KR102580704B1 - Curable composition for flexible hard coat - Google Patents

Abstract

[Problem] To provide a curable composition capable of forming a hard coat layer having extremely high scratch resistance, hardness, elongation, flexibility, and antifouling properties.
[Solution] (a) 100 parts by mass of an active energy ray-curable non-oxyethylene-modified polyfunctional monomer,
(b) 30 parts by mass to 150 parts by mass of active energy ray-curable oxyethylene-modified polyglycerin polyfunctional monomer,
(c) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray polymerizable group at both ends of its molecular chain through urethane bonds (however, , Excluding perfluoropolyether having a poly(oxyalkylene) group between this poly(oxyperfluoroalkylene) group and this urethane bond.) Total of component (a) and component (b) 100 mass. 0.05 parts by mass to 10 parts by mass, and
(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, based on a total of 100 parts by mass of components (a) and (b),
It is a hard coat film provided with a curable composition containing and a hard coat layer formed from this composition.

Description

Curable composition for flexible hard coat

The present invention relates to a curable composition useful as a forming material for a hard coat layer applied to the surface of various display elements such as a curved touch panel display. In detail, it relates to a curable composition capable of forming a hard coat layer having extremely high scratch resistance, hardness, elongation, bending resistance, and stain resistance.

Many electronic devices, such as home appliances such as TVs, communication devices such as mobile phones, office devices such as copiers, entertainment devices such as game machines, medical devices such as There is a touch panel display using a liquid crystal display device or OLED (organic EL) display device that can be manipulated. These touch panel displays have scratch resistance to prevent the surface of the touch panel from being scratched by fingernails, etc. when a person operates it with their fingers, anti-fouling properties to suppress the adhesion of fingerprints, and deformation when touched by a hard object. · A transparent plastic substrate on which a hard coat layer with hardness to prevent destruction is laminated, a so-called hard coat film, is provided.

Meanwhile, recently, in order to improve the design of the above electronic devices, a design in which the touch panel display portion is curved is sometimes adopted. When the touch panel side is curved to the outside, stress in the tensile direction is generated in the hard coat layer on the outermost surface. Therefore, this hard coat layer is required to have a certain stretchability.

In general, it is a method of imparting scratch resistance to a hard coat layer, for example, by forming a high-density cross-linked structure, that is, forming a cross-linked structure with low molecular mobility, thereby increasing surface hardness and providing resistance to external force. This is adopted. As materials for forming these hard coat layers, currently, multifunctional acrylate-based materials that are three-dimensionally crosslinked by radicals are most used. However, multifunctional acrylate-based materials usually do not have stretchability due to their high crosslinking density. In this way, the stretchability and scratch resistance of the hard coat layer are in a trade-off relationship, and making both properties compatible has become a problem. On the other hand, a technology for a hard coat layer that has both certain scratch resistance and stretchability has been reported by using a non-ethylene oxide-modified polyfunctional acrylate and an ethylene oxide-modified polyfunctional acrylate in combination (Patent Document 1).

Japanese Patent No. 6203715 Publication

However, the hard coat layer described in Patent Document 1 had relatively high scratch resistance and hardness, but had the problem of insufficient stretchability and flexibility.

That is, the purpose of the present invention is to provide a curable composition capable of forming a hard coat layer having extremely high scratch resistance, hardness, elongation, bending resistance, and stain resistance.

The present inventors have conducted extensive studies to achieve the above object, and as a result, have developed a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, and poly(oxyalkylene) at both ends of its molecular chain. A curable composition comprising a perfluoropolyether having an active energy ray polymerizable group through a urethane bond without a group, a non-oxyethylene-modified multifunctional monomer, and an oxyethylene-modified polyglycerin multifunctional monomer has scratch resistance. , it was discovered that a hard coat layer having hardness, extensibility, bending resistance, and stain resistance could be formed, and the present invention was completed.

That is, the present invention, as a first aspect,

(a) 100 parts by mass of an active energy ray-curable nonoxyethylene-modified polyfunctional monomer,

(b) 30 to 50 parts by mass of active energy ray-curable oxyethylene-modified polyglycerin polyfunctional monomer,

(c) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray polymerizable group at both ends of its molecular chain through urethane bonds (however, , Excluding perfluoropolyether having a poly(oxyalkylene) group between this poly(oxyperfluoroalkylene) group and this urethane bond.) Total of component (a) and component (b) 100 mass. 0.05 parts by mass to 10 parts by mass, and

(d) Polymerization initiator that generates radicals by active energy rays: 1 part by mass to 20 parts by mass based on a total of 100 parts by mass of component (a) and component (b)

It relates to a curable composition containing.

As a second aspect, the (c) perfluoropolyether relates to the curable composition according to the first aspect, wherein the perfluoropolyether (c) has at least two active energy ray polymerizable groups via urethane bonds at each end of its molecular chain. will be.

As a third aspect, the curable composition according to the second aspect, wherein the (c) perfluoropolyether has at least three active energy ray polymerizable groups via urethane bonds at both ends of its molecular chain.

