KR102593819B1 - Curable composition for anti-glare hard coat - Google Patents

Abstract

[Problem] To provide a material for forming a hard coat layer that has excellent anti-glare properties and scratch resistance, and also exhibits high initial water repellency.
[Solution] (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (b) a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, with urethane bonds at both ends of the molecular chain. Through, a perfluoropolyether having an active energy ray polymerizable group (however, a perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond. Excluded.) 0.05 parts by mass to 10 parts by mass, (c) 5 parts by mass to 40 parts by mass of fine particles having an average particle diameter of 0.2 μm to 15 μm, and (d) 1 mass of a polymerization initiator that generates radicals by active energy rays. It is a hard coat film comprising a curable composition containing 100 to 20 parts by mass, and a hard coat layer formed from this composition.

Description

Curable composition for anti-glare 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 touch panel displays and liquid crystal displays, and is particularly excellent in scratch resistance and anti-glare properties (anti-glare function). , relates to a curable composition capable of forming a hard coat layer with excellent initial water repellency.

A large number of products equipped with touch panel displays, such as personal computers, mobile phones, portable gaming devices, and ATMs, are being commercialized. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels with multi-touch functions is increasing at once.

On the surface of these touch panel displays, there is reflective glare (glare) of external light on the screen. ), a method of laminating an anti-glare hard coat film having a hard coat layer of the order of several μm with irregularities formed on the surface is used. As a method of forming irregularities on the surface, a method of containing fine particles having a particle diameter of about several μm in the hard coat layer is generally used.

However, in a capacitive touch panel, operations are performed by touching it with a human finger. For this reason, there was a risk that fingerprints would adhere to the surface of the touch panel every time an operation was performed, causing problems such as significantly impairing the visibility of images on the display or damaging the appearance of the display. Fingerprints contain moisture derived from sweat and oil derived from sebum, and in order to make it difficult for both of them to adhere, it is strongly desired to impart water and oil repellency to the hard coat layer on the display surface.

However, since people touch the capacitive touch panel with their fingers every day, even if the initial anti-fouling property has reached a significant level, the visibility of the display image and the anti-staining function are often reduced due to scratches occurring during use. . In particular, the anti-glare hard coat layer has irregularities on the surface, so it is prone to jamming and scratches. Therefore, the durability of antifouling properties during use was an issue.

Until now, in the hard coat layer having anti-glare and scratch resistance, as a component that imparts anti-fouling and scratch resistance to the surface of the hard coat layer, a poly(oxyperfluoroalkylene) structure and (meth)acrylic acid are contained within the molecule. A technology using methyl methacrylate-styrene copolymer (MS) resin microparticles as a surface modifier having a diary group and as a component for imparting anti-glare properties to the hard coat layer is disclosed (Patent Document 1). Meanwhile, perfluoropolyether having an active energy ray polymerizable group is added to both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group through a urethane bond to provide anti-glare properties to the hard coat layer as a surface modifier. As an imparting component, a technology using polymethyl methacrylate particles is disclosed (Patent Document 2).

Japanese Patent Publication No. 2013-257359 International Publication No. 2016/163478

In the method specifically described in Patent Document 1, the problem is that the fluorine content of the surface modifier having a poly(oxyperfluoroalkylene) structure and a (meth)acryloyl group in the molecule is low, and sufficient antifouling and scratch resistance cannot be obtained. there was. In addition, when the amount of MS resin particles added to obtain scratch resistance is reduced, sufficient anti-glare properties cannot be obtained, and when MS resin particles are added to the extent of obtaining sufficient anti-glare properties, there is a problem that scratch resistance is significantly reduced. Furthermore, the dispersibility of the resin particles in the hard coat layer was poor, and the resin particles formed into aggregates and damaged the appearance of the coating film. In addition, in the method specifically described in Patent Document 2, scratch resistance and sufficient anti-glare properties were obtained, but there was a problem in that the initial water contact angle was not sufficient and the water repellency was low. That is, a hard coat layer that is excellent in anti-glare and scratch resistance and also exhibits high initial water repellency was required.

