Antistatic hardcoat layer, and curable composition

Abstract

[Problem] To provide: a hardcoat layer having extremely high wear resistance due to having antistatic properties; and a curable composition for forming the hardcoat layer. [Solution] Provided are: a hardcoat layer which is provided on at least one surface of a substrate, and which has a surface resistance value of 1×106 to 1×1014 Ω / □ (exclusive of 1×1014 Ω / □), and a surface water contact angle of at least 90°; and a curable composition for forming the hardcoat layer, the curable composition comprising (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (b) 0.05-10 parts by mass of a surface modifier, (c) 1-20 parts by mass of a polymerization initiator that generates radicals by means of an active energy ray, and (d) 0.1-50 parts by mass of a conductive polymer material.

Description

Antistatic hard coat layer and curable composition

[0001] The present invention relates to a hard coat layer to be applied to the surface of various display devices such as flexible displays, and a curable composition useful as a material for forming the hard coat layer. More specifically, the present invention relates to a hard coat layer having antistatic properties, thereby excellent abrasion resistance, and also water repellency, and a curable composition capable of forming the hard coat layer.

[0002] In recent years, touch panels that can be operated with a finger, a pen, or the like while viewing the display have become widespread in displays of mobile phones, tablet PCs, and other portable information terminals, computers, televisions, and other home appliances, in-vehicle display panels, etc. Typically, a cover glass or plastic film with a scratch-resistant hard coat layer is applied to the surface of the touch panel to prevent scratches on the display.

[0003] Touch panels with hard coat layers are required to be operated with human fingers, pens, etc., and therefore must have water and oil repellency to prevent adhesion of moisture from sweat and oil from sebum contained in fingerprints, as well as slipperiness to achieve a smooth writing experience. However, repeated contact with fingers, pens, etc. causes wear on the surface of the hard coat layer due to friction, and even if the initial water and oil repellency reaches a sufficient level, these functions often deteriorate during use. Therefore, it is desirable for the hard coat layer to have extremely high abrasion resistance that can maintain the initial water and oil repellency.

[0004] Generally, in order to impart scratch resistance and abrasion resistance to a hard coat layer, for example, a method of forming a highly crosslinked structure, i.e., a crosslinked structure with low molecular mobility, is adopted to increase the surface hardness and provide resistance to external forces. Currently, multifunctional acrylate materials that undergo three-dimensional crosslinking by radicals are most commonly used as materials for forming this hard coat layer.

[0005] Furthermore, a fluorine-based surface modifier added to a coating solution for forming a hard coat layer is generally a material having active energy ray-polymerizable groups in order to impart scratch resistance and abrasion resistance to the hard coat layer (Patent Document 1). From the viewpoint of scratch resistance and abrasion resistance, a material with a low acrylic equivalent, which has a low molecular weight and many active energy ray-polymerizable groups and can form a high-density crosslinked structure, is preferred.

[0006] On the other hand, if the display surface becomes charged, dust will adhere to the surface, causing problems such as malfunction or destruction of electronic devices. Therefore, hard coat films applied to display surfaces are desired to have antistatic properties.

[0007] For example, known methods for imparting antistatic properties to polyfunctional acrylate materials that are three-dimensionally crosslinked by radicals include adding conductive materials such as metal oxide particles, conductive polymers, nanocarbons, and ionic liquids.

[0008] Patent Documents 2 and 3 disclose curable compositions containing metal oxide particles as an antistatic agent, which are capable of forming a hard coat layer having antistatic properties.

[0009] Patent Document 3 lists examples of other additives that can be added to the curable composition as needed, such as polythiophene-based polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT-PSS), as well as conductive polymers such as polyacetylene-based polymers, polyaniline-based polymers, and polypyrrole-based polymers. These conductive polymers are added as antistatic agents together with the metal oxide particles.

[0010] Furthermore, Patent Document 4 discloses a curable composition capable of forming an antistatic hard coat layer to which a conductive polymer is added as an antistatic agent.

[0011] International Publication No. WO 2016 / 163479 International Publication No. WO 2020 / 162323 International Publication No. WO 2020 / 162324 JP 2008-248098 A

[0012] An object of the present invention is to provide a hard coat layer having antistatic properties and therefore extremely high abrasion resistance, and a curable composition for forming the hard coat layer.

[0013] As a result of extensive research into achieving the above object, the present inventors have discovered a hard coat layer provided on at least one surface of a substrate, the hard coat layer having a surface resistance of 1×10 ６ Ω / □ or more 1×10 １４ The present inventors have found that a hard coat layer having a resistivity of less than Ω / □ and a surface water contact angle of 90° or more, and a curable composition for forming the hard coat layer, which comprises (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (b) 0.05 to 10 parts by mass of a surface modifier, (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals when exposed to active energy rays, and (d) 0.1 to 50 parts by mass of a conductive polymer material, can form a hard coat layer that has antistatic properties, and therefore excellent abrasion resistance, and also has water repellency, and have completed the present invention.

[0014] That is, in a first aspect, the present invention provides a hard coat layer provided on at least one surface of a substrate, the hard coat layer having a surface resistance of 1×10 ６ Ω / □ or more 1×10 １４ The hard coat layer has a water contact angle of 90° or more and a surface water contact angle of less than Ω / □, and the hard coat layer contains a conductive material, and the surface of the hard coat layer is subjected to a load of 3.54 kg / cm using an eraser for an eraser test. ２and after an abrasion resistance test in which the hard coat layer is rubbed back and forth 1,000 times or more at a speed of 4.5 m / min, the number of reciprocations at which the water contact angle of the surface of the hard coat layer becomes 90° or more is 1.3 times or more compared to a hard coat layer not containing the conductive material. As a second aspect, the hard coat layer according to the first aspect, in which the conductive material is a conductive polymer material. As a third aspect, the hard coat layer according to the second aspect, in which the conductive polymer material includes poly(3,4-ethylenedioxythiophene). As a fourth aspect, the hard coat layer according to the second or third aspect, in which the conductive polymer material includes poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid. As a fifth aspect, the hard coat layer according to the first aspect, in which the conductive material is metal oxide particles. As a sixth aspect, the hard coat layer according to any one of the first to fifth aspects, in which the hard coat layer consists of one or more layers.

