-polymerizable moieties.

In the present invention, (b) the perfluoropolyether having a polymerizable group at both terminals is preferably 0.1 to 10 parts by mass, preferably 0.1 to 10 parts by mass, per 100 parts by mass of the above (a) active energy ray-curable polyfunctional monomer. Use in a ratio of 0.2 to 5 parts by mass.

The above (b) a perfluoropolyether having a polymerizable group at both terminals, for example, by a compound having a hydroxyl group in a poly(oxyalkylene) group at both ends of a poly(oxyperfluoroalkylene) group, The hydroxyl group at both ends is subjected to an isocyanate compound having a polymerizable group such as 2-(meth)acryloxyethyl isocyanate or 1,1-bis((meth)acryloxymethyl)ethyl isocyanate. a method of urethanation reaction, a method of dehydrochlorinating (meth)acrylic acid chloride or chloromethylstyrene The method is a method in which (meth)acrylic acid is subjected to a dehydration reaction, and a method in which itaconic anhydride is subjected to an esterification reaction.

Wherein, in the compound having a poly(oxyalkylene) group having a hydroxyl group at both ends of the poly(oxyperfluoroalkylene) group, 2-(meth)acryloxyethyl group is bonded to the hydroxyl group at both ends thereof a method for performing a urethanization reaction of an isocyanate compound having a polymerizable group such as an isocyanate or 1,1-bis((meth)acryloxymethyl)ethyl isocyanate, or The method of dehydrochlorination of acrylic acid chloride or chloromethylstyrene is particularly preferable in terms of easy reaction.

Further, in the curable composition of the present invention, in addition to (b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, it passes through a poly(oxyalkylene) group or sequentially passes through a poly(oxygen extension). a perfluoropolyether having an active energy ray-polymerizable group and a perfluoropolyether having an active energy ray-polymerizable group, or may be contained at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group. An oxyalkylene group or a peroxyalkylene group and a urethane bond, having an active energy ray polymerizable group and having a poly(oxyalkylene) group at the other end thereof a perfluoropolyether of a hydroxyl group, or a perfluoropolyether having a hydroxyl group which is transmitted through a poly(oxyalkylene) group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group [having no active energy ray polymerizability) Base compound].

[(c) Organic microparticles 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 referred to simply as "(c) organic fine particles") are such that the surface of the hard coat layer formed of the curable composition becomes Concave shape It imparts anti-glare properties.

Further, the organic fine particles can also function to control the haze value of the hard coat layer by controlling the difference in refractive index between the refractive index and the hardenable composition of the hard coat layer forming material.

Although the shape of the organic fine particles is not particularly limited, for example, it may be a spherical shape, and may be an amorphous shape such as a powder. However, it is preferably a slightly spherical shape, and more preferably has an aspect ratio of 1.5 or less. Spherical particles, preferably true spherical particles.

Examples of the organic fine particles include polymethyl methacrylate particles (PMMA particles), xenon particles, polystyrene particles, polycarbonate particles, styrene acrylate particles, benzoguanamine particles, melamine particles, and polyolefin particles. Polyester particles, polyamide particles, polyamidene particles, polyfluorinated particles, and the like. These organic fine particles may be used alone or in combination of two or more.

Among them, as the organic fine particles, polymethyl methacrylate particles can be suitably used.

The organic fine particles used in the present invention have an average particle diameter of from 1 to 10 μm, preferably from 3 to 8 μm. The average particle diameter (μm) herein refers to a 50% by volume (median diameter) measured by a laser diffraction-scattering method according to the Mie theory. When the average particle diameter of the organic fine particles is larger than the above numerical range, the image sharpness of the display is lowered, and when the average value is smaller than the above numerical range, sufficient antiglare property is not obtained, and glare is also increased. Further, the organic fine particles are not particularly limited in their particle size distribution, but are preferably monodispersed in uniform particle size. Microparticles.