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. Excellent anti-glare properties and high scratch resistance are achieved by using perfluoropolyether having an active energy ray-polymerizable group through urethane bonds without intervening groups as a fluorine-based surface modifier, and by adopting a curable composition to which fine particles are further added. In addition, it was discovered that a hard coat layer exhibiting high initial water repellency could be formed, and the present invention was completed.

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

(a) 100 parts by mass of active energy ray-curable multifunctional monomer,

(b) 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 perfluoropolyethers having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.) 0.05 parts by mass to 10 parts by mass,

(c) 5 to 40 parts by mass of fine particles having an average particle diameter of 0.2 μm to 15 μm, and

(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays

It relates to a curable composition containing.

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

As a third aspect, the (b) perfluoropolyether relates to the curable composition according to the second aspect, wherein the perfluoropolyether (b) has at least three active energy ray polymerizable groups at each end of its molecular chain through urethane bonds. .

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 can be 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 (b) perfluoropolyether has a partial structure represented by the following formula [1].

[Formula 1]

(In equation [1] above,

n represents an integer of 5 to 30 as the total number of repeating units-[OCF ₂ CF ₂ ]- and the number of repeating units-[OCF ₂ ]-;

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.)

As a sixth aspect, it relates to the curable composition according to any one of the first to fifth aspects, wherein the fine particles of component (c) are organic fine particles.

As a seventh aspect, it relates to the curable composition according to the sixth aspect, wherein the organic fine particles of component (c) are polymethyl methacrylate fine particles.

As an eighth aspect, it relates to the curable composition according to any one of the first to seventh aspects, further comprising (e) a solvent.

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

As a tenth aspect, it relates to a hard coat film comprising a hard coat layer on at least one side of a film substrate, wherein this hard coat layer is made of the cured film according to the ninth aspect.

As an 11th aspect, it relates to the hard coat film according to the 10th aspect, wherein the hard coat layer has a layer thickness of 1 μm to 20 μm.

As a twelfth aspect, it relates to the hard coat film described in the eleventh aspect, wherein the hard coat layer has a layer thickness of 3 μm to 15 μm.

As a thirteenth 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 eighth 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.

As a fourteenth aspect, it relates to a display provided with the hard coat film according to any one of the tenth to twelfth aspects.

As a 15th viewpoint, it relates to a polarizing plate provided with the hard coat film according to any one of the 10th to 12th viewpoints.

According to the present invention, a curable composition useful for forming a cured film and a hard coat layer that not only has excellent scratch resistance and high anti-glare properties and excellent appearance even in thin films with a thickness of about 1 μm to 20 μm, but also exhibits high initial water repellency is provided. can be provided.

In addition, according to the present invention, it is possible to provide a hard coat film having on the surface a cured film obtained from the above curable composition or a hard coat layer formed therefrom, and has excellent anti-glare properties, scratch resistance and appearance, and initial water repellency. We can provide excellent hard coat films.

<Curable composition>

The curable composition of the present invention is specifically,

(a) 100 parts by mass of active energy ray-curable multifunctional monomer,

(b) 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 perfluoropolyethers having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.) 0.05 parts by mass to 10 parts by mass,

(c) 5 to 40 parts by mass of fine particles having an average particle diameter of 0.2 μm to 15 μm, and

(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays

It relates to a curable composition containing.

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

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

An active energy ray-curable polyfunctional monomer refers to a monomer that undergoes polymerization and hardens when irradiated with active energy rays such as ultraviolet rays.

Preferred (a) active energy ray-curable polyfunctional monomers in the curable composition of the present invention include monomers selected from the group consisting of polyfunctional (meth)acrylate compounds.

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, ethoxylated trimethylolpropane tri(meth) ) Acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 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, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, di Propylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tricyclo[ 5.2.1.0 ^2,6 ]Decanedimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2- Hydroxy-1,3-di(meth)acryloyloxypropane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, bis[4-(meth) Acryloylthiophenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantane dimethanol di(meth) Acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate 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. can be mentioned.