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 combined in blocks or randomly combined. , or, it relates to the curable composition according to any one of the first to third aspects, which is formed by combining block bonds and random bonds.

As a fifth aspect, it relates to the curable composition according to the fourth aspect, wherein the (c) perfluoropolyether has a partial structure represented by the following formula [1].

[Formula 1]

(In the above formula [1], n is the total number of repeating units - [OCF ₂ CF ₂ ] - and the number of repeating units - [OCF ₂ ] -, and represents an integer of 5 to 30, and the repeating units - [OCF ₂ CF ₂ ]- and the repeating unit-[OCF ₂ ]- are formed by combining block combination, random combination, or any one of block combination and random combination.)

As a sixth aspect, the polyfunctional monomer (b) has an average amount of oxyethylene modification of the polyfunctional monomer (b) of less than 2 mol per 1 mol of polymerizable groups of the polyfunctional monomer (b), and has 4 functional groups. Oxyethylene-modified polyglycerin multifunctional (meth)acrylate compounds (however, oxyethylene-modified polyglycerol multifunctional urethane (meth)acrylate compounds are excluded) and oxyethylene-modified polyglycerol multifunctional urethane ( It relates to the curable composition according to any one of the first to fifth aspects, comprising at least one selected from the group consisting of meth)acrylate compounds.

As a seventh aspect, it relates to the curable composition according to the sixth aspect, wherein the polyfunctional monomer (b) is oxyethylene-modified diglycerol tetra(meth)acrylate.

As an eighth viewpoint, it relates to the curable composition according to any one of the first to seventh viewpoints, which further contains (e) a solvent.

As a ninth aspect, it relates to the curable composition according to the eighth aspect, wherein the solvent (e) is propylene glycol monomethyl ether.

As a tenth viewpoint, it relates to a cured film obtained from the curable composition according to any one of the first to ninth viewpoints.

As an 11th viewpoint, it is a hard coat film provided with a hard coat layer on at least one side of a film substrate, and this hard coat layer is comprised of the cured film as described in the 10th viewpoint.

As a twelfth aspect, a hard coat film comprising a hard coat layer on at least one side of a film substrate, wherein the hard coat layer applies the curable composition according to any one of the first to ninth aspects onto the film substrate. It relates to a hard coat film formed by a method including a step of forming a coating film and a step of curing the coating film by irradiating active energy rays.

As a 13th viewpoint, it relates to the hard coat film described in the 11th viewpoint or the 12th viewpoint, wherein the hard coat layer has a layer thickness of 1 μm to 10 μm.

As a fourteenth aspect, a method for producing a hard coat film comprising a hard coat layer on at least one side of a film base, wherein the hard coat layer is formed by applying the curable composition according to any one of the first to ninth aspects to the film base. It relates to a method of manufacturing a hard coat film, including a process of forming a coating film by applying it on the coating film, and a process of curing the coating film by irradiating active energy rays.

According to the present invention, it is possible to provide a curable composition capable of forming a hard coat layer having very high scratch resistance, hardness, elongation, bending resistance and stain resistance.

<Curable composition>

The curable composition of the present invention is specifically,

(a) 100 parts by mass of an active energy ray-curable nonoxyethylene-modified polyfunctional monomer,

(b) 30 parts by mass to 150 parts by mass of active energy ray-curable oxyethylene-modified polyglycerin polyfunctional monomer,

(c) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray polymerizable group at both ends of its molecular chain through urethane bonds (however, , excluding perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.) 100 mass total of component (a) and component (b). 0.05 parts by mass to 10 parts by mass, and

(d) Polymerization initiator that generates radicals by active energy rays: 1 part by mass to 20 parts by mass based on a total of 100 parts by mass of component (a) and component (b)

It relates to a curable composition containing.

Hereinafter, each component of (a) to (d) above will first be described.

[(a) Active energy ray-curable non-oxyethylene-modified multifunctional monomer (hereinafter, also simply referred to as (a) multifunctional monomer)]

An active energy ray-curable non-oxyethylene-modified polyfunctional monomer refers to an oxyethylene-modified monomer that undergoes polymerization and hardens by irradiating active energy rays such as ultraviolet rays.

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

Meanwhile, in the present invention, a (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, and pentaerythritol tri( Meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(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-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate ) 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 Acrylate, tricyclo[5.2.1.0 ^2,6 ]decanedimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacrylate Iloxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 9,9-bis[4-(meth)acryloyloxyphenyl]fluorene, bis[4-(meth) Acryloylthiophenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantane dimethanol di(meth) Acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. can be mentioned.

Among them, preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. etc. can be mentioned.

The polyfunctional urethane (meth)acrylate compound is a compound that has multiple acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (-NHCOO-).

Examples of the polyfunctional urethane (meth)acrylate include those obtained by reaction between polyfunctional isocyanate and (meth)acrylate having a hydroxy group, and (meth)acrylate having a polyfunctional isocyanate and hydroxy group. and those obtained by reaction with polyol. However, the polyfunctional urethane (meth)acrylate compound usable in the present invention is not limited to these examples.

Meanwhile, examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.

