WO2018056370A1

WO2018056370A1 - Scratch-resistant hard coating material

Info

Publication number: WO2018056370A1
Application number: PCT/JP2017/034143
Authority: WO
Inventors: 将幸原口
Original assignee: 日産化学工業株式会社
Priority date: 2016-09-21
Filing date: 2017-09-21
Publication date: 2018-03-29
Also published as: TW201817825A; CN109715685B; CN109715685A; JPWO2018056370A1; KR20190055071A

Abstract

[Problem] To provide a material for forming a hard coating layer, which has excellent low-foaming properties, while enabling the achievement of high scratch resistance. [Solution] A curable composition which contains (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (b) 0.1-10 parts by mass of a perfluoropolyether which has an active energy ray-polymerizable group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group or via a poly(oxyalkylene) group and one urethane bond in this order, (c) 1-20 parts by mass of a polymerization initiator which generates radicals by means of an active energy ray, (d) 0.0001-0.004 part by mass of an antifoaming agent which is composed of a fluorosilicone compound that has a fluorine content of 31% by mass or more, while having a weight average molecular weight of 10,000 to 200,000 in terms of polystyrene, and (e) an organic solvent; and a hard coating film which comprises a hard coating layer that is composed of a cured film formed from this composition.

Description

Scratch resistant hard coat material

The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display elements such as a touch panel display and a liquid crystal display.

A large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM have been commercialized. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels having a multi-touch function is rapidly increasing.

Thin tempered glass is used on the surface of these touch panel displays, and a protective film is attached to the display surface in order to prevent the glass from scattering. Since the protective film uses a plastic film, it is more likely to be scratched than glass, and it is necessary to provide a hard coat layer having excellent scratch resistance on the surface. In order to impart scratch resistance to the surface of a plastic film, for example, a method is adopted in which a highly crosslinked structure is formed, that is, a crosslinked structure with low molecular mobility is formed to increase the surface hardness and provide resistance to external force. It is done.
Most of these polyfunctional acrylate materials currently used as hard coat layer forming materials are monomers that are liquid at room temperature, and are three-dimensionally cross-linked by radicals generated from a photopolymerization initiator. The acrylate system is cured by ultraviolet rays (UV), and the time of UV irradiation is very short and energy saving, and is characterized by high productivity. As a means for forming a hard coat layer on the surface of the plastic film, for example, a solution containing a polyfunctional acrylate, a photopolymerization initiator and an organic solvent is coated on the plastic film by gravure coating, etc. Then, a means for forming a hard coat layer is employed. In order to express functions such as hardness and scratch resistance in the formed hard coat layer at a level having no practical problem, the hard coat layer is usually formed with a thickness of 1 to 15 μm.

By the way, the capacitive touch panel is operated by touching it with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time an operation is performed, causing problems that the visibility of the image on the display is remarkably impaired and the appearance of the display is impaired. The fingerprint contains moisture derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the display surface in order to prevent both of them from adhering. ing.
From such a viewpoint, the touch panel display surface is desired to have antifouling properties against fingerprints and the like. However, in a capacitive touch panel, since a person touches it with a finger every day, even if the initial antifouling property has reached a considerable level, its function often deteriorates during use. Therefore, the durability of the antifouling property in the process of use has been a problem.

Conventionally, as a method for imparting antifouling properties to the surface of the hard coat layer, a method of adding a small amount of a fluorine-based surface modifier to the coating solution for forming the hard coat layer has been used. The added fluorine-based compound is segregated on the surface of the hard coat layer due to its low surface energy, and imparts water repellency and oil repellency. As the fluorine compound, an oligomer having a number average molecular weight of about 1,000 to 5,000 called a perfluoropolyether having a poly (oxyperfluoroalkylene) chain is used from the viewpoint of water repellency and oil repellency. . However, since perfluoropolyether has a high fluorine concentration, it is usually difficult to dissolve in an organic solvent used in a coating solution for forming a hard coat layer. Moreover, aggregation is caused in the formed hard coat layer.
In order to provide such perfluoropolyether with solubility in an organic solvent and dispersibility in the hard coat layer, a technique of adding an organic moiety to the perfluoropolyether is used. Furthermore, in order to impart scratch resistance, a method of bonding active energy ray-curable sites represented by (meth) acrylate groups is used.
So far, as an antifouling hard coat layer having scratch resistance, as a component (surface modifier) for imparting antifouling properties to the hard coat layer surface, both ends of the poly (oxyperfluoroalkylene) chain, A technique using a compound having a (meth) acryloyl group via a plurality of urethane bonds having an isophorone skeleton is disclosed (Patent Document 1).