Additionally, examples of the polyfunctional (meth)acrylate compound include polyfunctional urethane (meth)acrylate compounds. 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 compound include those obtained by reaction between a polyfunctional isocyanate and a (meth)acrylate having a hydroxy group, and (meth)acrylate having a polyfunctional isocyanate and a hydroxy group. Examples include those obtained by the reaction of urethane and polyol, but the polyfunctional urethane (meth)acrylate compounds usable in the present invention are 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 can be mentioned.

In the present invention, the active energy ray-curable polyfunctional monomer (a) is selected from the group consisting of the polyfunctional (meth)acrylate compound (compound not containing a urethane bond) and the polyfunctional urethane (meth)acrylate compound. One type can be used alone or in combination of two or more types. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth)acrylate compound (a compound not containing a urethane bond) and a polyfunctional urethane (meth)acrylate compound in combination.

In addition, as the above-mentioned polyfunctional (meth)acrylate compound, it is preferable to use a combination of a polyfunctional (meth)acrylate compound with 5 or more functions and a polyfunctional (meth)acrylate compound with 4 or less functions (in this case, the urethane bond is It does not matter whether it contains it or not; the same applies hereinafter).

In addition, when using the polyfunctional (meth)acrylate compound (a compound that does not contain a urethane bond) in combination with the polyfunctional (meth)acrylate compound, the polyfunctional (meth)acrylate compound (a compound that does not contain a urethane bond) is used in combination. It is preferable to use 20 to 100 parts by mass of the polyfunctional urethane (meth)acrylate compound, and more preferably 30 to 70 parts by mass, based on 100 parts by mass of the compound (not included).

Furthermore, in the above-mentioned polyfunctional (meth)acrylate compound, when the above-mentioned polyfunctional (meth)acrylate compound having 5 or more functions and the above-mentioned polyfunctional (meth)acrylate compound having 4 or less functions are used in combination, the polyfunctional (meth)acrylate compound having 5 or more functions is used in combination. It is preferable to use 10 to 100 parts by mass of a polyfunctional (meth)acrylate compound of 4 or less functions, and more preferably 20 to 60 parts by mass, based on 100 parts by mass of the polyfunctional (meth)acrylate compound. desirable.

In addition, 20 to 100 parts by mass of a polyfunctional urethane (meth)acrylate compound per 100 parts by mass of a polyfunctional (meth)acrylate compound (a compound not containing a urethane bond), and a polyfunctional (meth)acrylate having 5 or more functional functions. Using 10 to 100 parts by mass of a polyfunctional (meth)acrylate compound of 4 or less functions per 100 parts by mass of the rate compound,

20 to 100 parts by mass of a polyfunctional urethane (meth)acrylate compound per 100 parts by mass of a polyfunctional (meth)acrylate compound (compound not containing a urethane bond), and a polyfunctional (meth)acrylate compound of 5 or more functional groups. Using 20 to 60 parts by mass of a polyfunctional (meth)acrylate compound of 4 or less functions per 100 parts by mass,

30 to 70 parts by mass of a polyfunctional urethane (meth)acrylate compound per 100 parts by mass of a polyfunctional (meth)acrylate compound (compound not containing a urethane bond), and a polyfunctional (meth)acrylate compound of 5 or more functional groups. Using 10 to 100 parts by mass of a polyfunctional (meth)acrylate compound of 4 or less functions per 100 parts by mass,

30 to 70 parts by mass of a polyfunctional urethane (meth)acrylate compound per 100 parts by mass of a polyfunctional (meth)acrylate compound (compound not containing a urethane bond), and a polyfunctional (meth)acrylate compound of 5 or more functional groups. It is preferable to use 20 to 60 parts by mass of a polyfunctional (meth)acrylate compound of 4 or less functions per 100 parts by mass.