Additionally, (meth)acrylates having the hydroxy group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. Penta(meth)acrylate, tripentaerythritol hepta(meth)acrylate, etc. can be 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; polyester polyols that are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, and adipic acid; polyetherpolyol; Polycarbonate diol, etc. can be mentioned.

In the present invention, (a) the active energy ray-curable nonoxyethylene-modified polyfunctional monomer is selected from the group consisting of the polyfunctional (meth)acrylate compound and the polyfunctional urethane (meth)acrylate compound. , or a combination of two or more types can be used. From the viewpoint of scratch resistance and hardness of the resulting cured product, among the above-mentioned polyfunctional monomers, polyfunctional (meth)acrylate compounds having trifunctional or higher function, preferably polyfunctional (meth)acrylate compounds having tetrafunctional or higher function are used.

In addition, in the polyfunctional monomer (a) above, when a polyfunctional (meth)acrylate compound having 4 or more functions and a polyfunctional (meth)acrylate compound having 3 or less functionality are used in combination, the polyfunctional (meth)acrylate compound with 3 or less functions is used in combination. The amount of the functional (meth)acrylate compound used is 10 parts by mass to 100 parts by mass, preferably 20 parts by mass to 60 parts by mass, based on 100 parts by mass of the tetrafunctional or higher polyfunctional (meth)acrylate compound.

Furthermore, when the polyfunctional (meth)acrylate compound and the polyfunctional urethane (meth)acrylate compound are used in combination, the polyfunctional urethane (meth)acrylate compound is added to 100 parts by mass of the polyfunctional (meth)acrylate compound. It is preferable to use 20 parts by mass to 100 parts by mass of the rate compound, and it is more preferable to use 30 parts by mass to 70 parts by mass.

[(b) Active energy ray-curable oxyethylene-modified polyglycerol multifunctional monomer (hereinafter, also simply referred to as (b) multifunctional monomer)]

The active energy ray-curable oxyethylene-modified polyglycerol multifunctional monomer of the curable composition of the present invention refers to the polyglycerol polyfunctional monomer modified with oxyethylene among the monomers that polymerization reaction proceeds by irradiating active energy rays such as ultraviolet rays and curing. Point.

Examples of the oxyethylene-modified polyglycerol multifunctional monomer include compounds having an active energy ray polymerizable group at the terminal of polyglycerol modified with oxyethylene.

Examples of this polyglycerol include diglycerol, triglycerin, tetraglycerol, pentaglycerin, hexaglycerol, decaglycerin, and polyglycerol. From the viewpoint of scratch resistance, hardness, extensibility and flexibility of the resulting cured film, diglycerol and triglycerin are preferred.

From the viewpoint of scratch resistance, hardness, elongation, and flexibility of the resulting cured film, the polyfunctional monomer (b) used in the present invention is an oxyethylene-modified polyglycerin polyfunctional monomer having a functional group number of 4 or more, more preferably a polyfunctional monomer with a functional group number of 4 or more. to 6 oxyethylene-modified polyglycerin is a multifunctional monomer.

The average amount of oxyethylene modification in the polyfunctional monomer (b) is less than 3 mol per 1 mol of the active energy ray polymerizable group that the polyfunctional monomer (b) has, and preferably, the amount of oxyethylene modification in the polyfunctional monomer (b) is less than 3 mol. It is less than 2 mol per 1 mol.

(b) The addition number of oxyethylene per molecule of polyfunctional monomer is 1 to 30, preferably 1 to 12.

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

From the viewpoint of scratch resistance, hardness, elongation, and flexibility of the formed cured film, the present invention (b) active energy ray-curable oxyethylene-modified polyglycerol multifunctional monomer includes an oxyethylene-modified polyglycerol polyfunctional (meth)acrylate compound and Oxyethylene-modified polyglycerol polyfunctional urethane (meth)acrylate compounds are preferred. Among these compounds, oxyethylene-modified diglycerol tetra(meth)acrylate, oxyethylene-modified triglycerol tetra(meth)acrylate, and oxyethylene-modified triglycerol penta(meth)acrylate are preferred, and oxyethylene-modified diglycerol tetra(meth)acrylate is preferred. Meth)acrylate compounds are more preferable.

In the present invention, the above-described (b) active energy ray-curable oxyethylene-modified polyglycerin polyfunctional monomer can be used individually or in combination of two or more types.

In the present invention, (b) the active energy ray-curable oxyethylene-modified polyglycerol multifunctional monomer is 30 to 150 parts by mass based on 100 parts by mass of the above-mentioned (a) active energy ray-curable non-oxyethylene-modified polyfunctional monomer. , Preferably it is used in a ratio of 40 parts by mass to 120 parts by mass.

[(c) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, and having an active energy ray polymerizable group at both ends of the molecular chain through a urethane bond ( However, perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond is excluded.)]

In the present invention, the component (c) is a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, and the molecular chain has a urethane bond at both ends without a poly(oxyalkylene) group. Interveningly, a perfluoropolyether having an active energy ray polymerizable group (hereinafter also simply referred to as “perfluoropolyether having a polymerizable group at both ends of the (c) molecular chain”) is used. Component (c) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied.