JP 2013-76029 A

The perfluoropolyether compound described in Patent Document 1 is highly soluble in the coating liquid, but segregates at the gas-liquid interface of the coating liquid, greatly reduces the surface tension of the coating liquid, and a large number of bubbles are present in the coating liquid. appear. When it is applied to a film substrate while containing air bubbles, the air bubbles become defective, resulting in poor appearance of the coating film. Therefore, in order to eliminate the generated bubbles, it is necessary to leave for a long time, and the problem is that productivity deteriorates.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have made poly (oxyalkylene) groups or poly (oxyalkylene) groups at both ends of a molecular chain containing poly (oxyperfluoroalkylene) groups. A curable composition comprising an anti-foaming agent comprising a perfluoropolyether having an active energy ray-polymerizable group and a fluorosilicone compound via an alkylene) group and one urethane bond has excellent defoaming properties. In addition, the inventors have found that a hard coat layer having excellent scratch resistance and a uniform appearance can be formed, and the present invention has been completed.

That is, the present invention provides the first aspect as follows:
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) Active energy rays through a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of a perfluoropolyether having a polymerizable group,
(C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
(D) 0.0001 to 0.004 mass of an antifoaming agent comprising a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31 mass% or more. And (e) a curable composition containing an organic solvent.
As a 2nd viewpoint, it is related with the curable composition as described in a 1st viewpoint whose fluorine content of the said fluoro silicone compound is 35 mass% or more.
As a 3rd viewpoint, the organic solvent of the said component (e) is related with the curable composition as described in a 1st viewpoint or a 2nd viewpoint which is alkylene glycol monoalkyl ether.
As a 4th viewpoint, the organic solvent of the said component (e) is related with the curable composition as described in a 3rd viewpoint which is ethyl cellosolve or propylene glycol monomethyl ether.
As a fifth aspect, the present invention relates to the curable composition according to any one of the first aspect to the fourth aspect, in which the total concentration of the components (e) excluding the organic solvent is 30 to 40% by mass.
As a sixth aspect, any one of the first to fifth aspects, wherein the poly (oxyperfluoroalkylene) group is a group having — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — as repeating units. It relates to the curable composition according to any one of the above.
As a seventh aspect, the curability according to any one of the first to sixth aspects, in which the poly (oxyalkylene) group is a poly (oxyalkylene) group having 5 to 12 repeating units. Relates to the composition.
As an eighth aspect, the present invention relates to the curable composition according to any one of the first aspect to the seventh aspect, in which the poly (oxyalkylene) group is a poly (oxyethylene) group.
As a ninth aspect, the present invention relates to the curable composition according to any one of the first to eighth aspects, wherein the active energy ray polymerizable group is a group having at least two active energy ray polymerizable moieties. .
As a tenth aspect, the polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. It relates to the curable composition as described in any one of viewpoints.
As an 11th viewpoint, it is related with the cured film obtained from the curable composition as described in any one among a 1st viewpoint thru | or a 10th viewpoint.
As a twelfth aspect, the present invention relates to a hard coat film including a hard coat layer on at least one surface of a film base material, wherein the hard coat layer is formed of the cured film described in the eleventh aspect.
A thirteenth aspect relates to the hard coat film according to the twelfth aspect, wherein the hard coat layer has a thickness of 1 to 15 μm.
As a fourteenth aspect, there is provided a method for producing a hard coat film comprising a hard coat layer on at least one surface of a film base material, wherein the curable composition according to any one of the first aspect to the tenth aspect is used. It is related with the manufacturing method of a hard coat film including the process of apply | coating on a film base material, and forming a coating film, and the process of irradiating an active energy ray to this coating film, and hardening.