The organic fine particles are preferably organic fine particles having a refractive index difference from the cured product of the (a) active energy ray-curable polyfunctional monomer of 0 to 0.20, and more preferably the refractive index difference is 0. ~0.10.

Further, the average particle diameter of the organic fine particles is preferably selected to satisfy the average particle diameter b of the organic fine particles b/thickness a = 0.7 to 1.0 with respect to the film thickness of the cured film obtained by the curable composition of the present invention to be described later. range.

Commercially available products can be suitably used as the organic fine particles. For example, Techpolymer (registered trademark) MBX series, the same SBX series, the same MSX series, the same SMX series, the same SSX series, the same BMX series, the same ABX series, the same ARX series, and the same can be used. AFX series, same MB series, same MBP series, same MB-C series, same ACX series, same ACP series [above is Sekisui finished product industry (share) system]; TOSPEARL (registered trademark) series [Mitu high-tech materials. Japan (same) system]; EPOSTAR (registered trademark) series, the same MA series, the same ST series, the same MX series [above is the Japanese stock system]; Opto beads (registered trademark) series [Nissan Chemical Industry Co., Ltd. System]; Flow beads series [Sumitomo Refinery (share) system]; Toray Pearl (registered trademark) PPS, with PAI, with PES, with EP [above is Toray (share) system]; 3M (registered trademark) Dyneon TF micro powder series [made by 3M company]; Chemisnow (registered trademark) MX series, same MZ series, same MR series, same KMR series, same KSR series, same MP series, same SX series, same SGP series [above for comprehensive research chemistry (share) system]; TAFTIC (registered trademark) AR650 series, the same AR-750 series, the same FH-S system Column, the same A-20, the same YK series, the same ASF series, the same HU series, the same F series, the same C series, the same WS series [above is Toyobo (stock) system]; Art Pearl (registered trademark) GR series, the same SE series, the same G series, the same GS series, the same J series, the same MF series, the same BE series [above is the root industrial (share) system]; Shin-Etsu (oxygen) (registered trademark) KMP series [Shin-Etsu Chemical Industry Co., Ltd. ]Wait.

In the present invention, the (c) organic fine particle system is desirably used in an amount of 8 to 30 parts by mass, preferably 8 to 20 parts by mass, per 100 parts by mass of the above (a) active energy ray-curable polyfunctional monomer.

[(d) Polymerization initiator which generates radicals by active energy rays]

In the curable composition of the present invention, a polymerization initiator which generates a radical by an active energy ray (hereinafter also referred to simply as "(d) polymerization initiator"), for example, by electron beam, ultraviolet ray, X An active energy ray of light or the like, especially a polymerization initiator which generates radicals by ultraviolet irradiation.

Examples of the (d) polymerization initiator include benzoin, alkylphenones, thioxanthones, azos, azides, diazos, 0-quinonediazides, and sulfhydryl groups. Phosphonium oxides, oxime esters, organic peroxides, benzophenones, dicoumarins, biimidazoles, ferrocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines Or iodonium salts, barium salts, etc. These may be used alone or in combination of two or more.

In the present invention, from the viewpoints of transparency, surface hardenability, and film curability, it is preferred to use an alkyl benzophenone as the (d) polymerization initiator. By using alkyl benzophenones, scratch resistance can be improved Hardened film.

Examples of the alkylphenones include 1-hydroxycyclohexyl=phenyl=ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2-hydroxy-1-(4- (2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropenyl)benzyl) Alpha-hydroxyalkylphenones such as phenyl)-2-methylpropan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylpropane- α-Aminoalkylphenones such as 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one; 2,2- Dimethoxy-1,2-diphenylethane-1-one; methyl phenylglyoxylate and the like.

In the present invention, (d) the polymerization initiator is preferably used in an amount of from 1 to 20 parts by mass, preferably from 2 to 10 parts by mass, per 100 parts by mass of the above (a) active energy ray-curable polyfunctional monomer. .