In addition, component (c) has excellent compatibility with component (a) and component (b), thereby suppressing clouding of the hard coat layer and enabling the formation of a hard coat layer with a transparent appearance. do.

Meanwhile, the above-mentioned poly(oxyalkylene) group refers to 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 with 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyperfluoroalkylene group has 2 fluorocarbon groups with 1 to 4 carbon atoms. It refers to a group that has a structure in which a fluorocarbon group and an oxygen atom are connected. Specifically, -[OCF ₂ ]-(oxyperfluoromethylene group), -[OCF ₂ CF ₂ ]-(oxyperfluoroethylene group), -[OCF ₂ CF ₂ CF ₂ ]-(oxyperfluoro Groups such as propane-1,3-diyl group) and -[OCF ₂ C(CF ₃ )F]-(oxyperfluoropropane-1,2-diyl group) can be mentioned.

The oxyperfluoroalkylene group may be used individually, or two or more types may be used in combination. In that case, the bond of multiple types of oxyperfluoroalkylene groups may be a block bond or a random bond. It could be either.

Among these, from the viewpoint of obtaining a cured film with good scratch resistance, as the poly(oxyperfluoroalkylene) group, -[OCF ₂ ]-(oxyperfluoromethylene group) and -[OCF ₂ CF ₂ ]-( It is preferable to use a group having both oxyperfluoroethylene groups as repeating units.

Among them, the poly(oxyperfluoroalkylene) group has repeating units: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- in a molar ratio of [repeating units: -[OCF ₂ ]-]: [Repeating unit: -[OCF ₂ CF ₂ ]-] It is preferable that the group is included in a ratio of 2:1 to 1:2, and it is more preferable that the group is included in a ratio of approximately 1:1. The combination of these repeating units may be either a block combination or a random combination.

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, in terms of the total number of repeating units.

In addition, the weight average molecular weight (Mw) of the poly(oxyperfluoroalkylene) group measured in polystyrene conversion by gel permeation chromatography (GPC) is 1,000 to 5,000, preferably 1,500 to 3,000.

Examples of the active energy ray polymerizable group bonded through the urethane bond include (meth)acryloyl group and vinyl group.

(c) Perfluoropolyether having a polymerizable group at both ends of the molecular chain is not limited to having one active energy ray polymerizable group such as a (meth)acryloyl group at both ends of the molecular chain, but 2 It may have one or more active energy ray polymerizable groups at both ends of the molecular chain. For example, terminal structures containing active energy ray polymerizable groups include formulas [A1] to [A5] shown below. structures, and structures in which the acryloyl group in these structures is substituted with a methacryloyl group.

[Formula 2]

Examples of the perfluoropolyether having a polymerizable group at both ends of the (c) molecular chain include a compound represented by the following formula [2].

[Formula 3]

(In formula [2], A represents one of the structures represented by the formulas [A1] to [A5] and structures in which the acryloyl group in these structures is replaced with a methacryloyl group, and PFPE is the poly(oxy (perfluoroalkylene) group (however, the side directly bonded to L ¹ is the oxy terminal, and the side bonded to the oxygen atom is the perfluoro alkylene end.), and L ₁ represents 1 to 3 fluorine atoms. represents an alkylene group with 2 or 3 carbon atoms substituted with a , m each independently represents an integer of 1 to 5, and L ₂ represents an m+1 valent residue excluding OH from the m+1 valent alcohol.)

The alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms includes -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.

The partial structure (A-NHC(=O)O) _m L ² - in the compound represented by the above formula [2] includes structures represented by the formulas [B1] to [B12] shown below, etc. there is.

[Formula 4]

[Formula 5]

(In formulas [B1] to [B12], A represents one of the structures represented by the above formulas [A1] to formula [A5] and structures in which an acryloyl group in these structures is substituted with a methacryloyl group.)

Among the structures represented by the formulas [B1] to [B12], formulas [B1] and formulas [B2] correspond to the case where m = 1, and formulas [B3] to formulas [B6] correspond to the case where m = 2. Corresponds to , Equations [B7] to Equations [B9] correspond to the case of m = 3, and Equations [B10] to Equations [B12] correspond to the case of 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 especially preferable.

Preferred perfluoropolyethers having polymerizable groups at both terminals of the (c) molecular chain include compounds having a partial structure represented by the following formula [1].

[Formula 6]

The partial structure represented by the formula [1] corresponds to the portion excluding A-NHC (=O) from the compound represented by the formula [2].

n in the above formula [1] represents the total number of repeating units - [OCF ₂ CF ₂ ] - and the number of repeating units - [OCF ₂ ] -, and is preferably an integer in the range of 5 to 30, 7 An integer in the range of ~21 is more preferable. In addition, the ratio of the number of repeating units - [OCF ₂ CF ₂ ] - and the number of repeating units - [OCF ₂ ] - is preferably in the range of 2:1 to 1:2, and is approximately 1:1. It is more preferable to set it in the range of . The combination of these repeating units may be either a block combination or a random combination.