ADVANTAGE OF THE INVENTION According to this invention, it is useful for formation of the cured film and hard-coat layer which are excellent in abrasion resistance, and is excellent in an external appearance, and can provide the curable composition excellent in defoaming property.
In addition, according to the present invention, it is possible to provide a hard coat film provided on the surface with a cured film obtained from the curable composition or a hard coat layer comprising the cured film, and a hard having excellent scratch resistance and appearance. A method capable of efficiently producing a hard coat film including a coat layer can be provided.

<Curable composition>
In detail, the curable composition of the present invention includes:
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) Active energy rays through a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of a perfluoropolyether having a polymerizable group,
(C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
(D) 0.0001 to 0.004 mass of an antifoaming agent comprising a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31 mass% or more. And (e) a curable composition containing an organic solvent.
Hereinafter, the components (a) to (e) will be described first.

[(A) Active energy ray-curable polyfunctional monomer]
The active energy ray-curable polyfunctional monomer refers to a monomer that is cured by a polymerization reaction that proceeds by irradiation with an active energy ray such as ultraviolet rays.
In the curable composition of the present invention, the preferable (a) active energy ray-curable polyfunctional monomer is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate , Ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated bisphenol Nord A di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} de Candimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9 -Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantane Diol di (meth) acrylate, , 3-adamantane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.
Among them, preferred are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

The polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (—NHCOO—).
For example, the polyfunctional urethane (meth) acrylate compound is obtained by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group, or a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol. However, 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, and hexamethylene diisocyanate.
Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth). An acrylate, tripentaerythritol hepta (meth) acrylate, etc. are mentioned.
Examples of the polyol include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these diols, succinic acid, malein Examples include polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as acids and adipic acid; polyether polyols; polycarbonate diols and the like.

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

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

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

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

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

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

The active energy ray polymerizable group is not limited to one having one active energy ray polymerizable portion such as a (meth) acryloyl moiety, and may have two or more active energy ray polymerizable portions, For example, the following structures A1 to A5 and structures in which the acryloyl group in these structures is substituted with a methacryloyl group can be mentioned.

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

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

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

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

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

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

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

In the present invention, (c) the polymerization initiator is used in a ratio of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Is desirable.

[(D) Antifoaming agent comprising a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31% by mass or more]
In the present invention, as component (d), a fluoropolymer having a weight average molecular weight of 10,000 to 200,000 as measured by gel permeation chromatography (GPC) in terms of polystyrene and a fluorine content of 31% by mass or more. An antifoaming agent composed of a silicone compound (hereinafter also simply referred to as “(d) antifoaming agent”) is used.
The fluorosilicone compound in the antifoaming agent (d) used in the present invention has a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31% by mass or more. In particular, the structure is not limited.

The fluorosilicone compound in the antifoaming agent (d) used in the present invention has a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000, preferably 20,000 to 150,000, more preferably 30,000. 000 to 100,000.

(D) The fluorosilicone compound in the antifoaming agent used in the present invention has a fluorine content of 31% by mass or more, preferably 35% by mass or more.

Specific examples of the above (d) antifoaming agent include, for example, Floren AO-82, AO-98, AO-106, AO-108 [above, manufactured by Kyoeisha Chemical Co., Ltd.], AF 98/1000, AF 98/10000 [above, Asahi Kasei Wacker Silicone Co., Ltd.], FS 1265 [Toray Dow Corning Co., Ltd.], Shin-Etsu Silicone (registered trademark) FA-600, FA-630 [above, Shin-Etsu Chemical ( Co., Ltd.], BYK (registered trademark) -063, 065, 066N, 067A [above, manufactured by Big Chemie Japan Co., Ltd.], etc., but is not limited thereto.
Of these, Floren AO-82 and AO-106 are preferred.