[(e) Solvent]

The curable composition of the present invention may further comprise (e) a solvent, or may be in the form of a varnish (film forming material).

In the solvent, the components (a) to (d) are dissolved and dispersed, and the workability at the time of coating, which is formed by a cured film (hard coat layer) to be described later, or the drying property before and after curing, may be appropriately selected. Examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; and aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane. Class; halides such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; , propyl acetate, butyl acetate, methoxybutyl acetic acid Esters or ester ethers of esters, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, etc.; diethyl ether, tetrahydrofuran, 1,4-dioxane Methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, etc. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.; methanol, ethanol, n-propanol, isopropyl alcohol, n-butyl Alcohols, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol and the like; N,N-dimethylformamide, N,N-dimethyl An anthracene such as acetamide; an anthracene such as dimethyl hydrazine; a heterocyclic compound such as N-methyl-2-pyrrolidone; and a mixed solvent of two or more of these.

Further, for the purpose of controlling the dispersibility of the fine particles during drying after coating, a solvent having a high boiling point can also be used.

Examples of such a solvent include cyclohexyl acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, and 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 single 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.

The amount of the solvent used in the above (e) is not particularly limited, but for example, the solid content concentration of the curable composition of the present invention is 1 to 70. The mass % is preferably used in a concentration of 5 to 50% by mass. The solid content concentration (also referred to as the non-volatile component concentration) herein means the total mass of the above-mentioned (a) to (e) components (and other additives as desired) with respect to the curable composition of the present invention ( The total mass) solid content (the solvent component is removed from the total component).

[Other Additives]

Further, in the curable composition of the present invention, if it is not impaired by the effects of the present invention, if necessary, a generally added additive such as a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, Adhesion imparting agent, plasticizer, ultraviolet absorber, antioxidant, storage stabilizer, antistatic agent, inorganic filler, pigment, dye, and the like.

Further, inorganic fine particles such as titanium oxide may be blended for the purpose of controlling the haze value of the cured film.

<hardened film>

The curable composition of the present invention can be formed by coating on a substrate to form a coating film, and the coating film is irradiated with an active energy ray to be polymerized (hardened) to form a cured film. This cured film is also an object of the present invention. Further, a hard coat layer of a hard coat film to be described later may be formed of the cured film.

Examples of the substrate described above include various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), or polyethylene naphthalate (PEN). Polyester, polyolefin Hydrocarbon, polyamine, polyimine, epoxy resin, melamine resin, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), A decene-based resin, etc.), metal, wood, paper, glass, slate, and the like. The shape of these substrates may be a plate shape, a film shape or a ternary shape.

For the coating method on the substrate, a cast coating method, a spin coating method, a knife coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an inkjet method, or the like can be appropriately selected. Printing method (relief, gravure, lithography, screen printing, etc.), etc., which can be used in a roll-to-roll method, and from the viewpoint of film coating properties, it is desirable to use a relief printing method. In particular, gravure coating is used. Further, it is preferred to apply a filter curable composition such as a filter having a pore diameter of about 0.2 μm beforehand, and then apply it to the coating. Further, at the time of coating, a solvent may be further added to the curable composition if necessary. The solvent in this case is exemplified by the various solvents exemplified in the above [(e) solvent].

After applying a curable composition to a substrate to form a coating film, if necessary, the coating film is preliminarily dried by a hot plate or an oven to remove the solvent (solvent removal step). The heating and drying conditions at this time are, for example, preferably carried out at 40 to 120 ° C for about 30 seconds to 10 minutes.

After drying, the active energy rays such as ultraviolet rays are irradiated to harden the coating film. Examples of the active energy ray include ultraviolet rays, electron beams, and X-rays, and particularly preferred are ultraviolet rays. As a light source used for ultraviolet irradiation, a solar light, 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.