[0013] As a seventh aspect, the present invention relates to the curable composition for forming a hard coat layer according to any one of the first to fourth aspects and the sixth aspect, comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) 0.05 to 10 parts by mass of a surface modifier; (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals when exposed to active energy rays; and (d) 0.1 to 50 parts by mass of a conductive polymer material. As an eighth aspect, the present invention relates to the curable composition according to the seventh aspect, in which the (b) surface modifier is a perfluoropolyether having an active energy ray-polymerizable group at an end of a molecular chain containing a poly(oxyperfluoroalkylene) group. As a ninth aspect, the present invention relates to the curable composition according to the eighth aspect, in which the perfluoropolyether has the active energy ray-polymerizable group at an end of a molecular chain containing the poly(oxyperfluoroalkylene) group via a urethane bond. As a tenth aspect, the present invention relates to the curable composition according to the eighth or ninth aspect, in which the perfluoropolyether has at least two of the active energy ray-polymerizable groups via urethane bonds at each of both ends of a molecular chain containing the poly(oxyperfluoroalkylene) group. As an eleventh aspect, the present invention relates to the curable composition according to the eighth or ninth aspect, in which the poly(oxyperfluoroalkylene) group of the perfluoropolyether is a poly(oxyperfluoroalkylene) group having a repeating unit of -(CF２ CF ２ O)- and / or repeating units -(CF ２ The present invention relates to the curable composition according to any one of the eighth to tenth aspects, wherein the perfluoropolyether has a molecular chain containing the poly(oxyperfluoroalkylene) group, and when both repeating units are present, the molecular chain is formed by bonding these repeating units via block bonds, random bonds, or block bonds and random bonds. As a twelfth aspect, the present invention relates to the curable composition according to the eleventh aspect, wherein the perfluoropolyether has a molecular chain containing the poly(oxyperfluoroalkylene) group, and the molecular chain has a structure represented by the following formula [1] or [2]: (In the above formula [1] and formula [2], m represents a repeating unit -(CF ２ CF ２ O)-, and n is the number of repeating units -(CF ２ The number of repeating units -(CF ２ CF ２ O)-, and s is the number of repeating units -(CF ２ the number of repeating units -(CF)- satisfies 5≦(r+s)≦30, r and s each independently represent an integer of 0 or more, q is the number of oxyethylene groups and represents an integer of 2 to 20, ２ CF ２ O)- and the repeating unit -(CF ２and O)— are bonded via a block bond, a random bond, or a combination of a block bond and a random bond.) As a thirteenth aspect, the present invention relates to the curable composition according to any one of the seventh to twelfth aspects, in which the (d) conductive polymer material comprises poly(3,4-ethylenedioxythiophene). As a fourteenth aspect, the present invention relates to the curable composition according to the thirteenth aspect, in which the (d) conductive polymer material comprises poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid. As a fifteenth aspect, the present invention relates to the curable composition according to any one of the seventh to fourteenth aspects, further comprising (e) a solvent. As a sixteenth aspect, the present invention relates to a hard coat film comprising the hard coat layer according to any one of the first to sixth aspects on at least one surface of a film substrate. As a seventeenth aspect, the present invention relates to a hard coat film comprising the hard coat layer according to any one of the first to sixth aspects on at least one surface of a film substrate, and an upper hard coat layer on the hard coat layer that does not contain a conductive material.

[0023] As an eighteenth aspect, the present invention relates to the hard coat film according to the sixteenth or seventeenth aspect, wherein the hard coat layer has a film thickness of 1 μm to 20 μm. As a nineteenth aspect, the present invention relates to a method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, the hard coat layer being formed by a method comprising the steps of applying the curable composition according to any one of the seventh to fifteenth aspects onto the film substrate to form a coating film, and irradiating the coating film with active energy rays to cure it. As a twentieth aspect, the present invention relates to a method for producing a laminate of a film substrate and a hard coat layer, the method comprising the steps of applying the curable composition according to any one of the seventh to fifteenth aspects onto the film substrate to form a coating film, and irradiating the coating film with active energy rays to cure it. As a twenty-first aspect, the present invention relates to a method for producing a laminate according to the twentieth aspect, further comprising the step of forming an upper hard coat layer on the hard coat layer formed by the curing step. As a twenty-second aspect, the present invention relates to the method for producing a laminate according to the twenty-first aspect, wherein the hard coat upper layer does not contain a conductive material.

[0015] According to the present invention, it is possible to provide a curable composition useful for forming a cured film or hard coat layer having extremely high abrasion resistance and antistatic properties even in a thin film having a thickness of about 1 μm to 20 μm. Furthermore, according to the present invention, it is possible to provide a hard coat film having a surface to which a cured film or hard coat layer obtained from the curable composition is applied, and it is possible to provide a hard coat film having extremely high abrasion resistance and antistatic properties.

[0016] <Hard Coat Layer> The hard coat layer of the present invention is specifically a hard coat layer provided on at least one surface of a substrate, and has a surface resistance of 1×10 ６ Ω / □ or more 1×10 １４ It is characterized by a resistance of less than Ω / □ and a water contact angle of the surface of 90° or more.

[0017] The substrate is not particularly limited, but the substrates described below can be used. The surface resistance value of the hard coat layer is set to 1×10 ６ Ω / □ or more 1×10 １４ Less than Ω / □, preferably 1×10 ７ Ω / □ or more 1×10 １４ Less than Ω / □, more preferably 1×10 ８ Ω / □ or more 1×10 １４ Less than Ω / □, more preferably 1×10 ９ Ω / □ or more 1×10 １３ When the surface resistance value of the hard coat layer is within the above range, the hard coat layer has antistatic properties and abrasion resistance in which the decrease in water repellency of the hard coat layer due to abrasion is suppressed.

[0018] The hard coat layer contains a conductive material. The conductive material is a conductive material that can impart antistatic properties to the hard coat layer of the present invention. Examples of the conductive material include conductive polymers, metal oxide particles, nanocarbons, and ionic liquids.

[0019] Examples of the conductive polymers are not particularly limited, but include, for example, polythiophenes such as poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT-PSS), oligothiophenes, polyacetylenes, polyanilines, polypyrroles, poly(p-phenylenes), polyfluorenes, poly(p-phenylenevinylenes), and polythienylenevinylenes.

[0020] Examples of the metal oxide particles are not particularly limited, but include tin oxide (SnO ２ ), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AlZO), antimony-doped zinc oxide (AZO), indium-doped zinc oxide or zinc-doped indium oxide (IZO), and indium gallium zinc oxide (IGZO).

