JPWO2020162324A1 - Curable composition for antistatic hard coat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of forming a hard coat layer having both extremely high scratch resistance and stretchability and further having antistatic properties. SOLUTION: This is a perfluoropolyether containing (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer and (b) a poly (oxyperfluoroalkylene) group, and urethane bonds are attached to both ends of the molecular chain thereof. Perfluoropolyether having an active energy ray-polymerizable group (excluding the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond). () 0.05 parts by mass to 10 parts by mass, (c) 1 part by mass to 20 parts by mass of a polymerization initiator that generates a radical by an active energy ray, and (d) 5 parts by mass of metal oxide particles as an antistatic agent. A hard coat film comprising a curable composition containing 100 parts by mass and a hard coat layer formed from the composition. [Selection diagram] None

Description

The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to a surface of a flexible display or the like. More specifically, the present invention relates to a curable composition capable of forming a hard coat layer having both extremely high scratch resistance and stretchability and further having antistatic properties.

Smartphones are widely used as indispensable products in our daily lives. In recent years, bendable displays, so-called flexible displays, have been developed as displays for smartphones and the like. The flexible display can be deformed, for example, by bending and winding, and is expected to be widely used as a portable mobile display.

Normally, a cover glass is used on the surface of the smartphone to prevent the display from being scratched. However, in general, glass is hard and cannot be bent back, so that it cannot be applied to flexible displays. Therefore, an attempt has been made to apply a plastic film having a hard coat layer having scratch resistance. When the plastic film provided with these hardcourt layers is bent with the hardcourt layer on the outside, stress in the tensile direction is generated in the hardcourt layer. Therefore, the hardcourt layer is required to have a certain stretchability.

Generally, in order to impart scratch resistance to a hardcourt layer, for example, a highly crosslinked structure is formed, that is, a crosslinked structure having low molecular motion is formed to increase the surface hardness and impart resistance to external forces. The method is adopted. As these hardcourt layer forming materials, polyfunctional acrylate-based materials that are three-dimensionally crosslinked by radicals are currently most used. However, polyfunctional acrylate-based materials usually do not have stretchability due to their high crosslink density. As described above, there is a trade-off relationship between the stretchability of the hard coat layer and the scratch resistance, and it has been an issue to balance the characteristics of both.

As a method for achieving both stretchability and scratch resistance of the hard coat layer, a technique in which a polyfunctional urethane acrylate oligomer and a polyfunctional acrylate modified with oxyethylene having high molecular mobility are used in combination is disclosed (patented). Document 1).

Further, when the display surface is charged, dust adheres to the surface, causing a problem that the electronic device is damaged or destroyed. Therefore, antistatic properties are desired for the hard coat film applied to the display surface. There is.

For example, as a method of imparting antistatic properties to a polyfunctional acrylate-based material that is three-dimensionally crosslinked by radicals, a method of adding metal oxide fine particles exhibiting electron conductivity or ionic conductivity, an organic material exhibiting ionic conductivity, or the like is used. Are known.

As metal oxide fine particles exhibiting electron conductivity and ionic conductivity, for example, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), phosphorus-doped tin oxide (PTO), and the like are known. Has been done.

In addition, as an antifouling hard coat layer having scratch resistance, (meth) acryloyl is provided at both ends of a poly (oxyperfluoroalkylene) chain via a poly (oxyalkylene) group and one urethane bond. A technique using a compound having a group as a surface modifier is disclosed (Patent Document 2).

International Publication No. 2013/191254 International Publication No. 2016/16347

However, in the method described in Patent Document 1, since a polyfunctional urethane acrylate is blended in order to impart scratch resistance, there is a problem in its stretchability. Further, the plastic film provided with the hard coat layer having stretchability and scratch resistance has a problem that the contact surface is easily charged due to friction or the like.
Further, the surface modifier described in Patent Document 2 has a problem that its function (antifouling property) deteriorates during use when it is touched by a person every day like a touch panel, and it is prevented in the process of use. There was a problem with the durability of stains.
Further, the hard coat layer containing the metal oxide fine particles for antistatic has a problem that unevenness due to the particles is formed on the surface and the scratch resistance is lowered. Further, the hard coat layer containing an organic material exhibiting ionic conductivity for antistatic has a feature that antistatic property can be imparted without impairing flatness, but the organic material generally has a flexible structure. There is a problem that the scratch resistance of the hard coat layer tends to decrease.
That is, an object of the present invention is to provide a curable composition capable of forming a hard coat layer having both extremely high scratch resistance and stretchability and further having antistatic properties.

As a result of diligent studies to achieve the above object, the present inventors have obtained a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, and poly (oxyalkylene) at both ends of the molecular chain thereof. A curable composition containing a perfluoropolyether having an active energy ray-polymerizable group, an active energy ray-curable polyfunctional monomer, and metal oxide particles as an antistatic agent, not via a group but via a urethane bond. However, they have found that it is possible to form a hard coat layer having both extremely high scratch resistance and stretchability and further having antistatic properties, and completed the present invention.