In the present invention, (c) the perfluoropolyether having a polymerizable group at both ends of the molecular chain includes the above-mentioned (a) active energy ray-curable non-oxyethylene-modified polyfunctional monomer and (b) active energy ray-curable oxyethylene. It is used in a ratio of 0.05 parts by mass to 10 parts by mass, preferably 0.1 parts by mass to 5 parts by mass, based on a total of 100 parts by mass of the modified polyglycerin polyfunctional monomer.

(c) By using perfluoropolyether having polymerizable groups at both ends of the molecular chain in a ratio of 0.05 parts by mass or more, sufficient scratch resistance and anti-fouling properties (water and oil repellency) can be imparted to the hard coat layer. In addition, (c) by using perfluoropolyether having a polymerizable group at both ends of the molecular chain in a ratio of 10 parts by mass or less, it is sufficiently compatible with component (a) and component (b), resulting in a hard disk with less cloudiness. A coat layer is obtained.

The perfluoropolyether having a polymerizable group at both ends of the (c) molecular chain is, for example, of the following formula [3]

[Formula 7]

(In the formula [3], PFPE, L ¹ , L ² and m have the same meaning as the above formula [2].) With respect to the hydroxy groups present at both terminals of the compound represented by Isocyanate compounds, that is, structures represented by the above formulas [A1] to [A5] and structures in which an acryloyl group in these structures is replaced with a methacryloyl group, have an isocyanato group in the bond number. It can be obtained by reacting a combined compound (e.g., 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc.) to form a urethane bond.

Meanwhile, the curable composition of the present invention is a perfluoropolyether containing a (c) poly(oxyperfluoroalkylene) group, and has an active energy ray polymerizable group at both ends of its molecular chain through urethane bonds. In addition to perfluoropolyether (however, it does not have a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond), poly(oxyperfluoroalkylene) It is a perfluoropolyether containing a group, and has an active energy ray polymerizable group at one end of the molecular chain (one end) through a urethane bond, and also has an active energy ray polymerizable group at the other end of the molecular chain (another end). Perfluoropolyether having a hydroxy group (however, between the poly(oxyperfluoroalkylene) group and the urethane bond and between the poly(oxyperfluoroalkylene) group and the hydroxy group, poly( It does not have an oxyalkylene) group) or a perfluoropolyether containing a poly(oxyperfluoroalkylene) group as represented by the above formula [3], and hydroxyl groups are present at both ends of the molecular chain. Perfluoropolyether having a group (however, it does not have a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the hydroxy group) [Compound that does not have an active energy ray polymerizable group ] may be included.

As described above, the perfluoropolyether compound of the curable composition of the present invention has excellent compatibility with component (a), thereby suppressing whitening of the hard coat layer, thereby forming a hard coat that exhibits a transparent appearance. It shows an excellent effect of enabling the formation of a layer.

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

In the curable composition of the present invention, the polymerization initiator that generates radicals by active energy rays (hereinafter also simply referred to as "(d) polymerization initiator") is preferably used by active energy rays such as electron beams, ultraviolet rays, and X-rays. It is a polymerization initiator that generates radicals, especially when irradiated with ultraviolet rays.

The (d) polymerization initiator includes, for example, benzoins, alkylphenones, thioxanthone, azones, azides, diazides, o-quinonediazides, acylphosphine oxides, and oxime esters. , organic peroxides, benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These may be used individually or in combination of two or more types.

Among these, in the present invention, it is preferable to use alkylphenones as the (d) polymerization initiator from the viewpoints of transparency, surface hardenability, and thin film hardenability. By using alkylphenones, a cured film with improved scratch resistance can be obtained.

Examples of the alkylphenones include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2) -Hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2- α-hydroxyalkylphenones such as methylpropan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1- α-aminoalkylphenones such as onone; 2,2-dimethoxy-1,2-diphenylethan-1-one; Methyl phenylglyoxylate, etc. are mentioned.

In the present invention, the polymerization initiator (d) is used in a ratio of 1 part by mass to 20 parts by mass, preferably 2 parts by mass to 10 parts by mass, based on a total of 100 parts by mass of the above-mentioned components (a) and (b). It is desirable to use

[(e) Solvent]

The curable composition of the present invention may further contain a solvent (e), that is, it may be in the form of a varnish (film-forming material).

The solvent is selected appropriately by dissolving the components (a) to (d) and taking into account workability during coating and drying properties before and after curing in forming a cured film (hard coat layer), which will be described later. Just do it. 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; Halogenates such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene, and o-dichlorobenzene; Esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene 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 ether, propylene glycol ethers such as mono-n-propyl ether, propylene glycol monoisopropyl ether, and propylene glycol mono-n-butyl ether; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, and cyclohexanone; Alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); Examples include sulfoxides such as dimethyl sulfoxide (DMSO), and solvents that are a mixture of two or more of these solvents.

In particular, propylene glycol monomethyl ether (PGME) is preferable as the (e) solvent.

(e) The amount of solvent used is not particularly limited, but for example, it is used at a concentration such that the solid content concentration in the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass. . Here, the solid content concentration (also referred to as non-volatile content concentration) refers to the solid content (from all components) relative to the total mass (total mass) of the components (a) to (e) (and other additives as necessary) of the curable composition of the present invention. Indicates the content (excluding solvent components).