[0021] The metal oxide particles also include surface-coated metal oxide particles having a metal oxide core, the surface of which is coated with an acidic or basic oxide. Examples of the core include the above-mentioned metal oxide particles such as tin oxide, as well as titanium oxide, a titanium oxide-tin oxide composite, a zirconium oxide-tin oxide composite, a tungsten oxide-tin oxide composite, and a titanium oxide-zirconium oxide-tin oxide composite. Examples of the acidic or basic oxide include antimony pentoxide, a silicon oxide-antimony pentoxide composite, and a silicon oxide-tin oxide composite.

[0022] Examples of the nanocarbons include, but are not limited to, nanocarbons such as CNT (carbon nanotube), graphene, and fullerene.

[0023] Examples of the ionic liquids include, but are not limited to, ammonium-based, imidazolium-based, phosphonium-based, pyridinium-based, pyrrolidinium-based, and sulfonium-based ionic liquids.

[0024] The amount of the conductive material used is not particularly limited as long as the hard coat layer has the above-mentioned surface resistance value that allows antistatic properties and abrasion resistance to be reproducibly obtained, and the water contact angle of the surface is 90° or more.

[0025] The surface of the hard coat layer was subjected to a load of 3.54 kg / cm using an eraser for eraser testing. ２ After an abrasion resistance test in which the hard coat layer is rubbed back and forth 1,000 times or more at a speed of 4.5 m / min, the number of reciprocating strokes at which the water contact angle of the surface of the hard coat layer becomes 90° or more is 1.3 times or more, preferably 1.6 times or more, more preferably 2 times or more, and even more preferably 4 times or more, compared to a hard coat layer that does not contain a conductive material. The abrasion resistance test is evaluated, for example, using the equipment and measurement conditions described in the Examples. The ratio of the number of reciprocating strokes is calculated by (the number of reciprocating strokes at which the water contact angle of the hard coat layer of the present invention becomes less than 90° in the abrasion resistance test - 1,000) / (the number of reciprocating strokes at which the water contact angle of the non-conductive hard coat layer becomes less than 90° in the abrasion resistance test - 1,000).

[0026] The hard coat layer not containing a conductive material is obtained by removing the conductive component from the hard coat layer of the present invention. For example, a hard coat layer formed using a curable composition obtained by removing the conductive material from the curable composition for forming the hard coat layer of the present invention described below can be mentioned. Preferably, the curable composition for forming the hard coat layer not containing a conductive material is prepared using the same solvent as the curable composition for forming the hard coat layer of the present invention and has the same solid content concentration.

[0027] <Curable Composition> The curable composition of the present invention is specifically a curable composition for forming the hard coat layer, comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) 0.05 to 10 parts by mass of a surface modifier; (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals when exposed to active energy rays; and (d) 0.1 to 50 parts by mass of a conductive polymer material. Hereinafter, each of the components (a) to (d) will be described.

[0028] [(a) Active Energy Ray-Curable Polyfunctional Monomer] The (a) active energy ray-curable polyfunctional monomer (hereinafter also simply referred to as "(a) polyfunctional monomer") refers to a polyfunctional monomer that undergoes a polymerization reaction and is cured by irradiation with active energy rays such as ultraviolet rays.

[0029] Preferred examples of the (a) polyfunctional monomer in the curable composition of the present invention include a monomer selected from the group consisting of polyfunctional (meth)acrylate compounds, a monomer selected from the group consisting of polyfunctional urethane (meth)acrylate compounds described below, and a monomer selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds. In the present invention, the (a) polyfunctional monomer can be one selected from the group consisting of the above polyfunctional (meth)acrylate compounds, or a combination of two or more selected from the group consisting of the above polyfunctional (meth)acrylate compounds. In the present invention, the (meth)acrylate compound includes both an acrylate compound and a methacrylate compound, and for example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

[0030] The (a) polyfunctional monomer may also be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene-modified monomer include oxymethylene-modified, oxyethylene-modified (also referred to as EO-modified), and oxypropylene-modified. The oxyalkylene-modified polyfunctional monomer may be an oxyalkylene-modified compound of the above-mentioned polyfunctional (meth)acrylate compound or polyfunctional urethane (meth)acrylate compound. The oxyalkylene-modified polyfunctional monomer may also be used alone or in combination of two or more.

[0031] In addition, preferred examples of the polyfunctional monomer (a) in the present invention include a polyfunctional monomer having at least three (meth)acryloyl groups in one molecule, for example, at least four (meth)acryloyl groups in one molecule, such as a monomer selected from the group consisting of oxyalkylene-modified polyfunctional (meth)acrylate compounds having at least three (meth)acryloyl groups in one molecule.

[0032] Examples of the polyfunctional (meth)acrylate compound (provided that it does not have a urethane bond) include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, 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 A di(meth)acrylate, and 1,3-propanediol di(meth)acrylate. 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-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tricyclo[5.2.1.0 ２，６] decanedimethanol 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-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate can be mentioned. Among these, preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0033] Examples of the oxyalkylene-modified polyfunctional (meth)acrylate compound include (meth)acrylate compounds of polyols modified with oxyalkylene. Examples of the polyols include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0034] The polyfunctional urethane (meth)acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and having one or more urethane bonds [—NHC(═O)O—], and may further have a urea bond [—NHC(═O)NH—]. Examples of the polyfunctional urethane (meth)acrylate compound include a compound obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxy group, and a compound obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxy group, and a polyol, but the polyfunctional urethane (meth)acrylate compound that can be used in the present invention is not limited to these examples.

[0035] 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, dipentaerythritol penta(meth)acrylate, and tripentaerythritol hepta(meth)acrylate. 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; polyester polyols that are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, and adipic acid; polyether polyols; and polycarbonate diols.

[0036] The (a) polyfunctional monomer may be a lactone-modified polyfunctional (meth)acrylate compound, and the modifying lactone is preferably ε-caprolactone. Examples of the lactone-modified polyfunctional (meth)acrylate compound include ε-caprolactone-modified pentaerythritol tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tetra(meth)acrylate, ε-caprolactone-modified dipentaerythritol penta(meth)acrylate, and ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0037] [(b) Surface Modifier] The (b) surface modifier is not particularly limited, but is preferably a perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and this perfluoropolyether will hereinafter be referred to simply as "(b1) perfluoropolyether". The ends of the molecular chain containing the poly(oxyperfluoroalkylene) group having an active energy ray-polymerizable group may be all ends or some ends of the molecular chain. When the molecular chain is linear, all ends and some ends of the molecular chain are both ends and one end of the linear molecular chain, respectively. The (b1) perfluoropolyether preferably has an active energy ray-polymerizable group at the end of the molecular chain containing the poly(oxyperfluoroalkylene) group via a urethane bond. The molecular chain containing the poly(oxyperfluoroalkylene) group has, for example, a structure represented by formula [1] or formula [2].