上記式［１］中、ｎは、繰り返し単位−［ＯＣＦ_２ＣＦ_２］−の数と繰り返し単位−［ＯＣＦ_２］−の数との総数であって、５〜３０の整数を表し、
前記繰り返し単位−［ＯＣＦ_２ＣＦ_２］−及び前記繰り返し単位−［ＯＣＦ_２］−は、ブロック結合、ランダム結合、又は、ブロック結合及びランダム結合の何れかにて結合してなる。
第６観点として、前記（ａ）多官能モノマーが、オキシエチレン変性多官能モノマーである、第１観点乃至第５観点のうち何れか一つに記載の硬化性組成物に関する。
第７観点として、前記（ａ）多官能モノマーの平均オキシエチレン変性量が、該多官能モノマーの重合性基１ｍｏｌに対し３ｍｏｌ未満である第６観点のうち何れか一つに記載の硬化性組成物に関する。
第８観点として、前記（ａ）多官能モノマーが、多官能（メタ）アクリレート化合物（但し、後述の多官能ウレタン（メタ）アクリレート化合物を除く）及び多官能ウレタン（メタ）アクリレート化合物からなる群から選ばれる少なくとも１つを含む、第１観点乃至第７観点のうち何れか一つに記載の硬化性組成物に関する。
第９観点として、前記（ｃ）金属酸化物粒子がスズドープ酸化インジウム、フッ素ドープ酸化スズ、アンチモンドープ酸化スズ、リンドープ酸化スズ、ガリウムドープ酸化亜鉛、アルミニウムドープ酸化亜鉛、アンチモンドープ酸化亜鉛、インジウムドープ酸化亜鉛、酸化亜鉛ドープ酸化インジウム、及び酸化インジウムガリウム亜鉛からなる群から選ばれる少なくとも１つを含む、第１観点乃至第８観点のうち何れか一つに記載の硬化性組成物に関する。
第１０観点として、前記（ｃ）金属酸化物粒子がリンドープ酸化スズを含む、第１観点乃至第９観点のうち何れか一つに記載の硬化性組成物に関する。
第１１観点として、前記（ｃ）金属酸化物粒子の一次粒子径が４ｎｍ〜１００ｎｍである、第１観点乃至第１０観点のうち何れか一つに記載の硬化性組成物に関する。
第１２観点として、さらに（ｅ）溶媒を含む、第１観点乃至第１１観点のうち何れか一つに記載の硬化性組成物に関する。
第１３観点として、第１観点乃至第１１観点のうち何れか一つに記載の硬化性組成物より得られる硬化膜に関する。
第１４観点として、フィルム基材の少なくとも一方の面にハードコート層を備えるハードコートフィルムであって、該ハードコート層が第１３観点に記載の硬化膜からなる、ハードコートフィルムに関する。
第１５観点として、前記ハードコート層が１μｍ〜１５μｍの層厚を有する、第１４観点に記載のハードコートフィルムに関する。
第１６観点として、フィルム基材の少なくとも一方の面にハードコート層を備えるハードコートフィルムの製造方法であって、該ハードコート層が、第１観点乃至第１２観点のうち何れか一つに記載の硬化性組成物をフィルム基材上に塗布し塗膜を形成する工程と、該塗膜に活性エネルギー線を照射し硬化する工程とを含む、ハードコートフィルムの製造方法に関する。That is, the present invention, as a first aspect,
(A) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(B) A perfluoropolyether containing a poly (oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via a urethane bond (provided that the perfluoropolyether is a perfluoropolyether. Excluding perfluoropolyethers having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond.) 0.05 parts by mass to 10 parts by mass,
(C) 5 parts by mass to 100 parts by mass of metal oxide particles as an antistatic agent, and (d) 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
With respect to a curable composition comprising.
As a second aspect, the curable composition according to the first aspect, wherein the (b) perfluoropolyether has at least two active energy ray-polymerizable groups at both ends of the molecular chain via urethane bonds. Regarding.
As a third aspect, the curable composition according to the second aspect, wherein the perfluoropolyether (b) has at least three active energy ray-polymerizable groups at both ends of the molecular chain via urethane bonds. Regarding.
As a fourth aspect, the poly (oxyperfluoroalkylene) group has both a repeating unit- [OCF ₂ ]-and a repeating unit- [OCF ₂ CF ₂ ]-, and these repeating units are block-bonded or randomly bonded. , Or the curable composition according to any one of the first aspect to the third aspect, which is a group formed by a block bond and a random bond.
As a fifth aspect, the curable composition according to the fourth aspect, wherein the (b) perfluoropolyether has a partial structure represented by the following formula [1].

In the above equation [1], n is _{the total number of the number of repeating units − [OCF 2} CF ₂ ] − and the number of repeating units − [OCF ₂ ] −, and represents an integer of 5 to 30.
The repeating unit- [OCF ₂ CF ₂ ]-and the repeating unit- [OCF ₂ ]-are bound by either a block bond, a random bond, or a block bond or a random bond.
As a sixth aspect, the curable composition according to any one of the first aspect to the fifth aspect, wherein the polyfunctional monomer (a) is an oxyethylene modified polyfunctional monomer.
As a seventh aspect, the curable composition according to any one of the sixth aspect, wherein the average amount of oxyethylene modification of the (a) polyfunctional monomer is less than 3 mol with respect to 1 mol of the polymerizable group of the polyfunctional monomer. Regarding things.
From the eighth viewpoint, the (a) polyfunctional monomer consists of a group consisting of a polyfunctional (meth) acrylate compound (excluding the polyfunctional urethane (meth) acrylate compound described later) and a polyfunctional urethane (meth) acrylate compound. The curable composition according to any one of the first aspect to the seventh aspect, which comprises at least one selected.
As a ninth aspect, the metal oxide particles (c) are tin-doped indium oxide, fluorine-doped tin oxide, antimony-doped tin oxide, phosphorus-doped tin oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, antimonated zinc oxide, and indium-doped oxidation. The curable composition according to any one of the first to eighth aspects, comprising at least one selected from the group consisting of zinc, zinc oxide-doped indium oxide, and indium gallium oxide.
As a tenth aspect, the curable composition according to any one of the first aspect to the ninth aspect, wherein the metal oxide particles (c) contain phosphorus-doped tin oxide.
The eleventh aspect relates to the curable composition according to any one of the first aspect to the tenth aspect, wherein the primary particle diameter of the metal oxide particles (c) is 4 nm to 100 nm.
As a twelfth aspect, the present invention relates to the curable composition according to any one of the first aspect to the eleventh aspect, further comprising (e) a solvent.
As a thirteenth aspect, the present invention relates to a cured film obtained from the curable composition according to any one of the first aspect to the eleventh aspect.
As a fourteenth aspect, the present invention relates to a hardcoat film having a hardcoat layer on at least one surface of a film substrate, wherein the hardcoat layer is made of the cured film according to the thirteenth aspect.
The fifteenth aspect relates to the hardcourt film according to the fourteenth aspect, wherein the hardcoat layer has a layer thickness of 1 μm to 15 μm.
A sixteenth viewpoint is a method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is described in any one of the first viewpoint to the twelfth viewpoint. The present invention relates to a method for producing a hardcourt film, which comprises a step of applying the curable composition of the above to 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.