In the present invention, (d) the antifoaming agent is 0.0001 to 0.004 parts by mass, preferably 0.001 to 0.004 parts per 100 parts by mass of the aforementioned (a) active energy ray-curable polyfunctional monomer. It is desirable to use at a ratio of parts by mass.

The antifoaming agent (d) is composed of a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene within the above-described range, and a fluorine content equal to or higher than the above-described numerical value, and within the above-described range. When used in a proportion, the curable composition of the present invention exhibits further superior defoaming properties and coating properties.

[(E) Organic solvent]
As the organic solvent used in the present invention, the above-described components (a) to (d) are dissolved, and workability at the time of coating and drying before and after curing for forming a cured film (hard coat layer) to be described later are included. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane Halogens such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate Esters such as carbonates or ester ethers; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, Ethers such as propylene glycol monoisopropyl ether and propylene glycol mono-n-butyl ether or alkylene glycol monoalkyl ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n -Propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol , Alcohols such as 2-ethylhexyl alcohol, benzyl alcohol and ethylene glycol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide As well as a mixed solvent of two or more of these.
Among these, alkylene glycol monoalkyl ethers are preferable, and ethyl cellosolve and propylene glycol monomethyl ether are more preferable.

The amount of these (e) organic solvents used is not particularly limited. For example, the organic solvent is used at a concentration such that the solid content in the curable composition of the present invention is 1 to 70% by mass, preferably 30 to 40% by mass. Here, the solid content concentration (also referred to as non-volatile content concentration) means the solid content relative to the total mass (total mass) of the components (a) to (e) (and other additives as required) of the curable composition of the present invention. The content of (all solvent components are removed) is expressed.

[Other additives]
In addition, to the curable composition of the present invention, additives that are generally added as necessary, for example, polymerization inhibitors, photosensitizers, leveling agents, surface activity, unless the effects of the present invention are impaired. An agent, an adhesion-imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like may be appropriately blended.

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

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

<Hard coat film>
A hard coat film provided with a hard coat layer on at least one surface (surface) of a film substrate can be produced using the curable composition of the present invention. The hard coat film and the method for producing the hard coat film are also objects of the present invention, and the hard coat film is suitably used for protecting the surface of various display elements such as a touch panel and a liquid crystal display.

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

As the film substrate, various transparent resin films that can be used for optical applications among the substrates mentioned in the above-mentioned <cured film> are used. Preferably, for example, a resin selected from polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose, etc. A film is mentioned.
Moreover, the application method (coating film formation process) of the curable composition on the film substrate and the active energy ray irradiation method (curing process) to the coating film use the method described in the above <cured film>. Can do. Moreover, in this invention, the process of drying this coating film and removing a solvent as needed can be included after a coating-film formation process. In that case, the drying method (solvent removal process) of the coating film quoted to the above-mentioned <cured film> can be used.
The thickness of the hard coat layer thus obtained is preferably 1 to 15 μm, more preferably 1 to 10 μm.

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

(1) Bar coat application device: PM-9050MC manufactured by SMT Co., Ltd.
Bar: OSG Systems Products A-Bar OSP-25, maximum wet film thickness 25μm (corresponding to wire bar # 10)
Application speed: 4 m / min (2) Oven Equipment: Dust dryer DRC433FA manufactured by Advantech Toyo Co., Ltd.
(3) UV curing device: CV-110QC-G manufactured by Heraeus Co., Ltd.
Lamp: Heraeus high pressure mercury lamp H-bulb
(4) Gel permeation chromatography (GPC)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) GPC KF-804L, GPC KF-805L manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI
(5) Ion chromatography (F quantitative analysis)
Equipment: ICS-1500 manufactured by Nippon Dionex Co., Ltd.
Solvent: (2.7 mmol Na ₂ CO ₃ + 0.3 mmol NaHCO ₃ ) / L aqueous solution Detector: Electric conductivity (6) Light transmittance, haze Device: Nippon Denshoku Industries Co., Ltd. Haze Meter NDH5000
(7) Contact angle Device: Dropmaster DM-501, manufactured by Kyowa Interface Science Co., Ltd.
Measurement temperature: 20 ° C
(8) Scratch test device: Reciprocating wear tester manufactured by Shinto Kagaku Co., Ltd. TRIBOGEAR TYPE: 30S
Load: 250 g / cm ²
Scanning speed: 4.6m / min