Further, after the post-baking, specifically, heating can be carried out by using a hot plate, an oven or the like to complete the polymerization.

Further, the thickness of the formed cured film is usually 0.01 to 50 μm, preferably 0.05 to 20 μm after drying and hardening.

<hard coated film>

A hard coat film having a hard coat layer can be produced on the surface (surface) of at least one side of the film substrate by 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 example, to protect the surface of various display elements such as a touch panel or a liquid crystal display.

The hard coat layer of the hard coat film of the present invention may comprise a step of forming a coating film by applying the curable composition of the present invention to a film substrate, and an active energy ray for irradiating ultraviolet rays or the like on the coating film. The method of the step of hardening the coating film is formed.

As the film substrate, various transparent resin films which can be used for optical applications among the substrates listed in the above-mentioned "cured film" can be used. Preferred examples thereof include polyesters selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polycarbonate. A film made of a resin such as polymethacrylate, polystyrene, polyolefin, polyamine, polyimine or triacetyl cellulose.

Further, the method of applying the curable composition on the film substrate (coating film forming step) and the active energy ray irradiation method (hardening step) for the coating film can be carried out by the method described in the above-mentioned "cured film". Also, the film shape After the step, if necessary, a step of drying the coating film to remove the solvent may be included. In this case, the drying method (solvent removal step) of the coating film mentioned in the above-mentioned <hardened film> can be used.

The hard coat layer obtained in this manner is preferably set so as to have a thickness of 1 to 10/7 times as compared with the average particle diameter of the organic fine particles. For example, the thickness of the hard coat layer is preferably from 1 to 20 μm, more preferably from 3 to 10 μm.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples described below.

Further, in the examples, the apparatus and conditions for the preparation of the sample and the analysis of the physical properties are as follows.

(1) Bar coating coating

Device: (share) SMT system PM-9050MC

Stick 1: OSG system product (stock) A-Bar OSP-30, maximum wet film thickness 30μm (equivalent to Wire bar#12)

Stick 2: A-Bar OSP-22 made by OSG system product, the maximum wet film thickness is 22μm (equivalent to Wire bar#9)

Coating speed: 4m/min

(2) Oven

Device: Advantech Toyo Co., Ltd. DRC433FA

(3) UV hardening

Device: Heraeus (share) system CV-110QC-G

Light: Heraeus (Holdings) High Pressure Mercury Lamp H-bulb

(4) Film thickness

Device: (share) Nikon digital length measuring machine Digi micro MH-15M + counter TC-101

(5) Glossiness

Device: Konica Minolta Co., Ltd. Gloss meter GM-268Plus

Measuring angle: 60 degrees

(6) abrasion test

Device: Xindong Science (share) system Round-trip friction test machine TRIBOGEAR TYPE: 30S

Scanning speed: 3,000mm/min

Scanning distance: 50mm

(7) Total light transmittance, haze

Device: Japan Electro-Color Industry Co., Ltd. Haze meter NDH5000

(8) Contact angle

Device: Concord Interface Science (share) system DropMaster DM-501

Measuring temperature: 20 ° C

Also, the abbreviation indicates the following meaning.

PFPE1: a perfluoropolyether having a hydroxyl group at a poly(oxyalkylene) group (repeating unit number 8 to 9) at both ends [Fluorolink 5147X manufactured by Solvay Specialty Polymers Co., Ltd.]

PFPE2: a perfluoropolyether having a hydroxyl group at a poly(oxyalkylene) group (5 to 6 repeating units) at both ends [Fluorolink 5158X, manufactured by Solvay Specialty Polymers Co., Ltd.]

PFPE3: perfluoropolyether having a hydroxyl group at both ends [Fluorolink D manufactured by Solvay Specialty Polymers Co., Ltd.]

BEI: 1,1-bis(acryloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI by Showa Denko Co., Ltd.]