According to the present invention, a curable composition useful for forming a cured film and a hard coat layer having both extremely high scratch resistance and stretchability even in a thin film having a thickness of about 1 μm to 10 μm and having antistatic properties. Can be provided.
Further, according to the present invention, it is possible to provide a hard coat film having a hard coat film obtained from the curable composition or a hard coat layer formed thereof on the surface thereof, and has extremely high scratch resistance and stretching. It is possible to provide a hard coat film having both properties and antistatic properties.

<Curable composition>
The curable composition of the present invention, in detail,
(A) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(B) A perfluoropolyether containing a poly (oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via a urethane bond (provided that the perfluoropolyether is a perfluoropolyether. Excluding perfluoropolyethers having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond.) 0.05 parts by mass to 10 parts by mass,
(C) 5 parts by mass to 100 parts by mass of metal oxide particles as an antistatic agent, and (d) 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
With respect to a curable composition comprising.
Hereinafter, each component (a) to (d) will be described first.

[(A) Active energy ray-curable polyfunctional monomer]
(A) Active energy ray-curable polyfunctional monomer (hereinafter, also simply referred to as "(a) polyfunctional monomer") is a polyfunctional monomer in which the polymerization reaction proceeds and is cured by irradiating with active energy rays such as ultraviolet rays. Refers to a monomer.

Preferred (a) polyfunctional monomers in the curable composition of the present invention include oxyethylene-modified polyfunctional monomers, and examples thereof include oxyethylene-modified polyfunctional monomers having at least three active energy ray-polymerizable groups. ..
Examples of the oxyethylene-modified polyfunctional monomer having at least three active energy ray-polymerizable groups include oxyethylene-modified polyfunctional monomers having at least three active energy ray-polymerizable groups, preferably average oxy. Examples thereof include an oxyethylene-modified polyfunctional monomer having an ethylene modification amount of less than 3 mol with respect to 1 mol of the polymerizable group.
The more preferable oxyethylene-modified polyfunctional monomer in the curable composition of the present invention has at least three active energy ray-polymerizable groups, and the average amount of oxyethylene modification is less than 3 mol with respect to 1 mol of the polymerizable group. It is a monomer selected from the group consisting of an oxyethylene-modified polyfunctional (meth) acrylate compound and an oxyethylene-modified polyfunctional urethane (meth) acrylate compound.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

The average amount of oxyethylene modification in the oxyethylene-modified polyfunctional monomer is less than 3 mol with respect to 1 mol of the active energy ray-polymerizable group of the monomer, and preferably less than 2 mol with respect to 1 mol of the active energy ray-polymerizable group of the monomer. Is.
The average amount of oxyethylene modification in the oxyethylene-modified polyfunctional monomer is larger than 0 mol with respect to 1 mol of the active energy ray-polymerizable group of the monomer, preferably with respect to 1 mol of the active energy ray-polymerizable group of the monomer. It is 0.1 mol or more, more preferably 0.5 mol or more.

Examples of the oxyethylene-modified polyfunctional (meth) acrylate compound include (meth) acrylate compounds of oxyethylene-modified polyols.
Examples of the polyol include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like.

Examples of the active energy ray-polymerizable group in the oxy-modified polyfunctional monomer include (meth) acryloyl group and vinyl group.

The number of oxyethylene added to one molecule of the oxy-modified polyfunctional monomer is 1 to 30, preferably 1 to 12.

In the present invention, the above-mentioned (a) polyfunctional monomer can be used alone or in combination of two or more.

Further, in the curable composition of the present invention, examples of the (a) active energy ray-curable polyfunctional monomer include a polyfunctional monomer not modified with oxyethylene. As the polyfunctional monomer not modified with oxyethylene, a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound (excluding the polyfunctional urethane (meth) acrylate compound) and a polyfunctional urethane (meth) acrylate compound. Can be mentioned.

Examples of the polyfunctional (meth) acrylate compound include trimethylol propanetri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra. (Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerintri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di ( Meta) 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) isocia Nuratetri (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxy Propane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4- (meth) acryloylthiophenyl ] Sulfate, Bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantandiol di (meth) acrylate, 1,3-adamantandimethanol dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycoldi (meth) acrylate and the like can be mentioned.
Among them, trimethylolpropane tri (meth) acrylate and the like can be mentioned as a preferable polyfunctional (meth) acrylate compound.

The polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and having one or more urethane bonds (-NHCOO-).
For example, the polyfunctional urethane (meth) acrylate is obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxy group, or by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxy group and a polyol. Examples thereof include those obtained, but the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to such examples.

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

In the present invention, as the (a) active energy ray-curable polyfunctional monomer, the polyfunctional (meth) acrylate compound (excluding the polyfunctional urethane (meth) acrylate compound) and the polyfunctional urethane (meth) acrylate compound. One type can be used alone from the group consisting of two or more types, or two or more types can be used in combination.

[(B) A perfluoropolyether containing a poly (oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via urethane bonds (provided that it is a perfluoropolyether). , Excluding perfluoropolyethers having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond.)]
In the present invention, the component (b) is a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, and a urethane bond is interposed at both ends of the molecular chain of the perfluoropolyether without a poly (oxyalkylene) group. Therefore, a perfluoropolyether having an active energy ray-polymerizable group (hereinafter, also simply referred to as "(b) a perfluoropolyether having a polymerizable group at both ends of the molecular chain") is used. The component (b) serves as a surface modifier in the hardcoat layer to which the curable composition of the present invention is applied.
Further, the component (b) has excellent compatibility with the component (a), thereby suppressing the hard coat layer from becoming cloudy and enabling the formation of a hard coat layer having a transparent appearance.
The above-mentioned poly (oxyalkylene) group is intended to be a group in which the number of repeating units of the oxyalkylene group is 2 or more and the alkylene group in the oxyalkylene group is an unsubstituted alkylene group.

The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly (oxyperfluoroalkylene) group refers to a group having a structure in which divalent fluorocarbon groups having 1 to 4 carbon atoms and oxygen atoms are alternately linked, and the oxyperfluoroalkylene group is a carbon atom. It refers to a group having a structure in which a divalent fluorocarbon group of numbers 1 to 4 and an oxygen atom are linked. Specifically,-[OCF ₂ ]-(oxyperfluoromethylene group),-[OCF ₂ CF ₂ ]-(oxyperfluoroethylene group),-[OCF ₂ CF ₂ CF ₂ ]-(oxyperfluoropropane). -1,3-Diyl group),-[OCF ₂ C (CF ₃ ) F]-(oxyperfluoropropane-1,2-diyl group) and the like can be mentioned.
The above oxyperfluoroalkylene group may be used alone or in combination of two or more, in which case the bonds of the plurality of oxyperfluoroalkylene groups are block bonds and random bonds. It may be any of.

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

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

(B) The perfluoropolyether having a polymerizable group at both ends of the molecular chain is not limited to one having one active energy ray-polymerizable group such as a (meth) acryloyl group at both ends of the molecular chain. It may have one or more active energy ray-polymerizable groups at both ends of the molecular chain. For example, the terminal structure containing the active energy ray-polymerizable group includes the following formulas [A1] to [A1] to [ Examples thereof include the structure of A5] and a structure in which the acryloyl group in these structures is replaced with a methacryloyl group.

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

(In the formula [2], A represents one of the structures represented by the formulas [A1] to [A5] and the structure in which the acryloyl group is replaced with the methacryloyl group, and PFPE is the above-mentioned structure. Represents a poly (oxyperfluoroalkylene) group (however, ^{the side directly bonded to L 1} is the oxy terminal and the side bonded to the oxygen atom is the perfluoroalkylene terminal), and L ¹ is 1 to 3 fluorine atoms. Represents an alkylene group having 2 or 3 carbon atoms substituted with an element, m independently represents an integer of 1 to 5, and L ² is an m + 1 valent residue obtained by removing OH from an m + 1 valent alcohol. show.)

The alkylene group of the fluorine atom one carbon atoms substituted by to three 2 or _{3, -CH 2 CHF -, -} CH 2 CF 2 -, - CHFCF 2 -, - CH 2 CH 2 CHF-, -CH ₂ CH ₂ CF _2- , -CH ₂ CHFCF _2-, etc. are mentioned, and -CH ₂ CF _2- is preferable.

（式［Ｂ１］〜式［Ｂ１２］中、Ａは前記式［Ａ１］〜式［Ａ５］で表される構造及びこれらの構造中のアクリロイル基をメタクリロイル基に置換した構造のうちの１つを表す。）
上記式［Ｂ１］〜式［Ｂ１２］で表される構造の中で、式［Ｂ１］及び式［Ｂ２］がｍ＝１の場合に相当し、式［Ｂ３］〜式［Ｂ６］がｍ＝２の場合に相当し、式［Ｂ７］〜式［Ｂ９］がｍ＝３の場合に相当し、式［Ｂ１０］〜式［Ｂ１２］がｍ＝５の場合に相当する。
これらの中でも、式［Ｂ３］で表される構造が好ましく、特に式［Ｂ３］と式［Ａ３］の組合せが好ましい。The moiety structure _{(A-NHC (= O)} O) m L 2 in the compound represented by [2] - The structure and the like can be mentioned of the formula [B1] ~ formula [B12] below Be done.

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

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

The partial structure represented by the formula [1] corresponds to the portion obtained by removing A-NHC (= O) from the compound represented by the formula [2].
N in the formula [1] _{represents the total number of the number of repeating units − [OCF 2} CF ₂ ] − and the number of repeating units − [OCF ₂ ] −, and an integer in the range of 5 to 30 is preferable. Integers in the range ~ 21 are more preferred. Further, the ratio of the number of the repeating unit − [OCF ₂ CF ₂ ] − to the number of the repeating unit − [OCF ₂ ] − is preferably in the range of 2: 1 to 1: 2, and is approximately 1. It is more preferable to set it in the range of 1. The binding of these repeating units may be either a block binding or a random binding.