Abbreviations represent the following meanings.
PFPE1: Perfluoropolyether having a hydroxy group via a poly (oxyalkylene) group (repeating unit number 8 to 9) at both ends [Fluorolink 5147X manufactured by Solvay Specialty Polymers]
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko KK]
DOTDD: Dioctyltin dineodecanoate [MSCAT-05, manufactured by Nippon Chemical Industry Co., Ltd.]
DPHA: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [KAYALAD DN-0075 manufactured by Nippon Kayaku Co., Ltd.]
PETA: Pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture [Shin-Nakamura Chemical Co., Ltd. NK ester A-TMM-3LM-N]
UA: 6-functional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129, manufactured by Daicel Ornex Co., Ltd.]
I2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [IRGACURE (registered trademark) 2959 manufactured by BASF Japan Ltd.]
FS1: Fluorosilicone-based antifoaming agent [Kyoeisha Chemical Co., Ltd., Floren AO-82, active ingredient concentration 1.8 mass% butyl acetate / hexane solution]
FS2: fluorosilicone-based antifoaming agent [Kyoeisha Chemical Co., Ltd., Floren AO-106, active ingredient concentration 2 mass% butyl acetate / hexane solution]
FS3: fluorosilicone-based antifoaming agent (Shin-Etsu Chemical Co., Ltd., Shin-Etsu Silicone (registered trademark) FA-600, active ingredient concentration of 30% by mass methyl ethyl ketone solution)
FS4: Fluorosilicone antifoaming agent [FS 1265 manufactured by Toray Dow Corning Co., Ltd., active ingredient concentration: 100% by mass]
BA: butyl acetate CP: cyclopentanone EC: ethyl cellosolve MEK: methyl ethyl ketone PGME: propylene glycol monomethyl ether

[Production Example 1] Production of perfluoropolyether SM1 having a poly (oxyalkylene) group at both ends and an acryloyl group via one urethane bond In a screw tube, 1.05 g (0.5 mmol) of PFPE1 and BEI 0. 26 g (1.0 mmol), DOTDD 0.01 g (0.02 mmol), and MEK 1.30 g were charged. The mixture was stirred for 24 hours at room temperature (approximately 23 ° C.) using a stirrer tip. This reaction mixture was diluted with 3.93 g of MEK to obtain a 20 mass% MEK solution of SM1, which is the target compound.
The weight average molecular weight Mw measured by GPC of the obtained SM1 in terms of polystyrene was 3,400, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.1. The fluorine content calculated from the F1 quantitative analysis of SM1 was 36% by mass.

[Production Example 2] Preparation of antifoam FS1 solution Fluorosilicone antifoam FS1 2.22 parts by mass (0.04 parts by mass as an active ingredient) was diluted with 37.78 parts by mass of BA to obtain an active ingredient concentration of 0. A 1% by mass FS1 solution was prepared.
In addition, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the active ingredient FS1 was 32,000, and the fluorine content calculated from F quantitative analysis was 44% by mass.

[Production Example 3] Preparation of Antifoam FS2 Solution 2.0 parts by mass of fluorosilicone defoamer FS2 (0.04 parts by mass as an active ingredient) is diluted with 38 parts by mass of BA to obtain an active ingredient concentration of 0.1. A mass% FS2 solution was prepared.
In addition, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the active ingredient FS2 was 56,000, and the fluorine content calculated from F quantitative analysis was 35% by mass.