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

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

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 having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyperfluoroalkylene group has 2 fluorocarbon groups having 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 includes repeating units: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- in a molar ratio of [repeating units: -[OCF ₂ ]-]: [Repeating unit:-[OCF ₂ CF ₂ ]-]=2:1 to 1:2. It is preferable that the group is included in a ratio of approximately 1:1, and more preferably, it 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 terms of polystyrene by gel permeation chromatography is 1,000 to 5,000, preferably 1,500 to 3,000.

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

(b) 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 (b) 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 an acryloyl group in these structures is replaced with a methacryloyl group, and PFPE is the poly( Represents an oxyperfluoroalkylene) 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 terminal.), and L ¹ is 1 to 1 fluorine atom. represents an alkylene group having 2 or 3 carbon atoms substituted with 3, 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.)

Examples of the alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms include -CH ₂ CHF-, -CH ₂ CF ₂ -, -CHFCF ₂ -, -CH ₂ CH ₂ CHF- , -CH ₂ CH ₂ CF ₂ -, -CH ₂ CHFCF ₂ -, 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] is, for example, a structure represented by the formulas [B1] to [B12] shown below. can be mentioned.

[Formula 4]

[Formula 5]

(In formulas [B1] to [B12], A represents one of the structures represented by the formulas [A1] to [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 , Formulas [B7] to Formulas [B9] correspond to the case of m = 3, and Formulas [B10] to Formulas [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.

(b) Among perfluoropolyethers having polymerizable groups at both ends of the molecular chain, particularly preferable ones include compounds having a partial structure represented by the following formula [1].

[Formula 6]

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

n in 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, and is preferably 7 to 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 approximately in the range of 1:1. It is more desirable to do so. The combination of these repeating units may be either a block combination or a random combination.

In the present invention, (b) the perfluoropolyether having polymerizable groups at both ends of the molecular chain is 0.05 to 10 parts by mass, based on 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer, For example, it is used in a ratio of 0.1 parts by mass to 10 parts by mass, preferably 0.1 parts by mass to 5 parts by mass.

(b) 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 can be imparted to the hard coat layer. In addition, (b) by using perfluoropolyether having polymerizable groups at both ends of the molecular chain in a ratio of 10 parts by mass or less, it is sufficiently compatible with (a) the active energy ray-curable polyfunctional monomer, resulting in less clouding. A hard coat layer can be obtained.

The perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) 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, compounds in which an isocyanato group is bonded to the bond number in the structures represented by the above formulas [A1] to formula [A5] and structures in which the acryloyl group in these structures is replaced with a methacryloyl group (e.g. For example, it can be obtained by reacting 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate) to form a urethane bond.

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

[(c) Fine particles having an average particle diameter of 0.2 μm to 15 μm]

In the curable composition of the present invention, fine particles having an average particle diameter of 0.2 μm to 15 μm (hereinafter simply referred to as “(c) fine particles”) are formed by forming the surface of the hard coat layer formed from this curable composition into an uneven shape. Gives wisdom.

In the present invention, organic fine particles, inorganic fine particles, and organic-inorganic composite fine particles can be used as the (c) fine particles. Among these fine particles, it is preferable to use organic fine particles from the viewpoint of transparency. Organic fine particles can also play a role in controlling the haze value of the hard coat layer by controlling the difference between the refractive index and the refractive index of the curable composition that is the hard coat layer forming material.

The shape of the (c) fine particles is not particularly limited. For example, they may be roughly spherical in the form of beads, or may be of an irregular shape such as powder, but are preferably substantially spherical, and more preferably have an aspect ratio of 1.5 or less. They are approximately spherical particles, and most preferably are spherical particles.

The organic fine particles include, for example, polymethyl methacrylate fine particles (PMMA fine particles), silicon fine particles, polystyrene fine particles, polycarbonate fine particles, acrylic styrene fine particles, benzoguanamine fine particles, melamine fine particles, polyolefin fine particles, polyester fine particles, Examples include polyamide fine particles, polyimide fine particles, and polyfluoroethylene fine particles. These organic fine particles may be used individually, or two or more types may be used in combination.