[0038] From the viewpoint of obtaining a cured film (hard coat layer) having good abrasion resistance and scratch resistance, the poly(oxyperfluoroalkylene) group is -[CF ２ O]-(oxyperfluoromethylene group) and -[CF ２ CF ２ In this case, the bond between these oxyperfluoroalkylene groups may be either a block bond or a random bond.

[0039] (b1) perfluoropolyether is not limited to those having one active energy ray polymerizable group at the end of molecular chain containing poly(oxyperfluoroalkylene) group, but may have two or more active energy ray polymerizable groups.As the active energy ray polymerizable group, for example, (meth)acryloyl group and vinyl group can be mentioned, and as the terminal group having the active energy ray polymerizable group, for example, the group represented by the following formula [A1] or formula [A2] can be mentioned.Among these terminal groups, the group represented by formula [A2] having two active energy ray polymerizable groups is preferred. (In the above formula [A1] and formula [A2], R １ and R ２ each independently represents a hydrogen atom or a methyl group, and * represents a bond to the urethane bond.

[0040] (b1) perfluoropolyether is more preferred from the viewpoint that it can obtain the cured film (hard coating layer) with good abrasion resistance and scratch resistance, and has active energy ray polymerizable group at both ends of the molecular chain that comprises poly(oxyperfluoroalkylene) group, and more preferred is the one that has a large number of this active energy ray polymerizable group in one molecule.The number of this polymerizable group is preferably 2 or more, more preferably 3 or more at both ends of the molecular chain that comprises poly(oxyperfluoroalkylene) group.

[0041] In the curable composition of the present invention, the content of the (b) surface modifier is 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the (a) polyfunctional monomer. When the content of the (b) surface modifier is 0.05 parts by mass or more, sufficient abrasion resistance and scratch resistance can be imparted to the hard coat layer, and when the content of the (b) surface modifier is 10 parts by mass or less, sufficient compatibility with the (a) polyfunctional monomer can be achieved, resulting in a hard coat layer with little cloudiness.

[0042] The (b) surface modifier may be used alone or in combination of two or more. When two or more types are combined, a perfluoropolyether having an active energy ray polymerizable group via a urethane bond at one end (one end) of a molecular chain containing a poly(oxyperfluoroalkylene) group and a hydroxy group at the other end (the other end) of the molecular chain may be included.

[0043] [(c) Polymerization initiator capable of generating radicals when exposed to active energy rays] A preferred polymerization initiator capable of generating radicals when exposed to active energy rays in the curable composition of the present invention (hereinafter, also simply referred to as "(c) polymerization initiator") is a polymerization initiator that generates radicals when exposed to active energy rays such as electron beams, ultraviolet rays, and X-rays, particularly ultraviolet rays.

[0044] Examples of the (c) polymerization initiator include benzoins, alkylphenones, thioxanthones, azo compounds, azides, diazo compounds, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazoles, titanocene compounds, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These may be used alone or in combination of two or more. In the present invention, from the viewpoints of transparency, surface curability, internal curability, and thin film curability, it is preferable to use alkylphenones or acylphosphine oxides alone or in combination of two or more as the (c) polymerization initiator. The use of alkylphenones or acylphosphine oxides makes it possible to obtain a cured film (hard coat layer) with improved abrasion resistance.

[0045] Examples of the alkylphenones include α-hydroxyalkylphenones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; α-aminoalkylphenones such as 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one; 2,2-dimethoxy-1,2-diphenylethan-1-one; and methyl phenylglyoxylate. Examples of the acylphosphine oxides include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the like.

[0046] In the curable composition of the present invention, the content of the polymerization initiator (c) is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, per 100 parts by mass of the polyfunctional monomer (a).

[0047] (d) Conductive Polymer Material The conductive polymer material refers to a conductive material that can impart antistatic properties to the cured film (hard coat layer) obtained from the curable composition of the present invention.

[0048] Examples of the (d) conductive polymer material are not particularly limited, but include, for example, polythiophenes such as poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT-PSS), oligothiophenes, polyacetylenes, polyanilines, polypyrroles, poly(p-phenylenes), polyfluorenes, poly(p-phenylenevinylenes), and polythienylenevinylenes.

[0049] (d) Examples of commercially available conductive polymer materials include, for example, Denatron (registered trademark) F-120CD, P-502RG, P-557C, P-200HC, P-801, P-800SL, P-500NT, P-400MP-A, P-560ST, SP-801, SV4stab, SP-548AH, PT-432MF, PT-436, PT-557MF, PT-200HC, PT-432MFT, PT-432NT, [manufactured by Nagase ChemteX Corporation], Orgacon (registered trademark) ICP1010, ICP1020, ICP 1021, ICP1030, ICP1050, S300, S315, S305plus, EL-P3145, EL-P3155, EL-P3165, EL-P5015, HIL-1005, S305, N-1005, DRY [manufactured by Agfa Materials Japan, Inc.], Sepulgida (registered trademark) AS-D, AS-H, AS-M, AS-Q, AS-S, HC-A, HC-R, SAS-P, SAS-F, ASZ-A, ASZ-B, ASZ-C, ASZ-D, OC-AE, OCK [manufactured by Shin-Etsu Polymer Co., Ltd.], Clevios ( Registered trademark) PT2, F020, F010, FAS, FAS8, F141M, FEHO, FELO, PT4, PSB6, PH1000, F100T, FET, SV3, SV3STAB, SV4, SV4STAB, PJetOLED, PJet700N, PJet700 [manufactured by Heraeus], ​​Verazol (registered trademark) WED-S, WED-SM, ED-0130-M, ED-BF4, AN-S03-T [manufactured by Soken Chemical & Engineering Co., Ltd.], SELFTRON (registered trademark) S standard grade, H high conductivity grade, organic solvent grade [manufactured by Toso Chemical Industry Co., Ltd.] Manufactured by Sigma-Aldrich Co., Ltd.], PEDOT-PSS (product numbers) 483095, 560596, 655201, 739316, 900181, 768650, 739332, 739324, 768618, 649805, 687316, 649805, 736295, 736309, 736287, 687316, 649813, 649821, 678392, 675288, 483028, 687553, 759791, 660485, 660523, 669210 [manufactured by Sigma-Aldrich Co., Ltd.], and the like can be used.