[Production Example 4] Preparation of antifoam FS3 solution 0.13 parts by mass of fluorosilicone antifoam FS3 (0.04 parts by mass as an active ingredient) was diluted with 39.87 parts by mass of CP to obtain an active ingredient concentration of 0. A 1 mass% FS3 solution was prepared.
In addition, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the active ingredient FS3 was 43,000, and the fluorine content calculated from F quantitative analysis was 30% by mass.

[Production Example 5] Preparation of antifoam FS4 solution 0.04 parts by mass of fluorosilicone antifoam FS4 was diluted with 39.96 parts by mass of CP to prepare an FS4 solution having an active ingredient concentration of 0.1% by mass.
In addition, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the active ingredient FS4 was 1,000, and the fluorine content calculated from F quantitative analysis was 36% by mass.

[Examples 1 to 4, Comparative Examples 1 to 7]
According to the description in Table 1, the following components were mixed to prepare curable compositions 1 to 11. In the table, [part] represents [part by mass].
(1) Polyfunctional monomer: DPHA 7.5 g (50 parts by mass), UA 4.5 g (30 parts by mass), and PETA 3.0 g (20 parts by mass)
(2) Surface modifier: 0.75 g of SM1 solution produced according to Production Example 1 (1 part by mass as SM1)
(3) Polymerization initiator: 1.25 g (5 parts by mass) of I2959
(4) Antifoaming agent: The amount of antifoaming agent solution prepared according to Production Examples 2 to 5 described in Table 1 as the active ingredient (5) Solvent: PGME 23.85 g (159 parts by mass), EC 12.65 g ( 84 parts by mass)

This curable composition was bar-coated on an A4-sized double-sided easy-adhesion treated PET film [Lumirror (registered trademark) U403, manufactured by Toray Industries, Inc., thickness 100 μm] to obtain a coating film. This coating film was dried in an oven at 120 ° C. for 3 minutes to remove the solvent. The obtained film was exposed to UV light having an exposure amount of 300 mJ / cm ^{2 in} a nitrogen atmosphere to expose a hard coat film having a hard coat layer (cured film) having a thickness of about 6 μm.

The defoaming property and coating property of each curable composition, and the transparency, water / oil repellency and scratch resistance of the obtained hard coat film were evaluated. The procedure for each evaluation is shown below. The results are also shown in Table 2.

[Defoaming / foaming]
After putting 5 g of the curable composition into a 10 mL screw vial and shaking it vigorously by hand for 30 seconds, foaming was visually confirmed and evaluated according to the following criteria.
A: Little foaming C: Many foaming [Defoaming / Defoaming time]
After leaving the shaken curable composition, the time until no bubbles were confirmed was measured and evaluated according to the following criteria.
A: Bubbles disappear quickly within 1 minute B: Bubbles disappear within 30 minutes C: Bubbles do not disappear after 60 minutes

[Applicability]
The appearance when the curable composition was applied on the PET film was visually confirmed and evaluated according to the following criteria.
A: The curable composition is uniformly applied on the entire PET film. C: The curable composition is repelled on the PET film and aggregated in spots.

[transparency]
The light transmittance and haze of the hard coat film were measured and evaluated according to the following criteria.
A: Light transmittance of 91% or more and haze of less than 1.2 C: Light transmittance of less than 91% and / or haze of 1.2 or more

[Water and oil repellency]
1 μL of water or oleic acid was attached to the surface of the hard coat layer, and the contact angle θ after 5 seconds was measured at 5 points. The average value was defined as the contact angle value, and evaluated according to the following criteria.
A: Water contact angle of 105 ° or more and oleic acid contact angle of 74 ° or more C: Water contact angle of less than 105 ° and / or oleic acid contact angle of less than 74 °

[Abrasion resistance]
The hard coat layer surface was rubbed back and forth with steel wool [Kibaenti # 0000] attached to a reciprocating abrasion tester at a load of 250 g / cm ² for 2,000 reciprocations, and an oil marker [Zebra Co., Ltd. Made Mackey extra fine (blue), use fine side]. Subsequently, the drawn line was wiped off with a non-woven wiper [BEMCOT (registered trademark) M-1 manufactured by Asahi Kasei Co., Ltd.], and the degree of scratches was visually confirmed and evaluated according to the following criteria.
A: The line drawn with the oil-based marker can be wiped clean without scratching. C: The ink of the oil-based marker enters the wound and cannot be wiped off.