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

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

(Wherein [3], ^PFPE, L 1, ^{L 2} and m is the formula [2] represent the same meaning.) To the hydroxy group present at both ends of the compound represented by the polymerizable group Isocyanate compounds having an isocyanate compound, that is, a compound in which an isocyanato group is bonded to a bond in a structure represented by the above formulas [A1] to [A5] and a structure in which an acryloyl group is replaced with a methacryloyl group in these structures (for example, It can be obtained by reacting 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, etc.) to form a urethane bond.

The curable composition of the present invention is (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, and active energy ray polymerization is carried out at both ends of the molecular chain via urethane bonds. In addition to perfluoropolyether having a sex group (however, there is no poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond), poly (oxyperfluoroalkylene). ) A perfluoropolyether containing a group, having an active energy ray-polymerizable group at one end (one end) of the molecular chain via a urethane bond, and the other end (the other end) of the molecular chain. Perfluoropolyether having a hydroxy group (at the end of) (provided that it is poly between the poly (oxyperfluoroalkylene) group and the urethane bond and between the poly (oxyperfluoroalkylene) group and the hydroxy group. (No oxyalkylene) group) or a perfluoropolyether containing a poly (oxyperfluoroalkylene) group as represented by the above formula [3], at both ends of the molecular chain. Perfluoropolyether having a hydroxy group (However, there is no poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the hydroxy group.) [Having an active energy ray-polymerizable group. No compound] may be included.

As described above, the perfluoropolyether compound of the curable composition of the present invention has excellent compatibility with the component (a), and thus has an excellent effect of enabling the formation of a hard coat layer with less cloudiness. Play.

[(C) Metal oxide particles]
The metal oxide particles refer to an antistatic agent capable of imparting antistatic performance to a cured film (hardcoat layer) obtained from the curable composition of the present invention.

The metal oxide particles (c) are not particularly limited, and are, for example, tin oxide (SnO ₂ ), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimonated tin oxide (ATO), and phosphorus-doped oxidation. Tin (PTO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AlZO), antimony-doped zinc oxide (AZO), indium-doped zinc oxide or zinc oxide-doped indium oxide (IZO), indium gallium oxide zinc oxide (IGZO). Among them, conductive metal oxide particles containing tin oxide such as phosphorus-doped tin oxide and antimony-doped tin oxide are preferable. In particular, from the viewpoint of the transparency of the formed hardcoat layer, the curable composition of the present invention using phosphorus-doped tin oxide as an antistatic agent forms a transparent cured film (hardcoat layer) without fogging or coloring. It is preferable because it can be done.

Examples of the metal oxide particles include surface-coated metal oxide particles having a metal oxide as a nucleus and whose surface is coated with an acidic or basic oxide. As the nucleus, in addition to the metal oxide particles such as tin oxide, titanium oxide, titanium oxide-tin oxide complex, zirconium oxide-tin oxide complex, tungsten oxide-tin oxide complex, titanium oxide-zirconium oxide- The tin oxide complex can be mentioned. Examples of the acidic or basic oxide include antimony pentoxide, silicon oxide-antimony pentoxide complex, and silicon oxide-tin oxide complex. Of these, core-shell particles having tin oxide as a nucleus and whose surface is coated with antimony pentoxide are preferable.

The primary particle size of the (c) metal oxide particles may be a range as long as it can be uniformly dispersed in the curable composition and does not impair the scratch resistance of the hardcoat layer, preferably 4 nm to 100 nm. Is 4 nm to 50 nm.
In the present invention, the primary particle size of the metal oxide particles means the particle size of each particle observed using a transmission electron microscope (the average value of 100 randomly selected particles). ..

In the present invention, the (c) metal oxide particles are 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.

[(D) Polymerization initiator that generates radicals by active energy rays]
In the curable composition of the present invention, the polymerization initiator (hereinafter, also simply referred to as “(d) polymerization initiator”) that generates radicals with preferable active energy rays is, for example, active energy such as electron beam, ultraviolet rays, and X-rays. It is a polymerization initiator that generates radicals by rays, especially by irradiation with ultraviolet rays.
Examples of the (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinone diazides, acylphosphine oxides, oxime esters, organic peroxides, and benzophenones. , Biscmarins, bisimidazoles, titanosen, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salt and sulfonium salt. These may be used alone or in admixture of two or more.
Above all, in the present invention, it is preferable to use alkylphenones as the (d) polymerization initiator from the viewpoints of transparency, surface curability and thin film curability. By using alkylphenones, a cured film with further improved scratch resistance can be obtained.

Examples of the alkylphenones include 1-hydroxycyclohexylphenylketone, 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-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one and other α-hydroxy Alkylphenones; 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one Such as α-aminoalkylphenones; 2,2-dimethoxy-1,2-diphenylethane-1-one; methyl phenylglycoxylate and the like.

[(E) Solvent]
The curable composition of the present invention may further contain (e) a solvent, that is, it may be in the form of a varnish (film forming material).
As the solvent, the components (a) to (d) are dissolved or uniformly dispersed, and the workability at the time of coating for forming the cured film (hard coat layer) described later, the drying property before and after curing, and the like are improved. It may be selected appropriately in consideration. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, methyl bromide, etc. Halogens such as methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Esters or ester ethers such as glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl Ethers such as ethers, propylene glycol mono-n-propyl ethers, propylene glycol monoisopropyl ethers, propylene glycol mono-n-butyl ethers; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclohexanone. Ketones such as: methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol and other alcohols; N, N-dimethylformamide ( DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) and other amides; dimethylsulfoxide (DMSO) and other sulfoxides, and two or more of these solvents were mixed. Examples include solvents.