DBTDL: Dibutyltin dilaurate [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 [Naka Nakamura Chemical Industry Co., Ltd. NK ester A-TMM-3LM-N]

UA: 6-functional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 manufactured by DAICEL-ALLNEX Co., Ltd.]

SM4: UV-reactive fluorine-based surface modifier having a perfluoropolyether structure [Megafac (registered trademark) RS-75, manufactured by DIC Co., Ltd., active ingredient 40% by mass MEK/MIBK solution]

FP1: cross-linked polymethyl methacrylate true spherical particles [Technology (registered trademark) SSX-105, manufactured by Sekisui Chemicals Co., Ltd., average particle diameter 5 μm]

FP2: Crosslinked polymethyl methacrylate true spherical particles [Technology (registered trademark) SSX-103, manufactured by Sekisui Chemicals Co., Ltd., average particle diameter 3 μm]

FP3: melamine resin and cerium oxide composite true spherical particles [Opto beads (registered trademark) 2000M, Nissan Chemical Industry Co., Ltd., average particle diameter 2 μm]

FP4: cross-linked 矽 真 真 球 [ [ TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO

FP5: cross-linked yttrium-like spherical particles [TOTUEARL (registered trademark) 145, Meitu Gaoxin Material (same), average particle diameter 4.5 μm]

FP6: Polyorganopyral sesquioxane true spherical particles [Shin-Etsu Chemical Industry Co., Ltd.) Shin-Etsu (oxygen (registered trademark) KMP-590, average particle diameter 2 μm]

IP1: rutile-type titanium oxide particles [JR-600E manufactured by Tayca Co., Ltd., average particle diameter 0.27 μm]

I2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [IRAFCURE (registered trademark) 2959 manufactured by BASF Japan Co., Ltd.]

EPA: p-dimethylamino benzoic acid ethyl ester [KAYACURE (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.]

PET: easy to handle polyethylene terephthalate (PET) on both sides Film [Dongli Co., Ltd. Lumirror (registered trademark) U403, thickness 100μm]

PC: Both sides are easy to handle polycarbonate (PC) film [Mitsubishi Gas Chemical Co., Ltd. Iupilon (registered trademark) and film FE-2000, thickness 100μm]

TAC: Two-side easy treatment of cellulose triacetate (TAC) film [Fujifilm Co., Ltd. FUJITAC (registered trademark) TD80ULM, thickness 80μm]

AcOPr: propyl acetate

MEK: methyl ethyl ketone

MIBK: methyl isobutyl ketone

PGME: propylene glycol monomethyl ether

[Synthesis Example 1] Production of perfluoropolyether SM1 having a propylene group at the both ends thereof through a poly(oxyalkylene) group

PFPE1 1.05g (0.5mmol), BEI 0.26g (1.0mmol), DBTDL 0.01g (0.02mmol), and MEK 1.30g were placed in the threaded tube. This mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stir bar. This reaction mixture was diluted with MEK 3.93 g to obtain a 20% by mass MEK solution of the objective compound, that is, SM1.

[Synthesis Example 2] Production of perfluoropolyether SM2 having a propylene group at the both ends thereof through a poly(oxyalkylene) group

Put PFPE2 1.89g (1.0mmol) and BEI 0.52g into the threaded pipe (2.0 mmol), DBTDL 0.01 g (0.02 mmol), and MEK 2.41 g. This mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stir bar to obtain a 50% by mass MEK solution of the objective compound, that is, SM2.

[Synthesis Example 3] Production of perfluoropolyether SM3 having an acrylonitrile group at both terminals

PFPE3 2.0 g (1.0 mmol), BEI 0.52 g (2.0 mmol), DBTDL 0.01 g (0.02 mmol), and MEK 2.52 g were placed in a screw tube. This mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stir bar to obtain a 50% by mass MEK solution of the desired compound, SM3.