Among these organic fine particles, polymethyl methacrylate fine particles can be suitably used.

The average particle diameter of the (c) fine particles used in the present invention is preferably in the range of 0.2 μm to 15 μm, for example, 1 μm to 10 μm. Here, the average particle diameter (μm) is the 50% volume diameter (median diameter) obtained by measurement by a laser diffraction/scattering method based on Mie theory. If the average particle diameter of the above-mentioned (c) fine particles is larger than the above numerical range, the image clarity of the display deteriorates, and if it is smaller than the above numerical range, sufficient anti-glare properties cannot be obtained, causing a problem that glare also increases. It becomes easier to do. On the other hand, the particle size distribution of the (c) fine particles is not particularly limited, but the particle size is uniform ( ) It is preferable that they are monodisperse fine particles.

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

In addition, the above-mentioned (c) fine particles are selected so that their average particle diameter satisfies the range of average particle diameter b/film thickness a of the fine particles = 0.1 to 1.0 with respect to the film thickness of the cured film obtained from the curable composition of the present invention described later. It is desirable.

The organic fine particles can be commercially available, for example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, ARX series, AFX series, MB series, MBP series, MB-C series, ACX series, ACP series (manufactured by Sekisui Chemicals Co., Ltd.); Tospearl (registered trademark) series (Momentive Performance Materials Japan Co., Ltd.); Eposta (registered trademark) series, MA series, ST series, MX series [above, made by Nippon Catalyst Co., Ltd.]; Optobiz (registered trademark) series (manufactured by Nissan Chemical Co., Ltd.); Flow Biz series (manufactured by Sumitomo Seika Co., Ltd.); Toray Pearl (registered trademark) PPS, PAI, PES, EP [all manufactured by Toray Co., Ltd.]; 3M (registered trademark) Dainion TF Micropowder Series [manufactured by 3M]; Chemisnow (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, SGP series (manufactured by Soken Chemical Co., Ltd.); Taptic (registered trademark) AR650 series, AR-750 series, FH-S series, A-20, YK series, ASF series, HU series, F series, C series, WS series [ above, manufactured by Toyobo Co., Ltd.]; Artpearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, BE series (manufactured by Negami Industry Co., Ltd.); Shin-Etsu Silicone (registered trademark) KMP series (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

In the present invention, the (c) fine particles are 5 parts by mass to 40 parts by mass, for example, 5 parts by mass to 30 parts by mass, preferably, based on 100 parts by mass of the above-described (a) active energy ray-curable polyfunctional monomer. It is used at a ratio of 8 to 25 parts by mass.

[(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, oxime esters, Examples include organic peroxides, benzophenones, biscumarins, 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; and methyl phenylglyoxylate.

In the present invention, the (d) polymerization initiator is used in a ratio of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, based on 100 parts by mass of the above-described (a) active energy ray-curable polyfunctional monomer. do.

[(e) Solvent]

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

The solvent is used to dissolve and disperse the components (a) to (d), 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 choose appropriately. 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.

Additionally, for the purpose of controlling the dispersibility of the fine particles during drying after coating, a solvent with a high boiling point may be used.

Examples of such solvents include cyclohexyl acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, and ethylene glycol monobutyl ether. Acetate, Diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monomethyl ether Examples include propylene glycol monobutyl ether, 3-methoxybutanol, dipropylene glycol dimethyl ether, and dipropylene glycol-methyl-propyl-ether.

(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 (d) (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, and dyes can be appropriately mixed.

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

Furthermore, for the purpose of increasing the hardness and scratch resistance of the cured film, inorganic fine particles such as silicon dioxide (silica) having a reactive group such as an active energy ray curable group may be added. Meanwhile, as the inorganic fine particles of the other additives, nanoparticles with an average particle diameter of less than 0.2 μm can be used.

<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. 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 (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene series resin, etc.), metal, wood, paper, glass, and slate. The shape of these substrates may be plate-shaped, film-shaped, or a three-dimensional molded body.