[0050] In the curable composition of the present invention, the content of the (d) conductive polymer material is 0.1 to 50 parts by mass, preferably 0.15 to 40 parts by mass, and more preferably 0.2 to 30 parts by mass, relative to 100 parts by mass of the (a) polyfunctional monomer.

[0051] [(e) Solvent] The curable composition of the present invention may further contain (e) solvent, i.e., may be in the form of a varnish (film-forming material). The (e) solvent may be appropriately selected in consideration of dissolving or uniformly dispersing the components (a) to (d) and also of workability during application for forming a cured film (hard coat layer) described below, drying properties before and after curing, and the like. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetralin, etc.; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, cyclohexane, etc.; halides such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene, etc.; esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), etc.; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, etc. ethers such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclopentanone, cyclohexanone, etc.; alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, etc.; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), etc.; sulfoxides such as dimethyl sulfoxide (DMSO), etc., and mixtures of two or more of these solvents.

[0052] The amount of solvent (e) used in the curable composition of the present invention is not particularly limited, but is used at a concentration such that the solid content concentration in the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass. Here, the solid content concentration (also referred to as non-volatile content concentration) represents the content of solids (all components excluding the solvent component) relative to the total mass (total mass) of the components (a) to (e) (and other additives, if desired) in the curable composition of the present invention.

[0053] [Other Additives] Furthermore, to the curable composition of the present invention, additives that are generally added as needed, such as a polymerization accelerator, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion imparting agent, a plasticizer, an ultraviolet absorber, a light stabilizer, an antioxidant, a storage stabilizer, a conductive aid, an inorganic filler, a light diffusing agent, a pigment, a dye, an antifoaming agent, and a defoaming agent, may be appropriately blended, as long as the effects of the present invention are not impaired.

[0054] <Cured film> The curable composition of the present invention can be applied (coated) onto a substrate to form a coating film, and the coating film can be polymerized (cured) by irradiating it with active energy rays to form a cured film. The cured film is also within the scope of the present invention. Furthermore, the hard coat layer described above and the hard coat layer in the hard coat film described below can be made of the cured film.

[0055] Examples of the substrate include various resins (polycarbonate, polymethacrylate, polystyrene, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin), metal, wood, paper, glass, slate, and the like. These substrates may be in the form of a plate, a film, or a three-dimensional molded article. Furthermore, on the surface of the substrate, for example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near-infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather-resistant layer, an antireflection layer, an antistatic layer, a discoloration preventing layer, a gas barrier layer, a water vapor barrier layer, a light-scattering layer, an electrode layer, or the like may be formed as an underlayer of the hard coat layer, or a plurality of underlayers of the hard coat layer may be laminated. The layer formed on the surface of the substrate is not particularly limited as long as it does not impair the effects of the present invention.

[0056] The method for applying the composition to the substrate can be appropriately selected from cast coating, spin coating, blade coating, dip coating, roll coating, spray coating, bar coating, die coating, inkjet printing, and printing methods (such as relief printing, intaglio printing, lithographic printing, and screen printing). Among these, roll-to-roll methods are preferred. From the viewpoint of thin-film application, relief printing, particularly gravure coating, is preferred. The curable composition is preferably filtered before application using a filter having a pore size of approximately 0.2 μm to 5 μm. When applying the composition, a solvent may be added to the curable composition to form a varnish, if necessary. Examples of the solvent include the various solvents listed in the above section (e) Solvent.

[0057] After applying the curable composition to a substrate to form a coating film, the coating film is pre-dried as needed using a heating means such as a hot plate or oven to remove the solvent (solvent removal step). The heat drying conditions are preferably, for example, 40°C to 120°C for about 30 seconds to 10 minutes. After drying, the coating film is cured by irradiating it with active energy rays such as ultraviolet light. Examples of active energy rays include ultraviolet light, electron beams, and X-rays, with ultraviolet light being particularly preferred. Examples of light sources that can be used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs, and electrodeless lamps. The polymerization may then be completed by post-baking, specifically by heating using a heating means such as a hot plate or oven.

[0058] The thickness of the cured film formed after drying and curing is usually 0.1 μm to 20 μm, preferably 0.1 μm to 15 μm, and more preferably 0.1 μm to 10 μm.

[0059] <Hard Coat Film> Using the curable composition of the present invention, a hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced. This hard coat film is also within the scope of the present invention, and this hard coat film is suitably used for protecting the surfaces of various display elements such as touch panels and liquid crystal displays.

[0060] The hard coat layer in the hard coat film of the present invention can be formed by a method including the steps of applying the curable composition of the present invention to a film substrate to form a coating film, removing the solvent by heating as necessary, and irradiating the coating film with active energy rays such as ultraviolet rays to cure the coating film. A method for producing a hard coat film having a hard coat layer on at least one side of a film substrate, including these steps, is also within the scope of the present invention.

[0061] The film substrate may be any of various transparent resin films usable for optical applications among the substrates listed in the above section <Cured film>. Preferred resin films include films of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, and triacetyl cellulose (TAC).

[0062] The film substrate may be formed by laminating a plurality of layers. For example, a layer different from the resin film, such as a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near-infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather-resistant layer, an antireflection layer, an antistatic layer, a discoloration preventing layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, or an electrode layer, may be laminated on the surface of the resin film as an underlayer of the hard coat layer, or a plurality of underlayers of the hard coat layer may be laminated. The layer laminated on the surface of the resin film is not particularly limited as long as it does not impair the effects of the present invention.

[0063] The laminate may have one or more hard coat layers on at least one surface (surface) of the film substrate, or may have an underlying hard coat layer between the film substrate and the hard coat layer.

[0064] The method for applying the curable composition of the present invention to the film substrate (coating film forming step) and the method for irradiating the coating film with active energy rays (curing step) can be the methods listed above in <Cured film>. When the curable composition of the present invention contains a solvent (in the form of a varnish), the coating film may be dried to remove the solvent after the coating film forming step, if necessary. In this case, the method for drying the coating film (solvent removal step) listed above in <Cured film> can be used.

[0065] The thickness of the hard coat layer thus obtained is, for example, 1 μm to 20 μm, preferably 1 μm to 15 μm, and more preferably 1 μm to 10 μm.