[Other additives]

In addition, the curable composition of the present invention contains additives that are generally added as needed, such as polymerization accelerators, polymerization inhibitors, photosensitizers, leveling agents, surfactants, and adhesion agents, as long as they do not impair the effects of the present invention. Imparting agents, plasticizers, ultraviolet absorbers, light stabilizers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc. can be appropriately mixed.

Additionally, for the purpose of controlling the haze value of the cured film, inorganic fine particles such as titanium oxide or organic fine particles such as polymethyl methacrylate particles may be blended.

<cured film>

The curable composition of the present invention can be applied (coated) on a substrate to form a coating film, and then irradiated with active energy rays to polymerize (cure) the coating film, thereby forming a cured film. In addition, the curable composition containing a solvent of the present invention is applied (coated) on a substrate to form a coating film, the solvent is removed by heating or other methods, and the solvent-free coating film is irradiated with active energy rays. By polymerizing (curing), a cured film can be formed.

This cured film is also the subject of the present invention. Additionally, the hard coat layer in the hard coat film described later can be made of this cured film.

The substrate in this case includes, for example, various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane ( TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetylcellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin, etc.) , metal, wood, paper, glass, slate, etc. The shape of these substrates may be plate-shaped, film-shaped, or a three-dimensional molded body.

Application methods on the substrate include cast coating, spin coating, blade coating, dip coating, roll coating, spray coating, bar coating, die coating, inkjet printing, and printing (relief printing). , intaglio printing, flat printing, screen printing, etc.) can be appropriately selected, and among them, the roll-to-roll method can be used, and from the viewpoint of thin film applicability, the convex printing method can be used. It is preferable to use a printing method, especially a gravure coat method. Meanwhile, it is preferable to filter the curable composition in advance using a filter with a pore diameter of about 0.2 μm, and then apply it for application. On the other hand, when applying, if necessary, a solvent may be added to this curable composition to form a varnish. Solvents in this case include various solvents mentioned in [(e) solvent] above.

After applying the curable composition on a substrate to form a coating film, if necessary, the coating film is pre-dried using a heating means such as a hot plate or oven to remove the solvent (solvent removal process). The conditions for heat 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 active energy rays such as ultraviolet rays. Active energy rays include ultraviolet rays, electron rays, and X-rays, and ultraviolet rays are particularly preferable. Light sources used for ultraviolet irradiation include solar rays, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs.

Furthermore, polymerization can also be completed afterward by performing post-bake, specifically by heating using a heating means such as a hot plate or oven.

On the other hand, the thickness of the cured film formed after drying and curing is usually 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm.

<Hard coat film>

Using the curable composition of the present invention, a hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced. This hard coat film is also the object of the present invention, and this hard coat film is suitably used to protect the surfaces of various display elements such as touch panels and liquid crystal displays, for example.

The hard coat layer in the hard coat film of the present invention is formed by applying the above-described 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 to form this coating film. It can be formed by a method including a hardening process.

As the film substrate, among the substrates mentioned in the above <cured film>, various transparent resin films that can be used for optical purposes are used. Preferred resin films include, for example, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), and polycarbonate. , polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, and triacetylcellulose.

In addition, the method of applying the curable composition on the film substrate (coating film forming step) and the method of irradiating the coating film with active energy rays (curing step) can be any of the methods listed in the above <cured film>. In addition, when the curable composition of the present invention contains a solvent (in the form of varnish), after the coating film forming process, a step of drying the coating film and removing the solvent may be included, if necessary. In that case, the drying method (solvent removal process) of the coating film contained in the above-mentioned <cured film> can be used.

The layer thickness of the hard coat layer obtained in this way is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm.

Example

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to the following examples.

Meanwhile, in the examples, the equipment and conditions used for sample preparation and physical property analysis are as follows.

(1) Application by bar coater

Device: SMT Co., Ltd. PM-9050MC

Bar: A-Bar OSP-15 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 15μm (equivalent to wire bar #6.6)

Application speed: 4m/min

(2)Oven

Device: Dust-free dryer DRC433FA manufactured by Advantech Toyo Co., Ltd.

(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)

Device: HLC-8220GPC manufactured by Tosoh Corporation

Column: Showa Denko Co., Ltd. Shodex (registered trademark) GPC K-804L, GPC K-805L

Column temperature: 40℃

Eluent: tetrahydrofuran

Detector: RI

(5) Scratch resistance test

Equipment: Shinto Kagaku Co., Ltd. reciprocating abrasion tester TRIBOGEAR TYPE: 30S

Scanning speed: 5,000 mm/min

Scanning distance: 50mm

(6) Tensile test

Device: Autograph AGS-10kNX, tabletop precision universal testing machine manufactured by Shimadzu Works Co., Ltd.

Gripper: 1kN manual screw flat gripper

Gripping teeth: High-strength rubber coated gripping teeth

Tensile speed: 10mm/min

Measurement temperature: 23℃

(7)Optical microscope

Device: Digital Microscope VHX-6000 manufactured by Keyence Co., Ltd.