The amount of the solvent (e) used is not particularly limited, but is used, for example, 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 a non-volatile content concentration) is a solid with respect to the total mass (total mass) of the components (a) to (d) (and, if desired, other additives) of the curable composition of the present invention. Represents the content of minutes (all components minus solvent components).

[Other additives]
In addition, additives generally added to the curable composition of the present invention as needed, such as a polymerization accelerator, a polymerization inhibitor, a photosensitizer, and leveling, as long as the effects of the present invention are not impaired. Agents, surfactants, adhesion-imparting agents, plasticizers, ultraviolet absorbers, light stabilizers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes and the like may be appropriately blended.

Examples of the antistatic agent for the above other additives include nanocarbons such as CNT (carbon nanotube), graphene, and fullerene; ions composed of ammonium-based, imidazolium-based, phosphonium-based, pyridinium-based, pyrrolidinium-based, sulfonium-based, and the like. Liquids; polythiophene-based, polyacetylene-based, polyaniline such as poly (3,4-ethylenedioxythiophene ((PEDOT), poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonic acid) (PEDOT-PSS)) Examples thereof include conductive polymers such as polypyrrole type and polypyrrole type.

<Hardened film>
The curable composition of the present invention can be coated on a substrate to form a coating film, and the coating film is irradiated with active energy rays to polymerize (cure) to form a cured film. The cured film is also the subject of the present invention. Further, the hard coat layer in the hard coat film described later can be made of the cured film.
In this case, the base material includes, for example, various resins (polyester, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, etc. Polyethylene, epoxy resin, melamine resin, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass, slate, etc. Can be mentioned. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.

The coating method on the substrate is a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an inkjet method, and a printing method (platepan printing method). , Intaglio printing method, lithographic printing method, screen printing method, etc.) can be appropriately selected, and among them, it can be used for the roll-to-roll method, and from the viewpoint of thin film coatability, the letterpress printing method In particular, it is desirable to use the gravure coat method. It is preferable that the curable composition is filtered in advance using a filter having a pore size of about 0.2 μm and then applied for coating. At the time of application, a solvent may be added to the curable composition as needed to form a varnish. As the solvent in this case, various solvents mentioned in the above-mentioned [(e) solvent] can be mentioned.
After the curable composition is applied onto the substrate to form a coating film, the coating film is pre-dried by a heating means such as a hot plate or an oven as necessary to remove the solvent (solvent removal step). The conditions for heating and drying at this time 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 rays. Examples of the active energy beam include ultraviolet rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. As the light source used for ultraviolet irradiation, a sunbeam, 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 that, the polymerization may be completed by performing post-baking, specifically by heating using a heating means such as a hot plate or an oven.
The thickness of the cured film formed is usually 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm after drying and curing.

<Hardcourt film>
The curable composition of the present invention can be used to produce a hardcourt film having a hardcourt layer on at least one surface (surface) of the film substrate. The hard-coated film is also an object of the present invention, and the hard-coated film is suitably used for protecting the surface of various display elements such as touch panels and liquid crystal displays.

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

As the film base material, among the base materials mentioned in the above-mentioned <cured film>, various transparent resin films that can be used for optical applications are used. Preferred resin films include, for example, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPUs), polycarbonates, polymethacrylates, polystyrenes, polyolefins, and the like. Examples thereof include films such as polyamide, polyimide, and triacetyl cellulose.
Further, as the method for applying the curable composition onto the film substrate (coating film forming step) and the method for irradiating the coating film with active energy rays (curing step), the methods mentioned in the above-mentioned <cured film> should be used. Can be done. When the curable composition of the present invention contains a solvent (in the form of a varnish), a step of drying the coating film and removing the solvent can be included, if necessary, after the coating film forming step. In that case, the method for drying the coating film (solvent removing step) described in the above-mentioned <cured film> can be used.
The layer thickness of the hard coat layer thus obtained is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm.

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

(1) Coating device by bar coater: Automatic Filmaplicator AB3125 manufactured by TQC Sheen Co., Ltd.
Bar: A-Bar OSP-25 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 25 μm (equivalent to wire bar # 10)
Coating speed: 4 m / min (2) Oven device: Sanki Keiso Co., Ltd. 2-layer clean oven (upper and lower type) PO-250-45-D
(3) UV curing device: CV-110QC-G manufactured by Heraeus Co., Ltd.
Lamp: High-pressure mercury lamp H-bulb manufactured by Heraeus Co., Ltd.
(4) Gel Permeation Chromatography (GPC)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Showa Denko Corporation Shodex® GPC K-804L, GPC K-805L
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI
(5) Scratch resistance test equipment: Reciprocating wear tester manufactured by Shinto Kagaku Co., Ltd. TRIBOGEAR TYPE: 30H
Scanning speed: 3,000 mm / min Scanning distance: 50 mm
(6) Tensile test equipment: Shimadzu Corporation desktop precision universal testing machine Autograph AGS-10kNX
Grip: 1kN Manual screw type flat grip Grip: High-strength rubber-coated grip Tooth Tensile speed: 50 mm / min Measurement temperature: 23 ° C
(7) Surface resistance measuring device: Mitsubishi Chemical Corporation High Restor-UP MCP-HT450
Probe: URS probe Registration table: UFL
Applied voltage: 10V
(8) HAZE measuring device: Haze meter NDH 5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