[0066] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows:

[0067] (1) Coating by bar coater Apparatus: Automatic Film applicator AB3125 manufactured by TQC Co., Ltd. Bar: A-Bar OSP-22 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 22 μm (equivalent to wire bar #9) Bar: A-Bar OSP-25 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 25 μm (equivalent to wire bar #10) Bar: A-Bar OSP-30 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 30 μm (equivalent to wire bar #12) Coating speed: 4 m / min (2) Oven Apparatus: Two-layer clean oven (top and bottom type) PO-250-45-D manufactured by Sanki Keiso Co., Ltd. (3) UV curing Apparatus: CV-110QC-G manufactured by Heraeus K.K. (4) Gel permeation chromatography (GPC) Apparatus: HLC-8420GPC manufactured by Tosoh Corporation Column: TSKgel (registered trademark) G2000HXL, G3000HXL manufactured by Tosoh Corporation Column temperature: 40 ° C. Eluent: tetrahydrofuran Detector: UV (5) Abrasion resistance test Apparatus: Reciprocating abrasion tester TRIBOGEAR TYPE: 30H manufactured by Shinto Scientific Co., Ltd. Scanning speed: 4.5 m / min Scanning distance: 50 mm (6) Contact angle measurement Apparatus: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measurement temperature: 23 ° C. (7) Surface resistance measurement Apparatus: High resistivity meter Hirestar-UP manufactured by Nitto Seiko Analytech Co., Ltd. (formerly Mitsubishi Chemical Analytech Co., Ltd.) MCP-HT450 Probe: URS probe Applied voltage: 100V (8) Total light transmittance and haze measurement Apparatus: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0068] The abbreviations have the following meanings: A1: Oxyethylene-modified multifunctional acrylate [New Frontier (registered trademark) MF-001, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] A2: Diglycerin EO-modified acrylate [Aronix (registered trademark) M-460, manufactured by Toagosei Co., Ltd.] A3: Multifunctional acrylate [Aronix (registered trademark) MT-3010, manufactured by Toagosei Co., Ltd.] A4: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [KAYARAD (registered trademark) DN-0075, manufactured by Nippon Kayaku Co., Ltd.] A5: Multifunctional urethane acrylate [Art Resin (registered trademark) UN-904, manufactured by Negami Chemical Industrial Co., Ltd.] C1: PEDOT-PSS aqueous dispersion [Sigma-Aldrich PEDOT-PSS 1.3 mass% aqueous dispersion, conductive grade] C1: PEDOT-PSS aqueous dispersion [Sigma-Aldrich PEDOT-PSS 3.0% to 4.0% by mass aqueous dispersion, high conductivity grade, Product No. 655201] C2: PEDOT-PSS aqueous dispersion [Sigma-Aldrich PEDOT-PSS 3.0% to 4.0% by mass aqueous dispersion, high conductivity grade, Product No. 655201] C3: 30% by mass methanol dispersion sol of core-shell particles with a primary particle diameter of 30 nm to 40 nm, consisting of tin oxide cores and surfaces coated with antimony pentoxide [Nissan Chemical Industries, Ltd., Suncolloid (registered trademark) HX-307M1] *Here, primary particle diameter refers to the average particle diameter measured by transmission electron microscopy. The particle diameter was determined by dropping the sol onto a copper mesh, drying it, and observing it with a transmission electron microscope (JEOL Ltd., JEM-1020) at an accelerating voltage of 100 kV, averaging the measurements of 100 particles, and calculating the average primary particle diameter. PFPE1: A perfluoropolyether having the following structure, which has two hydroxy groups at each end of a molecular chain containing a poly(oxyperfluoroalkylene) group, without a poly(oxyalkylene) group interposed therebetween [Fomblin (registered trademark) T4, manufactured by Solvay Specialty Polymers]. (In the above formula, m represents the repeating unit -(CF ２ CF ２ O)-, and n is the number of repeating units -(CF ２PFPE2: a perfluoropolyether having one hydroxy group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyethylene) group, and having the following structure [Fomblin (registered trademark) 4102X manufactured by Solvay Specialty Polymers]. (In the above formula, r represents the repeating unit -(CF ２ CF ２ O)-, and s is the number of repeating units -(CF ２ 0)-, satisfying 5≦(r+s)≦30, r and s each independently represent an integer of 0 or more, and q is the number of oxyethylene groups and represents an integer of 2 to 20. BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI, manufactured by Showa Denko K.K.] DOTDD: dioctyltin dineodecanoate [Neostan (registered trademark) U-830, manufactured by Nitto Kasei Co., Ltd.] O2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [OMNIRAD (registered trademark) 2959, manufactured by IGM Resins] OTPO: diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide [OMNIRAD (registered trademark) TPO H, manufactured by IGM Resins] L1: surface modifier [MEGAFAC (registered trademark) R-40, manufactured by DIC Corporation] PGME: propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate MeOH: Methanol IPA: 2-propanol

[0069] [Production Example 1] Production of perfluoropolyether (S1) having four acryloyl groups via urethane bonds at each end of a molecular chain containing a poly(oxyperfluoroalkylene) group. 1.19 g (0.5 mmol) of PFPE1, 0.52 g (2.0 mmol) of BEI, 0.017 g of DOTDD (0.01 times the total mass of PFPE1 and BEI), and 1.67 g of PGMEA were charged into a screw tube. This mixture was stirred at room temperature (approximately 23 ° C.) for 24 hours using a stirrer tip to obtain a 50 wt% PGMEA solution of the target compound S1. The weight average molecular weight (Mw) of the obtained S1 measured in polystyrene equivalent by GPC was 2,300, and the dispersity (Mw (weight average molecular weight) / Mn (number average molecular weight)) was 1.0.

[0070] [Production Example 2] Production of perfluoropolyether (S2) having an acryloyl group via a urethane bond at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group. 3.08 g (1.6 mmol) of PFPE2, 0.39 g (1.6 mmol) of BEI, 0.035 g of DOTDD (0.01 times the total mass of PFPE2 and BEI), and 3.5 g of PGMEA were charged into a screw tube. This mixture was stirred at room temperature (approximately 23 ° C.) for 72 hours using a stirrer tip to obtain a 50 wt% PGMEA solution of the target perfluoropolyether compound S2. The weight average molecular weight (Mw) of the obtained S2 measured in polystyrene equivalent by GPC was 1908, and the dispersity (Mw (weight average molecular weight) / Mn (number average molecular weight)) was 1.0.