Application methods on the substrate include, for example, cast coat method, spin coat method, blade coat method, dip coat method, roll coat method, spray coat method, bar coat method, die coat method, inkjet method, and printing. The method (convex printing method, intaglio printing method, flatbed printing method, screen printing method, etc.) can be appropriately selected, and among these methods, the roll-to-roll method can be used, and thin films can also be used. From the viewpoint of foamability, it is preferable to use a relief printing method, especially a gravure coating 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 to application. Meanwhile, when applying, a solvent may be additionally added to this curable composition as needed. As the solvent in this case, various solvents mentioned in [(e) solvent] above can be used.

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. Examples of active energy rays include ultraviolet rays, electron rays, and X-rays, and ultraviolet rays are particularly preferable. Light sources used for ultraviolet irradiation include, for example, solar rays, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs.

Additionally, polymerization can also be completed by post-baking, 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, for example, 0.05 μm to 20 μm, preferably 1 μm to 20 μm, more preferably 3 μm to 15 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 manufactured. 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. A method for producing a hard coat film including a hard coat layer on at least one side of a film substrate including these steps is also the subject of the present invention.

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), polycarbonate, Films such as polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, and triacetylcellulose (TAC) can be mentioned.

In addition, the method of applying the curable composition on the film substrate (coating film forming process) and the method of irradiating the coating film with active energy rays (curing process) 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-described <cured film> can be used.

The layer thickness (film thickness) of the hard coat layer thus obtained is preferably set to be 1 to 10 times the thickness of the average particle diameter of the above-mentioned (c) fine particles. For example, the thickness of the hard coat layer is preferably 1 μm to 20 μm, more preferably 3 μm to 15 μm.

The hard coat film of the present invention described above can be used as a hard coat film for a display or a polarizing plate, and displays and polarizing plates provided with the hard coat film are also subject to the present invention.

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: Automatic Filmapplicator AB3125 from TQC Sheen

Bar 1: A-Bar OSP-42 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 42μm (equivalent to wire bar #16)

Bar 2: A-Bar OSP-22 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 22μm (equivalent to wire bar #9)

Bar 3: A-Bar OSP-52 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 52μm (equivalent to wire bar #20)

Application speed: 4m/min

(2)Oven

Equipment: Sanki Keiso Co., Ltd. two-layer clean oven (top and bottom) PO-250-45-D

(3) UV curing

Device: CV-110QC-G manufactured by Heraeus Co., Ltd.

Lamp: High-pressure mercury lamp H-bulb manufactured by Heraeus Co., Ltd.

(4)Film thickness (layer thickness)

Device: Digimicro MH-15M+ counter TC-101 digital measuring instrument manufactured by Nikon Co., Ltd.

(5) Glossiness measurement

Device: Glossmeter GM-268Plus manufactured by Konica Minolta Co., Ltd.

Measuring angle: 60 degrees

(6) Scratch resistance test

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

Scanning speed: 4,500 mm/min

Scanning distance: 50mm

(7)Total light transmittance, haze

Device: Haze meter NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

(8) 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.

PFPE1: 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)

PFPE2: Perfluoropolyether having hydroxy groups through poly(oxyalkylene) groups (repeating unit number 8 or 9) at both ends of the molecular chain (Fluorolink 5147X 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 [Neostane (registered trademark) U-830 manufactured by Nitto Chemical Co., Ltd.]

DBTDL: dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

DPHA: Dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [KAYALAD (registered trademark) DN-0075 manufactured by Nippon Explosives Co., Ltd.]

PETA: Pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture [NK ester A-TMM-3LM-N manufactured by Shin Nakamura Chemical Co., Ltd.]

UA: Hexafunctional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 manufactured by Daicel Allnex Co., Ltd.]