The abbreviations have the following meanings.
a-1: Oxyethylene-modified pentaerythritol tetraacrylate [KAYALAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., oxyethylene group 4 mol]
a-2: Oxyethylene-modified trimethylolpropane triacrylate [Aronix (registered trademark) M-350 manufactured by Toagosei Co., Ltd., oxyethylene group 3 mol]
a-3: Oxyethylene-modified tetraglycerin polyacrylate [SA-TE6 manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., number of functional groups 6, oxyethylene group 6 mol]
a-4: Trimethylolpropane triacrylate [NK ester A-TMPT manufactured by Shin Nakamura Chemical Industry Co., Ltd.]
CM-1: Lin-doped tin oxide 20% by mass isopropyl alcohol dispersion sol [Cernax (registered trademark) CX-S204IP manufactured by Nissan Chemical Industries, Ltd., primary particle size: 5 nm to 20 nm, secondary particle size: 10 nm to 20 nm]
CM-2: Antimony-doped tin oxide 40% by mass methanol dispersion sol [Cernax (registered trademark) CX-Z410M manufactured by Nissan Chemical Industries, Ltd., primary particle size: 20 nm to 30 nm, secondary particle size: 80 nm to 120 nm]
Here, the primary particle diameter and the secondary particle diameter refer to the particle diameter measured by observation with a transmission electron microscope. The particle size is determined by dropping a sol from a transmission electron microscope onto a copper mesh, drying it, and observing it with a transmission electron microscope (JEM-1020 manufactured by Nippon Denshi Co., Ltd.) at an acceleration voltage of 100 kV. The measured and averaged value was obtained as the average primary particle size.
CM-3: Quaternary ammonium salt type antistatic polymer [Acryt Standard Type 1SX-1090 manufactured by Taisei Fine Chemical Co., Ltd.]
CM-4: Quaternary ammonium salt type antistatic polymer [Acryt reactive type 8SX-1071 manufactured by Taisei Fine Chemical Co., Ltd.]
CM-5: Ionic group-containing silicone oligomer [Shin-Etsu Silicone (registered trademark) X-40-2750 manufactured by Shin-Etsu Chemical Co., Ltd.]
CM-6: Core-shell particles 30% by mass methanol-dispersed sol with tin oxide as the nucleus and its surface coated with antimony pentoxide [Nissan Chemical Industries, Ltd., Cernax (registered trademark) HX-307M1, primary particle diameter: 30 nm ~ 40nm]
PFPE1: Perfluoropolyether having two hydroxy groups at both ends of the molecular chain without interposing a poly (oxyalkylene) group [Fombin (registered trademark) T4 manufactured by Solvay Specialty Polymers Co., Ltd.]
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Showa Denko KK Karens (registered trademark) BEI]
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® 2959 manufactured by IGM Resins]
MEK: Methyl ethyl ketone MeOH: Methanol IPA: Isopropyl alcohol

[Production Example 1] Production of perfluoropolyether (SM1) having four acryloyl groups via urethane bonds (without interposing poly (oxyalkylene) groups) at both ends of the molecular chain. .19 g (0.5 mmol), BEI 0.52 g (2.0 mmol), DOTDD 0.017 g (0.01 times the total mass of PFPE1 and BEI), and MEK 1.67 g were charged. This mixture was stirred at room temperature (approximately 23 ° C.) for 24 hours using a stirrer chip to obtain a 50% by mass MEK solution of SM1 which is the target compound.
The weight average molecular weight: Mw measured by GPC of the obtained SM1 in terms of polystyrene was 3,000, and the dispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.2.

[Examples 1 to 8, Comparative Examples 1 to 4]
The following components were mixed according to the description in Table 1 to prepare a curable composition having a solid content concentration shown in Table 1. Here, the solid content refers to a component other than the solvent. Further, in Table 1, [part] represents [mass part].
(1) Polyfunctional monomer: 100 parts by mass of the polyfunctional monomer shown in Table 1 (2) Surface modifier: 0.2 parts by mass of the surface modifier shown in Table 1 (in terms of solid content)
(3) Antistatic agent: Conductive material shown in Table 1 Amount shown in Table 1 (4) Polymerization initiator: O2959 3 parts by mass (5) Solvent: MeOH / IPA Amount shown in Table 1 This curable composition Was applied on an A4 size double-sided easy-adhesion-treated PET film [Toray Industries, Inc. Lumirror (registered trademark) U403, thickness 100 μm] with a bar coater to obtain a coating film. The coating was dried in an oven at 120 ° C. for 3 minutes to remove the solvent. By irradiating the obtained film with UV light having an exposure amount of 300 mJ / cm ² under a nitrogen atmosphere, a hard coat film having a hard coat layer (cured film) having a layer (film) thickness of about 5 μm can be obtained. Made.

The scratch resistance, surface resistance, stretchability and HAZE value of the obtained hard coat film were evaluated. The procedure for each evaluation is shown below. The results are also shown in Table 2.