[Examples 1 to 5, Comparative Examples 1 to 6]

The following components were mixed as described in Table 1, and the curable composition of the solid content concentration shown in Table 1 was prepared. Further, the term "solid fraction" as used herein refers to a component other than a solvent. In addition, the "parts" in the table means [parts 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: The amount of the surface modifier described in Table 1 is in accordance with the amount described in Table 1 (solid content or active ingredient conversion)

(3) Organic fine particles: The amount of the organic fine particles described in Table 1 is as shown in Table 1.

(4) Polymerization initiator: I2959 5 parts by mass

(5) Solvent: PGME is the amount shown in Table 1.

The curable composition was applied by bar coating on both sides of the A4 size using a bar described in Table 2, and then the PET film [Lumirror (trademark) U403, thickness: 100 μm] was obtained. Coating film. The coating film was dried in an oven at 120 ° C for 3 minutes to remove the solvent. The obtained film was exposed to UV light having an exposure amount of 500 mJ/cm ² in a nitrogen atmosphere to prepare a hard coat film having a hard coat layer (cured film) having a thickness shown in Table 2.

[Examples 6 to 12]

The following components were mixed as described in Table 1, and a curable composition having a solid concentration of 40% by mass was prepared.

(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: SM1 1 part by mass (solid fraction conversion)

(3) Organic fine particles: The amount of the organic fine particles described in Table 1 is as shown in Table 1.

(4) Inorganic fine particles: The amount of the inorganic fine particles described in Table 1 is as shown in Table 1.

(5) Polymerization initiator: I2959 5 parts by mass

(6) Polymerization accelerator: EPA 0.1 parts by mass

(7) Solvent: The amount of the solvent described in Table 1 is as shown in Table 1.

This curable composition was applied by a bar 1 to a film described in Table 2 of A4 size using a bar 1 to obtain a coating film. The 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 prepare a hard coat film having a hard coat layer (cured film) having a thickness shown in Table 2.

The appearance, anti-glare, scratch resistance, total light transmittance, haze, and contact angle of water and oleic acid of the obtained hard coat film were evaluated. The evaluation procedures of appearance, anti-glare property, scratch resistance, and contact angle are shown below. The results are shown together in Table 3.

[Exterior]

The appearance of the hard coat film was visually confirmed and evaluated based on the following criteria.

A: There is no unevenness throughout the hard coating.

C: The aggregates are precipitated in the hard coating layer, and the unevenness of the spots is obvious.

[anti-glare]

The obtained hard coat film was placed on a black stage having a gloss Gs (60°) of 11.8, and the gloss Gs (60°) of the surface of the hard coat layer was measured and evaluated on the basis of the following. Also, as a hard coat layer, assuming at the actual use, it is required to be at least B, and it is expected to be A.

A: Gs (60 °) ≦ 120

B: 120 < Gs (60 °) ≦ 125

C: Gs (60 °) > 125

[scratch resistance]

The surface of the hard coat layer was wound with a steel wool (Bonstar (registered trademark) #0000 (Ultra-fine) manufactured by Bonstar Trading Co., Ltd.), and a load of 1 kg/cm ² was applied thereto for 1,000 round-trip wiping. The wiping portion is drawn with an oily mic pen [Zebra's McKee is very fine (cyan), using a thin side]. Then, the line to be drawn was wiped with a non-woven wiper [BEMCOT M-1 made by Asahi Kasei Fiber Co., Ltd.], and the degree of scratch was visually confirmed and evaluated according to the following criteria. Also, as a hard coat layer, assuming at the actual use, it is required to be at least B, and it is expected to be A.

A: No scratches can be cleaned with a line drawn by an oily mic.

B: It is rare to scratch, but the line drawn with oily mic pen can be wiped clean.

C: The ink of the oily microphone pen penetrates into the scar and cannot be wiped off.

[Contact angle]

1 μL of water or oleic acid was attached to the surface of the hard coat layer, and the contact angle θ after 5 seconds was measured at 5 points, and the average value was defined as a contact angle value.