Measurement magnification: 20 times

Measurement method: reflection

(8)Bending test

Equipment: Cylindrical mandrel bending tester manufactured by Allgood Co., Ltd.

(9) Pencil hardness test

Device: Yasuda Seiki Manufacturing Co., Ltd. Pencil Scratching Hardness Tester No.553-M

Scraping speed: 60mm/min

(10) Contact angle measurement

Device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd.

Measurement temperature: 20℃

In addition, the abbreviated symbols indicate the following meanings.

A1: Non-oxyethylene-modified pentaerythritol tri/tetraacrylate (Kayarad (registered trademark) PET-30 manufactured by Nippon Explosives Co., Ltd.)

EOA1: Oxyethylene-modified diglycerine tetraacrylate [Aronics (registered trademark) M-460 manufactured by Dong-A Synthetic Co., Ltd., oxyethylene group 4 mol]

EOA2: Oxyethylene-modified pentaerythritol tetraacrylate (SR494NS manufactured by Sartomer, 4 mol of oxyethylene group)

EOA3: Oxyethylene-modified trimethylolpropane triacrylate (Aronics (registered trademark) M-350 manufactured by Dong-A Synthetic Co., Ltd., 3 mol of oxyethylene group)

PFPE: Perfluoropolyether having two hydroxy groups at each end of the molecular chain without a poly(oxyalkylene) group (Fomblin (registered trademark) T4 manufactured by Solbase Specialty Polymers)

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

DOTDD: Dioctyltin dineodecanoate [Neostan (registered trademark) U-830 manufactured by Nitto Chemical Co., Ltd.]

O2959: 2-Hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [OMNIRAD (registered trademark) 2959, manufactured by IGM Resins]

PGME: propylene glycol monomethyl ether

MEK: Methyl ethyl ketone

[Preparation Example 1] Preparation of surface modifier SM

Into the screw tube, 1.19 g (0.5 mmol) of PFPE1, 0.52 g (2.0 mmol) of BEI, 0.017 g of DOTDD (0.01 times the total mass of PFPE1 and BEI), and 1.67 g of MEK were added. 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 the surface modifier SM, the target compound. The weight average molecular weight of the obtained SM measured in polystyrene conversion by GPC: Mw was 3,000, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Example 1 to Example 3, Comparative Example 1 to Comparative Example 4]

The following components were mixed according to the description in Table 1, and a curable composition having the solid concentration shown in Table 1 was prepared. Meanwhile, solid content here refers to components other than the solvent. In addition, in Table 1, [part] indicates [part by mass]. This curable composition was applied by a bar coater onto an A4 size double-sided adhesive PET film (Toray Co., Ltd. Lumiror (registered trademark) U403, 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 at an exposure dose of 1200 mJ/cm ² under air to produce a hard coat film having a hard coat layer (cured film) with a layer (film) thickness of approximately 2 μm.

The scratch resistance, stretchability, bending resistance, pencil hardness, and stain resistance of the obtained hard coat film were evaluated. The evaluation procedures for scratch resistance, elongation, bending resistance, pencil hardness, and stain resistance are shown below. The results are shown together in Table 2.

[Scratch resistance]

The surface of the hard coat layer of the hard coat film was subjected to 100 reciprocations by applying a load of 200 g/cm ² with steel wool (Born Star (registered trademark) #0000 (ultrafine) manufactured by Bone Star Sales Co., Ltd.) attached to the reciprocating abrasion tester. After rubbing, the degree of scratches was visually checked and evaluated according to the following standards A and C.

A: No scratches

C: Scratches occur

[Stretchability]

The hard coat film was cut into a rectangle with a length of 60 mm and a width of 10 mm, and a test piece was produced. The test piece is attached to the gripper of the universal testing machine so as to hold 20 mm from both ends in the longitudinal direction, and the elongation (= (increase in distance between grippers) ÷ (distance between grippers) × 100) is 2.5%, 5%, 7.5%, 10%. So, a tensile test was conducted at 2.5% intervals. The hard coat film after the tensile test was observed under an optical microscope, and the maximum elongation at which no cracks occurred was taken as the elongation, and evaluated according to the following standards A and C.

A: More than 10%

C: less than 10%

[Bending resistance]

The hard coat film was cut into a rectangle with a length of 80 mm and a width of 20 mm, and a test piece was produced. The short side of the test piece was fixed to the bending tester equipped with a mandrel, and bent 180 degrees for 1 to 2 seconds so that the hard coat layer was on the outside. The hard coat film after bending was observed with the naked eye to confirm the presence or absence of cracks. Tests were conducted with mandrels with curvature radii of 1mmR, 2mmR, 3mmR, 5mmR, and 10mmR, and the minimum bending radius at which no cracks occurred was considered bending resistance, and was evaluated according to the following standards A and C.

A: Less than 3mmR

C: 3mmR or more

[Pencil hardness]

The surface of the hard coat layer of the hard coat film was rubbed with a pencil (manufactured by Mitsubishi Pencil Co., Ltd., hardness H) attached to the pencil scratch hardness tester by applying a load of 750 g, and the hard coat film after the test was observed with an optical microscope. It was evaluated according to the criteria A and C below.