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

FP2: Cross-linked polymethyl methacrylate spherical particles [Techpolymer (registered trademark) SSX-108 manufactured by Sekisui Chemicals Co., Ltd., average particle diameter 8 μm]

FP3: Cross-linked polymethyl methacrylate spherical particles [Techpolymer (registered trademark) SSX-110 manufactured by Sekisui Chemicals Co., Ltd., average particle diameter 10 μm]

FP4: Cross-linked polymethyl methacrylate spherical particles [Techpolymer (registered trademark) SSX-103, manufactured by Sekisui Chemicals Co., Ltd., average particle diameter 3 μm]

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

EPA: ethyl p-dimethylaminobenzoate [KAYACURE (registered trademark) EPA manufactured by Nippon Explosives Co., Ltd.]

PET: Double-sided adhesive treated polyethylene terephthalate (PET) film (Lumiror (registered trademark) U403, manufactured by Toray Co., Ltd., thickness 100 μm)

TAC: Double-sided adhesive treated cellulose triacetate (TAC) film (Fujitac (registered trademark) TD80ULP, manufactured by Fujifilm Co., Ltd., thickness 80μm)

MEK: Methyl ethyl ketone

MIBK: Methyl isobutyl ketone

PGME: propylene glycol monomethyl ether

[Preparation Example 1] Preparation of perfluoropolyether (SM1) having four acryloyl groups through urethane bonds (without poly(oxyalkylene) groups) at both ends of the molecular chain.

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 SM1, the target compound.

The weight average molecular weight of the obtained SM1 measured in polystyrene conversion by GPC: Mw was 3,000, and the dispersion degree: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Preparation Example 2] Preparation of perfluoropolyether (SM2) having an acryloyl group through a poly(oxyalkylene) group at both ends of the molecular chain.

Into the screw tube, 1.05 g (0.5 mmol) of PFPE2, 0.26 g (1.0 mmol) of BEI, 0.01 g (0.02 mmol) of DBTDL, and 1.30 g of MEK were added. This mixture was stirred at room temperature (approximately 23°C) for 24 hours using a stirrer chip. This reaction mixture was diluted with 3.93 g of MEK to obtain a 20 mass% MEK solution of SM2, the target compound.

[Examples 1 to 9, Comparative Examples 1 to 4]

The following components were mixed according to the description in Table 1, and a curable composition with a solid content concentration of 40% by mass was prepared. Meanwhile, solid content here refers to components other than the solvent. In addition, in Table 1, [part] indicates [part by mass], and [%] indicates [mass %].

(1) Multifunctional monomer: 50 parts by mass of DPHA, 30 parts by mass of UA, and 20 parts by mass of PETA

(2) Surface modifier: Surface modifier listed in Table 1 in the amount shown in Table 1 (converted to solid content or active ingredient)

(3) Organic fine particles: Organic fine particles listed in Table 1 in the amount listed in Table 1

(4) Polymerization initiator: 5 parts by mass of O2959

(5) Polymerization accelerator: Amount listed in EPA Table 1

(6) Solvent: Solvent shown in Table 1 in the amount shown in Table 1

This curable composition was applied onto the A4 size film shown in Table 2 using a bar coater using the method shown in Table 2 to obtain a coating film. This coating film was dried in an oven under the conditions shown in Table 2 to remove the solvent. The obtained film was exposed to UV light at the exposure amount shown in Table 2 under a nitrogen atmosphere to produce a hard coat film having a hard coat layer (cured film) with a thickness shown in Table 2.

The obtained hard coat film was evaluated for anti-glare properties, scratch resistance, water contact angle, haze, and total light transmittance. The evaluation procedures for anti-glare properties, scratch resistance, and water contact angle are shown below. In addition, the results are shown together in Table 3.

[Bang Hyun-seong]

The obtained hard coat film was placed on a black table with a glossiness Gs (60°) of 11.8, the glossiness Gs (60°) of the surface of the hard coat layer of this hard coat film was measured, and the following criteria A, Evaluated according to B and C. On the other hand, when actual use as a hard coat layer is assumed, it is required to be at least B, and A is preferable.