As shown in Tables 1 to 3, as a surface modifier for a hard coat layer, perfluoropolyethers SM1 and SM2 having a propylene group at the both ends and having a poly(oxyalkylene) group are used, and blending is used. Each of the hard coat films produced in the curable composition of Examples 1 to 12 of the organic fine particles was excellent in scratch resistance in a film thickness of 4 to 6 μm, and had no uneven appearance. Moreover, the anti-glare property is all based on the case of considering the actual use compared with the comparative example mentioned later.

On the other hand, the amount of the organic fine particles added was Comparative Example 1 and Comparative Example 2 which were not in the numerical range determined by the present invention, and Comparative Example 6 in which the organic fine particles were not added, and the desired antiglare property was not obtained.

Further, as a surface modifier of a hard coat layer, instead of a perfluoropolyether having an acrylonitrile group which is transmitted through both poly(oxyalkylene) groups at both ends, it is used instead of a poly(oxyalkylene) group at both ends. In Comparative Example 3 of the perfluoropolyether SM3 having an acrylonitrile group, the scratch resistance was deteriorated as compared with the examples, and the appearance of the aggregates in the hard coat layer and the unevenness of the spots were observed.

Further, Comparative Example 4 and Comparative Example 5 using a UV-reactive fluorine-based surface modifier SM4 having a perfluoropolyether structure as a surface modifier have a large deterioration in scratch resistance.

As described above, as a result of the examples, the structure of the end of the perfluoropolyether used as the surface modifier is only slightly different, that is, it is difficult to obtain the results of the scratch resistance and the appearance of the hard coat layer, and When the amount of addition of the organic fine particles is outside the predetermined range, the anti-glare property cannot be obtained, and only the hardenable composition of the present invention can obtain a hard coat film which satisfies all of the properties.

Claims (13)

A curable composition comprising the following (a) to (e), (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, and (b) comprising a poly(oxyperfluoroalkylene) group; a perfluoropolyether having an active energy ray polymerizable group at both ends of the molecular chain, through a poly(oxyalkylene) group or sequentially passing through a poly(oxyalkylene) group and a urethane bond. ~10 parts by mass, (c) 8 to 30 parts by mass of the organic fine particles having an average particle diameter of 1 to 10 μm, (d) 1 to 20 parts by mass of a polymerization initiator which generates radicals by an active energy ray, and (e) )Organic solvents. The hardenable composition of claim 1, wherein the poly(oxyperfluoroalkylene) group has -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as a repeating unit. The hardenable composition of claim 1 or claim 2, wherein the poly(oxyalkylene) group is a poly(oxyethylene) group. The sclerosing composition according to any one of the preceding claims, wherein the polyfunctional single system of the component (a) is selected from the group consisting of polyfunctional (meth) acrylate compounds and polyfunctional urethanes. At least one of the group consisting of (meth) acrylate compounds. The sclerosing composition according to any one of Claims 1 to 4, wherein the organic fine particles of the component (c) are true spherical particles. The sclerosing 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 alkyl phenone. A cured film obtained by the curable composition according to any one of claims 1 to 7. A hard coat film comprising a hard coat film of a hard coat layer on a surface of at least one side of a film substrate, the hard coat layer being composed of the cured film of claim 8. A hard coat film comprising a hard coat film having a hard coat layer on a surface of at least one side of a film substrate, the hard coat layer comprising: hardening according to any one of claim 1 to claim 7 The step of applying a composition on a film substrate to form a coating film, and a step of curing the coating film by irradiating an active energy ray to form a film. The hard coat film of claim 9 or claim 10, wherein the hard coat layer has a thickness of 1 to 10/7 times as compared with an average particle diameter of the organic fine particles. The hard coat film according to any one of the preceding claims, wherein the hard coat layer has a film thickness of 1 to 20 μm. The hard coat film of claim 12, wherein the hard coat layer has a film thickness of 3 to 10 μm.