[0071] [Examples 1 to 11, Comparative Examples 1 to 10] The following components listed in Table 1 were mixed to prepare curable compositions with the solid content concentrations listed in Table 1. Here, solid content refers to components other than the solvent. In Table 1, [parts] represents [parts by mass] and [%] represents [mass %]. Multifunctional monomer: 100 parts by mass of the multifunctional monomer listed in Table 1. Conductive material: The amount of the conductive material listed in Table 1 (solid content equivalent) listed in Table 1. *The solid content of C2 was calculated as a 3.5 mass% aqueous dispersion. Surface modifier: The amount of the surface modifier listed in Table 1 (solid content equivalent) listed in Table 1. Polymerization initiator: 3 parts by mass of O2959. Solvent: The amount of the solvent listed in Table 1 (solid content equivalent) listed in Table 1.

[0072]

[0073] The curable compositions prepared according to Table 1 were applied using a bar coater onto an A4-sized PET film (Lumirror (registered trademark) U403 (also known as U40), 100 μm thick, manufactured by Toray Industries, Inc.) on both sides of which a primer layer had been formed by easy-adhesion treatment, to obtain a coating film. This coating film was dried in an oven at 65°C for 3 minutes to remove the solvent. The obtained film was then exposed to light at an exposure dose of 300 mJ / cm under a nitrogen atmosphere. ２ The film was exposed to UV light of 1000 kJ / cm 2 , thereby producing a hard coat film having a hard coat layer (cured film) with a thickness of approximately 3 μm.

[0074] The water repellency, abrasion resistance, antistatic property, haze, and total light transmittance of the obtained hard coat film having a hard coat layer were evaluated. The procedures for evaluating the water repellency, abrasion resistance, and antistatic property are shown below. The results are also shown in Table 2.

[0075] [Water repellency] 1 μL of water was applied to the surface of the hard coat layer, and the contact angle θ was measured five times after 5 seconds. The average value was used to evaluate the water repellency according to the following criteria. When considering actual use as a hard coat layer, at least B is required, and A is desirable. A: θ≧105° B: 90°≦θ<105° C: θ<90°

[0076] [Abrasion Resistance] The surface of the hard coat layer was subjected to a pressure of 1 kg, i.e., 3.54 kg / cm, using a cylindrical eraser [RUBBER STICK, manufactured by Minoan Co., Ltd., φ6.0 mm] attached to the reciprocating abrasion tester. ２ The sample was rubbed 1,000 times with a load of 1 μL. 1 μL of water was applied to the rubbed area, and the contact angle θ was measured 5 times after 5 seconds, and the average value was used as the contact angle value. If the contact angle value was 90° or more, the same procedure was repeated until the contact angle value was less than 90°, and the number of tests before the contact angle value became less than 90° was calculated.

[0077] [Surface Resistivity Value] A hard coat film was placed on the Teflon (registered trademark) surface of a resitable UFL attached to the high resistivity meter, and a probe was pressed against the surface of the hard coat layer of the hard coat film. After 10 seconds, the surface resistance value was measured five times, and the average value was calculated.

[0078]

[0079] As shown in Table 2, the hard coat layers obtained from the curable compositions of Examples 1 to 11 had a surface resistance of 1×10 ６ Ω / □ or more 1×10 １４ It was found that the hard coat layer exhibited antistatic properties of less than Ω / □, good water repellency with a surface water contact angle of 105° or more, and was 1.7 times more abrasion resistant than the hard coat layer obtained from a curable composition that did not contain a conductive material (Comparative Example 1 and Comparative Examples 4 to 10).

[0080] The curable composition of Comparative Example 2 contains the same amount of conductive material as the curable composition of Example 4, but the hard coat layer obtained from the curable composition of Comparative Example 2 has a surface resistance of 1×10 １４ The hard coat layer obtained from the curable composition of Comparative Example 3 had a surface resistance of 3×10 １１ Although the antistatic property was Ω / □, the water contact angle of the surface was less than 90°, resulting in poor water repellency.

[0081] [Composition Example 1, Comparative Example 11] The following components shown in Table 3 were mixed to prepare curable compositions having the solid content concentrations shown in Table 3. Here, the solid content refers to components other than the solvent. In Table 3, [parts] represents [parts by mass] and [%] represents [% by mass]. Polyfunctional monomer: 100 parts by mass of the polyfunctional monomer shown in Table 3. Conductive material: The conductive material shown in Table 3 in the amount shown in Table 3 (solid content equivalent). Surface modifier: The surface modifier shown in Table 3 in the amount shown in Table 3 (solid content equivalent). Polymerization initiator: The polymerization initiator shown in Table 3 in the amount shown in Table 3. Solvent: The solvent shown in Table 3 in the amount shown in Table 3.

[0082] The curable composition of Comparative Example 11 was applied with a bar coater onto an A4-sized PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., thickness 100 μm] on both sides of which a primer layer had been formed by easy-adhesion treatment, to obtain a coating film. This coating film was dried in an oven at 65°C for 3 minutes to remove the solvent. The obtained film was then exposed to light at an exposure dose of 300 mJ / cm under a nitrogen atmosphere. ２ The film was exposed to UV light of 1000 kJ / cm 2 , thereby producing a hard coat film having a hard coat layer (cured film) with a thickness of approximately 3 μm.

[0083] [Example 12] The curable composition of Composition Example 1 was applied using a bar coater onto an A4-sized PET film (Lumirror (registered trademark) U403 (also known as U40), 100 μm thick, manufactured by Toray Industries, Inc.) on both sides of which a primer layer had been formed by an easy-adhesion treatment, to obtain a coating film. This coating film was dried in an oven at 65°C for 3 minutes to remove the solvent. The obtained film was then exposed to light at an exposure dose of 300 mJ / cm under a nitrogen atmosphere. ２ The film was exposed to UV light of 1000 kJ / cm 2 , thereby producing a hard coat film having a hard coat layer (cured film) with a thickness of approximately 2 μm.

[0084] Thereafter, the curable composition of Comparative Example 11 was applied onto the hard coat layer to obtain a coating film. The coating film was dried in an oven at 65°C for 3 minutes to remove the solvent. The obtained film was exposed to light at an exposure dose of 300 mJ / cm under a nitrogen atmosphere. ２By irradiating and exposing the hard coat layer with UV light, a hard coat film (total thickness of 5 μm) further having a hard coat layer (cured film) with a thickness of approximately 3 μm obtained from the curable composition of Comparative Example 11 on the hard coat layer was produced.