A: Gs(60°)≤120

B: 120<Gs(60°)≤125

C: Gs(60°)>125

[Scratch resistance]

The surface of the hard coat layer of the hard coat film was rubbed with steel wool (Liberon #0000 manufactured by Liberon) attached to the reciprocating abrasion tester for 2,000 reciprocations by applying a load of 500 g/cm ² . The degree of scratches was visually confirmed under a three-color light source and evaluated according to the following criteria A, B, and C. On the other hand, when actual use as a hard coat layer is assumed, it is required to be at least B, and A is preferable.

A: No scratches

B: Several fine scratches occur.

C: Scratches appear on the entire surface

[Contact angle]

1 μL of water was attached 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 water contact angle value, and evaluation was made according to the following standards A and C. On the other hand, when actual use as a hard coat layer is assumed, the water contact angle (initial water repellency) is required to be A (108° or more).

A: Water contact angle value≥108°

C: Water contact angle value <108°

[Table 1]

[Table 2]

[Table 3]

As shown in Tables 1 to 3, the surface modifier in the hard coat layer has four acryloyl groups at each end of the molecular chain through a urethane bond (without a poly(oxyalkylene) group). Each hard coat film having a hard coat layer produced using the curable composition of Examples 1 to 9 using perfluoropolyether SM1 and also mixing organic fine particles, the layer thickness of this layer is 10 μm to 10 μm. A hard coat film having a hard coat layer with excellent scratch resistance and anti-glare properties at 14 μm was obtained. In addition, the initial water repellency was 108° or higher, and compared to the comparative example described later, it satisfied all the standards considering actual use.

On the other hand, the hard coat film of Comparative Example 1, which has a hard coat layer produced using perfluoropolyether SM2, which has an acryloyl group through a poly(oxyalkylene) group at both ends of the molecular chain as a surface modifier, , the desired initial water repellency could not be obtained.

Additionally, Comparative Examples 2 and 3, which did not contain organic fine particles, did not provide the desired anti-glare properties. In addition, Comparative Example 4 containing 50 parts by mass of organic fine particles achieved high anti-glare properties, but resulted in poor scratch resistance.

Claims (15)

(a) 100 parts by mass of active energy ray-curable multifunctional monomer,
(b) 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 perfluoropolyethers having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.) 0.05 parts by mass to 10 parts by mass,
(c) 5 to 40 parts by mass of organic fine particles having an average particle diameter of 0.2 μm to 15 μm, and
(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays
A curable composition comprising,
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 it is a group formed by combining random bonds,
A curable composition wherein the (b) perfluoropolyether is a compound represented by the following formula [2].

(In formula [2], A represents one of the structures represented by the following formulas [A1] to [A5] and structures in which an acryloyl group in these structures is replaced with a methacryloyl group, and PFPE is the poly( Represents an oxyperfluoroalkylene) 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 terminal.), and L ¹ is 1 to 1 fluorine atom. It represents an alkylene group having 2 or 3 carbon atoms substituted by 3, and the partial structure (A-NHC(=O)O) _m L ² - represents the structure represented by the following formula [B3].)

delete According to paragraph 1,
A curable composition in which the (b) perfluoropolyether has at least three active energy ray polymerizable groups at each end of its molecular chain through urethane bonds. delete delete delete According to paragraph 1,
A curable composition wherein the organic fine particles of component (c) are polymethyl methacrylate fine particles. According to claim 1 or 3,
(e) A curable composition further comprising a solvent. A cured film obtained from the curable composition according to claim 1 or 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 9. According to clause 10,
A hard coat film wherein the hard coat layer has a layer thickness of 1 μm to 20 μm. According to clause 11,
A hard coat film wherein the hard coat layer has a layer thickness of 3 μm to 15 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 forms a coating film by applying the curable composition according to claim 1 or 3 onto the film substrate. A method of manufacturing a hard coat film, including a process of curing the coating film by irradiating active energy rays. A display provided with the hard coat film according to claim 10. A polarizing plate provided with the hard coat film according to claim 10.