A: No scratches

C: Scratches occur

[Antifouling]

1 μL of water was adhered to the surface of the hard coat layer of the hard coat film, the contact angle θ after 5 seconds was measured at 5 points, the average value was taken as the contact angle value, and evaluation was made according to the following standards.

A: Water contact angle value is 110° or more

C: Difference in water contact angle value is less than 110°

[Table 1]

[Table 2]

As shown in Table 2, the hard coat film having a hard coat layer obtained from the curable composition of Examples 1 to 3 containing oxyethylene-modified polyglycerin tetraacrylate EOA1 as an oxyethylene-modified polyfunctional monomer has scratch resistance. , it was shown to be excellent in elongation, bending resistance, pencil hardness, and stain resistance.

On the other hand, a hard coat layer obtained from the curable composition of Comparative Examples 1 and 2 containing oxyethylene-modified pentaerythritol tetraacrylate EOA2 and oxyethylene-modified trimethylolpropane triacrylate EOA3 as oxyethylene-modified polyfunctional monomers. The coat film was found to be inferior in scratch resistance, stretchability, and pencil hardness. In addition, it was shown that the hard coat film having a hard coat layer obtained from the curable composition of Comparative Example 3 that does not contain an oxyethylene-modified polyfunctional monomer was inferior in stretchability and bending resistance. Furthermore, it was shown that the hard coat film having a hard coat layer obtained from the curable composition of Comparative Example 4 not containing the surface modifier SM was inferior in scratch resistance and antifouling properties.

Claims (14)

(a) 100 parts by mass of an active energy ray-curable nonoxyethylene-modified polyfunctional monomer selected from the group consisting of polyfunctional (meth)acrylate compounds and polyfunctional urethane (meth)acrylate compounds,
(b) an active energy ray-curable oxyethylene-modified polyglycerol polyfunctional monomer selected from the group consisting of oxyethylene-modified polyglycerol polyfunctional (meth)acrylate compounds and oxyethylene-modified polyglycerol polyfunctional urethane (meth)acrylate compounds; 30 parts by mass to 150 parts by mass,
(c) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, with a (meth)acryloyl group or vinyl group as an active energy ray polymerizable group at both ends of the molecular chain through a urethane bond. Perfluoropolyether having a poly(oxyperfluoroalkylene) group (however, perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond is excluded.) (a) Component and (b) 0.05 parts by mass to 10 parts by mass based on a total of 100 parts by mass of the components, and
(d) Polymerization initiator that generates radicals by active energy rays: 1 part by mass to 20 parts by mass based on a total of 100 parts by mass of component (a) and component (b)
A curable composition containing. According to paragraph 1,
A curable composition in which the (c) perfluoropolyether has at least two (meth)acryloyl groups or vinyl groups through urethane bonds at both ends of the molecular chain. According to paragraph 2,
A curable composition in which the (c) perfluoropolyether has at least three (meth)acryloyl groups or vinyl groups through urethane bonds at each end of its molecular chain. According to any one of claims 1 to 3,
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. and a curable composition formed by combining random bonds. According to clause 4,
A curable composition in which the (c) perfluoropolyether has a partial structure represented by the following formula [1].

(In equation [1] above,
n is the total 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 formed by combining block combination, random combination, or any one of block combination and random combination.) According to any one of claims 1 to 3,
The polyfunctional monomer (b) has an average oxyethylene-modified amount of the polyfunctional monomer (b) of less than 2 mol per 1 mol of polymerizable groups of the polyfunctional monomer (b), and is an oxyethylene-modified poly having a functional group number of 4 or more. Glycerin multifunctional (meth)acrylate compounds (excluding oxyethylene-modified polyglycerol multifunctional urethane (meth)acrylate compounds) and oxyethylene-modified polyglycerol multifunctional urethane (meth)acrylate compounds with a functional group number of 4 or more. A curable composition containing at least one selected from the group consisting of. According to clause 6,
A curable composition wherein the polyfunctional monomer (b) is oxyethylene-modified diglycerol tetra(meth)acrylate. According to any one of claims 1 to 3,
(e) A curable composition further comprising a solvent. According to clause 8,
A curable composition wherein the solvent (e) is propylene glycol monomethyl ether. A cured film obtained from the curable composition according to any one of claims 1 to 3. A hard coat film comprising a hard coat layer on at least one side of a film substrate, wherein the hard coat layer consists of the cured film according to claim 10. A hard coat film comprising a hard coat layer on at least one side of a film substrate, wherein the hard coat layer forms a coating film by applying the curable composition according to any one of claims 1 to 3 on the film substrate. A hard coat film formed by a method including a step of curing the coating film by irradiating active energy rays. According to clause 11,
A hard coat film wherein the hard coat layer has a layer thickness of 1 μm to 10 μm. A method for producing a hard coat film comprising a hard coat layer on at least one side of a film substrate, wherein the hard coat layer is formed by applying the curable composition according to any one of claims 1 to 3 on a film substrate, A method of producing a hard coat film, comprising a step of forming a coating film, and a step of curing the coating film by irradiating active energy rays.