As shown in Table 2, perfluoropolyether SM1 having an acryloyl group via a poly (oxyalkylene) group and one urethane bond at both ends as a surface modifier in the hard coat layer, and FS1 as an antifoaming agent Alternatively, the curable compositions of Examples 1 to 4 using a predetermined amount of FS2 have excellent defoaming properties and coating properties, and each hard coat film produced using these curable compositions is transparent. Excellent water and oil repellency and scratch resistance.

On the other hand, Comparative Example 1 and Comparative Example 2 in which the amount of the antifoaming agent FS1 used exceeded 0.004 parts by mass resulted in greatly inferior applicability of the curable composition.
In addition, Comparative Example 3 using FS3 having an F content of 30% by mass resulted in greatly inferior foaming in the defoaming property of the curable composition and inferior in the defoaming time in the defoaming property, Even when the amount of FS3 used was 10 times, the results of foaming and defoaming time in the defoaming property of the curable composition were not different from those of Comparative Example 3 (Comparative Example 4).
Further, Comparative Example 5 using FS4 whose Mw of the fluorosilicone compound is 1,000 resulted in a greatly inferior defoaming property of the curable composition, and the curable composition even when the amount of FS4 used was 10 times. The antifoaming property of the product was not different from that of Comparative Example 5 (Comparative Example 6).

As described above, as shown in the results of Examples, any of the weight average molecular weight and F content measured in polystyrene conversion of the fluorosilicone compound used as the antifoaming agent, and the amount of the antifoaming agent used is within a predetermined numerical range. It is not possible to obtain a curable composition satisfying the defoaming property and coating property only by detachment, and only the curable composition of the present invention has excellent defoaming property and coating property, and transparency, repellency. A hard coat film satisfying all of water / oil repellency and scratch resistance can be formed.

Claims

(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) Active energy rays through a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of a perfluoropolyether having a polymerizable group,
(C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
(D) 0.0001 to 0.004 mass of an antifoaming agent comprising a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31 mass% or more. And (e) a curable composition comprising an organic solvent.
The curable composition of Claim 1 whose fluorine content of the said fluorosilicone compound is 35 mass% or more.
The curable composition of Claim 1 or Claim 2 whose organic solvent of the said component (e) is alkylene glycol monoalkyl ether.
The curable composition according to claim 3, wherein the organic solvent of the component (e) is ethyl cellosolve or propylene glycol monomethyl ether.
The curable composition according to any one of claims 1 to 4, wherein the total concentration of the components (e) excluding the organic solvent is 30 to 40% by mass.
6. The poly (oxyperfluoroalkylene) group according to any one of claims 1 to 5, wherein the poly (oxyperfluoroalkylene) group is a group having — [OCF 2 ] — and — [OCF 2 CF 2 ] — as repeating units. Curable composition.
The curable composition according to any one of claims 1 to 6, wherein the poly (oxyalkylene) group is a poly (oxyalkylene) group having 5 to 12 repeating units.
The curable composition according to any one of claims 1 to 7, wherein the poly (oxyalkylene) group is a poly (oxyethylene) group.
The curable composition according to any one of claims 1 to 8, wherein the active energy ray polymerizable group is a group having at least two active energy ray polymerizable portions.
The polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. The curable composition according to one item.
The cured film obtained from the curable composition as described in any one of Claims 1 thru | or 10.
A hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to claim 11.
The hard coat film according to claim 12, wherein the hard coat layer has a thickness of 1 to 15 μm.
It is a manufacturing method of the hard coat film which equips at least one surface of a film base material with a hard coat layer, Comprising: The curable composition as described in any one of Claims 1 thru | or 10 on a film base material. The manufacturing method of a hard coat film including the process of apply | coating and forming a coating film, and the process of irradiating this coating film with an active energy ray, and hardening.