[0085] The water repellency, abrasion resistance, and surface resistivity of the hard coat film having the hard coat layer thus obtained were evaluated according to the above-mentioned evaluation methods. The results are shown in Table 4.

[0086] As shown in Tables 3 and 4, the hard coat film of Example 12 is a laminate having an upper layer of a hard coat layer obtained from the curable composition of Comparative Example 11 which does not contain a conductive material, and a lower layer of a hard coat layer obtained from the curable composition of Composition Example 1 which contains a conductive material C3. As shown in Table 4, the hard coat layer of the hard coat film of Example 12 has a surface resistance of 1×10 １２ On the other hand, the hard coat layer obtained from the curable composition of Comparative Example 11 had a surface resistance of 1×10 １４ Ω / □ or more, which is higher than the surface resistance value of the hard coat layer of the hard coat film of Example 12. As a result, the hard coat layer of the hard coat film of Example 12 had 1.38 times improved abrasion resistance compared to the hard coat layer obtained from the curable composition of Comparative Example 11.

[0087] The surface resistance of the hard coat layer is high (1×10 １４ When the surface resistance of the hard coat layer is low (1×10 Ω / □ or more), eraser chips detached from the eraser used in the abrasion resistance test tend to adhere to and remain on the surface of the hard coat layer. Therefore, it is considered that the abrasion resistance of the hard coat layer having a high surface resistance value is reduced as a result of the abrasion resistance test using an eraser. On the other hand, when the surface resistance of the hard coat layer is low (1×10 ６ Ω / □ or more 1×10 １４ When the surface resistivity is less than Ω / □, eraser dust detached from the eraser used in the abrasion resistance test is less likely to remain on the surface of the hard coat layer. Therefore, it is thought that the abrasion resistance of a hard coat layer with a low surface resistivity is improved as a result of the abrasion resistance test using an eraser.

Claims

1. A hard coat layer provided on at least one surface of a substrate, the hard coat layer having a surface resistance of 1×10 ６ Ω / □ or more 1×10 １４ Ω / □ or less, and the water contact angle of the surface is 105° or more; The hard coat layer contains a conductive material, and the surface of the hard coat layer is subjected to a load of 3.54 kg / cm with an eraser for an eraser test. ２ and after an abrasion resistance test in which the hard coat layer is rubbed back and forth 1,000 times or more at a speed of 4.5 m / min, the number of reciprocating strokes at which the water contact angle of the surface of the hard coat layer becomes 105° or more is 1.3 times or more compared to a hard coat layer not containing the conductive material.

2. 2. The hard coat layer according to claim 1, wherein the conductive material is a conductive polymer material.

3. The hard coat layer of claim 2, wherein the conductive polymer material comprises poly(3,4-ethylenedioxythiophene).

4. The hard coat layer according to claim 2 or claim 3, wherein the conductive polymer material comprises poly(3,4-ethylenedioxythiophene) doped with polystyrenesulfonic acid.

5. 2. The hard coat layer according to claim 1, wherein the conductive material is a metal oxide particle.

6. The hard coat layer according to claim 1 , which comprises one or more layers.

7. (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (b) 0.05 parts by weight to 10 parts by weight of a surface modifier; (c) 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals when exposed to active energy rays, and The curable composition for forming a hard coat layer according to claim 1 , further comprising: (d) 0.1 to 50 parts by mass of a conductive polymer material.

8. The curable composition according to claim 7, wherein the surface modifier (b) is a perfluoropolyether having an active energy ray-polymerizable group at an end of a molecular chain containing a poly(oxyperfluoroalkylene) group.

9. The curable composition according to claim 8 , wherein the perfluoropolyether has the active energy ray-polymerizable group via a urethane bond at an end of a molecular chain containing the poly(oxyperfluoroalkylene) group.

10. The curable composition according to claim 8 or 9, wherein the perfluoropolyether has at least two of the active energy ray-polymerizable groups via urethane bonds at each of both ends of a molecular chain containing the poly(oxyperfluoroalkylene) group.

11. The poly(oxyperfluoroalkylene) group of the perfluoropolyether is a repeating unit -(CF ２ CF ２ O)- and / or repeating unit -(CF ２ 11. The curable composition according to claim 8, wherein the repeating units are each a group having a repeating unit selected from the group consisting of a block bond, a random bond, or a block and random bond.

12. The curable composition according to claim 11, wherein the molecular chain containing the poly(oxyperfluoroalkylene) group of the perfluoropolyether has a structure represented by the following formula [1] or formula [2]: [Formula 1] (In the above formula [1] and formula [2], m is a repeating unit -(CF ２ CF ２ O)-, and n is the number of repeating units -(CF ２ m and n each independently represent an integer of 0 or more, and r represents the number of repeating units -(CF ２ CF ２ O)-, and s is the number of repeating units -(CF ２The number of repeating units -(CF)- satisfies 5≦(r+s)≦30, r and s each independently represent an integer of 0 or more, q represents the number of oxyethylene groups and represents an integer of 2 to 20, ２ CF ２ O)- and the repeating unit -(CF ２ O)- is bonded in a block bond, a random bond, or a block bond and a random bond.

13. The curable composition according to any one of claims 7 to 12, wherein the (d) conductive polymer material comprises poly(3,4-ethylenedioxythiophene).

14. The curable composition of claim 13, wherein the (d) conductive polymer material comprises poly(3,4-ethylenedioxythiophene) doped with polystyrenesulfonic acid.

15. The curable composition according to claim 7 , further comprising (e) a solvent.

16. A hard coat film comprising the hard coat layer according to any one of claims 1 to 6 on at least one surface of a film substrate.

17. 7. A hard coat film comprising the hard coat layer according to claim 1 on at least one surface of a film substrate, and an upper hard coat layer not containing a conductive material on the hard coat layer.

18. 18. The hard coat film according to claim 16, wherein the hard coat layer has a thickness of 1 μm to 20 μm.

19. 16. A method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, the hard coat layer being formed by a method including the steps of: applying the curable composition according to claim 7 onto the film substrate to form a coating film; and irradiating the coating film with active energy rays to cure the coating film.

20. 16. A method for producing a laminate of a film substrate and a hard coat layer, comprising: a step of applying the curable composition according to claim 7 onto a film substrate to form a coating film; and a step of irradiating the coating film with active energy rays to cure the coating film.

21. The method for producing a laminate according to claim 20, further comprising the step of forming an upper hard coat layer on the hard coat layer formed by the curing step.

22. The method of claim 21 , wherein the hardcoat top layer does not include a conductive material.

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