[Scratch resistance]
The surface of the hard coat layer of the hard coat film is reciprocated 10 times with a load ^{of 500 g / cm 2 using} steel wool [Bonster (registered trademark) # 0000 (ultra-fine) manufactured by Bonstar Sales Co., Ltd.] attached to a reciprocating wear tester. The degree of rubbing and scratches was visually confirmed and evaluated according to the following criteria A, B and C. Assuming actual use as a hard coat layer, it is required to be at least B, and preferably A.
A: No scratches B: Several small scratches occur C: Scratches occur on the entire surface

[Surface resistance]
The hardcourt film with the surface of the hardcourt layer facing up was placed on the cash register table, and the probe was pressed against the hardcourt film to measure 10 seconds later. The same operation was performed three times, and the average value was used as the surface resistance value and evaluated according to the following criteria A, B and C.
A: 1 × 10 ¹¹ Ω / □ or less B: 1 × 10 ¹¹ Ω / □ or more 1 × 10 ¹⁴ Ω / □ or less C: 10 ¹⁴ Ω / □ or more

[Stretchability]
A hardcourt film was cut into a rectangle having a length of 60 mm and a width of 10 mm to prepare a test piece. Attach it to the grip of the universal testing machine so that it grips 20 mm from both ends in the longitudinal direction of the test piece, and the draw ratio (= (increase in distance between grips) ÷ (distance between grips) x 100) is 2.5. The tensile test was carried out so as to be%, 7.5% and 10%. The hardcourt layer of the test piece was visually observed and evaluated according to the following criteria A, B and C with the maximum stretch ratio at which cracks did not occur as the stretchability.
A: 10% or more B: 2.5% or more and less than 10% C: less than 2.5%

As shown in Tables 1 and 2, a polyfunctional monomer, metal oxide particles as an antistatic agent, and a perfluoroyl group having four acryloyl groups at both ends of the molecular chain as a surface modifier via urethane bonds. A hard coat film having a hard coat layer obtained from a curable composition containing polyether SM1 (Examples 1 to 8) has scratch resistance, appropriate stretchability, and antistatic property. It became clear that it was excellent. In particular, a hard coat film having a hard coat layer obtained from a curable composition using an oxyethylene modified acrylate as a polyfunctional monomer (Examples 1 to 5, 5, 7 and 8) is more stretchable. It became clear that it was excellent.

On the other hand, the hard coat film (Comparative Example 1) having a hard coat layer obtained from a curable composition containing no metal oxide particles as an antistatic agent did not exhibit antistatic properties. Further, the hard coat film having a hard coat layer (Comparative Example 2 and Comparative Example 3) obtained from a curable composition using a quaternary ammonium salt type polymer having ionic conductivity as an antistatic agent is scratch resistant. Was inferior. Further, the hard coat film having a hard coat layer (Comparative Example 4) obtained from the curable composition using the ionic group-containing silicone oligomer resulted in inferior scratch resistance and antistatic property.

Claims (16)

(A) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(B) A perfluoropolyether containing a poly (oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via a urethane bond (provided that the perfluoropolyether is a perfluoropolyether. Excluding perfluoropolyethers having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond.) 0.05 parts by mass to 10 parts by mass,
(C) 5 parts by mass to 100 parts by mass of metal oxide particles as an antistatic agent, and (d) 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
A curable composition comprising. The curable composition according to claim 1, wherein the perfluoropolyether (b) has at least two active energy ray-polymerizable groups at both ends of the molecular chain via a urethane bond. The curable composition according to claim 2, wherein the perfluoropolyether (b) has at least three active energy ray-polymerizable groups at both ends of the molecular chain via urethane bonds. The poly (oxyperfluoroalkylene) group has both a repeating unit- [OCF ₂ ]-and a repeating unit- [OCF ₂ CF ₂ ] -, and these repeating units are block-bonded, random-bonded, or block-bonded. The curable composition according to any one of claims 1 to 3, which is a group bonded by a random bond. The curable composition according to claim 4, wherein the (b) perfluoropolyether has a partial structure represented by the following formula [1].

(In the above formula [1],
n is the total number of the number of repeating units − [OCF ₂ CF ₂ ] − and the number of repeating units − [OCF ₂ ] −, and represents an integer of 5 to 30.
The repeating unit- [OCF ₂ CF ₂ ]-and the repeating unit- [OCF ₂ ]-are bound by either a block bond, a random bond, or a block bond or a random bond. ) The curable composition according to any one of claims 1 to 5, wherein the polyfunctional monomer (a) is an oxyethylene-modified polyfunctional monomer. The curable composition according to claim 6, wherein the average amount of oxyethylene modification of the (a) polyfunctional monomer is less than 3 mol with respect to 1 mol of the polymerizable group of the (a) polyfunctional monomer. The (a) polyfunctional monomer is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound (excluding the polyfunctional urethane (meth) acrylate compound described later) and a polyfunctional urethane (meth) acrylate compound. The curable composition according to any one of claims 1 to 7, which comprises. The metal oxide particles (c) are tin-doped indium oxide, fluorine-doped tin oxide, antimonated tin oxide, phosphorus-doped tin oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, antimonated zinc oxide, indium-doped zinc oxide, and zinc oxide-doped. The curable composition according to any one of claims 1 to 8, which comprises at least one selected from the group consisting of indium oxide and zinc oxide indium gallium. The curable composition according to any one of claims 1 to 9, wherein the metal oxide particles (c) contain phosphorus-doped tin oxide. The curable composition according to any one of claims 1 to 10, wherein the primary particle diameter of the (c) metal oxide particles is 4 nm to 100 nm. The curable composition according to any one of claims 1 to 11, further comprising (e) a solvent. A cured film obtained from the curable composition according to any one of claims 1 to 11. A hard-coated film having a hard-coat layer on at least one surface of a film substrate, wherein the hard-coat layer is made of the cured film according to claim 13. The hard coat film according to claim 14, wherein the hard coat layer has a layer thickness of 1 μm to 15 μm. The curable composition according to any one of claims 1 to 12, wherein the hard coat layer is provided on at least one surface of the film substrate. A method for producing a hard-coated film, which comprises a step of forming a coating film by applying the film on a film substrate and a step of irradiating the coating film with active energy rays to cure the film.